JP6923338B2 - Water-in-oil emulsified cosmetics - Google Patents

Description

The present invention adds a partially crosslinked organopolysiloxane polymer and a specific amphipathic associative thickener to a water-in-oil emulsified cosmetic containing a volatile oil, a silicone surfactant and a hydrophobic powder. This relates to a cosmetic that not only improves stickiness and uniformity of the makeup film, but also prevents pores from falling off and improves makeup durability.

Water-in-oil emulsified cosmetics are skin care cosmetics and make-up cosmetics, especially cosmetics often used in base makeup items such as foundations.

In the water-in-oil emulsified cosmetic, since the oil agent easily blends with the skin and easily spreads, there is a problem that the powder dispersed in the cosmetic generally easily enters the pores and easily falls off over time. An example of a water-in-oil emulsified cosmetic is a cosmetic that reduces stickiness and realizes a light spread and spread by combining a volatile oil agent, a silicone surfactant, and a hydrophobic powder. However, water-in-oil emulsified cosmetics that simply contain volatile oils, silicone surfactants, and hydrophobic powders have weak adhesion of powders on the skin, easily penetrate into pores during application, and pores over time. It was easy to drop. Pore drop of powder at the time of application is caused by the fact that the cosmetic and the powder spread too much together and occur. Therefore, in order to prevent pores from falling off and to increase the viscosity of the oily component in the cosmetic, an oily gelling agent may be contained. However, when an oil-based gelling agent is contained, the spread and spread are appropriately suppressed, and although the pore dropout is suppressed to some extent, stickiness occurs, and the cosmetic film tends to be uneven, and as a result, the pore dropout becomes conspicuous. there were.

Similarly, in order to increase the viscosity of the aqueous component in cosmetics, a technique containing a specific amphoteric associative thickener (Patent Document 1) has been developed, but this technique alone can prevent pores from falling off. When trying to prevent it, the pores did not fall off immediately after application, but the pores of the powder fell off over time, and the quality was not satisfactory. If an oil-soluble polymer was further contained in order to prevent the powder from dropping pores over time, stickiness and sliminess would occur, and the cosmetic film would tend to be uneven during application, resulting in uneven application.

JP-A-2010-111634

However, with the conventional technology, even if pores are prevented from falling off during application and over time, stickiness, sliminess, and uneven coating occur, resulting in an uneven cosmetic film. It was difficult to realize the quality of a uniform cosmetic film without unevenness. That is, an object of the present invention is the development of a water-in-oil emulsified cosmetic that does not cause pores to fall off during application and over time, has no stickiness or sliminess, and can obtain a uniform cosmetic film without uneven coating.

In view of these circumstances, the present inventors have made water-in-oil emulsified cosmetics containing a volatile oil agent, a silicone surfactant, and a hydrophobic powder, which are less sticky, have a uniform cosmetic film, and are used at the time of application as well as at the time of application. As a result of diligent studies to achieve a quality that does not easily cause pores to fall off over time and does not impair the finish at the time of application, the above-mentioned water-in-oil emulsified cosmetics are partially cross-linked organopolysiloxane polymers and specific amphoteric associations. By combining a sex thickener, a smooth and uniform cosmetic film can be formed, and a water-in-oil emulsified cosmetic that can maintain excellent finish quality without powder falling off over time is realized. We have found that we can do it, and based on these findings, we have completed the present invention.

That is, in the present invention, the following components (A) to (E):
(A) Volatile oil agent (B) Silicone surfactant (C) Hydrophobic powder (D) Partially crosslinked organopolysiloxane polymer (E) Hydrophobic-modified polyether urethane R _{1 represented by the following general formula (1)} ─ {(O ─ _{R 2} ) _{k ─ OCONH ─ R 3} [─ NHCOO ─ (R _{4 ―} O) _n ─ _{R 5} ] _h } _m (1)
[In the formula, R ₁ , R ₂ and R ₄ represent hydrocarbon groups that may be the same or different from each other, R ₃ represents a hydrocarbon group that may have a urethane bond, and R ₅ represents a straight chain. , Branch chain or secondary hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, and k and n are independently numbers in the range 0 to 1000. ]
To provide a water-in-oil emulsified cosmetic containing.

Further, it is to provide a water-in-oil emulsified cosmetic having an HLB of the silicone surfactant of the component (B) of 2 to 7.

Further, the present invention provides a water-in-oil emulsified cosmetic having an average particle size of the hydrophobic powder of the component (C) of 0.1 to 30 μm.

INDUSTRIAL APPLICABILITY The present invention can provide a water-in-oil emulsified cosmetic that can form a smooth and uniform cosmetic film and can maintain excellent finish quality without powder falling off pores over time.

Hereinafter, the present invention will be described in detail. In addition, in this specification, when the numerical value range is expressed by using ~, the range includes the numerical values at both ends.

The volatile oil agent of the component (A) used in the present invention refers to an oil agent that is volatile at room temperature, and has a low boiling point (boiling point at normal pressure is 260 ° C. or less), a hydrocarbon oil such as isoparaffin, a silicone oil, or the like. Is preferably used. Examples of hydrocarbon oils (light isoparaffins) such as low boiling isoparaffins include isododecane, isohexadecane and the like. Commercially available products are Isopar A, Isopar C, Isopar E, Isopar G, Isopar H, Isopar K, Isopar L, Isopar M (all manufactured by Exxon), Shellzol 71 (manufactured by Shell), Saltrol 100, Salt. Examples thereof include roll 130 and salt roll 220 (both manufactured by Philippe) ISODODECANCE (INEOS OLIGOMERS). Specific examples of the cyclic silicone oil (cyclomethicone) include hexamethylcyclotrisiloxane, octamethyltetracyclosiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetradecamethylcycloheptasiloxane, which are commercially available. Examples of products include Execol D-4 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SH244, SH344 (all manufactured by Toray Dow Corning) as octamethyltetracyclosiloxane, and Execol D as decamethylcyclopentasiloxane. -5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), SH245, DC345 (all manufactured by Toray Dow Corning Co., Ltd.), and examples of dodecamethylcyclohexasiloxane include DC246 (manufactured by Toray Dow Corning Co., Ltd.). (A) can be used alone or in combination of two or more, if necessary. In the present invention, low boiling point silicone oil is preferable as the component (A) from the viewpoint of emulsion stability, and cyclomethicane or the like is preferable. More preferably used.

The content of the component (A) is not particularly limited, but is preferably 10 to 50% by mass (hereinafter abbreviated as%), more preferably, in the total amount of the cosmetic, from the viewpoint of uniformity of the cosmetic film and no loss of pores. Is 15-35%.

The silicone surfactant of the component (B) used in the present invention is an amphipathic surfactant having a silicone chain, and a polyether-modified silicone having a polyether chain as a hydrophilic group or a polyglycerin chain as a hydrophilic group is used. Examples thereof include polyglycerin-modified silicone having.

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

The component (B) of the present invention is not particularly limited, but a polyoxyalkylene-modified organoxane having a linear structure organopolysiloxane group as a main chain and a polyoxyalkylene group as a side chain is specifically defined. Examples thereof include polysiloxane, polyoxyalkylene-alkyl co-modified organopolysiloxane, and examples of commercially available products include KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 5200 Formulation Aid (manufactured by Toray Dow Corning Co., Ltd.). .. Further, as a material obtained by grafting a polyoxyalkylene group with an organopolysiloxane group having a branched structure as a main chain (silicone branched polyether-modified silicone), specifically, PEG-9 polydimethylsiloxyethyl dimethicone and lauryl. Examples thereof include PEG-9 polydimethylsiloxyethyl dimethicone and cetyl PEG-9 polydimethylsiloxyethyl dimethicone, and examples of these commercially available products include KF-6028 and KF-6038 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Be done. Specific examples of the grafted polyglycerin group (silicone branched polyglycerin-modified silicone) having an organopolysiloxane group having a branched structure as a main chain include lauryl polyglyceryl 3-polydimethylsiloxyethyl dimethicone. Examples of commercially available products include KF-6105 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Specific examples of the block copolymer type include polyoxyethylene / butylene / dimethylpolysiloxane copolymer, polyoxyethylene / polyoxypropylene / butylene / dimethylpolysiloxane copolymer, and the like, which are commercially available. Examples of the product include FZ-2250, FZ-2233 (all manufactured by Toray Dow Corning Co., Ltd.), SILWET 236-L manufactured by Nippon Unicar Co., Ltd., and the like. Among these, polyether-modified silicone having a polyoxyethylene group has good spreadability and is particularly preferable.
The component (B) may be, for example, one or more of the components (B) used in the following examples. Specifically, component (B) is selected from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, and PEG-9 dimethicone. It may be one kind or two or more kinds.

As the component (B), one kind or two or more kinds can be used including these examples. The HLB of the component (B) is preferably 2 to 7, and particularly preferably 3 to 5. Within this range, it is excellent and preferable because of its emulsification stability and no loss of pores. The HLB (hydrophilic-lipophilic balance) value used in the present invention is a value obtained by the Griffin method. The weight average molecular weight of the component (B) is not particularly limited, but is preferably 500 to 200,000, more preferably 1000 to 10000. Further, as the hydrophilic group to be added, a polyoxyalkylene chain is preferable, and a polyether-modified silicone having a polyoxyethylene chain of 7 to 11 is particularly preferable.

The content of the component (B) in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but is 0.5 to 10% from the viewpoint of forming a uniform cosmetic film with less stickiness and no unevenness. Preferably, 1 to 7.5% is more preferable, and 2 to 5% is further preferable.

The component (C) hydrophobic powder used in the present invention includes a powder that is hydrophobic in itself, a powder in which the surface of a hydrophilic powder is treated with a commonly known hydrophobic agent, and the hydrophobicity is further enhanced. Therefore, a powder obtained by further treating a hydrophobic powder with a hydrophobic agent can be mentioned. The hydrophobic powder referred to here is a powder that is dispersed in the hexane phase when the powder is dispersed in a mixed solvent having a mass ratio of water and hexane of 1: 1.

Among these, hydrophobic powders that are themselves hydrophobic include, for example, polystyrene powder, polyethylene powder, N-acyllysine powder, epoxy resin powder, (vinyldimethicone / methicone silsesquioxane) crosspolymer powder, and (diphenyl). Examples thereof include organic resin powders such as dimethicone / vinyldiphenyldimethicone / silsesquioxane) crosspolymer powder, and metal soap powders such as aluminum stearate, zinc laurate, and magnesium stearate.

The powder to be hydrophobized may be any raw material that is usually used for cosmetics, and examples thereof include inorganic powders, organic powders, and brilliant powders. Specifically, titanium oxide, black titanium oxide, corn, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, carbon black, silicic acid. Inorganic powders such as aluminum, magnesium silicate, magnesium silicate, mica, synthetic mica, synthetic sericite, sericite, talc, silicon carbide, barium sulfate, boron nitride, nylon powder, acrylic powder, silk powder, crystals Organic powders such as cellulose, N-acyllysine and tar pigments, bismuth oxychloride, mica titanium, iron oxide coated mica, iron mica titanium oxide, organic pigment treated mica titanium, composite powders such as aluminum powder, etc. Therefore, one or more of these can be appropriately selected and used.

Examples of the treatment agent used for the hydrophobization treatment include silicone compounds such as dimethylpolysiloxane, methylhydrogenpolysiloxane, high-viscosity silicone, crosslinked silicone, fluorine-modified silicone, acrylic-modified silicone, and silicone resin, and perfluoroalkylsilane. , Surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, metal soaps such as zinc laurate and zinc stearate, oils such as polyisobutylene, wax, higher fatty acids and higher alcohols, N- Examples thereof include acyl amino acids, perfluoroalkyl phosphoric acid and salts thereof, perfluoropolyethers, fluorine compounds such as perfluoropolyether alkyl phosphoric acid and salts thereof, polyvinylpyrrolidone-modified polymers such as a copolymer of polyvinylpyrrolidone-hexadecene, and the like. Can be used alone or in combination of two or more.

Further, the method for treating the powder with these treatment agents is usually a known method and is not particularly limited, but for example, a wet method using a solvent, a vapor phase method, a mechanochemical method and the like. Can be mentioned. The amount treated with the treatment agent varies depending on the type, but is preferably 0.5 to 7% of the hydrophobized powder in terms of adhesion to the skin, uniformity of finish, and longevity of makeup, and further 1 to 1 5% is more preferable.

The average particle size of the hydrophobic powder used in the present invention is preferably 0.1 to 30 μm, more preferably 5 to 20 μm. This range is preferable in terms of a uniform coating film. The average particle size can be measured as a volume average particle size (D50) using, for example, a laser scattering type particle size distribution meter (manufactured by HORIBA).

The content of the hydrophobic powder used in the present invention is not particularly limited, but is preferably 0.1 to 20%, and even more preferably 0.5 to 15%. Within this range, an appropriate amount of powder adheres, it is difficult for unevenness to occur, the uniformity of the cosmetic film can be maintained, and it is difficult for the powder to fall into the pores, and an excellent cosmetic effect can be obtained, which is preferable.
The component (C) may be, for example, one or more of the components (C) used in the following examples. Specifically, the component (C) is hydrophobized titanium oxide, hydrophobized red iron oxide, hydrophobized iron yellow oxide, hydrophobized iron black oxide, (vinyldimethicone / methicone silsesquioxane) crosspolymer, poly. It may be one or more selected from the group consisting of methyl methacrylate, hydrophobized fine particle titanium oxide, polyethylene powder, and spherical nylon.

By using a partially crosslinked organopolysiloxane polymer in combination, it has an excellent cosmetic durability and has an effect of imparting a uniform makeup film uniformity due to the non-stickiness of the finish. The component (D) partially crosslinked organopolysiloxane polymer used in the present invention is a polymer obtained by crosslinking an organopolysiloxane and having a partially three-dimensional crosslinked structure. This is described in, for example, Japanese Patent Application Laid-Open No. 8-6035, Japanese Patent Application Laid-Open No. 4-272932, Japanese Patent Application Laid-Open No. 5-140320, Japanese Patent Application Laid-Open No. 2001-342255, and International Publication No. 2003/024413 pamphlet. ..

The partially crosslinked organopolysiloxane polymer of component (D) is, for example, an organohydrogenpolysiloxane containing 1.5 or more hydrogen atoms bonded to silicon atoms shown in (a) below on average in the molecule. , (B) can be obtained by addition polymerization with a compound having an average of 1.5 or more vinyl reaction sites in the molecule.

(A) is SiO ₂ unit, HSiO _1.5 unit, RSiO _1.5 unit, RHSiO unit, R ₂ SiO unit, R ₃ SiO _0.5 unit and R ₂ HSiO _0.5 unit (where R is Substituent or unsubstituted monovalent hydrocarbon groups having 1 to 30 carbon atoms excluding aliphatic unsaturated groups. The monovalent hydrocarbon groups are alkyl groups such as methyl group, ethyl group, propyl group, phenyl group, and the like. An aryl group such as a trill group, an aliphatic unsaturated group such as a vinyl group, an aralkyl group in which a hydrogen atom such as a methyl group, an ethyl group or a propyl group is replaced with an aryl group such as a phenyl group or a trill group, a cyclohexyl group or the like. It is composed of at least one structural unit selected from the group consisting of a cycloalkyl group, a halogenated hydrocarbon group containing a fluoro group, a hydrocarbon group containing an ethylene oxide group, etc., and is composed of a silicon atom. It is an organohydrogenpolysiloxane containing 1.5 or more bonded hydrogen atoms in the molecule on average.

(B) is one kind or two or more kinds selected from the following (b-1) to (b-3).
(B-1) is 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 _0.5 unit (where R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms excluding aliphatic unsaturated groups. Monovalent hydrocarbon. Examples of the group include 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 trill group, an aliphatic unsaturated group such as a vinyl group, and a hydrogen atom such as a methyl group, an ethyl group and a propyl group. Examples thereof include an aralkyl group substituted with an aryl group such as a phenyl group and a trill group, a cyclohexyl group, a halogenated hydrocarbon group containing a fluoro group, and a hydrocarbon group containing an ethylene oxide group.) It is an organopolysiloxane composed of at least one selected structural unit and containing an average of 1.5 or more vinyl groups bonded to silicon atoms in the molecule.

(B-2) is a polyoxyalkylene represented by the following general formula (2).
C _m H _2m-1 O (C ₂ H ₄ O) _p (C ₃ H ₆ O) _q C _m H _2m-1 (2)
(In the formula, p is an integer of 2 to 200, q is an integer of 0 to 200, p + q is an integer of 3 to 200, and m is an integer of 2 to 6).

(B-3) is an unsaturated hydrocarbon represented by the following general formula (3).
C _n H _2n-1 (CH2) _r C _n H _2n-1 (3)
(However, n is an integer of 2 to 6 and r is an integer of 1 or more.)

Specific examples of the component (D) include partially cross-linked methylpolysiloxane such as (dimethicone / vinyldimethicone) crosspolymer, (dimethicone / phenyldimethicone) crosspolymer, etc. Partially cross-linked methylphenylpolysiloxane of. Examples of the polymer containing a polyoxyalkylene group in the molecule include partially crosslinked polyether-modified silicone such as (dimethicone / (PEG-10 / 15)) cross-polymer. Examples of the polymer containing a long-chain alkyl group in the molecule include partially crosslinked alkyl-modified silicones such as (vinyldimethicone / lauryldimethicone) crosspolymer. Examples of the polymer containing a polyoxyalkylene group and a long-chain alkyl group in the molecule include partially crosslinked alkyl-polyether co-modified silicone such as (PEG-15 / lauryldimethicone) crosspolymer, and (lauryldimethicone / poly). Glycerin-3) Partially crosslinked polyglycerin-modified silicone such as cross-polymer can be mentioned. Examples of the polymer containing a halogenated hydrocarbon group in the molecule include partially crosslinked fluorine-modified silicone such as (trifluoropropyldimethicone / trifluoropropyldivinyldimethicone) crosspolymer. These can be used alone or in combination of two or more.

Further, although not particularly limited, a partially crosslinked methylpolysiloxane such as (dimethicone / vinyldimethicone) crosspolymer, a partially crosslinked methylphenylpolysiloxane such as (dimethicone / phenyldimethicone) crosspolymer, (dimethicone / (PEG-10 /) 15)) Partially crosslinked polyether-modified silicone such as crosspolymer, (PEG-15 / lauryldimethicone) partially crosslinked alkyl-polyether co-modified silicone such as crosspolymer, (lauryldimethicone / polyglycerin-3) crosspolymer, etc. The partially crosslinked polyglycerin-modified silicone is more preferable in terms of long-lasting makeup and evenness of the decorative film due to the non-stickiness of the finish.

When the component (D) is contained in a swollen state with an oil agent such as silicone oil, it is more uniformly dispersed and the formulation is excellent in stability. Therefore, the component (D) in the powder state is the component (D) of the present invention. ) Is not included. It is often marketed in the form of a mixture with a solvent, and such commercial products can be used in the present invention. Commercially available products include, for example, KSG-15 (solid content 5%) as a mixture of partially crosslinked methylpolysiloxane and cyclic silicone, and KSG-16 (solid content 20) as a mixture of partially crosslinked methylpolysiloxane and dimethylpolysiloxane. ~ 30%), KSG-18 (solid content 10-20%) as a mixture of partially crosslinked methylphenylpolysiloxane and phenyltrimethicone, KSG-210 as a mixture of partially crosslinked polyether-modified silicone and dimethylpolysiloxane (Solid content 20 to 30%), KSG-41 (solid content 25 to 35%), KSG-42 (solid content 20 to 30%), KSG-43 (solid content) as a mixture of partially crosslinked alkyl-modified silicone and an oil agent. 25-35% (25-35%) and KSG-44 (25-35% solid), KSG-310 (25-35% solid), KSG- as a mixture of partially crosslinked alkyl-polyether co-modified silicone and oil. Examples thereof include 320 (solid content 20 to 30%), KSG-330 (solid content 15 to 25%) and KSG-340 (solid content 25 to 35%) (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Further, the partially crosslinked fluorine-modified silicone is used as a mixture with a cyclic fluorine-containing silicone such as a fluoroalkyl group-containing cyclic organopolysiloxane, for example, KSG-51 (solid content 15 to 25%: manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. There is. These can be used alone or in combination of two or more.

As the component (D), one type or two or more types can be used as needed, and the content thereof is not particularly limited, but the cosmetic film has excellent long-lasting makeup and has no unevenness due to the non-stickiness of the finish. From the viewpoint of uniformity, 0.05 to 8% is preferable, and more preferably 0.3 to 3%, based on the total amount of the cosmetic.

The component (E) used in the present invention is a hydrophobically modified polyether urethane represented by the following general formula (1), and has a uniform makeup film without unevenness due to the non-stickiness of the finish and a makeup having a long-lasting makeup. It forms a film.
(Chemical 1)
R ₁ ─ {(O ─ _{R 2} ) _{k ─ OCONH ─ R 3} [─ NHCOO ─ (R _{4 ―} O) _n ─ _{R 5} ] _h } _m (1)
[In the formula, R ₁ , R ₂ and R ₄ represent hydrocarbon groups that may be the same or different from each other, R ₃ represents a hydrocarbon group that may have a urethane bond, and R ₅ represents a straight chain. , Branch chain or secondary hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, and k and n are independently numbers in the range 0 to 1000. ]

In the above formula (1), preferable R ₁ , R ₂ and R ₄ are an alkylene group having 2 to 4 carbon atoms or a phenylethylene group, and R ₃ is an alkylene group having 1 to 10 carbon atoms as a hydrocarbon group. a group, R ₅ is preferable that is an alkyl group having 8 to 36 carbon atoms.

The component (E) of the present invention is not particularly limited as long as it satisfies the above formula (1), but any component (E) used in ordinary cosmetics can be used, for example, (PEG-240 / decyltetradeceth-). 20 / HDI) Copolymer and the like. Examples of commercially available products include ADEKA NOL GT-700 (manufactured by ADEKA Corporation) and the like.

The content of the component (E) in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but is 0.01 to 3% from the viewpoint of non-greasy feel, uniform finish, and long-lasting makeup. The range is preferable, and 0.1 to 2% is more preferable in terms of uniform finish.

In addition to the above components (A) to (E), the present invention includes oily components other than the component (A), surfactants other than the component (B), and other than (C), as long as the effects of the present invention are not impaired. Can contain commonly known ingredients such as powders, aqueous components, UV absorbers, moisturizers, antioxidants, cosmetological ingredients, preservatives, pigments, fragrances and the like.

The oily component other than the component (A) may be a solid, semi-solid, or liquid oil generally used in cosmetics, and is considered safe for the human body regardless of animal oil, vegetable oil, mineral oil, or synthetic oil. Can be used. For example, fats and oils such as olive oil, castor oil, jojoba oil and mink oil, waxes such as beeswax, lanolin and candelilla wax, hydrocarbons such as liquid paraffin, squalane, vaseline, paraffin wax and microcrystallin wax, stearic acid, Fatty acids such as oleic acid, higher alcohols such as cetanol, stearyl alcohol and behenyl alcohol, esters such as isopropyl myristate, glyceryl trioctanoate and distearyl triisostearate, lanolin derivatives such as isopropyl fatty acid and lanolin alcohol, dimethylpolysiloxane, Examples thereof include silicone oils such as methylphenylpolysiloxane, and fluorine-based oils such as perfluorodecane and perfluorooctane.

The surfactant other than the component (B) is not particularly limited as long as it is generally used in cosmetics such as an ionic surfactant and a nonionic surfactant. Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct. Examples thereof include sorbitol fatty acid esters and alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, glyceride fatty acid esters, glycerin alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene hydrogenated castor oil and the like. Examples of anionic surfactants include fatty acids such as stearic acid and lauric acid and their inorganic and organic salts, alkylbenzene sulfates, alkyl sulfonates, α-olefin sulfonates, dialkyl sulfosuccinates and α-sulfones. Chemical fatty acid salt, acylmethyl taurine salt, N-methyl-N-alkyl taurine salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxy Examples thereof include ethylene alkylphenyl ether phosphate, N-acyl amino acid salt, N-acyl-N-alkyl amino acid salt, ο-alkyl substituted malate, alkyl sulfosuccinate and the like. Examples of amphoteric tenside agents include amino acid type and betaine type carboxylic acid type, sulfate ester type, sulfonic acid type, and phosphoric acid ester type, and those that are safe for the human body can be used. For example, N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N-dialkylaminoalkylenecarboxylic acid, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N- Examples thereof include dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine and the like. Examples of the cationic surfactant include a mono-long-chain alkyl-type quaternary ammonium salt, a di-long-chain alkyl-type quaternary ammonium salt, an ethylene oxide (EO) -added quaternary ammonium salt, and the like. Specifically, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, disetyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, dilauryldimethylammonium chloride, Dipolyoxyethylene chloride (15EO) palm oil alkylmethylammonium, dipolyoxyethylene chloride (4EO) lauryl ether dimethylammonium and the like can be mentioned.

As the powder other than the component (C), if it is a powder generally used for cosmetics, it has a spherical shape, a plate shape, a needle shape, etc. The particle structure such as non-porous material is not particularly limited, and examples thereof include inorganic powders, glittering powders, pigment powders, metal powders, and composite powders. Specifically, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate, colored inorganic pigments such as iron oxide, titanium / titanium oxide sintered body, chromium oxide, chromium hydroxide, dark blue, and ultramarine blue. , White mica, Gold mica, Red mica, Black mica, Synthetic mica, Silk mica (Serisite), Synthetic sericite, Kaolin, Silicon carbide, Bentnite, Smectite, Silica anhydride, Aluminum oxide, Magnesium oxide, Zinc oxide, Silica White constitution powder such as sawdust, aluminum silicate, aluminum magnesium metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, titanium dioxide coated mica, titanium dioxide coated Luminous powders such as bismuth oxychloride, titanium oxide mica, navy blue treated mica titanium, carmine treated mica titanium, bismuth oxychloride, fish scale foil, natural organic powders such as silk powder and cellulose powder, aluminum powder, gold powder and silver powder. Metal powders such as, fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and other composite powders. Can use one or more of them.

Aqueous components include polyhydric alcohols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyethylene glycol, sorbitol, martitol, carboxyvinyl polymer, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone and the like. Examples thereof include water-soluble polymers and mucilages such as resins, and the present invention is not particularly limited as long as it is generally used in cosmetics.

Examples of the ultraviolet absorber include ultraviolet absorbers such as benzophenone-based, PABA-based, silicic acid-based, and salicylic acid-based, such as 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone, and paramethoxycinnamic acid 2. -Ethylhexyl, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, hexyl diethylaminohydroxybenzoyl benzoate, bisethylhexyloxyphenol methoxyphenyl triazine, etc. Be done.

Examples of the moisturizer include proteins, mucopolysaccharides, collagen, elastin, keratin and the like, examples of the antioxidant include α-tocopherol, ascorbic acid and the like, and examples of the beauty ingredient include vitamins. , Anti-inflammatory agents, crude drugs and the like, and examples of preservatives include paraoxybenzoic acid ester, phenoxyethanol, 1,2-pentadiol and the like.

The method for producing the water-in-oil emulsified cosmetic of the present invention is not particularly limited and is prepared by a conventional method. For example, by dispersing the components (A) to (D) in an oil agent, heating and dissolving the components (A) to (D) as necessary, and then adding and mixing an aqueous component containing the uniformly swollen component (E) to emulsify. Can be prepared.

The water-in-oil emulsified cosmetic of the present invention is not particularly limited, but can be applied to a foundation, a foundation, a daytime beauty essence, a sunscreen, and the like. In addition, examples of the method of use include a method of using it with a hand or a finger, a method of impregnating it with a puff, a sponge, or the like. In addition, the properties can be implemented as cosmetics having various properties such as solid, gel, and liquid.

The present invention will be further described below with reference to examples. It should be noted that these do not limit the present invention in any way.

Examples 1 to 9 and Comparative Examples 1 to 7: Base cosmetics The base cosmetics having the compositions shown in Tables 1 and 2 are prepared by the following production methods, and <1> finish (pore removal) is performed by the evaluation method shown below. Nothing), <2> Finish (makeup persistence), <3> Usability (moist feeling), and <4> Usability (no unevenness) were evaluated. The results are shown in Tables 1 and 2.

(Evaluation method)
<1-2> Finish (no pores falling off, makeup lasting)
<3-4> Usability (moist feeling, no unevenness)
When each sample was applied to the face, the degree of application and the degree of finish of the cosmetic film were visually determined. The evaluation was made by five specialized panels according to the following evaluation criteria, and the average value was applied to the following criteria for judgment.
[Evaluation criteria]
<1> Evaluation Criteria for No Pore Drops 5: No Pore Drops 4: No Pore Drops 3: Neither can be said 2: Pore Drops 1: Pore Drops and Pore Conspicuous

<2> Evaluation criteria for makeup persistence 5: No makeup breakup 4: No makeup breakup 3: Neither can be said 2: Makeup breakage is noticeable 1: Makeup breakage is noticeable and makeup needs to be retouched

<3> Moist feeling evaluation criteria 5: Very moist feeling 4: Moist feeling 3: Neither can be said 2: No moist feeling 1: No moist feeling, dry feeling

<4> Evaluation criteria for no unevenness 5: No unevenness 4: No unevenness 3: Neither can be said 2: There is unevenness 1: There is unevenness and the cosmetic film is easily broken

[criterion]
⊚: 4.3 or more and less than 5.0 ○: 3.5 or more and less than 4.3 Δ: 2.0 or more and less than 3.5 ×: 1.0 or more and less than 2.0

* 1 Triethoxyoctylsilane 2% treatment * 2 Perfluorooctylsilyl 3% treatment * 3 KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 4 Silicon KF96-10CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 5 KSG-210 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 6 ADEKA NOL GT-700 (manufactured by ADEKA)

(Production method)
A. The components (1) to (7) are uniformly dispersed.
B. After the components (8) to (18) are uniformly dispersed, A is added with stirring.
C. The components (21) to (23) are uniformly dissolved while being heated to 80 ° C. as necessary, and then the components (19) to (20) are added and mixed.
D. C was added to B at room temperature, and the mixture was uniformly stirred and emulsified to obtain a base cosmetic.

As is clear from the results in Tables 1 and 2, the base cosmetics of Examples 1 to 9 can form a smooth and uniform cosmetic film, and the powder does not fall off the pores over time. The quality was sustainable. Further, in Example 8 using a silicone surfactant having an HLB of more than 7, the result was that Example 1 was superior in terms of the absence of pore dropout, and a hydrophobic powder having an average particle size of less than 0.1 μm was produced. In Example 9 used, the result was that Example 1 was superior in terms of excellent finish quality and moist feeling in which the powder did not drop pores over time.

On the other hand, in Comparative Example 1 containing no component (A), although the moist feeling was not bad, pores were dropped in the finished quality, and good results could not be obtained. In Comparative Example 2 which does not contain the silicone surfactant of the component (B), unevenness and pore dropout immediately after application are conspicuous, and in Comparative Example 3 which does not contain the hydrophobic powder of the component (C), it is moist. Although the feeling and spread were not bad, pores fell off, and good results were not obtained in terms of finished quality. Further, Comparative Example 4 which does not contain the partially crosslinked organopolysiloxane polymer of component (D) and Comparative Example 5 which is changed to another one become uneven due to stickiness during use, and pores fall off over time. Was observed, and good results were not obtained. In Comparative Example 6 which did not contain the component (E) and Comparative Example 7 which was changed to another one, stickiness occurred at the time of use, and pores were dropped in the finished quality, and good results could not be obtained.

Example 10 Foundation A foundation was prepared by the composition and production method shown below.
(Composition) (%)
(1) Treatment with 3% dimethylpolysiloxane Titanium oxide (average particle size 300 nm) 9
(2) Dimethylpolysiloxane 2% treated black iron oxide 0.3
(3) Dimethylpolysiloxane 2% treated iron oxide 1.8
(4) Didimethylpolysiloxane 2% treated Bengala 0.6
(5) Didimethylpolysiloxane 3% treated sericite 1
(6) Polyethylene powder 2
(7) Lauryl PEG-9
Polydimethylsiloxyethyl dimethicone (HLB: 3) 5
(8) Decamethylcyclopentasiloxane 15
(9) Isododecane 10
(10) Glyceryl tri2-ethylhexanoate 3
(11) Di-lauroyl glutamate (octyldodecyl / phytosteryl / behenyl) 0.5
(12) 2-ethylhexyl paramethoxycinnamate 5
(13) 2- (4-diethylamino-2-hydroxybenzoyl)
Benzoic acid hexyl ester 0.7
(14) (Dimethicone / Phenylvinyl Dimethicone)
Cross polymer (* 7) 1
(15) Methylparaben 0.1
(16) Remaining amount of purified water (17) Ethanol 5
(18) Dipropylene glycol 5
(19) (PEG-240 / decyltetradeceth-20)
Copolymer 0.2
* 7 KSG-18 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. The components (1) to (8) are uniformly dispersed.
B. If necessary, the components (9) to (14) are heated to 80 ° C. to uniformly disperse them, and the components (9) to (14) are added to A with stirring.
C. After the components (18) to (19) are heated and dissolved at 80 ° C., the uniformly mixed components (15) to (17) are added and uniformly mixed at room temperature.
D. While stirring C, it was added and mixed with B and emulsified at room temperature to obtain a foundation.

The foundation of Example 10 obtained as described above can form a smooth and uniform decorative film, and can maintain excellent finish quality without powder falling off even with time. rice field.

Example 11 Sunscreen A sunscreen was prepared according to the composition and manufacturing method shown below.
(Composition) (%)
(1) Decamethylcyclopentasiloxane 15
(2) Methyltrimethicone 15
(3) Neopentyl glycol diethylcaproate 1
(4) Lauryl PEG-9
Polydimethylsiloxyethyl dimethicone (HLB: 3) 1
(5) Isotridecyl isononanoate 1
(6) Cetyl 2-ethylhexanoate 3
(7) 2-Ethylhexyl paramethoxycinnamate 3
(8) 4-tert-Butyl-4'-methoxy-dibenzoylmethane 1
(9) Dimethylpolysiloxane (* 8) 1
(10) (Lauryl Dimethicone / Polyglycerin-3)
Cross polymer (* 9) 1
(11) Spherical nylon (average particle size 6 μm) 0.5
(12) Fragrance 0.03
(13) Remaining amount of purified water (14) (PEG-240 / decyltetradeceth-20 / HDI)
Copolymer (* 6) 0.1
(15) 1,3-butylene glycol 5
(16) Sodium chloride 0.1
(17) Ethanol 2
(18) Phenoxyethanol 0.05
* 8 Silicon KF96A-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 9 KSG-710 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. The components (1) to (12) are heated to 80 ° C. as needed and uniformly dispersed.
B. After the components (13) to (15) are heated and dissolved at 80 ° C., the uniformly mixed components (16) to (18) are added and uniformly mixed.
C. B was added to A with stirring, mixed and emulsified at room temperature to obtain a sunscreen.

The sunscreen of Example 11 obtained as described above can form a smooth and uniform cosmetic film, and can maintain excellent finish quality without powder falling off over time. Met.

Example 12 Daytime beauty essence A daytime beauty essence was prepared by the composition and production method shown below.
(Composition) (%)
(1) Decamethylcyclopentasiloxane 20
(2) Neopentyl glycol diethylcaproate 5
(3) 2-Ethylhexyl paramethoxycinnamate 1
(4) Mineral oil 1
(5) Squalene 3
(6) Lauryl polyglyceryl-3
Polydimethylsiloxyethyl dimethicone (HLB: 3) 3
(7) Dimethylpolysiloxane (* 4) 3
(8) Dimethicone / octylsilylation treatment Fine particle titanium oxide (average particle size 35 nm) 3
(9) Methyl methacrylate crosspolymer (average particle size 15 μm) 0.5
(10) (PEG-15 / lauryl dimethicone)
Cross polymer (* 10) 6
(11) Remaining amount of purified water (12) Tripropylene glycol 5
(13) 1,3-butylene glycol 0.2
(14) (PEG-240 / decyltetradeceth-20 / HDI)
Copolymer (* 6) 0.5
(15) Sodium chloride 1
(16) Ethanol 2
(17) Chlorphenesin 0.03
* 10 KSG-310 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. The components (1) to (10) are uniformly dispersed.
B. After the components (11) to (15) are heated to 80 ° C. and uniformly dissolved, they are added together with the components (16) to (17) to A at room temperature with stirring.
C. After stirring B at room temperature and emulsifying, a daytime beauty essence was obtained.

The daytime beauty essence of Example 12 obtained as described above can form a smooth and uniform cosmetic film, and maintains excellent finish quality without powder falling off over time. It was possible.

Example 13 Concealer A concealer was prepared by the composition and production method shown below.
(Composition) (%)
(1) Titanium oxide treated with 3% dimethylpolysiloxane (average particle size 250 nm) 15
(2) Dimethylpolysiloxane 2% treated black iron oxide 0.3
(3) Dimethylpolysiloxane 2% treated iron oxide 1.0
(4) Didimethylpolysiloxane 2% treated Bengala 0.5
(5) Dimethylpolysiloxane 3% treated mica titanium 3
(6) PEG-9 Polydimethylsiloxyethyl Dimethicone (HLB: 4.1) 3
(7) Glyceryl tri2-ethylhexanoate 3
(8) 2-ethylhexyl paramethoxycinnamate 5
(9) t-Butylmethoxybenzoylmethane 1
(10) Decamethylcyclopentasiloxane 5
(11) Isododecane 5
(12) Methyltrimethicone 5
(13) Fragrance 0.2
(14) (Dimethicone / Phenylvinyl Dimethicone)
Cross polymer (* 7) 1
(15) Methylparaben 0.1
(16) Ethanol 10
(17) Remaining amount of purified water (18) Butylene glycol 5
(19) (PEG-240 / decyltetradeceth-20)
Copolymer (* 6) 0.2
(20) Na hyaluronate 0.1
(21) Hydrolyzed silk 0.1
(22) Glycine 0.1

(Production method)
A. Ingredients (1) to (7) are uniformly kneaded.
B. After the components (8) to (10) are heated and dissolved at 80 ° C., the uniformly mixed components (11) to (14) are added, A is further added, and the components (8) to (10) are uniformly mixed at room temperature.
C. After dissolving the components (15) to (16), the uniformly mixed components (17) to (22) are added, and the components (17) to (22) are uniformly mixed at room temperature.
D. While stirring C, it was added and mixed with B and emulsified at room temperature to obtain a foundation.

The concealer of Example 13 obtained as described above can form a smooth and uniform cosmetic film, and can maintain excellent finish quality without powder falling off over time. rice field.

Claims (6)

The following components (A) to (E):
(A) Volatile oil agent (B) Silicone surfactant (C) Hydrophobic powder (D) Partially crosslinked organopolysiloxane polymer (E) Hydrophobic-modified polyether urethane R _{1 represented by the following general formula (1)} ─ {(O ─ _{R 2} ) _{k ─ OCONH ─ R 3} [─ NHCOO ─ (R _{4 ―} O) _n ─ _{R 5} ] _h } _m (1)
[In the formula, R ₁ , R ₂ and R ₄ represent hydrocarbon groups that may be the same or different from each other, R ₃ represents a hydrocarbon group that may have a urethane bond, and R ₅ represents a straight chain. , Branch chain or secondary hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, and k and n are independently numbers in the range 0 to 1000. ]
Water-in-oil emulsified cosmetic containing
(However,
Cyclomethicone, water, glycerin, DPG, BG, (dimethicone / vinyl dimethicone) crosspolymer, polymethyl methacrylate, PEG-10 dimethicone, al distearate, sorbitan sesquiisostearate, hot spring water, lavender oil, yukinoshita extract, biwa leaf Extract, Al hydroxide, disteardimonium hectrite, (PEG-240 / decyltetradeceth-20 / HDI) copolymer, EDTA-3Na, (dimethicone / methicone) copolymer, silica, ethanol, tocopherol, tin oxide, cellulose , Tetrahydrotetramethylcyclotetrasiloxane, orange oil, tetradecene, BHT, phenoxyethanol, titanium oxide, mica, iron oxide, and Benibana red cosmetics,
and,
Water, cyclomethicone, BG, methyl polymethacrylate, ethylhexyl methoxycinnamate, dimethiconcopolyester, phenyltrimethicone, disteardimonium hectrite, (dimethicone / vinyldimethicone) crosspolymer, Na chloride, tocopherol acetate, lauroyl lysine, Water-soluble collagen, clara extract, hydrolyzed elastin, aluminum hydroxide, al distearate, isostearic acid, glycerin, EDTA-3Na, BHT, (PEG-240 / decyltetradeceth-20 / HDI) copolymer, tocopherol, triethoxy (Excluding cosmetics consisting of caprylylsilane, Mg myristate, phenoxyethanol, titanium oxide, Ba sulfate, iron oxide, and synthetic gold mica) . The water-in-oil emulsified cosmetic according to claim 1, wherein the silicone surfactant of the component (B) has an HLB of 2 to 7. The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the content of the component (D) is 0.05 to 8% by mass. The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the content of the component (E) is 0.01 to 3% by mass. The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, wherein the hydrophobic powder of the component (C) has an average particle size of 0.1 to 30 μm. The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, wherein the component (B) is a polyether-modified silicone.