JP6334167B2 - Cosmetic composition - Google Patents

Description

  The present invention relates to a cosmetic composition in the form of an emulsion with a particularly creamy feel.

  Cosmetic compositions in the form of emulsions can take various forms such as W / O, O / W, W / O / W and O / W / O. In most cases, an emulsifier or surfactant is essential to stabilize the emulsion form.

  However, emulsifiers have potential problems such as irritation to the skin and unpleasant touch (eg, stickiness).

  Pickering reported on emulsions stabilized with powder particles (J. Chem. Soc. 1907, September 2001). Since then, several emulsions called Pickering emulsions have been proposed which are stabilized by powder particles and contain no or only small amounts of emulsifiers. For example, WO98 / 42300 discloses a Pickering emulsion containing fine particles having a particle diameter of less than 200 nm and coated with silicone or the like.

  However, such Pickering emulsions may have lost stability, and therefore, new designs that stabilize Pickering emulsions are desired.

WO98 / 42300 French Patent No. 2697971 European Patent No. 1184426 U.S. Pat.No. 4,578,266 EP-A-1068854 EP-A-1086945 WO-A-02 / 47031 WO-93 / 23008 WO2008 / 155059

J. Chem. Soc. 1907, September 2001 Ullmann's encyclopedia CTFA (6th edition, 1995) "Specialist Surfactants", edited by D. Robb, 1997, pp. 209-263, Chapter 8 by P. Terech

  The object of the present invention is a cosmetic composition in the form of a novel Pickering emulsion with a particularly creamy feel, which can be accompanied by good stability even if it contains no or only a small amount of emulsifier. Is to provide.

The object of the present invention described above is
a) continuous phase,
b) disperse phase, and
c) a cosmetic composition in the form of a water-in-oil emulsion or an oil-in-water emulsion comprising particles having a number average particle size of 200 nm or more and surface-treated with at least one amphiphile,
Achieved by a cosmetic composition wherein the particles are present at the interface between the continuous phase and the dispersed phase and may comprise at least one emulsifier in an amount of not more than 1% by weight relative to the total weight of the composition. Can do.

  It is preferable that the continuous phase is an oily phase and the dispersed phase is an aqueous phase.

  The particles are preferably partially surface treated with an amphiphile.

  The amphiphile preferably comprises at least one hydrophobicized amino acid. The hydrophobized amino acid can be a glutamic acid derivative or a condensate of a glutamic acid derivative and an amino acid.

  The particles can include at least one inorganic material. The inorganic material can be a metal oxide.

The cosmetic composition according to the present invention has the following formula:
1.5 <{B / (AC)} <8
[Where
A represents (a) the mass of the continuous phase;
B represents (b) the mass of the dispersed phase, and
C represents (c) particle mass]
It is preferable to satisfy.

  In the cosmetic composition according to the present invention, the mass ratio of (a) continuous phase, (b) dispersed phase, and (c) particles can be 15 to 35:40 to 75: 3 to 25.

  The continuous phase can include at least one nonpolar oil or low polarity oil.

  The continuous phase can include at least one rheological agent.

  The dispersed phase can include at least one water soluble polymer.

  The cosmetic composition according to the invention may comprise at least one hydrophobic filler and / or at least one hydrophobic pigment.

  The cosmetic composition according to the invention may further comprise at least one untreated surface filler and / or at least one untreated surface pigment.

  When the cosmetic composition of the present invention contains an emulsifier, the HLB value of the emulsifier is preferably 10 or less.

  The invention also relates to a cosmetic method comprising the step of applying the composition of the invention on a keratin substance, in particular on the skin, preferably on the facial skin.

  As a result of intensive studies, the present inventors have found that cosmetic compositions in the form of so-called Pickering emulsions are relatively larger particles than those used in conventional Pickering emulsions, and have at least one hydrophobic type. It has been found that stabilization can be achieved by using particles that have been surface-treated or coated with at least one amphiphile, which can preferably contain a modified amino acid.

  Accordingly, the present invention can provide a novel Pickering emulsion that can exhibit good stability even if it contains no or only a small amount of a surfactant. Thus, the cosmetic composition of the present invention can maintain a uniform appearance and exhibits no or only slight irritation to the skin.

  The cosmetic composition of the present invention can have better stability compared to conventional Pickering emulsions. Furthermore, the cosmetic composition of the present invention can exhibit a good creamy feel.

The cosmetic composition of the present invention comprises:
a) continuous phase,
b) disperse phase, and
c) including particles having a number average particle diameter of 200 nm or more and surface-treated with at least one amphiphile;
The particles are present at the interface between the continuous phase and the dispersed phase, and the composition optionally includes at least one emulsifier in an amount of 1% by weight or less based on the total weight of the composition. Is characterized by including in.

  The cosmetic composition of the present invention can be used in a cosmetic method comprising the step of applying the composition of the present invention on a keratin material, in particular on the skin, preferably the facial skin.

  Below, the cosmetic composition of this invention is demonstrated in detail.

(1) Form of emulsion The cosmetic composition of the present invention comprises a continuous phase and a dispersed phase, and is in the form of a water-in-oil (W / O) emulsion or an oil-in-water (O / W) emulsion. Therefore, when the cosmetic composition of the present invention is in the form of a W / O emulsion, the continuous phase is an oily phase and the dispersed phase is an aqueous phase. On the other hand, when the cosmetic composition of the present invention is in the form of an O / W emulsion, the continuous phase is an aqueous phase and the dispersed phase is an oily phase. The cosmetic composition of the present invention is preferably in the form of a W / O emulsion.

(2) Particles The cosmetic composition of the present invention includes particles having a number average particle diameter of 200 nm or more. The average particle size of the particles is preferably 250 nm or more, more preferably 300 nm or more, still more preferably 350 nm or more, preferably 1 μm or less, more preferably 800 nm or less, and even more preferably 500 nm or less. The number average particle diameter can be measured by, for example, Nicomp Z380 by a dynamic light scattering method.

  The particles are preferably in solid form. More preferably, the particles can be a powder. The powder can be a pigment and / or a filler.

  Non-surface treated pigments have a solubility in water of less than 0.01%, such as less than 0.0001% at 20 ° C., the absorption ranges from 350 to 700 nm, and in at least one embodiment, the absorption is maximal.

  A pigment that has not been surface-treated (hereinafter referred to as “pigment”) can be an organic pigment. As used herein, the term “organic pigment” means any pigment that meets the definition in the chapter on organic pigments in the Ullmann's encyclopedia. Organic pigments include, for example, nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone. It can be selected from compounds.

  At least one organic pigment, for example, carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, classified under the reference names CI 42090, 69800, 69825, 73000, 74100 and 74160 in the Color Index Blue pigments, yellow pigments classified under the reference names CI 11680, 11710, 15985, 19140, 200040, 21100, 21108, 47000 and 47005 in the Color Index, classified by reference names CI 61565, 61570 and 74260 in the Color Index Green pigments, orange pigments classified under the reference names CI 11725, 15510, 45370 and 71105 in the Color Index, reference names CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620 in the Color Index , 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and, for example, French Patent No. 2697971 Selected from pigments obtained by oxidative polymerization of indole derivatives or phenol derivatives.

  These pigments can also be in the form of composite pigments described for example in EP 1184426. These composite pigments may comprise, for example, particles comprising an inorganic core at least partially coated with an organic pigment and at least one binder for fixing the organic pigment to the core.

Other examples may include pigment pastes of organic pigments, such as products sold by the company Hoechst under the following name:
Jaune Cosmenyl IOG: Pigment Yellow 3 (CI 11710),
Jaune Cosmenyl G: Pigment Yellow 1 (CI 11680),
Orange Cosmenyl GR: Pigment Orange 43 (CI 71105),
Rouge Cosmenyl R``: Pigment Red 4 (CI 12085),
Carmine Cosmenyl FB: Pigment Red 5 (CI 12490),
Violet Cosmenyl RL: Pigment Violet 23 (CI 51319),
Bleu Cosmenyl A2R: Pigment Blue 15.1 (CI 74160),
Vert Cosmenyl GG: Pigment Green 7 (CI 74260) and
Noir Cosmenyl R: Pigment Black 7 (CI 77266).

  The at least one pigment can also be selected from lakes. As used herein, the term “lake” means an insolubilized dye adsorbed on insoluble particles, and the aggregates thus obtained remain insoluble during use.

  The inorganic substrate to which the dye is adsorbed may include, for example, alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate, and aluminum.

  Non-limiting examples of organic dyes include cochineal carmine and products known under the following names: D & C Red 21 (CI 45380), D & C Orange 5 (CI 45370), D & C Red 27 (CI 45410), D & C Orange 10 (CI 45425), D & C Red 3 (CI 45430), D & C Red 4 (CI 15510), D & C Red 33 (CI 17200), D & C Yellow 5 (CI 19140), D & C Yellow 6 (CI 15985), D & C Green (CI 61570), D & C Yellow 10 (CI 77002), D & C Green 3 (CI 42053) and D & C Blue 1 (CI 42090).

  An example of an additional non-limiting rake is the product known under the following name: D & C Red 7 (CI 15850: 1).

  The at least one pigment can also be a pigment with a special effect. As used herein, the term `` pigment with special effects '' generally varies depending on the viewing conditions (light, temperature, viewing angle, etc.), (specific hue, specific saturation and Means a pigment that produces a non-uniform colored appearance (characterized by a specific brightness). This is therefore in contrast to white or colored pigments that impart a standard, uniform, opaque, translucent, transparent tone.

  There are two types of pigments with special effects. That is, it has a low refractive index such as a fluorescent pigment, a photochromic pigment, and a thermochromic pigment, and a high refractive index such as a pearlescent agent and flakes.

  Examples of pigments with special effects include pearlescent pigments, such as white pearlescent pigments (e.g. mica coated with titanium or bismuth oxychloride), colored pearlescent pigments (mica titanium coated with iron oxide, e.g. And mica titanium coated with ferric blue or chromium oxide, mica titanium coated with organic pigments of the type described above), and bismuth oxychloride pearlescent pigments.

  The at least one pigment is selected from pigments with interference effects not fixed on the substrate, for example liquid crystals (Helicones HC from Wacker) and holographic interference flakes (Geometric Pigment or Spectra f / x from Spectratek) You can also Pigments with special effects are fluorescent pigments, phosphorescent pigments, photochromic pigments, thermochromic pigments and, for example, Quantum Dots Corporation, regardless of whether they are fluorescent substances in the sunlight or substances that emit ultraviolet fluorescence. Quantum dots sold by the company can also be included.

  Pigments with special effects can include fluorescent pigments, phosphorescent pigments, photochromic pigments and thermochromic pigments, regardless of whether they are substances that fluoresce in sunlight or substances that fluoresce ultraviolet.

In a preferred embodiment, the at least one pigment can also be an inorganic pigment. As used herein, the term “inorganic pigment” means any pigment that meets the definition in the inorganic pigments chapter of the Ullman Encyclopedia. Preferably, the inorganic pigment comprises at least one inorganic material. Non-limiting examples of inorganic pigments useful in the present invention include metal oxides such as zirconium oxide, cerium oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue and dioxide. Titanium is included. The following inorganic pigments can also be used. Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₂ O ₃ , TiO, and ZrO ₂ , ZrO ₂ , Nb ₂ O ₅ , CeO ₂ and ZnS as a mixture with TiO ₂ .

  In certain embodiments, the at least one pigment is an inorganic pigment. Preferably, the inorganic pigment is a metal oxide such as titanium oxide and / or iron oxide.

The at least one pigment is a pearlescent pigment, such as a white pearlescent pigment (e.g. mica coated with titanium or bismuth oxychloride), a colored pearlescent pigment (mica coated with titanium and iron oxide, titanium and e.g. ferric Mica coated with blue or chromium oxide, mica coated with titanium and organic pigment as defined above), and pearlescent pigments based on bismuth oxychloride. Examples of such pigments, Cellini pigments sold by Engelhard (mica -TiO ₂ - lake), Colorona sold sold by being Prestige (mica -TiO ₂₎ and from Merck from Eckart (mica -TiO _{2 -} Fe ₂ O ₃₎ may be included.

  In addition to pearlescent agents on mica carriers, multilayer pigments based on synthetic substrates such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum are useful according to the present disclosure There is.

  As used herein, the term “filler” is solid at room temperature and atmospheric pressure, even in the various components of the cosmetic composition of the present invention, even when these components are brought to temperatures above room temperature. It means a substantially uncolored compound that is insoluble.

  The at least one filler can be selected from inorganic fillers and organic fillers. The at least one filler is in any form, for example platelet-shaped, spherical and oval particles, regardless of its crystallographic form (e.g. layered, cubic, hexagonal and orthorhombic). be able to.

  Suitable fillers that can be used in the cosmetic composition of the present invention may include, but are not limited to, the following. Talc; natural or synthetic mica; silica; kaolin; polyamide [Nylon®], poly-β-alanine and polyethylene powder; tetrafluoroethylene polymer [Teflon®] powder; lauroyl lysine; starch; boron nitride Acrylic polymer powder; silicone resin microbeads such as “Tospearl (registered trademark)” manufactured by GE Toshiba Silicone Co., Ltd .; bismuth oxychloride; precipitated calcium carbonate; magnesium carbonate and magnesium bicarbonate; hydroxyapatite; hollow silica microspheres; For example, `` SilicaBeads SB 700 (registered trademark) '' and `` Silica Beads SB 700 (registered trademark) '' manufactured by Maprecos, `` Sunsphere H-33 (registered trademark) '' and `` Sunsphere H-51 (registered trademark) manufactured by Asahi Glass Co., Ltd. ) "; Acrylic polymer microspheres such as the crosslinked acrylate copolymer" Polytrap 6603 Adsor "from RP Scherrer ber (registered trademark) '' and polymethylmethacrylate `` Micropearl M100 (registered trademark) '' manufactured by SEPPIC; polyurethane powder, for example, the name `` Plastic Powder D- Copolymer powder of hexamethylene diisocyanate and trimethylol hexyl lactone sold under `` 400® ''; glass or ceramic microcapsules; organic containing 8 to 22 carbon atoms, e.g. 12 to 18 carbon atoms Metal soaps derived from carboxylic acids, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate and magnesium myristate; polymers or copolymers of methyl acrylate or methacrylate or copolymers of vinylidene chloride and acrylonitrile Capse Such as “Expancel®” from Expancel; an elastomeric crosslinked organopolysiloxane powder, such as that sold under the name “Trefil Powder E-506C” by Dow Corning; and mixtures thereof.

  According to the present invention, the particles described above are surface treated with at least one amphiphile. Specifically, the above-described particles are partially or completely surface treated with at least one amphiphile. The particles are preferably partially treated with an amphiphile. The particles are positioned between the continuous phase and the dispersed phase of the cosmetic composition of the present invention to form a Pickering emulsion. The dispersed phases are preferably interconnected via particles.

  Amphiphiles can impart both hydrophilic and hydrophobic properties to the particles. Preferably the particles have an amphiphilic surface.

  The amphiphile may include at least one compound selected from the following. For example, amino acids; waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants Lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids such as aluminum stearate or aluminum laurate; metal alkoxides; polysaccharides such as chitosan, cellulose and These derivatives; polyethylene; (meth) acrylic polymers such as polymethyl methacrylate; polymers and copolymers containing acrylate units; proteins; alkanolamines.

  For the purposes of the present invention, the surface treatment is such that the surface-treated pigment maintains its inherent pre-treatment coloring characteristics and the surface-treated filler maintains its inherent pre-treatment filling characteristics. To do. For example, inorganic substrates such as alumina and silica on which organic dyes are adsorbed are not surface treated fillers for the purposes of the present invention.

  The particles may be surface treated with a mixture of amphiphiles and / or may be subjected to several types of surface treatment with amphiphiles.

  The surface treated particles may be prepared by surface treatment techniques well known to those skilled in the art or may be obtained commercially in the desired form.

  Preferably, the surface treated particles are coated with an organic layer. The organic layer can be deposited on the particles by evaporation of the solvent, chemical reaction between the molecules in the amphiphile, or the occurrence of a covalent bond between the molecules in the amphiphile and the particles.

  Thus, the surface treatment can be performed, for example, by a chemical reaction between the amphiphile and the particle surface and the generation of a covalent bond between the amphiphile and the particle. This method is described in particular in US Pat. No. 4,578,266.

  Particles in which the amphiphile is covalently or ionically bonded can preferably be used.

  The amphiphile may occupy 0.1 wt% to 50 wt%, preferably 0.5 wt% to 30 wt%, more preferably 1 wt% to 10 wt%, based on the total weight of the surface-treated particles. it can.

  The amphiphile preferably contains at least one hydrophobic amino acid. The hydrophobized amino acid can be a glutamic acid derivative or a condensate of at least one glutamic acid derivative and an amino acid.

  The glutamic acid derivative can be N-acylated glutamic acid or a salt thereof. Examples of the salt include metal salts, ammonium salts, and onium salts of organic alkanolamines. As metals, Na, K, Ba, Zn, Ca, Mg, Fe, Zr, Co, Al, and Ti can be used. As the organic alkanolamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol and triisopropanolamine can be used. The acyl group bonded to the nitrogen atom of glutamic acid is a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, such as capric acid, lauric acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, stearic acid, It can be derived from isostearic acid, arachidic acid, undecylenic acid, oleic acid, myristic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, palm oil fatty acid, beef tallow fatty acid and resin acid (abietic acid).

  The condensate of at least one glutamic acid derivative and an amino acid can be a condensate of N-acylated glutamic acid and an amino acid such as lysine, or a salt thereof. Examples of the salt include metal salts, ammonium salts, and onium salts of organic alkanolamines as described above. Preferred is the sodium salt. The acyl group bonded to the nitrogen atom of glutamic acid can be derived from the above saturated or unsaturated fatty acid having 8 to 22 carbon atoms. Preference is given to lauric acid. Accordingly, for example, dilauroyl glutamic acid sodium lysine (Pellicer L-30 commercially available from Asahi Kasei Chemicals Corporation) is preferred as the condensate.

The amphiphilic surface treatment of the particles can be selected from the following treatments.
-PEG-silicone treatment, eg AQ surface treatment sold by LCW
-Lauroyl lysine treatment, eg LL surface treatment sold by LCW
-Lauroyl lysine dimethicone treatment, eg LL / SI surface treatment sold by LCW,
-Stearoyl glutamate disodium treatment, for example, NAI surface treatment sold by Miyoshi Kasei Co., Ltd.
-Dimethicone / stearoyl glutamate disodium treatment, such as SA / NAI surface treatment sold by Miyoshi Kasei Co., Ltd.
-Microcrystalline cellulose and carboxymethyl cellulose treatment, for example, AC surface treatment sold by Daito Kasei Kogyo Co., Ltd.
-Acrylate copolymer treatment, for example, APD surface treatment sold by Daito Kasei Kogyo Co., Ltd.
-Dilauroyl glutamate lysine sodium treatment, for example, ASL treatment sold by Daito Kasei Kogyo Co., Ltd., and
-Dilauroyl glutamate sodium lysine / isopropyl titanium triisostearate treatment, for example, ASL treatment sold by Daito Kasei Kogyo Co., Ltd.

  The amphiphile can be ionically bonded to the particles with a metal salt or metal hydroxide, such as aluminum hydroxide and magnesium chloride, where the metal can be selected from Mg, Al, Ca, Zn.

  Treatment with disodium stearoyl glutamate (and) aluminum hydroxide is more preferred.

  Other treatments with sodium lauryl dilauroyl glutamate or sodium lysine dilauroyl glutamate / isopropyl titanium triisostearate are also preferred.

  At least one surface-treated pigment is generally in the cosmetic composition of the present invention, generally from 0.01% to 30%, such as from% to 25% by weight, or based on the total weight of the composition, or It can be present in a total amount ranging from 1% to 10% by weight.

  At least one surface-treated filler is present in the cosmetic composition according to the invention in an amount of 0.01% to 50%, such as 0.1% to 30%, or 1%, based on the total weight of the composition. It can be present in a total amount ranging from wt% to 15 wt%.

(3) Oily phase The oily phase in the cosmetic composition of the present invention contains at least one oil. Two or more oils may be used.

  As used herein, “oil” means an aliphatic compound or fatty substance that is in the form of a liquid or paste (non-solid) at room temperature (25 ° C.) and atmospheric pressure (760 mmHg).

  As oil, what is normally used for cosmetics can be used individually or in combination. These oils may be volatile or non-volatile.

  The oil may be a non-polar or low-polar oil such as hydrocarbon oil, silicone oil, polar oil such as vegetable oil or animal oil and ester oil, or a mixture thereof.

  Examples of hydrocarbon oils include, for example, mineral oil (e.g. liquid paraffin), linear or branched hydrocarbons such as paraffin, petrolatum or petrolatum, hydrogenated polyisobutene, isoeicosane, and decene / butene copolymers, and mixtures thereof Can be mentioned.

  Examples of silicone oils include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, cyclic rings such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Mention may be made of organopolysiloxanes, as well as mixtures thereof.

  Examples of vegetable oils include, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil Sesame oil, soybean oil, peanut oil and mixtures thereof.

  Examples of animal oils include squalene and squalane.

  Examples of ester oils include, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethyl hexanoate 2- Ethylhexyl, 2-ethylhexyl octanoate, caprylic acid / 2-ethylhexyl caprate, methyl palmitate, ethyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, Examples include tri (2-ethylhexanoic acid) glyceryl, tetra (2-ethylhexanoic acid) pentaerythrityl, 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof. That.

  Oils are derived from animal or vegetable derived oils, mineral oils, ester oils and synthetic oils such as synthetic triglycerides, silicone oils and hydrocarbons, specifically aliphatic hydrocarbons, provided that the following are liquid at room temperature: It may be selected from the group consisting of

  The amount of oil is 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, even more preferably 40 to 60% by weight, based on the total weight of the cosmetic composition of the present invention. It can be.

  The oily phase can include at least one fatty alcohol. Two or more fatty alcohols may be used.

The term “aliphatic alcohol” as used herein means an alcohol having a long aliphatic carbon chain. Aliphatic alcohol, any pure, saturated or unsaturated, and is preferably selected from C ₈ -C ₃₀ aliphatic alcohols, linear or branched chain.

Among C ₈ -C ₃₀ aliphatic alcohols, for example, C ₁₂ -C ₂₂ aliphatic alcohols are used. C ₁₆ -C ₁₈ aliphatic alcohols are more preferred.

  Among these, lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, linoleyl alcohol, undecylenyl alcohol, palmitoleyl alcohol, linolenyl alcohol, myristyl alcohol, arachidonyl alcohol and erucyl Mention may be made of alcohols as well as mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol or mixtures thereof (eg cetearyl alcohol) and behenyl alcohol can be used as the fatty component.

  The amount of the higher alcohol can be 0.0001 to 30% by weight, preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight, based on the total weight of the cosmetic composition of the present invention.

  The oily phase may have a low viscosity.

  Viscosity can be measured at 25 ° C. using a Rheomat 180 instrument at 200 rpm (per revolution). The Rheomat 180 includes a rotor that varies depending on the viscosity, for example, the rotor 3 in a viscosity range of 0.2 to 4 Pa.s, and the rotor 4 in a viscosity range exceeding 2 Pa.s. This viscosity is usually measured 10 minutes after the start of rotation of the rotor. When measured under the conditions described above, the viscosity of the oily phase can be in the range of, for example, 1 to 500 Pa.s, preferably 10 to 100 Pa.s.

  The oily phase can include at least one rheological agent.

  This rheological agent can thicken and / or gel the oil phase. The rheological agent can be present in an amount effective to increase the viscosity of this phase, in particular until a solid gel is obtained, ie a product that does not flow under its own weight.

  The rheological agent is advantageously selected from lipophilic gelling agents, organic gellers and mixtures thereof. When the rheological agent is a solid, the particle size of the rheological agent is preferably 300 nm or less, more preferably 100 nm or less.

  The lipophilic gelling agent can be organic or inorganic, high molecular or low molecular.

The inorganic lipophilic gelling agents, clay modified with optionally, for example, C ₁₀ -C ₂₂ fatty hectorite modified with ammonium chloride, for example can be cited hectorite modified with distearyldimethylammonium chloride.

Mention may also be made of calcined silica, optionally having a hydrophobic surface and having a particle size of less than 1 μm. In effect, it is possible to chemically modify the surface of the silica by a chemical reaction that reduces the number of silanol groups present on the surface of the silica. Specifically, the silanol group can be substituted with a hydrophobic group, and in this case, hydrophobic silica is obtained. The hydrophobic group can be:
-Those obtained by treating calcined silica in the presence of trimethylsiloxyl groups, specifically hexamethyldisilazane. Silicas thus treated are named “silylated silica” according to the CTFA (6th edition, 1995). This is for example sold under the name Aerosil R812® from Degussa and under the name CAB-O-SIL TS-530® from Cabot.
-Those obtained by treating calcined silica in the presence of dimethylsilyloxyl groups or polydimethylsiloxane groups, specifically polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are named “dimethylsilylated silica” according to the CTFA (6th edition, 1995). This is the name Aerosil R972 (registered trademark), Aerosil R974 (registered trademark) from Degussa, for example, and the names CAB-O-SIL TS-610 (registered trademark) and CAB-O-SIL TS-720 (registered trademark) from Cabot. It is sold at.

  The particle size of the hydrophobic calcined silica can preferably be in the nanometer to micrometer range, for example in the range of about 5 to 200 nm.

Polymeric organic lipophilic gelling agents are, for example, partially or fully crosslinked elastomeric organopolysiloxanes having a three-dimensional structure, such as the names KSG6, KSG16 and KSG18 from Shin-Etsu Silicone Co., Ltd. and named from Dow-Corning Trefil E-505C or Trefil E-506C from Grant Industries with names Gransil SR-CYC, SR DMF10, SR-DC556, SR 5CYC gel, SR DMF 10 gel, SR DC 556 gel and names from General Electric SF 1204 and JK Ethyl cellulose, such as that sold under the name Ethocel from Dow Chemical; polyamide, for example a copolymer of C ₃₆ diacid condensed with ethylene-diamine having a number average molecular weight of about 6000, such as Arizona Chemical Compounds sold under the names Uniclear 80 and Uniclear 100, rubbers, especially silicone rubbers, eg PDMS with a viscosity> 100,000 centistokes, sugars substituted with saturated or unsaturated alkyl chains Galactomannans containing ₁ to ₆ , more preferably 2 to 4 hydroxy groups per unit, such as C ₁ -C ₆ alkyl chains, and even better alkylated with C ₁ -C ₃ alkyl chains Guar gum, and mixtures thereof.

  As a preferred lipophilic gelling agent, a non-polymeric organic gelling agent, also called an organic gelling agent, is used. This is a compound in which molecules can establish physical interactions between themselves, resulting in the molecules self-aggregating and forming a 3D polymer network that is a factor in the gelation of the liquid fatty phase.

  The liquid fatty phase meant by the present invention is a fatty phase that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg or 105 Pa), also called oil, usually compatible, liquid at ambient temperature, It is a fatty phase composed of one or more fatty substances.

  The polymer network can occur as a result of the formation of a fibril network (due to the deposition or aggregation of organic gel agent molecules) and immobilizes the molecules of the liquid fatty phase.

  The ability to form this fibril network and hence gel is determined by the nature (or chemical classification) of the organic gel, the nature of the substituents of the organic gel molecules of a given chemical classification, and the liquid fat Depends on the nature of the phase.

  The physical interactions are diverse but co-crystallization is excluded. Specifically, these physical interactions include, for example, self-complementary hydrogen interactions, π interactions between unsaturated rings, dipole interactions, coordination bonds with organometallic derivatives, and combinations thereof. Is the interaction. Typically, each molecule of an organic gel can establish several physical interactions with neighboring molecules. Thus, the molecules of the organogel according to the invention advantageously have at least one group capable of establishing hydrogen bonds, and better still at least two groups capable of establishing hydrogen bonds, at least It contains one aromatic ring and better still at least two aromatic rings, at least one or more bonds with ethylenic unsaturation, and / or at least one or more asymmetric carbons. The groups capable of forming hydrogen bonds are preferably selected from hydroxy, carbonyl, amine, carboxylic acid, amide, urea and benzyl groups, and combinations thereof.

  One or more organic gels according to the present invention are dissolved in the liquid fatty phase after heating to obtain a transparent and homogeneous liquid phase. These may be solid or liquid at ambient temperature and atmospheric pressure.

  One or more low molecular weight organic gels that can be used in the cosmetic composition of the present invention are specifically described in the document “Specialist Surfactants”, edited by D. Robb, 1997, pages 209-263, P. As described in Chapter 8 by Terech, European applications EP-A-1068854 and EP-A-1086945 or application WO-A-02 / 47031.

Specific examples of the organic gel agent include the following. Carboxylic acids, in particular amides of tricarboxylic acids, such as cyclohexane-tricarbohexamide (see European patent application EP-A-1068854), each containing 1 to 22 carbon atoms, for example 6 to 18 carbon atoms Diamide having a hydrocarbon chain, said chain being unsubstituted or substituted with at least one substituent selected from an ester group, a urea group and a fluoro group (see application EP-A-1086945) And, in particular, diaminocyclohexane, particularly diamide obtained from the reaction of trans-type diaminocyclohexane with an acid chloride such as N, N′-bis (dodecanoyl) -1,2-diamino-cyclohexane, N-acylamino acid amides such as diamides obtained from the action of N-acylamino acids with amines containing 1 to 22 carbon atoms, such as those described in WO-93 / 23008, and in particular acyl Group N-acyl glutamic acid amides representing C ₈ -C ₂₂ alkyl chains, such as N-lauroyl-L-glutamic acid dibutylamide manufactured or sold under the name GP-1 by Ajinomoto Co., Inc., and mixtures thereof.

  The cosmetic composition of the present invention may contain 1-50% by weight, preferably 1-20% by weight of rheological agent, based on the total weight of the oily phase. Preferably, the cosmetic composition of the present invention may contain 0.1-10% by weight, and better still 1-5% by weight of the rheological agent, based on the total weight of the composition.

(4) Aqueous phase The aqueous medium in the cosmetic composition of the present invention may contain water. The amount of water is 70 wt% or less, preferably 5 wt% to 60 wt%, more preferably 10 wt% to 50 wt%, even more preferably 20 wt% to 50 wt%, relative to the total weight of the composition. %.

The aqueous medium can further include at least one organic solvent to increase the solubility of the compound that may not be sufficiently soluble in water. Two or more organic solvents may be used. The organic solvent is preferably water miscible. Examples of the organic solvent include the following. For example, C ₁ -C ₄ alkanols such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol; and aromatic alcohols Benzyl alcohol and phenoxyethanol; similar products; and mixtures thereof.

  The organic solvent can be present in an amount ranging from 1 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 30% by weight, based on the total weight of the cosmetic composition of the present invention.

  Specifically, ethanol may be contained in an amount of preferably 10% by weight or more based on the total weight of the cosmetic composition of the present invention in order to impart a sufficient antiseptic effect. Furthermore, when the cosmetic composition of the present invention is a W / O emulsion, irritation with ethanol is surely prevented.

  According to one embodiment of the present invention, the aqueous phase can include at least one water soluble polymer or latex polymer.

Examples of water-soluble polymers that may be mentioned include:
Proteins, for example, plant-derived proteins such as wheat protein and soy protein;
Animal-derived proteins, such as keratins, such as keratin hydrolysates and sulfonated keratins,
Cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose and ethylhydroxyethylcellulose;
Acrylic polymers or copolymers, such as polyacrylates or polymethacrylates,
Vinyl polymers such as polyvinyl pyrrolidone, copolymers of methyl vinyl ether and maleic anhydride, copolymers of vinyl acetate and crotonic acid, copolymers of vinyl pyrrolidone and vinyl acetate, copolymers of vinyl pyrrolidone and caprolactam,
Polyvinyl alcohol,
Naturally modified polymers that are optionally modified, such as gum arabic, guar gum, xanthan derivatives, karaya gum,
Alginate and carrageenan,
Glycoaminoglycan, hyaluronic acid and its derivatives,
Shellac resin, sandalac rubber, dammar resin, elemi rubber and copal resin,
Deoxyribonucleic acid,
Mucopolysaccharides such as chondroitin sulfate,
Polysaccharides such as xanthan gum, pullulan and pectin,
Polyamino acids such as polyglutamic acid, and mixtures thereof.

  The water-soluble polymer can be present in an amount ranging from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 1 to 2% by weight, based on the total weight of the cosmetic composition of the present invention. .

(5) Amount of component The amount of the above-mentioned particles, oily phase and aqueous phase in the cosmetic composition of the present invention is not limited as long as they form a Pickering emulsion.

The cosmetic composition of the present invention has the following formula:
1.5 <{B / (AC)} <8
[Where
A represents (a) the mass of the continuous phase;
B represents (b) the mass of the dispersed phase, and
C represents (c) particle mass]
It is preferable to satisfy. “Mass” in the above formula may mean “weight”.

  If the above formula is not satisfied, the stability of the cosmetic composition of the present invention may be impaired. Outside this range, the creamy feel may be impaired.

  For the cosmetic composition of the present invention, the mass ratio of (a) continuous phase, (b) dispersed phase and (c) particles is more preferably 15 to 35:40 to 75: 3 to 25, even more preferably. Is 25-35: 40-60: 10-20. “Mass” in the above may mean “weight”.

  If the above-described ratio is not within the above-described range, the stability or creamy feel of the cosmetic composition of the present invention may be impaired.

(6) Emulsifier The cosmetic composition of the present invention preferably contains no emulsifier. However, the cosmetic composition of the present invention contains a very small amount, that is, 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less, still more preferably 0.001%, based on the total weight of the composition. It is possible that at least one weight percent of at least one emulsifier can be included. Two or more emulsifiers may be used. When an emulsifier is added, the stability of the cosmetic composition of the present invention may be increased.

  The emulsifier can be selected from nonionic, cationic, anionic and amphoteric surfactants. The emulsifier is preferably a nonionic surfactant.

  According to the invention, the HLB value of the emulsifier is preferably 10 or less.

  It should be noted that the HLB value of a mixture of two or more emulsifiers is determined by the weight average of the emulsifier HLB values.

Nonionic surfactants with an HLB value of 10 or less are alcohol, α-diol, alkylphenol, or polyethoxylated, polypropoxylated or polyglycerolated, provided that the HLB value of the following is 10 or less. Fatty acid having a fatty chain, ethylene oxide and / or propylene oxide copolymer, condensation product of ethylene oxide and / or propylene oxide and aliphatic alcohol, polyethoxylated fatty amide, polyglycerolated fatty amide, polyethoxylated fat amines, ethoxylated fatty acid esters of sorbitan, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, (C ₆ ~C ₂₄₎ alkylpolyglycosides, N- (C ₆ ~C ₂₄₎ alkylglucamine derivatives, amine oxides, and N - (C ₁₀ ~C ₁₄₎ acylaminopropylmorpholine Oki It is preferably selected from the group consisting of de.

(7) Other components The cosmetic composition of the present invention may contain at least one hydrophobic filler and / or at least one hydrophobic pigment.

  The particle size of the hydrophobic filler or the hydrophobic pigment is preferably 200 nm or more, preferably 300 nm or more, and 10 μm or less, preferably 5 μm or less.

  The hydrophobic filler and / or the hydrophobic pigment may be surface-treated with at least one hydrophobicizing agent such as silicone.

  If a hydrophobic filler and / or a hydrophobic pigment is present, the amount may range from 0.1% to 10% or 1% to 5% by weight of the total weight of the cosmetic composition of the present invention. it can.

  The cosmetic composition of the present invention may comprise at least one untreated surface filler and / or at least one untreated pigment.

  The particle size of the surface untreated filler or the surface untreated pigment is preferably 200 nm or more, preferably 300 nm or more, and 10 μm or less, preferably 5 μm or less.

  If surface-untreated fillers and / or surface-untreated pigments are present, the amount ranges from 0.01% to 5% or from 0.1% to 2% by weight of the total weight of the cosmetic composition of the present invention. It can be. It is preferred that the cosmetic composition of the present invention does not contain surface untreated particles.

  The cosmetic compositions of the present invention include other effective amounts of agents already known elsewhere in oxidative dyeing, such as various common adjuvants, such as sequestering agents such as EDTA and etidronic acid, UV blockers, silicones, organically modified silicones (eg with amine groups), preservatives, ceramides, pseudoceramides, vitamins or provitamins such as panthenol, opacifiers and the like can also be included.

  The amount of other agents mentioned above can range from 0.01% to 10% or from 0.1% to 5% by weight of the total weight of the cosmetic composition of the present invention.

EXAMPLES The present invention will be described in more detail by way of examples, but these examples should not be construed as limiting the scope of the invention.

Example 1 (surface-treated pigment) and comparative example 1 (surface-treated pigment)
A liquid foundation in the form of an emulsion in the form of a W / O according to Example 1 and Comparative Example 1 shown in Table 1 was prepared by mixing the components shown in Table 1. All numerical values of the components shown in the table are based on weight percentage.

  The material in Phase A was mixed with a discontinuous pulverizer for 30 minutes to obtain a pigment dispersion having a number average particle size of about 200 to 300 nm. The material in Phase B was charged into the pigment dispersion and mixed at 3000 rpm using MORITZ. The material in Phase C was then charged into this mixture to prepare a W / O emulsion.

[Emulsion stability]
The stability of the emulsions according to Example 1 and Comparative Example 1 was observed with an optical microscope. The emulsion according to Example 1 was uniform during observation and the shape of the emulsion particles was good. However, the shape of the emulsion particles according to Comparative Example 1 was not spherical, and the emulsion particles collapsed after several minutes. When the uniformity was maintained, it was evaluated as “good”, but when the uniformity was not maintained, it was evaluated as “bad”. The results are shown in Table 1.

Example 2, Example 3 (using different gels and amphiphilic surface treated pigments) and Comparative Example 2 (using silicone surface treated pigments)
Makeup bases in the form of emulsions according to Examples 2 and 3 and Comparative Example 2 shown in Table 2 were prepared by mixing the ingredients shown in Table 2. All the numerical values of the components shown in the table are based on "parts by weight".

  The material in Phase A2 was mixed for 30 minutes with a discontinuous pulverizer to obtain a pigment dispersion having a number average particle size of about 200 to 300 nm. This dispersion was mixed with the material in Phase A1 at 2000 rpm using MORITZ. The material in Phase B was charged into the mixture of materials in Phase A1 and A2, and mixed at 3000 rpm using MORITZ. The material in Phase C was then charged into this mixture to prepare a W / O emulsion.

[Emulsion stability]
The stability of the emulsions according to Examples 2 and 3 and Comparative Example 2 was observed with an optical microscope. The emulsions according to Examples 2 and 3 were uniform during observation and the shape of the emulsion particles was good. However, the shape of the emulsion according to Comparative Example 2 was not spherical, and some of the emulsion particles disintegrated after 1 minute. When the uniformity was maintained, it was evaluated as “good”, but when the uniformity was not maintained, it was evaluated as “bad”. The results are shown in Table 2.

[sensory evaluation]
Sensory evaluation was performed on Example 2 and Comparative Example 2. It was found that Example 2 was creamier, less sticky, and better adapted to the skin than Comparative Example 2.

Claims (13)

a) a continuous phase which is an oily phase,
b) a dispersed phase that is an aqueous phase, and
c) a cosmetic composition in the form of a water-in-oil emulsion comprising particles having a number average particle size of 200 nm to 1 μm and surface-treated with at least one N-acylated glutamate salt,
The N-acylated glutamate is ionically bonded to the particles with a metal hydroxide selected from Mg, Al, Ca, Zn ;
The particles are present at the interface between the continuous phase and the dispersed phase, and contain at least one emulsifier in an amount of 1% by weight or less based on the total weight of the composition;
Cosmetic composition.   The cosmetic composition according to claim 1, wherein the particles are partially surface-treated with the N-acylated glutamate.   The cosmetic composition according to claim 1 or 2, wherein the particles contain at least one inorganic material.   4. The cosmetic composition according to claim 3, wherein the inorganic material is a metal oxide. The following formula:
1.5 <{B / (AC)} <8
[Where
A represents the mass of the continuous phase (a),
B represents the mass of the (b) dispersed phase, and
C represents the mass of the particle (c)]
The cosmetic composition according to any one of claims 1 to 4, which satisfies the following conditions.   The mass ratio of the (a) continuous phase, the (b) dispersed phase, and the (c) particles is 15 to 35:40 to 75: 3 to 25, according to any one of claims 1 to 5. Cosmetic composition.   The cosmetic composition according to any one of claims 1 to 6, wherein the continuous phase comprises at least one nonpolar oil or low polarity oil.   The cosmetic composition according to any one of claims 1 to 7, wherein the continuous phase comprises at least one rheological agent.   The cosmetic composition according to any one of claims 1 to 8, wherein the dispersed phase comprises at least one water-soluble polymer.   10. A cosmetic composition according to any one of the preceding claims, wherein the particles comprise at least one hydrophobic filler and / or at least one hydrophobic pigment.   11. A cosmetic composition according to any one of claims 1 to 10, further comprising at least one untreated surface filler and / or at least one untreated surface pigment.   The cosmetic composition according to any one of claims 1 to 11, wherein the emulsifier has an HLB value of 10 or less.   A cosmetic method comprising a step of applying the composition according to any one of claims 1 to 12 onto a keratin substance.