Water-in-oil emulsion cosmetic composition

Abstract

A water-in-oil emulsion cosmetic composition, wherein the composition comprises (a) a polyglycerol fatty acid ester having an HLB value of less than or equal to 9, (b) a sorbitan fatty acid ester having an HLB value of less than or equal to 8, (c) a volatile hydrocarbon oil, and (d) barium sulfate and titanium dioxide composite powder.

Description

WATER-IN-OIL EMULSION COSMETIC COMPOSITION

[0001] The present invention relates to a water-in-oil emulsion cosmetic composition.

[0002] Liquid foundations of water-in-oil emulsion cosmetics spread lightly on the skin, providing an excellent natural finish and long-lasting cosmetic effect, and are therefore suited for base makeup products. Cushion foundations that are used by impregnating a cushion (puff) with a liquid foundation (WO20217 / 016608, for example), can easily provide a beautiful skin finish, and have received wide consumer support in recent years.

[0003] When a matte or blur finish is desired, it has been common in the past to add microplastic beads made of polymethyl methacrylate or polymethylsiloxane to liquid foundations (EP1980238A2, for example).

[0004] Given recent trends in light of SDGs, however, consumers are increasingly tending to avoid silicone compounds or microplastic beads. Silica is a common potential substitute for microplastic beads, but it has a significant adverse effect on stability and tends to create a dry feel.

[0005] It is an object of the invention to provide a water-in-oil emulsion cosmetic composition having the following characteristics 1) to 5). 1) A matte or blur finish 2) A high coverage effect 3) A comfortable skin finish 4) A long-lasting effect 5) A robust stability

[0006] The present invention provides the following (<1>).

[0007] <1> A water-in-oil emulsion cosmetic composition, wherein the composition comprises (a) a polyglycerol fatty acid ester having an HLB value of less than or equal to 9, (b) a sorbitan fatty acid ester having an HLB value of less than 8, (c) a volatile hydrocarbon oil and (d) barium sulfate and titanium dioxide composite powder. Hereunder, (a) will be referred to as "component (a)", and likewise for the other components.

[0008] The water-in-oil emulsion cosmetic composition can exhibit 1) an excellent matte or blur finish, and 2) a high coverage effect. It can also provide 3) a comfortable skin finish with a fresh sensation and light texture. In addition, the 4) long-lasting effect and the 5) robust stability of the composition itself are also excellent.

[0009] These effects are not the original effects of components (a) to (d), but rather are exhibited when components (a) to (d) are combined. When the water-in-oil emulsion cosmetic composition lacks either component (a) or component (b), the 3) comfortable skin finish and 5) robust stability are inadequate.

[0010] When the water-in-oil emulsion cosmetic composition lacks component (c), the 1) matte / blur finish, 3) comfortable skin finish and 4) long-lasting effect are poor, and when the water-in-oil emulsion cosmetic composition lacks component (d), it is not possible to obtain the 1) matte / blur finish and 2) high coverage effect. When silica is used instead of component (d), it is still possible to maintain performance but the 5) robust stability is exceedingly inferior.

[0011] The present invention also provides the following <2> to <10>. <2> The water-in-oil emulsion cosmetic composition according to <1>, wherein component (d) is flake-shape barium sulfate coated with titanium dioxide.

[0012] Component (d) is not a simple powder mixture of barium sulfate and titanium dioxide, but rather a composite. Composites exists in various forms, but using flake-shape barium sulfate coated with titanium dioxide as component (d) provides marked effects for 1) to 5) above. For example, when silica is used instead of component (d), the texture is smooth but is also accompanied by a dry feeling, producing gelation and silica separation during storage of the water-in-oil emulsion cosmetic composition and resulting in very poor stability. In the water-in-oil emulsion cosmetic composition of the invention, however, the texture is smooth and no dry feeling is produced, and very satisfactory storage stability is exhibited. A makeup cosmetic using powder comprising a metal oxide covering barium sulfate is described in Japanese Unexamined Patent Publication No. 2018-90558, but the cosmetic bases described in the Examples are oil-in-water compositions and therefore the continuous phase is opposite from that of the present invention (water-in-oil emulsion).

[0013] <3> The water-in-oil emulsion cosmetic composition according to <1> or <2>, wherein component (a) comprises at least one selected from the group consisting of an ester of a hydroxy fatty acid polycondensate and polyglycerin, and a difatty acid ester of polyglycerin.

[0014] When component (a) is the reaction product of a hydroxy fatty acid polycondensate (a polycondensate of the hydroxy fatty acid itself) and polyglycerin, then it is possible to further increase the effect described in 5) above.

[0015] <4> The water-in-oil emulsion cosmetic composition according to any one of <1> to <3>, wherein component (b) comprises mono-, sesqui- or di-fatty acid esters of sorbitan.

[0016] Sorbitan has four fatty acid-reactable hydroxyl groups per molecule, and preferred examples of component (b) are mono-fatty acid esters of sorbitan obtained by reacting one of the four hydroxyl groups with a fatty acid, di-fatty acid esters of sorbitan obtained by reacting two of the hydroxyl groups with a fatty acid, and sesqui-fatty acid esters of sorbitan which are mixtures of these and obtained by reacting sorbitan with an average of 1.5 fatty acids. By using component (b) having such a structure, it is possible to further increase the effects described in 3) and 5) above.

[0017] <5> The water-in-oil emulsion cosmetic composition according to any one of <1> to <4>, wherein the composition further comprises (e) an organic modified clay mineral.

[0018] The organic modified clay mineral is not an essential component of the water-in-oil emulsion cosmetic composition, but its addition can notably improve the long-term stability of the water-in-oil emulsion cosmetic composition itself.

[0019] <6> The water-in-oil emulsion cosmetic composition according to any one of <1> to <5>, wherein the composition further comprises (f) a hydrophobic treated metal oxide.

[0020] The hydrophobic treated metal oxide is a type of hydrophobic pigment, and since hydrophobized titanium dioxide functions as a white pigment while hydrophobized iron oxide functions as a red, yellow or black colored pigment, for example, their appropriate combinations can modify the color tone as desired, or can provide an ultraviolet ray-blocking function, while maintaining the effects of 1) to 5) above.

[0021] <7> The water-in-oil emulsion cosmetic composition according to any one of <1> to <6>, wherein the composition further comprises (g) a film-former.

[0022] If the water-in-oil emulsion cosmetic composition comprises component (g), its performance including adhesion to skin and long-lasting effect can be increased.

[0023] <8> The water-in-oil emulsion cosmetic composition according to any one of <1> to <7>, wherein the composition further comprises (h) cellulose powder.

[0024] When the water-in-oil emulsion cosmetic composition comprises component (h), the matte / blur performance can be increased.

[0025] <9> The water-in-oil emulsion cosmetic composition according to any one of <1> to <8>, wherein the component (a) comprises at least one selected from the group consisting of an ester of a hydroxy fatty acid polycondensate and polyglycerin, and a difatty acid ester of polyglycerin, the component (b) comprises mono-, sesqui- or di-fatty acid esters of sorbitan, the component (c) comprises a volatile hydrocarbon oil of 8 to 19 carbon atoms, and the component (d) comprises flake-shape barium sulfate coated with titanium dioxide.

[0026] <10> The water-in-oil emulsion cosmetic composition according to any one of <1> to <9>, wherein the water-in-oil emulsion cosmetic composition comprises 1.0 to 10 mass% of the component (a), 1.0 to 10 mass% of the component (b), 1.0 to 30 mass% of the component (c), and 1.0 to 15 mass% of the component (d), based on the total amount of the water-in-oil emulsion cosmetic composition.

[0027] The present invention further provides a cosmetic process according to the following <11> or <12>. <11> A cosmetic process for caring for and / or making-up keratinic materials, wherein the cosmetic process comprises the application onto keratinic materials, in particular onto skin, of the water-in-oil emulsion cosmetic composition according to any one of <1> to <10>.

[0028] <12> The cosmetic process according to <11>, wherein the water-in-oil emulsion cosmetic composition provides the keratinic materials on which it is applied with a matte / blur finish, a high coverage effect and a long-lasting effect.

[0029] According to the invention there is provided a water-in-oil emulsion cosmetic composition having the properties of: 1) a matte or blur finish, 2) a high coverage effect, 3) a comfortable skin finish, 4) a long-lasting effect and 5) a robust stability.

[0030] The water-in-oil emulsion cosmetic composition of the embodiment comprises (a) a polyglycerol fatty acid ester having an HLB value of less than or equal to 9. Component (a) functions as a surfactant, and it is used in combination with component (b) which likewise functions as a surfactant. When component (a) alone is used as the surfactant the stability is lower, and when component (b) alone is used, not only is the stability lower but the texture also becomes slightly sticky.

[0031] Component (a) may be of a single type having an HLB value of less than or equal to 9, or several different such types may be used in combination.

[0032] Polyglycerin fatty acid esters include polyglycerin esters of fatty acids of 12 to 24, 16 to 22 or 16 to 20 carbon atoms. Such fatty acids may be saturated or unsaturated, and may also have hydroxyl groups. Examples of fatty acids for the polyglycerin fatty acid ester include palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, isostearic acid, arachidic acid, arachidonic acid, behenic acid and ricinolic acid. Such fatty acids wherein one or more hydrogens of hydrocarbon groups in the fatty acids are replaced by hydroxyl groups may also be used, or their polycondensation products may be used.

[0033] The number of glycerin units in the polyglycerin fatty acid ester (also known as the glycerin polymerization degree) may be 2 to 12, 2 to 10, 2 to 8 or 2 to 6.

[0034] As mentioned above, the polyglycerin fatty acid ester may be of many different types depending on the type of fatty acid, and since the structure will differ depending on the glycerin polymerization degree even if the same fatty acid is used, it may have different HLB values, but a polyglycerin fatty acid ester with an HLB value of less than or equal to 9 is used as component (a). The HLB value of the polyglycerin fatty acid ester may be less than or equal to 8, or less than or equal to 7.

[0035] The HLB value is an index representing the ratio of the relative affinity of a surfactant with respect to both liquids in an oil-aqueous system, and the HLB value used for the purpose of the invention is based on the definition of Griffin, at 25°C. The Griffin HLB value is described in J. Soc. Cosm. Chem., 1954, 5:249-256.

[0036] Particularly preferred for component (a) are those comprising (a1) an ester of a hydroxy fatty acid polycondensate and polyglycerin and (a2) a difatty acid ester of polyglycerin.

[0037] Component (a1) is the reaction product of a polyglycerin and a polycondensate of the hydroxy fatty acid itself, and it can be represented by the following general formula (1). (In the formula, R10is a group represented by general formula (2) below or a hydrogen atom, with at least one of the R10groups being a group represented by general formula (2). The letter n represents a number of 2 or greater.) The letter n may be 2 to 12, 2 to 10, 2 to 8 or 2 to 6.

[0038] (In the formula, R20represents a divalent saturated or unsaturated hydrocarbon group as the residue of a hydroxy fatty acid, and m represents a number of 1 or greater. The symbol * represents a bonding site.) The number of carbon atoms of R20may be 11 to 23, 15 to 21 or 15 to 19.

[0039] Examples of component (a1) having the structure of general formula (1) above with an HLB value of less than or equal to 9 include polyglyceryl-6 polyricinoleate, polyglyceryl-3 polyricinoleate, polyglyceryl-4 polyricinoleate, polyglyceryl-5 polyricinoleate, polyglyceryl-10 polyricinoleate, polyglyceryl-2 dipolyhydroxystearate and polyglyceryl-6 polyhydroxystearate.

[0040] Component (a2) can be represented by the following general formula (3).

[0041] (In the formula, two of the R11groups is a divalent saturated or unsaturated hydrocarbon group as a residue of a fatty acid, and the other R11groups are hydrogen atoms. The letter r represents a number of 1 or greater.) The letter r may be 1 to 12, 1 to 10, 1 to 8 or 1 to 6.

[0042] Examples of component (a2) having the structure of general formula (3) above with an HLB value of less than or equal to 9 include polyglyceryl-3 diisostearate and polyglyceryl-2 diisostearate.

[0043] The content of component (a) may be 1.0 to 10 mass%, 2.0 to 8.0 mass%, 3.0 to 6.0 mass%, 3.0 to 5.0 mass%, 2.0 to 6.0 mass%, 2.0 to 5.0 mass% or 2.0 to 4.0 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0044] The water-in-oil emulsion cosmetic composition of the embodiment comprises (b) a sorbitan fatty acid ester having an HLB value of less than 8. Component (b) functions as a surfactant, and is used in combination with component (a). Component (b) may be of a single type having an HLB value of less than 8, or several different such types may be used in combination.

[0045] Sorbitans that may compose component (b) include 1,4-sorbitan having a tetrahydrofuran backbone and 1,5-sorbitan having a tetrahydropyran backbone, and component (b) may comprise any of these backbones or it may be a mixture of compounds having such backbones.

[0046] Sorbitan has four fatty acid-reactive hydroxyl groups per molecule, with 1, 2, 3 or 4 of the four hydroxyl groups potentially reacting with fatty acids to form component (b). Sorbitan fatty acid esters include sorbitan esters of fatty acids of 12 to 24, 16 to 22 or 16 to 20 carbon atoms. Such fatty acids may be saturated or unsaturated. Examples of fatty acids to compose the sorbitan fatty acid ester include stearic acid, isostearic acid and oleic acid.

[0047] As explained above, the sorbitan fatty acid ester may be of many different types depending on the type of fatty acid and the number of fatty acids to be reacted with the sorbitan, and it may therefore have different HLB values, but a sorbitan fatty acid ester with an HLB value of less than 8 is used as component (b). The HLB value of the sorbitan fatty acid ester may be less than or equal to 7, or less than or equal to 6.

[0048] Particularly preferred examples for component (b) include (b1) mono-fatty acid esters of sorbitan, (b2) di-fatty acid esters of sorbitan and (b3) sesqui-fatty acid esters of sorbitan.

[0049] Such sorbitan fatty acid esters include sorbitan sesquioleate, sorbitan sesquiisostearate, sorbitan isostearate and sorbitan oleate.

[0050] The content of component (b) may be 1.0 to 10 mass%, 1.0 to 8.0 mass%, 1.0 to 6.0 mass%, 1.0 to 4.0 mass%, 1.0 to 3.0 mass%, 2.0 to 8.0 mass%, 2.0 to 6.0 mass% or 2.0 to 4.0 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0051] The ratio of component (b) to component (a) [component (b) / component (a)] may be 0.2 to 0.8, 0.25 to 0.8, 0.25 to 0.75, 0.3 to 0.75 or 0.4 to 0.75, as the mass ratio.

[0052] The water-in-oil emulsion cosmetic composition of the embodiment also comprises (c) a volatile hydrocarbon oil.

[0053] Component (c) may be a volatile straight-chain hydrocarbon oil or a volatile branched-chain hydrocarbon oil, and it may be a polar oil or non-polar oil.

[0054] The term "volatile oil" means an oil which has lost 4% or more (preferably 5% or more, more preferably 10% or more, and most preferably 20% or more) by mass after 60 minutes of drying at a temperature of 33°C and a humidity of 55%, according to the following protocol: 20 mg of the oil to be examined is weighed on a 5 cm × 5 cm polymethyl methacrylate (PMMA) plate using a micropipette and a precision balance. The oil to be examined is spread with a finger over the entire plate. The plate is then placed in a ventilated enclosure thermostatically controlled to 25% humidity. The test is carried out 3 times for each oil. The loss of mass during drying is measured after 60 minutes. The mass lost is expressed according to the following formula (1):

[0055] In formula (1), mtxrepresents the mass of the plate as measured 60 minutes after the start of drying, and mt0represents the mass of the plate as measured before drying. A volatile hydrocarbon oil is a liquid at ordinary temperature and ordinary pressure, and may also be considered to be a gradually-vaporizing oily component.

[0056] Component (c) may be a volatile hydrocarbon oil of 8 to 19 carbon atoms. Component (c) may be one or more selected from the group consisting of branched C8-C19 alkanes (such as isoparaffins, isododecane, isodecane and isohexadecane), linear C8-C19 alkanes (such as nonane, decane, undecane, dodecane, tridecane, pentadecane and hexadecane), mixtures of C9-C15 alkanes, mixtures of C9-C17 alkanes, mixtures of C10-C14 alkanes, mixtures of undecane and tridecane, mixtures of C15-C19 alkanes, mixtures of C9-C12 alkanes, mixtures of C13-C15 alkanes, mixtures of C12-C14 alkanes, n-dodecane and n-tetradecane. Component (c) preferably includes a volatile linear hydrocarbon having 9 to 12 carbon atoms, a volatile linear hydrocarbon having 13 to 15 carbon atoms, a volatile linear hydrocarbon having 15 to 19 carbon atoms, or a mixture of the foregoing.

[0057] The content of component (c) may be 1.0 to 30 mass%, 1.0 to 25 mass%, 1.0 to 20 mass%, 1.0 to 15 mass%, 2.0 to 20 mass%, 3.0 to 20 mass%, 4.0 to 20 mass%, 5.0 to 20 mass%, 2.0 to 15 mass%, 3.0 to 15 mass%, 4.0 to 15 mass% or 5.0 to 15 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0058] The water-in-oil emulsion cosmetic composition of the embodiment also comprises (d) barium sulfate and titanium dioxide composite powder.

[0059] Component (d) is a composite of barium sulfate and titanium dioxide, whereas a simple mixture of barium sulfate and titanium dioxide does not qualify as component (d).

[0060] Component (d) includes (d1) flake-shape barium sulfate coated with titanium dioxide and (d2) barium sulfate in a form other than flake-shape (such as particulate), coated with titanium oxide. Component (d) may have a mean particle size of 2 to 20 μm, 3 to 15 μm or 5 to 15 μm. Component (d) preferably includes at least component (d1).

[0061] As the component (d1), a composite powder having a two-layer structure in which a plate-shaped barium sulfate is coated with titanium oxide, or a composite powder having a three-layer structure in which a plate-shaped barium sulfate is coated with titanium oxide and further coated with barium sulfate can be used. Component (d1) can be produced by the method described in Japanese Unexamined Patent Publication HEI No. 8-176459 or Japanese Unexamined Patent Publication HEI No. 10-8028, for example.

[0062] Component (d) may be, specifically, MiyoHAZE BT (Manufacturer: Miyoshi Kasei) or SILSEEM BT-HLW (Manufacturer: Nihon Koken Kogyo Co., Ltd.).

[0063] The content of component (d) may be 1.0 to 15 mass%, 1.0 to 10 mass%, 1.0 to 8.0 mass%, 2.0 to 10 mass%, 2.0 to 8.0 mass%, 2.0 to 6.0 mass%, 3.0 to 10 mass%, 3.0 to 8.0 mass% or 3.0 to 6.0 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0064] Component (d) may also be hydrophobically surface-treated. Component (d) may also be, specifically, MiyoHAZE BT-SA (Manufacturer: Miyoshi Kasei) or SILSEEM BT-HLW-03 (Manufacturer: Nihon Koken Kogyo Co., Ltd.).

[0065] The other hydrophobic agent may be one or more selected from the group consisting of silicone compounds, silane compounds, amino acid derivatives, sugar derivatives, organic titanates, phospholipids, metal soaps, fatty acids, lubricants and organic polymers.

[0066] Silicone compounds include monomethylpolysiloxane (methicone) and dialkylpolysiloxanes such as dimethylpolysiloxane (dimethicone). Silane compounds include trialkylalkoxysilanes such as trimethylmethoxysilane and triethoxycaprylylsilane.

[0067] An amino acid derivative may be a derivative of an amino acid such as glycine, alanine, sarcosine, proline, hydroxyproline, aspartic acid, glutamic acid or lysine. The derivative is preferably an amino acid acylated with a fatty acid. Fatty acids used for acylation are preferably saturated or unsaturated fatty acids of 1 to 22 carbon atoms, and more preferably saturated or unsaturated fatty acids of 8 to 20 carbon atoms.

[0068] Saturated fatty acids of 8 to 20 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid. Examples of unsaturated fatty acids of 8 to 20 carbon atoms include myristic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linolelaidic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, ersinic acid and docosahexaenoic acid.

[0069] Acylated amino acids include stearoylglutamic acid, lauroylglutamic acid, myristoylglutamic acid, cocoylglutamic acid, stearoyllysine, lauroyllysine and myristoyllysine. Preferred acylated amino acids are stearoylglutamic acid and myristoylglutamic acid. An acylated amino acid may also be a salt of sodium, potassium, calcium, magnesium or aluminum.

[0070] A sugar derivative as a hydrophobic agent may be a polysaccharide fatty acid ester, and an organic titanate may be a titanate-based coupling agent such as isopropyltriisostearoyl titanate. A phospholipid may be lecithin or hydrogenated lecithin, and the fatty acid may be lauric acid, myristic acid, stearic acid, isostearic acid, palmitic acid, or a fatty acid ester or fatty acid amide.

[0071] Metal soaps, as hydrophobic agents, include stearic acid soaps, 12-hydroxystearic acid soaps, behenic acid soaps, montanic acid soaps and lauric acid soaps, and lubricants include waxes, and fats and oils. Examples of organic polymers include urethane compounds, acrylic compounds, (meth)acrylic compounds, polyisobutylene and polyethylene.

[0072] The water-in-oil emulsion cosmetic composition of the embodiment may also comprise (e) an organic modified clay mineral. Component (e) is clay that has been modified to hydrophobicity with an organic molecule, and it has a thickening effect.

[0073] Examples of clay to be used for component (e) include kaolinite, dickite, nacrite, donbassite, antigorite, berthierine, pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, saponite, chlorite and sepiolite, which are modified to hydrophobicity with organic molecules. Examples of organic molecules include quaternary ammonium salts, and more specifically disteardimonium chloride and stearalkonium chlorides. Examples for component (e) include disteardimonium hectorite and stearalkonium hectorite.

[0074] Component (e) may be handled in a state dispersed in a volatile oil and / or a non-volatile oil, in which case it may be utilized together with a volatile oil and / or a non-volatile oil. Such volatile oils include cyclopentasiloxane, octamethyltrisiloxane, isododecane, isohexadecane, petroleum volatiles and methyltrimethicone. Non-volatile oils include propylene carbonate, crambe abyssinica seed oil, castor oil, olive fruit oil, octyldodecanol, isopropyl myristate, liquid lanolin, mineral oil, hydrogenated polyisobutene, phenyltrimethicone, pentaerythrityl tetraisostearate and alkyl benzoates.

[0075] The content of component (e) may be 0.1 to 2.0 mass%, 0.1 to 1.5 mass%, 0.1 to 1.2 mass%, 0.1 to 1.0 mass%, 0.1 to 0.8 mass%, 0.2 to 1.2 mass%, 0.2 to 1.0 mass% or 0.2 to 0.8 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0076] The water-in-oil emulsion cosmetic composition of the embodiment may also comprise (f) a hydrophobic treated metal oxide. Component (f) may be provided as a hydrophobized pigment that has been surface-treated with a hydrophobic agent.

[0077] Examples of surface-treated inorganic pigments (metal oxides) include titanium dioxide, iron oxide, zinc oxide, cerium oxide, aluminum oxide, bengala, Prussian blue chromium oxide and chromium hydroxide. Titanium dioxide is known as a white pigment, and iron oxide is known as a red, yellow or black colored pigment. These may be appropriately combined for adjustment to a desired color tone.

[0078] The other hydrophobic agent may be one or more selected from the group consisting of silicone compounds, silane compounds, amino acid derivatives, sugar derivatives, organic titanates, phospholipids, metal soaps, fatty acids, lubricants and organic polymers.

[0079] Silicone compounds include monomethylpolysiloxane (methicone) and dialkylpolysiloxanes such as dimethylpolysiloxane (dimethicone). Silane compounds include trialkylalkoxysilanes such as trimethylmethoxysilane and triethoxycaprylylsilane.

[0080] An amino acid derivative may be a derivative of an amino acid such as glycine, alanine, sarcosine, proline, hydroxyproline, aspartic acid, glutamic acid or lysine. The derivative is preferably an amino acid acylated with a fatty acid. Fatty acids used for acylation are preferably saturated or unsaturated fatty acids of 1 to 22 carbon atoms, and more preferably saturated or unsaturated fatty acids of 8 to 20 carbon atoms.

[0081] Saturated fatty acids of 8 to 20 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid. Examples of unsaturated fatty acids of 8 to 20 carbon atoms include myristic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linolelaidic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, ersinic acid and docosahexaenoic acid.

[0082] Acylated amino acids include stearoylglutamic acid, lauroylglutamic acid, myristoylglutamic acid, cocoylglutamic acid, stearoyllysine, lauroyllysine and myristoyllysine. Preferred acylated amino acids are stearoylglutamic acid and myristoylglutamic acid. An acylated amino acid may also be a salt of sodium, potassium, calcium, magnesium or aluminum.

[0083] A sugar derivative as a hydrophobic agent may be a polysaccharide fatty acid ester, and an organic titanate may be a titanate-based coupling agent such as isopropyltriisostearoyl titanate. A phospholipid may be lecithin or hydrogenated lecithin, and the fatty acid may be lauric acid, myristic acid, stearic acid, isostearic acid, palmitic acid, or a fatty acid ester or fatty acid amide.

[0084] Metal soaps, as hydrophobic agents, include stearic acid soaps, 12-hydroxystearic acid soaps, behenic acid soaps, montanic acid soaps and lauric acid soaps, and lubricants include waxes, and fats and oils. Examples of organic polymers include urethane compounds, acrylic compounds, (meth)acrylic compounds, polyisobutylene and polyethylene.

[0085] In order to obtain a hydrophobized pigment, aluminum hydroxide may be used as a surface treatment agent in addition to the hydrophobic agent. Particularly when the inorganic pigment is one with catalytic activity, such as titanium oxide, aluminum hydroxide is effective for sealing the catalytic activity.

[0086] Component (f) has a particulate form with a mean particle size of 100 to 900 nm, 200 to 800 nm, 300 to 700 nm or 400 to 600 nm.

[0087] The content of component (f) may be 1.0 to 40 mass%, 1.0 to 35 mass%, 1.0 to 30 mass%, 5.0 to 40 mass%, 5.0 to 35 mass%, 5.0 to 30 mass%, 10 to 40 mass%, 10 to 35 mass% or 10 to 30 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0088] The water-in-oil emulsion cosmetic composition of the embodiment may also comprise (g) a film-former. The film-former (g) is a substance (such as a polymer substance) that is able to form a film at room temperature (25°C).

[0089] Component (g) may be trimethylsiloxysilicic acid, polypropylsilsesquioxane, (acrylates / polytrimethylsiloxy methacrylate) copolymer, (eicosene / vinylpyrrolidone) copolymer, (trimethylsiloxysilicic acid / dimethiconol) cross polymer or candelilla wax extract. Component (g) may also be a wax such as carnauba wax, candelilla wax, rice wax, Japan wax, stearyl stearate or myristyl myristate.

[0090] The content of component (g) may be 1.0 to 10 mass%, 1.0 to 8.0 mass%, 1.0 to 6.0 mass%, 1.0 to 5.0 mass%, 2.0 to 10 mass%, 2.0 to 8.0 mass%, 2.0 to 6.0 mass%, 2.0 to 5.0 mass%, 3.0 to 10 mass%, 3.0 to 8.0 mass%, 3.0 to 6.0 mass% or 3.0 to 5.0 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0091] The water-in-oil emulsion cosmetic composition of the embodiment may also comprise (h) cellulose powder. Component (h) is obtained by molding cellulose particles into a spherical or amorphous shape, and it can enhance the matte / blur performance.

[0092] Component (h) may be Cellulobeads D-5 (Manufacturer: Daito Kasei).

[0093] The content of component (h) may be 1.0 to 15 mass%, 1.0 to 10 mass%, 1.0 to 8.0 mass%, 2.0 to 10 mass%, 2.0 to 8.0 mass%, 2.0 to 6.0 mass%, 3.0 to 10 mass%, 3.0 to 8.0 mass% or 3.0 to 6.0 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0094] Component (h) may be hydrophobically surface-treated, an example of a hydrophobically surface-treated product being Cellulobeads D-5 ASG3 (Manufacturer: Kobo Products Inc.).

[0095] The other hydrophobic agent may be one or more selected from the group consisting of silicone compounds, silane compounds, amino acid derivatives, sugar derivatives, organic titanates, phospholipids, metal soaps, fatty acids, lubricants and organic polymers.

[0096] Silicone compounds include monomethylpolysiloxane (methicone) and dialkylpolysiloxanes such as dimethylpolysiloxane (dimethicone). Silane compounds include trialkylalkoxysilanes such as trimethylmethoxysilane and triethoxycaprylylsilane.

[0097] An amino acid derivative may be a derivative of an amino acid such as glycine, alanine, sarcosine, proline, hydroxyproline, aspartic acid, glutamic acid or lysine. The derivative is preferably an amino acid acylated with a fatty acid. Fatty acids used for acylation are preferably saturated or unsaturated fatty acids of 1 to 22 carbon atoms, and more preferably saturated or unsaturated fatty acids of 8 to 20 carbon atoms.

[0098] Saturated fatty acids of 8 to 20 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid. Examples of unsaturated fatty acids of 8 to 20 carbon atoms include myristic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linolelaidic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, ersinic acid and docosahexaenoic acid.

[0099] Acylated amino acids include stearoylglutamic acid, lauroylglutamic acid, myristoylglutamic acid, stearoyllysine, lauroyllysine and myristoyllysine. Preferred acylated amino acids are stearoylglutamic acid and myristoylglutamic acid. An acylated amino acid may also be a salt of sodium, potassium, calcium, magnesium or aluminum.

[0100] A sugar derivative as a hydrophobic agent may be a polysaccharide fatty acid ester, and an organic titanate may be a titanate-based coupling agent such as isopropyltriisostearoyl titanate. A phospholipid may be lecithin or hydrogenated lecithin, and the fatty acid may be lauric acid, myristic acid, stearic acid, isostearic acid, palmitic acid, or a fatty acid ester or fatty acid amide.

[0101] Metal soaps, as hydrophobic agents, include stearic acid soaps, 12-hydroxystearic acid soaps, behenic acid soaps, montanic acid soaps and lauric acid soaps, and lubricants include waxes, and fats and oils. Examples of organic polymers include urethane compounds, acrylic compounds, (meth)acrylic compounds, polyisobutylene and polyethylene.

[0102] The water-in-oil emulsion cosmetic composition of the embodiment may also include a non-volatile oil.

[0103] The non-volatile oil is an oil that does not satisfy the conditions of formula (1) above, and in most cases it is a non-volatile oil component that is liquid at ordinary temperature (15 to 25°C) and ordinary pressure (1 atmosphere).

[0104] The non-volatile oil may be a non-volatile hydrocarbon oil, higher alcohol, ester oil or vegetable oil, for example.

[0105] Examples of non-volatile hydrocarbon oils include squalane, liquid paraffin, vaseline, polybutene, polyisobutene, hydrogenated polyisobutene, hydrogenated polydecene and olefin oligomers.

[0106] Higher alcohols are aliphatic monoalcohols of 6 or more carbon atoms, and preferably aliphatic monoalcohols of 12 to 28 carbon atoms. Examples of higher alcohols include octyl alcohol, dodecyl alcohol, oleyl alcohol, stearyl alcohol, octyldodecanol, cetyl alcohol, ceryl alcohol and myristyl alcohol.

[0107] Ester oils are carboxylic acid esters that are liquid in environments at ordinary temperature and pressure (for example, 25°C, 1 atmosphere) and do not gasify, and they are preferably carboxylic acid alkyl esters wherein the carboxylic acid or alcohol of the ester has 8 to 18 carbon atoms. Examples of ester oils include propylene glycol fatty acid esters such as propylene glycol dicaprylate and propylene glycol dicaprate; fatty acid alkyl esters such as ethylhexyl palmitate, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, coco-caprylates / caprates and isononyl isononanoate; carbonic acid esters such as dicaprylyl carbonate; tri and greater fatty acid esters of polyglycerins, such as polyglyceryl-2 triisostearate, polyglyceryl-2 tetraisostearate and polyglyceryl-10 decaisostearate; glycerin tri-fatty acid esters such as glyceryl tri 2-ethylhexanoate, glyceryl tribehenate, glyceryl tri(caprylate / caprate) and triheptanoin (also known as triglyceride oils); benzoic acid derivatives such as diisostearyl malate and alkyl benzoate (C12-15); salicylic acid derivatives such as homosalates and ethylhexyl salicylate; alkyl esters such as cocoalkyl (caprylates / caprates); and cinnamic acid derivatives such as octyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, cinnoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, glyceryl-ethyl hexanoate-dimethoxy cinnamate and di-(2-ethylhexyl)-4'-methoxybenzalmalonate.

[0108] Examples of vegetable oils include meadowfoam seed oil, olive fruit oil, camellia oil, coconut oil, macadamia nut oil, rosehip oil, avocado oil, sunflower seed oil, rice bran oil, castor oil and almond oil.

[0109] The content of the non-volatile oil may be 1.0 to 30 mass%, 1.0 to 25 mass%, 1.0 to 20 mass%, 1.0 to 15 mass%, 2.0 to 20 mass%, 3.0 to 20 mass%, 4.0 to 20 mass%, 5.0 to 20 mass%, 2.0 to 15 mass%, 3.0 to 15 mass%, 4.0 to 15 mass% or 5.0 to 15 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0110] The water-in-oil emulsion cosmetic composition of the embodiment may also include an aqueous phase (aqueous media). The aqueous phase may comprise one or more components selected from the group consisting of purified water and alcohols.

[0111] An alcohol may include a polyol of 1 to 8 carbon atoms. Examples of polyols of 1 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol and glycerin.

[0112] The alcohol may also include a monool of 1 to 3 carbon atoms. Examples of monools of 1 to 3 carbon atoms include ethanol, 1-propanol and 2-propanol (isopropanol).

[0113] The aqueous phase may further include magnesium sulfate, sodium chloride, a humectant (such as trehalose), a water-soluble UV protection material such as phenylbenzimidazole sulfonate), an amino acid (such as arginine) or a preservative (chlorphenesin).

[0114] The content of the aqueous phase may be 1.0 to 50 mass%, 1.0 to 40 mass%, 1.0 to 30 mass%, 5.0 to 50 mass%, 5.0 to 40 mass%, 5.0 to 30 mass%, 10 to 50 mass%, 10 to 40 mass%, 10 to 30 mass% or 15 to 30 mass%, based on the total amount of the water-in-oil emulsion cosmetic composition.

[0115] The water-in-oil emulsion cosmetic composition of the embodiment may further include an antimicrobial agent, antioxidant, aromatic or active ingredients. A surfactant other than component (a) and component (b) may also be included in a range that does not inhibit the effect of the invention.

[0116] The water-in-oil emulsion cosmetic composition of the embodiment can be produced by mixing each of the components, but it can also be produced by separately mixing the water-soluble components and the oil-soluble components, and preparing a final mixture of the two.

[0117] The water-in-oil emulsion cosmetic composition of the embodiment may be filled into a tube, jar or bottle container for use as a liquid foundation or cream foundation. It may also be impregnated into a cushion (puff) for use as a cushion foundation.

[0118] A cosmetic product, according to one embodiment, comprises a support and a cosmetic composition (a water-in-oil emulsion cosmetic composition) of the invention impregnated in the support. The support may be in a non-compressed state. The support may be a water-insoluble support. Water-insoluble supports include nonwoven fabrics made of simple or composite materials such as resins, pulp or cotton; resin-coated fiber materials; foamed bodies such as sponges and porous bodies with continuous structures. The material of the support may be, for example, NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), NR (natural rubber), urethane, nylon, polyolefin, polyester, EVA (ethylene-vinyl acetate), PVA (polyvinyl alcohol) or silicone elastomer, but there is no limitation to these materials so long as they can be impregnated with the cosmetic composition.

[0119] The cosmetic composition of the present invention is preferably impregnated in an open-cell type foam. The hardness and porosity of the foam can be commonly adapted to allow effective impregnation of the composition and to avoid excessive flow out when the foam is being pressured for dispensation of the composition. The composition may be dispensed by applying pressure on the surface of the impregnated foam. More specifically, the impregnated foam may be contained in a non-compressed state in a container.

[0120] The cosmetic product according to one embodiment may be a cushion foundation, cushion BB cream, cushion concealer, cushion make-up base or cushion make-up primer. For example, a cushion foundation is a foamed body such as a sponge impregnated with a cosmetic composition of the invention (foundation).

[0121] A cosmetic package according to one embodiment comprises a container and a cosmetic product of the invention placed inside of the container. The cosmetic package may be an air-tight (airless) cosmetic package wherein the container has an air-tight function. The container of the cosmetic package, being designed for opening and closing for use, is preferably sufficiently air-tight without causing difficulty during opening and closing. Specifically, the air-tight cosmetic package may be a cosmetic compact.

[0122] The present invention will now be explained by the following Examples, with the understanding that the invention is not limited by the Examples.

[0123] (Examples 1 to 12 and Comparative Examples 1 to 7) Water-in-oil emulsion cosmetic compositions were prepared with the compositions listed in Tables 1,2 and 3, by the following steps 1 to 3. Step 1: Component (a), component (b), component (c), component (c'), component (d), component (d'), component (e), component (f), component (g) and component (h) were mixed using a homogenizer at room temperature. Step 2: Component (i) was mixed using a homogenizer at room temperature. Step 3: The mixture obtained in step 2 was added to the mixture obtained in step 1, and the resulting mixture was emulsified using a homogenizer. Step 4: The obtained cosmetic was filled into a bottle container and evaluated. In Tables 1, 2 and 3, the components indicated by "*" are listed in Table 4 under "Trade name of raw materials" and "Supplier for raw materials".

[0124] Tables 1, 2 and 3 show the results of evaluating the matte / blur finish, coverage, long lasting effect, fresh sensation (for comfortable skin finish) and light weight finish (for comfortable skin finish), when the water-in-oil emulsion cosmetic compositions of the Examples and Comparative Examples were applied onto the skin by an evaluation panel of 10 cosmetic experts (ages 25 to 55). The definitions of the symbols in the tables are as follows. The evaluations A to F are in descending order, with A, B and C indicating acceptability in terms of performance and D, E and F indicating unacceptable performance.

[0125] With assigned scores of: A = 6 points, B = 5 points, C = 4 points, D = 3 points, E = 2 points and F = 1 point, the total score for the 10 evaluators (total of 60 points) was judged on the following scale. A: ≧51 points B: 42 to 50 points C: 33 to 41 points D: 18 to 32 points E: 9 to 17 points F: ≦8 points

[0126] Matte / blur finish A: Excellent (e.g.: very strong matte / blur finish). B: Very good (e.g.: strong matte / blur finish). C: Good (e.g.: matte / blur finish). D: Poor (e.g.: slight matte / blur finish). E: Very poor (e.g.: almost no matte / blur finish). F: Extremely poor (e.g.: no matte / blur finish).

[0127] Coverage effect A: Excellent (e.g.: complete covering of redness and blemishes). B: Very good (e.g.: no visible redness, but 1 or 2 evaluators out of 10, had slightly visible blemishes). C: Good (e.g.: no visible redness, but 3 to 5 evaluators had slightly visible blemishes). D: Poor (e.g.: 1 or 2 evaluators had visible redness and blemishes). E: Very poor (e.g.: 3 to 5 evaluators had visible redness and blemishes). F: Extremely poor (e.g.: 6 to 10 evaluators had visible redness and blemishes).

[0128] Long-lasting effect A: Excellent (e.g.: no breakup of cosmetic even after 8 hours.) B: Very good (e.g.: no breakup of cosmetic after 4 hours, but breakup of cosmetic experienced by 1 or 2 evaluators after 8 hours.) C: Good (e.g.: no breakup of cosmetic after 4 hours, but breakup of the cosmetic experienced by 3 to 5 evaluators after 8 hours.) D: Poor (e.g.: breakup of cosmetic experienced by 1 or 2 evaluators after 4 hours.) E: Very poor (e.g.: breakup of cosmetic experienced by 3 to 5 evaluators after 4 hours.) F: Extremely poor (e.g.: breakup of cosmetic experienced by 6 to 10 evaluators after 4 hours.)

[0129] Fresh sensation A: Excellent (e.g.: very strong fresh sensation, absolutely no dryness felt). B: Very good (e.g.: strong fresh sensation, virtually no dryness felt). C: Good (e.g.: fresh sensation but slight dryness felt). D: Poor (e.g.: fresh sensation but dryness felt). E: Very poor (e.g.: no fresh sensation, dryness felt). F: Extremely poor (e.g.: no fresh sensation, considerable dryness felt).

[0130] Each of the prepared water-in-oil emulsion cosmetic compositions of the Examples and Comparative Examples was filled into a transparent container and sealed with a cap, and then stored for 1 month at 4°C and for 1 month at 50°C. As a control, each water-in-oil emulsion cosmetic composition was also used after storage for 1 month at room temperature. The difference in appearance after storage was compared with a control and judged on the following scale. A: Acceptable (no difference in outer appearance) B: Acceptable (difference in outer appearance, but small enough to constitute no problem for use) C: Not acceptable (difference in outer appearance with separation of water hindering use)

[0131]

[0132]

[0133]

[0134]

Claims

1. A water-in-oil emulsion cosmetic composition, wherein the composition comprises (a) a polyglycerol fatty acid ester having an HLB value of less than or equal to 9, (b) a sorbitan fatty acid ester having an HLB value of less than 8, (c) a volatile hydrocarbon oil, and (d) barium sulfate and titanium dioxide composite powder.

2. The water-in-oil emulsion cosmetic composition according to claim 1, wherein component (d) is flake-shape barium sulfate coated with titanium dioxide.

3. The water-in-oil emulsion cosmetic composition according to claim 1 or 2, wherein component (a) comprises at least one selected from the group consisting of an ester of a hydroxy fatty acid polycondensate and polyglycerin, and a difatty acid ester of polyglycerin.

4. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 3, wherein component (b) comprises mono-, sesqui- or di-fatty acid esters of sorbitan.

5. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 4, wherein the composition further comprises (e) an organic modified clay mineral.

6. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 5, wherein the composition further comprises (f) a hydrophobic treated metal oxide.

7. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 6, wherein the composition further comprises (g) a film-former.

8. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 7, wherein the composition further comprises (h) cellulose powder.

9. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 8, wherein the component (a) comprises at least one selected from the group consisting of an ester of a hydroxy fatty acid polycondensate and polyglycerin, and a difatty acid ester of polyglycerin, the component (b) comprises mono-, sesqui- or di-fatty acid esters of sorbitan, the component (c) comprises a volatile hydrocarbon oil of 8 to 19 carbon atoms, and the component (d) comprises flake-shape barium sulfate coated with titanium dioxide.

10. The water-in-oil emulsion cosmetic composition according to any one of claims 1 to 9, wherein the water-in-oil emulsion cosmetic composition comprises 1.0 to 10 mass% of the component (a), 1.0 to 10 mass% of the component (b), 1.0 to 30 mass% of the component (c), and 1.0 to 15 mass% of the component (d), based on the total amount of the water-in-oil emulsion cosmetic composition.

11. A cosmetic process for caring for and / or making-up keratinic materials, wherein the cosmetic process comprises the application onto keratinic materials, in particular onto skin, of the water-in-oil emulsion cosmetic composition according to any one of claims 1 to 10.

12. The cosmetic process according to claim 11, wherein the water-in-oil emulsion cosmetic composition provides the keratinic materials on which it is applied with a matte / blur finish, a high coverage effect and a long-lasting effect.

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