JP6359295B2 - Water-in-oil emulsified cosmetic and method for producing the same - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic that is excellent in feel during use while blending metal oxide powder, has no squeakiness or stickiness, and has high emulsification stability, and a method for producing the same.

  Metal oxide powders are widely used for the purpose of coloring cosmetics, concealing skin defects, and blocking ultraviolet rays because of their high refractive index. For example, foundations with high hiding power that contain high amounts of metal oxides and sunscreen cosmetics that contain fine particles of metal oxides and organic UV absorbers to prevent the harmful effects of UV rays on the skin have been developed. It is used.

  In recent years, since skin-friendly cosmetics have been demanded, sunscreen cosmetics have been developed that contain high amounts of metal oxide fine particles as UV-scattering agents without or reducing the amount of UV absorbers. ing. However, when a large amount of metal oxide fine particles are blended, the cosmetic film has a pale and unnatural appearance, and when applied to the skin, it feels strongly and the spread becomes worse. In addition, the smaller the particle size, the stronger the cohesive force, and there is a problem that it is difficult to disperse during blending. When blended into a cosmetic, there is a problem of improving the drawbacks in the feeling of use such as a squeaky sensation during application and insufficient elongation performance.

  Therefore, a water-in-oil emulsified cosmetic containing a hydrophobized metal oxide powder is blended with a silicone-branched polyglycerin-modified silicone and isostearic acid in the oil phase, making it easy to stretch and with very little stickiness. A method of imparting usability (Patent Document 1), blending with extender pigments to adjust the finish such as extensibility, adhesion to the skin, absorbability of sweat and sebum, and gloss (non-patent) Document 1) is known.

JP 2010-159229 A

"New Cosmetics" (2nd edition), Takeo Mitsui, Nanzan-do, 2001, p. 401

  However, in these methods, when the metal oxide powder is highly blended, the extensibility and the squeaking feeling are deteriorated, and it is impossible to achieve both the high blending of the metal oxide powder and a good feeling of use. In addition, the influence of the water-in-oil emulsified cosmetic on the extensibility and feeling of use is considered to be greater in the outer phase (oil phase) than in the inner phase (water phase). Although the type and amount of the oil component used have been studied, problems such as reduced extensibility of cosmetics and squeaky sensation due to the blending of metal oxide powders have not been solved. . Therefore, it has been difficult to develop cosmetics with high compounding of metal oxides using conventional techniques.

  It is an object of the present invention to provide a water-in-oil emulsified cosmetic that is excellent in touch during use while containing a metal oxide, has no squeaky feeling or stickiness, and has high emulsification stability.

  As a result of intensive studies in view of the above problems, the present inventors have made a water-in-oil type emulsified cosmetic in which a specific water-dispersible silicone wax is combined with a hydrophobized metal oxide powder at the time of use. It has been found for the first time that it is possible to realize the performance of having excellent emulsification feeling, no squeakiness and stickiness, and high emulsification stability.

（ｍ及びｎは、独立して１０〜２４の整数である。）
で表される水分散性シリコーンワックスを油中水型化粧料の総量中に１．０〜１０．０質量％含有し、
前記疎水化処理された金属酸化物粉体として、酸化亜鉛、又は酸化亜鉛と酸化チタンを油中水型化粧料の総量中に１．５〜４０．０質量％含有する油中水型乳化化粧料を提供する。 That is, the present invention is a water-in-oil emulsified cosmetic containing a metal oxide powder that has been hydrophobized in order to achieve the above object,
The oil phase contains the metal oxide powder that has been hydrophobized,
In the aqueous phase, the following formula (I):

(M and n are each independently an integer of 10 to 24.)
Containing 1.0 to 10.0% by mass of a water-dispersible silicone wax represented by
As the hydrophobized metal oxide powder, zinc oxide or zinc oxide and titanium oxide are contained in a total amount of water-in-oil cosmetic of 1.5 to 40.0% by mass in water-in-oil emulsion makeup. Provide a fee.

（ｍ及びｎは、独立して１０〜２４の整数である。）
で表される水分散性シリコーンワックスを含有する水相とを乳化する工程を含み、前記水分散性シリコーンワックスを総量中に１．０〜１０．０質量％含有し、前記疎水化処理された金属酸化物粉体として、酸化亜鉛、又は酸化亜鉛と酸化チタンを総量中に１．５〜４０．０質量％含有する油中水型乳化化粧料の製造方法を提供する。 Another aspect of the present invention is a method for producing a water-in-oil emulsified cosmetic, wherein an oil phase in which a metal oxide powder subjected to a hydrophobic treatment is dispersed, and the following formula (I):

(M and n are each independently an integer of 10 to 24.)
In viewing including the step of emulsifying the aqueous phase containing the water-dispersible silicone wax represented, the water dispersible silicone wax containing 1.0 to 10.0 wt% in total, are treated the hydrophobic A method for producing a water-in-oil emulsified cosmetic containing zinc oxide or zinc oxide and titanium oxide in a total amount of 1.5 to 40.0% by mass as the metal oxide powder is provided.

  INDUSTRIAL APPLICABILITY The present invention can provide a water-in-oil emulsified cosmetic that is excellent in touch during use while containing a metal oxide, has no squeakiness or stickiness, and has high emulsification stability.

  The water-in-oil emulsified cosmetic according to the present invention comprises an oil phase and an aqueous phase, the oil phase contains at least a hydrophobized metal oxide powder, and the water phase has a specific water dispersibility. Contains at least silicone wax. The hydrophobized metal oxide powder is contained in an amount of 1.5% by mass or more based on the total amount of the water-in-oil emulsified cosmetic. The water-in-oil emulsified cosmetic can further contain an oil component constituting the oil phase, a water component constituting the water phase, and an emulsifier emulsifying the oil phase and the water phase.

(A) Hydrophobized metal oxide powder Hydrophobized metal oxide powder is not particularly limited as long as it is generally blended into cosmetics, and usually white pigments and colored pigments. Those used as an ultraviolet scattering agent or an infrared scattering agent can be used. Examples of metal oxide powders include titanium oxide, iron oxide (yellow iron oxide (iron oxyhydroxide / ferric hydroxide), red iron oxide (iron trioxide), and black iron oxide (iron trioxide). Include), zinc oxide, cerium oxide, zirconium oxide, chromium oxide, and aluminum oxide. The metal oxide may have any particle size of pigment grade and fine particles. A metal oxide powder may be used individually by 1 type, and can be used in combination of 2 or more type.

  As the metal oxide powder, a powder whose surface is hydrophobized by a known method can be used. Hydrophobic treatment methods include silicone treatment such as methylpolysiloxane, fluorine treatment with perfluoroalkyl phosphate, etc., amino acid treatment with N-acyl glutamic acid, etc., lecithin treatment, metal soap treatment, fatty acid treatment, and alkyl Examples include phosphate ester treatment.

  The average primary particle size of the hydrophobized metal oxide powder is preferably 10 nm to 1.0 μm. Here, the average primary particle diameter can be obtained as the number average particle diameter of the primary particle diameter measured by observation with a scanning electron microscope and the particle diameter corresponding to an integrated value of 50% in the particle size distribution measured by the laser diffraction method. Any of these may be in the above range.

  The hydrophobized metal oxide is contained in the oil phase of the water-in-oil emulsified cosmetic in an amount of 1.5% or more based on the total amount of the water-in-oil emulsified cosmetic. The total content of the metal oxide powder subjected to the hydrophobization treatment is preferably 1.5 to 40.0% by mass, more preferably 3.0 to 4% by mass in the total amount of the water-in-oil emulsified cosmetic. It is 30.0 mass%, More preferably, it is 5.0-25.0 mass%. This is because if the content is less than 1.5% by mass, a squeaky feeling is not produced in the feeling of use of the cosmetic, and it is not necessary to suppress the squeaky feeling according to the present invention. In a general cosmetic formulation, when the content of the hydrophobized metal oxide is 1.5% by mass or more, particularly 5.0% by mass or more, a squeaky feeling is produced in the feeling of use. The formulation of water-in-oil emulsified cosmetics is effective. Moreover, when content exceeds 40 mass%, the effect corresponding to the increase in content will not be acquired, and formulation may become difficult.

（ｍ及びｎは、独立して１０〜２４の整数を示す。）
で表される化合物である。
水分散性シリコーンワックスは、上記式（Ｉ）を満足する化合物を１種単独で、又は２種以上を組み合わせて用いることができる。式（Ｉ）で表される水分散性シリコーンワックスは、例えば、ＩＮＣＩ名「ビスＰＥＧ−１８メチルエーテルジメチルシラン」として、東レ・ダウコーニング社から「２５０１ Ｃｏｓｍｅｔｉｃ Ｗａｘ（製）」の商品名で市販されている。この商品は、式（Ｉ）において、ｍ及びｎがそれぞれ平均１８である構造を有する化合物である。 (B) Water-dispersible silicone wax The water-dispersible silicone wax has the following formula (I):

(M and n independently represent an integer of 10 to 24.)
It is a compound represented by these.
As the water-dispersible silicone wax, compounds satisfying the above formula (I) can be used alone or in combination of two or more. The water-dispersible silicone wax represented by the formula (I) is commercially available, for example, under the trade name “2501 Cosmetic Wax (manufactured)” from Toray Dow Corning under the INCI name “bisPEG-18 methyl ether dimethylsilane”. Has been. This product is a compound having a structure in which m and n each have an average of 18 in formula (I).

  The water-dispersible silicone wax of the formula (I) is a polyether-modified silicone wax that is paste-like to solid at room temperature, has high affinity with water, and is excellent in water-dispersibility. So far, the water dispersible silicone wax of formula (I) has been used in cosmetics mainly for the purpose of emollient effect. In contrast, the present inventors have included the water-dispersible silicone wax of the formula (I) in the water phase of a water-in-oil cosmetic, so that the feeling of use of the cosmetic can be improved even if the metal oxide is highly blended. Found for the first time not to fall.

  The water dispersible silicone wax of the formula (I) is present in a dispersed state in the aqueous phase without being dissolved. Unlike conventional silicone oils, the water-dispersible silicone wax of formula (I) can provide a silicone feel without being added to the oil phase, so it is moist and smooth while suppressing oiliness and stickiness. You can get a feel. However, in water-in-oil emulsified cosmetics whose continuous phase is oil, it is difficult to reduce the roughness and spread well with ingredients added to the aqueous phase because the oil content in the oil phase is strongly felt. However, it has been found that by blending the water-dispersible silicone wax of the formula (I) into the aqueous phase, the spread is good and the roughness can be reduced while suppressing oiliness and stickiness. This is because when the water and volatile oil in the water-in-oil emulsified cosmetic are evaporated after the water-in-oil emulsified cosmetic is applied, the water-dispersible silicone wax and the metal oxide of the formula (I) are It is thought that the smoothness peculiar to silicone wax is exhibited without feeling the squeaky feeling of the metal oxide when combined for the first time. By blending such a water-dispersible silicone wax of formula (I) into the aqueous phase, it suppresses the squeaky sensation during use while containing a high amount of metal oxide, and is excellent in extensibility and feel during use. Can be. Furthermore, the emulsification stability of the water-in-oil cosmetic can be improved by blending the water dispersible silicone wax of the formula (I) into the water phase. This is presumably because the water-dispersible silicone wax of the formula (I) dispersed in the water phase has some effect on the interface between the water phase and the oil phase together with the surfactant.

  The content of the water-dispersible silicone wax of the formula (I) is preferably 1.0 to 10.0% by mass, more preferably 2.0 to 8.0% by mass in the total amount of the water-in-oil emulsified cosmetic. %. When the content is less than 1.0% by mass, the effect of improving the extensibility and suppressing the squeaky feeling due to the water-dispersible silicone wax of the formula (I) may not be sufficiently obtained. Moreover, when it mixes exceeding 10.0 mass%, stickiness may be produced at the time of use.

(C) Oil component The oil component is not particularly limited as long as it is usually used in cosmetics. For example, hydrocarbons such as liquid paraffin and squalane; olive oil, jojoba oil, avocado oil, soybean oil, and mead home Natural animal and vegetable fats and oils such as oil and lanolin; fatty acids such as cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, stearyl stearate Esters; triglycerides such as tri (caprylic / caprylic acid) glyceryl, glyceryl tri-2-ethylhexanoate, and polyhydric alcohol fatty acid ester oils; cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol Higher alcohols such as lauric acid, higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and isostearic acid; chain silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane; cyclic silicone oils such as decamethylcyclopentanesiloxane And liquid or solid silicone oil such as trimethylsiloxysilicic acid, silicone gel, and silicone powder. These oil components can be used singly or in combination of two or more.

  The content of the oil component is preferably 5.0 to 90.0% by mass, more preferably 10.0 to 70.0% by mass in the total amount of the water-in-oil emulsified cosmetic.

(D) Water component As a water component, distilled water, purified water, natural water, hot spring water, seawater, etc. can be used. The content of the water component is preferably 0.1 to 70.0% by mass, more preferably 5.0 to 60.0% by mass in the total amount of the water-in-oil emulsified cosmetic.

(E) Emulsifier As long as the effect of this invention is not impaired, what is generally used for cosmetics can be used for an emulsifier. Examples of the emulsifier include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. The emulsifier is preferably a silicone-based surfactant when focusing on the hydrophobic group, and polyether-modified silicone or polyglycerin-modified silicone can be used as the silicone-based surfactant. The content of the emulsifier is preferably 0.1 to 10.0% by mass in the total amount of the water-in-oil emulsified cosmetic.

  Nonionic surfactants include polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil and derivatives thereof; sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan palm oil fatty acid, sorbitan tristearate Sorbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, etc. Polyoxyethylene sorbitan fatty acid ester; polyoxyethylene sorbite monolaurate, polyoxyethylene sorbite tetrastearate Glycerol fatty acid esters such as glyceryl monostearate, glyceryl monostearate, glyceryl monoisostearate; polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monoisostearate, polyoxyethylene glyceryl tristearate, tri Polyoxyethylene glyceryl fatty acid esters such as polyoxyethylene glyceryl isostearate and polyoxyethylene glyceryl trioleate; polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl ethers such as octyldodecyl ether; polyethylene monolaurate Polyglycol fatty acid esters such as polyglycolyl monolaurate, polyglyceryl monolaurate, polyglyceryl monomyristate, polyglyceryl monostearate, polyglyceryl monooleate, polyglyceryl tristearate, polyglyceryl tristearate, etc. Can be mentioned.

  Polyether-modified silicones include PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-10 methyl ether dimethicone, PEG-12 dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl. Examples include dimethicone, PEG / PPG-19 / 19 dimethicone, polysilicone-13, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-10 tris (trimethylsiloxy) silylethyl dimethicone, and the like. Examples of the polyglycerin-modified silicone include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

(F) Other components In addition to the components (A) to (E) described above, the water-in-oil emulsified cosmetics include polyhydric alcohols, moisturizers, sugars, antiseptics, antibacterial agents, metals An ion sequestering agent, a polymer thickener such as a water-soluble polymer, a lower alcohol, a film forming agent, a neutralizing agent, a pH adjusting agent, a powder component, an ultraviolet absorber, and the like can be contained. In addition, other cosmetic ingredients such as vitamins, skin activators, blood circulation promoters, anti-inflammatory agents, whitening agents, and other medicinal ingredients, physiologically active ingredients, fragrances, and pigments can be contained. The content of these components can be appropriately adjusted by those skilled in the art within a range that does not impair the feeling of use and the emulsion stability of the water-in-oil emulsion cosmetic.

  The polyhydric alcohol is not particularly limited, and those generally used as cosmetic compositions can be used. Examples include 1,3-butylene glycol, dipropylene glycol, propylene glycol, glycerin, 1,2-pentanediol, isoprene glycol, polyethylene glycol, methyl glucoside, sorbitol, diglycerin and the like.

  Examples of the humectant include hyaluronic acid, collagen, elastin, sodium lactate, cyclodextrin, pyrrolidone carboxylic acid and salts thereof, natural and synthetic ceramides, and the like.

  Examples of antiseptics and antibacterial agents include benzoic acid, salicylic acid, coalic acid, sorbic acid, p-oxybenzoic acid ester, parachloromethcresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol Etc.

  Examples of the sequestering agent include edetate salts such as disodium ethylenediaminetetraacetate, edetic acid, and sodium edetate.

  Examples of the water-soluble polymer or thickener include gum arabic, gum tragacanth, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, dextrin, pullulan, carboxymethyl starch, collagen, casein, gelatin, methylcellulose, methyl Examples thereof include hydroxypropylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, sodium alginate, carboxymethyldextran sodium, carboxyvinyl polymer, bentonite and the like.

  The lower alcohol is not particularly limited as long as it is usually blended in cosmetics, and examples thereof include ethanol.

  Examples of the film forming agent include polyalkyl acrylate, eicosene vinylpyrrolidone polymer, ester gum and the like. Examples of the neutralizing agent include potassium hydroxide, sodium hydroxide, triethanolamine, sodium carbonate and the like. Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

  Examples of the powder component include talc, mica, kaolin, silica, sericite, zeolite, polyethylene powder, polystyrene powder, cellulose powder, nylon powder, lauroyl lysine, polymethyl methacrylate powder, boron nitride, barium sulfate, hydroxyapatite, Surfactant metal salt powder such as magnesium carbonate, calcium carbonate, magnesium silicate, aluminum silicate, inorganic white pigment, magnesium stearate, zinc stearate, magnesium myristate, titanium oxide coated mica, titanium oxide coated talc, colored titanium oxide Examples thereof include pearl pigments such as coating mica and organic pigments such as red No. 201 and red No. 202, and those obtained by treating these with silicone, a fluorine compound or the like are preferable.

  Examples of the ultraviolet absorber include 2-methoxyhexyl paramethoxycinnamate, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester, benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, and paramethoxy. Cinnamic acid UV absorbers such as 2-ethoxyethyl cinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, isopropyl dimethoxycinnamate and diisopropyl cinnamate ester, hydroxymethoxybenzophenone, Hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, dihydroxymethoxybenzophenone, dihydroxymethoxybenzophenone sodium disulfonate, dihydroxybenzophenone Benzophenone-based ultraviolet absorbers such as tetrahydroxybenzidiphenone, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N-di (2 -Hydroxypropyl) amino] ethyl benzoate, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid ester UV absorbers such as hexyl benzoate, ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, Salicylic acid UV absorbers such as p-tert-butylphenyl salicylate and homomenthyl salicylate, 2,4,6-trianilino-p- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-to Triazine UV absorbers such as azine, 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone, octocrylene, menthyl anthranilate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, dimethoxybenzylidene dioxo Imidazolidinepropionate 2-ethylhexyl, 2-phenylbenzimidazole-5-sulfonic acid, 2-cyano-3,3-diphenyl acrylate and the like can be used.

The medicinal ingredient, for example, coenzyme Q10, vitamin A oil, vitamin A such as retinol, vitamin B ₂ such as riboflavin, B ₆ such as pyridoxine hydrochloride, L- ascorbic acid, L- ascorbic acid magnesium phosphate Vitamin C such as L-ascorbic acid monopalmitate, L-ascorbic acid dipalmitate, L-ascorbic acid-2-glucoside, pantothenic acids such as calcium pantothenate, vitamin D ₂ , cholecalciferol, etc. Vitamin Ds: Vitamins such as vitamin E such as α-tocopherol, tocopherol acetate, and DL-α-tocopherol nicotinate. Whitening agents such as arbutin, ellagic acid, tranexamic acid, placenta extract, glutathione, and cypress extract, skin activators such as royal jelly, linden extract, capsaicin, gingeron, cantalis tincture, ictamol, caffeine, tannic acid, γ-oryzanol And the like, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, anti-inflammatory agents such as azulene and allitein, and amino acids such as arginine, serine, leucine and tryptophan. In addition, horse chestnut seed extract, chamomile flower extract, Sakuhakhi extract, button extract, parsley extract, beech extract, wine yeast extract, grapefruit extract, honeysuckle extract, rice extract, grape extract, hop extract, rice bran extract, loquat extract, agaric extract, yokuinin extract , Assembly extract, merirot extract, birch extract, licorice extract, peony extract, bonito extract, loofah extract, red pepper extract, lemon extract, gentian extract, perilla extract, aloe extract, rosemary extract, sage extract, cinnamon extract, thyme extract, Tea extract, seaweed extract, cucumber extract, clove extract, carrot extract, horse chestnut extract, hamamelis extract, mulberry extract, ougon extract Hypericum extract, hawthorn extract, Centella asiatica extract, kudzu root nodule extract, artichoke leaf extract, rose fruit extract, may be mentioned various extracts such as Edelweiss extract. The fragrance | flavor and pigment | dye can use what is normally used for cosmetics.

  Below, the manufacturing method of the water-in-oil type emulsified cosmetics which concern on this invention is demonstrated. The method for producing a water-in-oil emulsified cosmetic according to the present invention comprises an oil phase in which a metal oxide powder subjected to a hydrophobic treatment is dispersed, and a water-dispersible silicone wax represented by the formula (I). A step of emulsifying the aqueous phase.

  The oil phase can be prepared by uniformly mixing and dispersing the hydrophobized metal oxide powder in the oil component. In the oil phase, before dispersing the hydrophobized metal oxide powder, if necessary, a film forming agent, a lipophilic UV absorber, a lipophilic medicinal component, a hydrophobized powder component, etc. Other lipophilic components may be optionally mixed. If necessary, the other component powder may be dispersed in the oil component together with the hydrophobized metal oxide powder. The aqueous phase can be prepared by dispersing the water-dispersible silicone wax represented by the formula (I) in the water component by a known method. In the aqueous phase, polyhydric alcohol, humectant, saccharide, preservative, antibacterial agent, sequestering agent, polymer thickener, lower alcohol, neutralizer, powder component, UV absorber, if necessary In addition, other hydrophilic components such as an ultraviolet blocking agent and a hydrophilic medicinal component may be optionally contained. The emulsification of the oil phase and the aqueous phase can be performed by a known method. The temperature during emulsification of the oil phase and the aqueous phase is preferably 20.0 to 90.0 ° C. The content of each component is such that the final concentration in the water-in-oil emulsified cosmetic is within the preferred range described above.

  The preferred use of the water-in-oil emulsified cosmetic according to the present invention is a cosmetic applied to the skin. For example, skin care cosmetics such as milky lotion, cream, cosmetic liquid, sunscreen, lip balm, foundation, cosmetics. Makeup cosmetics such as foundation, cheek red, eye shadow, lipstick.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, the water-in-oil type emulsion cosmetics which concern on this invention are not limited by these Examples.

[Examples 1-5, Comparative Examples 1-5: Sunscreen Cream]
Sunscreen creams (water-in-oil emulsified cosmetics) having the compositions shown in Table 1 were prepared by the following method.
The components (1) to (13) were stirred at a room temperature with a disper (3000 rpm, 10 minutes) and mixed uniformly to obtain an oil phase. Next, after the components (14) to (19) were dissolved by heating (70 ° C.), the aqueous phase prepared by cooling to room temperature was slowly added to the oil phase with stirring. Next, the mixture was emulsified and mixed by high-speed stirring (7000 rpm, 5 minutes) using a homomixer, deaerated, and then filled into a container to obtain a sunscreen cream that is a water-in-oil emulsified cosmetic.

  The sunscreen creams of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated by the following methods for feeling of use (no squeaky feeling, familiarity to skin, non-stickiness) and emulsification stability. did.

[Usage feeling]
To 10 female subjects (30 to 50 years old), cosmetics were applied to the forearms, and the feeling of use at that time was sensory evaluated. Three items (no squeaky feeling, familiarity with skin, non-stickiness) were evaluated according to the following criteria from the results of the questionnaire.
(Evaluation criteria)
A: All 10 responded that they were good.
○: Among 10 people, 7 to 9 people answered good.
(Triangle | delta): 3-6 persons answered that it was favorable among 10 persons.
X: Less than 2 out of 10 responded good.

[Emulsification stability]
An 80 ml glass bottle of sunscreen cream was filled with 50 g at room temperature, and the state after one week at 50 ° C. was observed with the naked eye, and the emulsion stability was evaluated based on the following evaluation criteria.
(Evaluation criteria)
(Double-circle): Separation is not seen.
○: Water droplets are slightly seen on the surface of the sunscreen cream.
Δ: Water droplets are clearly seen on the surface of the sunscreen cream.
X: Clearly separated into two layers.

From the results of Table 1, Examples 1 to 5 were superior to Comparative Examples 1 to 3 in all of the feelings of use such as no squeaky feeling, skin familiarity, and no stickiness. Moreover, all of the sunscreen creams of Examples 1 to 5 had high emulsion stability. In particular, the sunscreen cream of Example 5 had excellent usability and emulsification stability even though it contained 40% by mass of the hydrophobized fine particle zinc oxide. Moreover, although the sunscreen cream of Examples 2-4 did not change the viscosity of the cream itself compared with Example 1, separation was not observed at all and the emulsion stability was improved. From this, it is considered that the interface is strengthened by bisPEG-18 methyl ether dimethylsilane, which is a water-dispersible silicone of formula (I).
On the other hand, Comparative Examples 1 to 3 that do not use bisPEG-18 methyl ether dimethylsilane, which is a water-dispersible silicone of formula (I), have all of squeaky feeling, skin familiarity, and non-stickiness. There wasn't. In Comparative Examples 1 to 3, the emulsion stability was low, and it was observed that oil floating occurred on the liquid surface. In Comparative Example 4, the squeaky feeling was suppressed and a high emulsification stability effect was obtained, but stickiness was generated. In Comparative Example 5 containing a metal oxide that was not hydrophobized, a squeakish sensation occurred and the emulsion stability was poor.

[Example 6: Sunscreen emulsion]
A sunscreen emulsion having the composition shown below was prepared by the following method.
(Composition) (mass%)
(1) Decamethylcyclopentasiloxane 25.0
(2) Dimethicone 7.0
(3) Diphenylsiloxyphenyl trimethicone 3.0
(4) PEG-9 polydimethylsiloxyethyl dimethicone 3.0
(5) Sorbitan sesquiisostearate 1.0
(6) Trimethylsiloxysilicic acid 3.0
(7) Cross-linked methylpolysiloxane (* 6) 2.0
(8) Olive oil 0.3
(9) Polymethyl methacrylate 5.0
(10) Ultraviolet absorber composite fine particle titanium oxide (* 8) 15.0
(11) Purified water Residue (12) BisPEG-18 methyl ether dimethylsilane (* 7) 2.0
(13) DPG 3.0
(14) Glycerin 1.0
(15) Sodium chloride 1.0
(16) Methylparaben 0.3
(17) Rosemary extract 0.1
* 8: HXMT-10EXA (t-butylmethoxydibenzoylmethane, aluminum hydroxide, isostearic acid treatment, titanium oxide with an average particle size of 10 nm, manufactured by Teika)
(Manufacturing method)
Components (1) to (10) are uniformly mixed to form an oil phase, and then components (11) to (17) are uniformly dissolved at 70 ° C., and then an aqueous phase cooled to room temperature is added to the oil phase. The mixture was then emulsified and mixed, and filled in a container to obtain a sunscreen emulsion that was a water-in-oil emulsified cosmetic.
(Evaluation)
When the obtained sunscreen emulsion was evaluated in the same manner as in Examples 1 to 5, it was excellent in all usability and stability (evaluation: A).

[Example 7: Makeup base]
A makeup base having the following composition was prepared by the following method.
(Composition) (mass%)
(1) Decamethylcyclopentasiloxane 25.0
(2) Neopentyl glycol diethylhexanoate 6.0
(3) Diphenylsiloxyphenyl trimethicone 2.0
(4) PEG-9 polydimethylsiloxyethyl dimethicone 3.0
(5) Polyglyceryl-3 polydimethylsiloxyethyl dimethicone (* 9) 1.5
(6) Isostearic acid 1.0
(7) Cross-linked methylpolysiloxane (* 6) 3.0
(8) Olive oil 1.0
(9) Coenzyme Q10 0.3
(10) Fine particle titanium oxide (* 1) 3.0
(11) Fine zinc oxide (* 2) 10.0
(12) Silicone-treated yellow iron oxide 0.5
(13) Silicone-treated Bengala 0.2
(14) (Vinyl Dimethicone / Methicon Silsesquioxane) Cross Polymer 2.0
(15) Purified water Residual (16) BisPEG-18 methyl ether dimethylsilane (* 7) 3.0
(17) Glycerin 5.0
(18) 1,3-butylene glycol 3.0
(19) Magnesium sulfate 1.0
(20) Phenoxyethanol 0.3
* 9: KF-6104 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Manufacturing method)
Components (1) to (9) are uniformly mixed at 75 ° C. to obtain an oil phase, then components (10) to (14) are separately mixed with a Henschel mixer, added to the oil phase, and uniformly mixed at 75 ° C. Next, the components (15) to (20) are heated and dissolved at 75 ° C. to obtain an aqueous phase, which is slowly added to the oil phase and emulsified and mixed. A makeup base that is an emulsified cosmetic was obtained.
(Evaluation)
When the same evaluation as Example 1-5 was performed about the obtained makeup | decoration base | substrate, it was what was excellent in all the usability and stability (evaluation: (double-circle)).

[Example 8: Liquid foundation]
A liquid foundation having the following composition was prepared by the following method.
(Composition) (mass%)
(1) Silicone-treated titanium oxide (* 10) 7.5
(2) Silicone-treated Bengala 1.5
(3) Silicone-treated yellow iron oxide 2.5
(4) Silicone-treated black iron oxide 0.3
(5) Silicone-treated talc 1.2
(6) Polymethyl methacrylate 3.0
(7) Decamethylcyclopentasiloxane 15.0
(8) Isododecane 10.0
(9) Squalane 5.0
(10) Polyhydroxystearic acid 1.0
(11) Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 3.0
(12) Sorbitan isostearate 2.0
(13) Dimethyl distearyl ammonium hectorite 1.0
(14) Purified water residue (15) BisPEG-18 methyl ether dimethylsilane (* 7) 5.0
(16) Glycerin 5.0
(17) 1,3-butylene glycol 3.0
(18) Magnesium sulfate 0.7
(19) Methylparaben 0.3
* 10: SA-titanium CR-50 (100%) (Miyoshi Kasei Co., Ltd. aluminum hydroxide treated with dimethicone, average particle size 250 nm titanium oxide)
(Manufacturing method)
Components (7) to (13) are uniformly mixed at 75 ° C. to obtain an oil phase, then components (1) to (6) are separately mixed with a Henschel mixer, added to the oil phase, and uniformly mixed at 75 ° C. Next, the components (14) to (19) are heated and dissolved at 75 ° C. to obtain an aqueous phase, which is slowly added to the oil phase and emulsified and mixed. A liquid foundation, an emulsified cosmetic, was obtained.

(Evaluation)
When the obtained liquid foundation was evaluated in the same manner as in Examples 1 to 5, it was excellent in all usability and stability (evaluation: A).

（ｍ及びｎは、独立して１０〜２４の整数である。）
で表される水分散性シリコーンワックスを含有する油中水型乳化化粧料。
請求項２：
前記疎水化処理された金属酸化物粉体が、酸化チタン、酸化鉄、酸化亜鉛、酸化セリウム、酸化ジルコニウム、酸化クロム、及び酸化アルミニウムからなる群から選択される少なくとも１種である請求項１に記載の油中水型乳化化粧料。
請求項３：
前記疎水化処理された金属酸化物粉体の含有量が、油中水型化粧料の総量中に１．５〜４０．０質量％である請求項１又は２に記載の油中水型乳化化粧料。
請求項４：
前記水分散性シリコーンワックスの含有量が、油中水型化粧料の総量中に１．０〜１０．０質量％である請求項１〜３のいずれかに記載の油中水型乳化化粧料。
請求項５：
疎水化処理された金属酸化物粉体を分散させた油相と、下記式（Ｉ）：

（ｍ及びｎは、独立して１０〜２４の整数である。）
で表される水分散性シリコーンワックスを含有する水相とを乳化する工程を含む、疎水化された金属酸化物粉体を１．５質量％以上含有する油中水型乳化化粧料の製造方法。
請求項６：
請求項５に記載の製造方法によって製造された油中水型乳化化粧料。 ADVANTAGE OF THE INVENTION According to this invention, the water-in-oil type emulsified cosmetics which are excellent in the touch at the time of use, mix | blending a metal oxide, have neither a squeaky feeling nor stickiness, and have high emulsification stability can be provided.
Each claim described in the scope of claims at the time of filing was as follows.
Claim 1:
A water-in-oil emulsified cosmetic containing 1.5% by mass or more of a hydrophobized metal oxide powder,
The oil phase contains the metal oxide powder that has been hydrophobized,
In the aqueous phase, the following formula (I):

(M and n are each independently an integer of 10 to 24.)
A water-in-oil emulsified cosmetic containing a water-dispersible silicone wax represented by the formula:
Claim 2:
The hydrophobized metal oxide powder is at least one selected from the group consisting of titanium oxide, iron oxide, zinc oxide, cerium oxide, zirconium oxide, chromium oxide, and aluminum oxide. The water-in-oil emulsified cosmetic described .
Claim 3:
The water-in-oil emulsification according to claim 1 or 2, wherein the content of the hydrophobized metal oxide powder is 1.5 to 40.0 mass% in the total amount of the water-in-oil cosmetic. Cosmetics.
Claim 4:
The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the content of the water-dispersible silicone wax is 1.0 to 10.0% by mass in the total amount of the water-in-oil cosmetic. .
Claim 5:
An oil phase in which the metal oxide powder subjected to the hydrophobization treatment is dispersed, and the following formula (I):

(M and n are each independently an integer of 10 to 24.)
A method for producing a water-in-oil emulsified cosmetic containing 1.5% by mass or more of a hydrophobized metal oxide powder, comprising emulsifying a water phase containing a water-dispersible silicone wax represented by .
Claim 6:
A water-in-oil emulsified cosmetic produced by the production method according to claim 5.

Claims (2)

A water-in-oil emulsified cosmetic containing a hydrophobized metal oxide powder,
The oil phase contains the metal oxide powder that has been hydrophobized,
In the aqueous phase, the following formula (I):

(M and n are each independently an integer of 10 to 24.)
Containing 1.0 to 10.0% by mass of a water-dispersible silicone wax represented by
As the hydrophobized metal oxide powder, zinc oxide or zinc oxide and titanium oxide are contained in a total amount of water-in-oil cosmetic of 1.5 to 40.0% by mass in water-in-oil emulsion makeup. Fee. An oil phase in which the metal oxide powder subjected to the hydrophobization treatment is dispersed, and the following formula (I):

(M and n are each independently an integer of 10 to 24.)
In viewing including the step of emulsifying the aqueous phase containing the water-dispersible silicone wax represented, the water dispersible silicone wax containing 1.0 to 10.0 wt% in total, are treated the hydrophobic A method for producing a water-in-oil emulsified cosmetic containing zinc oxide or zinc oxide and titanium oxide in a total amount of 1.5 to 40.0% by mass as the metal oxide powder .