JP6130094B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic in which a particulate metal oxide surface-treated with a trialkoxyalkylsilane is dispersed in an oil layer with polyhydroxystearic acid. More specifically, the present invention is excellent in stability over time and without stickiness. The present invention relates to an oil-in-water emulsified cosmetic material that spreads well.

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

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

A number of techniques for dispersing these metal oxides in aqueous systems have been studied. For example, metal oxides using organosilicon resins and hydrophilic nonionic surfactants, lipophilic nonionic silicone surfactants. Metal oxide powder and base coated with a polymer (see Patent Document 11) having improved dispersibility and stability over time, and a polymer containing a monomer obtained by adding a fatty acid to acrylic acid or acrylamide as a structural monomer Studies have been made on oil-in-water cosmetics (see Patent Document 12) that are stable and excellent in usability by using an active compound.
Furthermore, as a study using an emulsifier for stably dispersing a metal oxide in an oil-in-water cosmetic, a study using a cationic surfactant (see Patent Document 13) has been made.

JP-A-9-175721 JP 2003-226615 A JP 2003-335649 A JP-A-9-208438 JP 2006-131547 A JP 2007-161648 A JP-A-11-263708 JP 2004-169015 A JP-A-6-39272 Special table 2009-508920 JP 2003-171230 A JP 2008-150299 A JP 2007-176867 A

  However, as disclosed in Patent Document 1, if the metal oxide is made into fine particles in order to improve the transparency, the surface area of the powder increases, the cohesive force becomes strong, and it becomes difficult to disperse. The dispersants used in Patent Documents 2 and 3 are semi-solid and sticky, and when used in cosmetics, there are problems in usability such as stickiness and poor spread. The silicone-based dispersant used in Patent Documents 4 to 8 is a low HLB surfactant in which a hydrophilic portion is introduced into a silicone chain, and is an oil-in-water emulsified cosmetic or water-in-oil emulsified blended with water. In cosmetics, the silicone dispersant may be oriented at the interface between oil and water, and the dispersibility of the particulate metal oxide may be reduced. Further, the silicone-based dispersants used in Patent Documents 4 to 8 are designed to have a large molecular weight for stabilizing the dispersion, and have problems in usability such as stickiness and poor spread. In particular, trimethylsiloxysilicic acid disclosed in Patent Document 4 is an adhesive resin and has a significant stickiness and a problem in usability. Furthermore, when a non-silicone oil is used as a dispersion medium, Patent Document 9 using non-silicone-based ricinoleic acid or hydroxystearic acid as a dispersant, and Patent Document 10 using polyhydroxystearic acid as a dispersant are: It was necessary to add a large amount of a dispersant, resulting in sticky usability, poor spread and poor temporal stability.

  In addition, as in Patent Document 11, a silicone-treated powder is excellent in dispersibility if it is a silicone-based oil, but is poorly dispersed if a non-silicone-based solvent is used. As in Patent Document 12, a treated powder in which it is essential to use a basic compound in the aqueous phase is easily affected by pH, temperature change, electrolyte, and the like, and there is a concern about stability. When a cationic surfactant is blended as in Patent Document 13, skin irritation is a concern.

  As described above, an oil-in-water emulsified cosmetic having excellent dispersibility and stability over time, having no stickiness and good spreadability has not been sufficiently examined.

  Under such circumstances, the present inventor has conducted extensive research to solve the above problems, and as a result, when the fine metal oxide is dispersed in the oil layer containing the non-silicone oil agent, the surface treatment is performed with trialkoxyalkylsilane. In addition, the use of polyhydroxy stearic acid as a dispersant improves the dispersibility of the fine metal oxide in the oil layer, and in addition, it is selected from alkyl methyl taurine salts and / or phospholipids. The oil-in-water emulsified cosmetic with excellent dispersibility and temporal stability of the fine particle metal oxide, good stickiness, and good spread can be obtained by emulsifying with a surfactant, and the present invention is completed. It came to.

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

That is, the present invention
[1] The following components (A) to (D);
(A) Fine particle metal oxide surface-treated with trialkoxyalkylsilane (B) Polyhydroxystearic acid (C) Non-silicone oil agent (D) Surfactant selected from alkylmethyl taurate and / or phospholipid The present invention provides an oil-in-water emulsified cosmetic.

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

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

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

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

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

  [7] The oil-in-water emulsified cosmetic according to any one of [1] to [6], wherein the amount of component (D) is 0.1 to 5% by mass.

  [8] A fine particle metal oxide dispersion composition in which the component (A) is previously dispersed in the component (B) and the component (C) is prepared, and then the fine particle metal oxide dispersion composition and the component (D) are blended. The oil-in-water emulsified cosmetic according to any one of [1] to [7] is provided.

  [9] The oil-in-water emulsified cosmetic according to [8], wherein the compounding amount of the component (A) in the fine particle metal oxide dispersion composition is 30 to 70% by mass. is there.

  [10] The above-mentioned [8], wherein the blending mass ratio (B) / (A) of the component (A) and the component (B) in the fine particle metal oxide dispersion composition is 0.01 to 0.5. Or an oil-in-water emulsified cosmetic according to [9].

  [11] The oil-in-water emulsified cosmetic according to any one of the above [1] to [10], wherein the blending amount of the silicone oil in all the oils is 20% by mass or less. is there.

  The oil-in-water emulsified cosmetic of the present invention is excellent in stability over time, has no stickiness, and has good usability of spreading.

  Hereinafter, the present invention will be described in detail.

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

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

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

  Among these trialkoxyalkylsilanes, it is preferable that the alkyl group has 8 or more carbon atoms because the dispersion stability of the component (A) in the oil layer becomes good. In the general formula (1), m = 7, n It is preferable to use triethoxyoctylsilane in which = 2 because the dispersion stability of the component (A) in the oil layer is very excellent.

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

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

  When the component (A) used in the present invention is further surface-treated with a (dimethicone / methicone) copolymer, the oil absorption of the component (A) decreases, and more of the component (A) is blended in the water-in-oil emulsified cosmetic. Can be preferable. The (dimethicone / methicone) copolymer is a compound listed as DIMETHICONE / METHICONE COPOLYMER in INTERNATIONAL NOMENCLATURE of COSMETIC INGREDIENTS, and is a copolymer composed of dimethylsiloxane and methylhydrogensiloxane. Usually, it is used as a surface treatment agent for powders, and is widely used as a surface treatment agent that imparts water repellency to powders and hardly generates hydrogen over time. Specifically, the compound shown by following General formula (2) can be illustrated as a preferable compound.

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

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

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

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

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

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

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

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

  The blending amount of the component (A) in the components (A) to (C) (hereinafter sometimes referred to as fine particle metal oxide dispersion composition) mixed and dispersed in advance is preferably 30 to 70%, more preferably. Is 40-60%. If it is this range, it will become an oil-in-water-type emulsified cosmetic which is further excellent in stability over time.

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

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

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

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

  The alkylmethyl taurine salt and / or phospholipid of component (D) used in the present invention is a surfactant for oil-in-water cosmetics, contributes to improving the dispersion stability of fine metal oxides, and is an oil-in-water cosmetic. Significantly improve the stability of the material over time. Furthermore, it contributes to improvement in usability such as no stickiness during use. The alkylmethyl taurine salt (D) used in the present invention is not particularly limited as long as it is usually used in cosmetics. Among them, N-acylmethyl is preferred from the viewpoint of the temporal stability and the effect of improving the feeling of use. Taurine salts are preferred, and examples include coconut oil fatty acid methyl taurine sodium, lauroyl methyl taurine sodium, myristoyl methyl taurine sodium, palmitoyl methyl taurine sodium, stearoyl methyl taurine sodium and the like. In addition, the phospholipid of component (D) is not particularly limited as long as it is usually used in cosmetics, but if specifically exemplified, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidyl Examples thereof include phospholipids such as inositol, sphingophospholipid, soybean lecithin, egg yolk lecithin, and hydrogenated products thereof, and phospholipid complexes such as phospholipid / cholesterol complex and phospholipid / phytosterol complex. These alkylmethyl taurine salts and / or phospholipids of component (D) can be used by appropriately selecting one or two or more as necessary.

  The compounding amount of component (D) is preferably 0.01 to 10%, more preferably 0.1 to 5%. If it is in this range, the emulsified state is good, the usability is good, and a product having sufficient aging stability is obtained.

  In the oil-in-water emulsified cosmetic of the present invention, water is used as a dispersion medium for the purpose of obtaining freshness, an oily component, and a fine particle metal oxide, but it is not particularly limited as long as it is used in cosmetics. Examples include purified water, hot spring water, deep water, or steam distilled water such as plants. Purified water such as ion-exchanged water or distilled water is particularly preferable because there are few impurities such as metal ions.

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

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

  In the oil-in-water type emulsified cosmetic of the present invention, in addition to the components (A) to (D), components other than the components (A) to (D) are added as necessary, as long as the effects of the present invention are not impaired. Surfactants other than (A) to (D), silicone oils, polyhydric alcohols, lower alcohols, water-soluble polymers, aqueous components such as humectants, saccharides, ultraviolet absorbers, antioxidants, anti-fading agents, Preservatives, medicinal ingredients, stabilizers, pigments, fragrances and the like can be appropriately blended for imparting various effects.

  Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the component (D). For example, as the nonionic surfactant, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, hydrogenated castor oil, polyoxyethylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester , Polyglycerin fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside, N-alkyldimethylamine oxide polyoxyethylene glyceryl fatty acid ester, polyoxyethylene cholesteryl ether, polyoxyethylene phytosteryl ether, polyoxyethylene alkyl ether, polyoxyethylene Examples include polyoxypropylene alkyl ether and polyoxyethylene alkylphenyl ether. For example, anionic surfactants include sodium salts or triethanolamine salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate And polyoxyethylene alkyl ether phosphates such as polyoxyethylene oleyl ether phosphate and polyoxyethylene nonylphenyl ether phosphate. Examples of cationic surfactants include stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, odor Distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, dibehenyldimethylammonium bromide, dicetyldimethylammonium chloride, dicetyldimethylammonium bromide, stearyldimethylbenzylammonium chloride, dilauryldimethylammonium chloride, dipolyoxyethylene chloride ( 15 mol) Palm oil alkylmethylammonium chloride dipolyoxyethylene (4 mol) lauryl A Le dimethyl ammonium, stearic acid amide propyl trimethyl ammonium chloride, go up self coil ethyl hydroxyethyl methyl ammonium methylsulfate and the like. For example, as the amphoteric surfactant, N, N-dimethyl-N-alkyl-N-carboxylmethyl ammonium betaine, N, N-dialkylaminoalkylene carboxylic acid, N, N, N-trialkyl-N-sulfoalkylene ammonium Examples include betaine, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine. Among these, it is preferable that polyoxyethylene hydrogenated castor oil is used in combination with components (A) to (D) from the viewpoint of the temporal stability and the usability improvement effect.

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

  The aqueous component may be any component that is soluble in water, for example, alcohols such as ethyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol, glycerin, Examples thereof include glycerols such as diglycerol and polyglycerol.

  Although the manufacturing method of the oil-in-water type emulsion cosmetics of this invention is not specifically limited, what mixed component (A)-(C) and other additives etc. as needed was used for component (D ), An optional aqueous component, and a surfactant are mixed and dispersed, and then water is added and emulsified, and this is filled into a container or mold. Moreover, it is preferable to mix | blend, after mixing and dispersing component (A)-(C) previously as mentioned above.

  The oil-in-water emulsified cosmetic of the present invention is not particularly limited, but examples of the shape include liquid, semi-solid, and solid. The product forms include facial cleansing foams, creams, cleansings, massage creams, packs, skin lotions, milky lotions, creams, serums, makeup bases, sunscreens and other skin cosmetics, foundations, white powder, eye shadows, eyeliners. , Mascara, eyebrow, concealer, lipstick, lip balm and other cosmetics for finish, hair mist, shampoo, rinse, treatment, hair tonic, hair cream, pomade, tic, liquid hair conditioner, set lotion, hair spray, etc. Cosmetics etc. can be illustrated. Among these, sunscreens, foundations, makeup bases and the like are oil-in-water emulsified cosmetics in which the effects of the present invention are easily exhibited.

  Hereinafter, the present invention will be described in detail with reference to production examples and examples. Note that these do not limit the present invention.

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

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

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

Production Examples 8 to 16: Fine-particle metal oxide dispersion composition Fine-particle metal oxide dispersion compositions having the compositions shown in Table 2 were prepared by the following production method.

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

(Production method)
Ingredients (1) to (10) were mixed uniformly, and a bead mill (LMZ-0.6) manufactured by Ashizawa Co., Ltd. was used with 3 mm of zirconia beads, a bead filling rate of 60%, and an agitator rotation speed of 2000 rpm for 5 hours. Dispersion was performed to obtain a fine particle metal oxide dispersion composition.

Examples 1 to 8 and Comparative Examples 1 to 8: Oil-in-water emulsified cosmetics Oil-in-water emulsified cosmetics having the compositions shown in Tables 3 and 4 were prepared by the following production method. ”,“ No stickiness ”, and“ goodness of spread ”were evaluated, and the results are also shown in Tables 3 and 4.

(Note 8) Lecithin CLO (manufactured by J-Oil Mills)
(Note 9) KP-540 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Manufacturing method>
A. Components (1) to (8) are uniformly mixed and dispersed at 70 ° C.
B. Ingredients (9) to (20) are uniformly mixed and dissolved at 70 ° C.
C. Ingredients (21) and (22) are uniformly mixed and dissolved at 70 ° C.
D. B is uniformly mixed with A and gelled at 70 ° C.
E. C is uniformly mixed and dispersed in D and emulsified at 70 ° C.
F. Cool E.
G. Components (23) to (26) were added to F and mixed and dispersed uniformly to obtain an oil-in-water emulsion cosmetic.

(Evaluation method) Stability over time The stability over time was evaluated by the following accelerated test. The accelerated test here is to store in a constant temperature bath at 50 ° C. for 4 weeks. If the oil-in-water emulsified cosmetic has good stability over time, the aggregation of the particulate metal oxide can be suppressed, and the viscosity change of the cosmetic before and after the acceleration test is small. On the other hand, when the stability over time is poor, the fine particle metal oxide aggregates, thereby generating a volume effect and causing the fine particle metal oxide to settle, resulting in a large change in viscosity before and after the acceleration test. As a specific method of the evaluation by the acceleration test, after manufacturing the oil-in-water type emulsified cosmetic, the viscosity value measured with a B-type viscometer after being stored in a 30 ° C. constant temperature bath for 1 day, and in a 50 ° C. constant temperature bath for 4 weeks After storage, the viscosity values measured after storage in a thermostatic bath at 30 degrees for one day were compared and judged according to the following criteria.
(Evaluation): (Judgment)
Viscosity change is 0 mPa · s or more and less than ± 10000 mPa · s;
Viscosity change is ± 10000 mPa · s or more and less than ± 20000 mPa · s;
Viscosity change is ± 20000 mPa · s or more and less than ± 40000 mPa · s;
Viscosity change is ± 40000 mPa · s or more; ×

(Evaluation method) No stickiness and good spread The oil-in-water emulsified cosmetic was tested by 20 panelists specializing in cosmetic evaluation. Ask each panel to use each sample, evaluate it in 6 grades according to the following absolute evaluation criteria, give a score, calculate the average value from the total scores of all the panel members of each sample, and according to the following 4 criteria Judged.

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

  As shown in Tables 3 and 4, Examples 1 to 8 were excellent in all items of “time stability”, “no stickiness”, and “goodness of spread”. On the other hand, the comparative example 1 which mix | blended the surface treatment fine particle metal oxide of the manufacture example 7 surface-treated with the dimethylposilyloxane instead of the component (A) is a nonuniform emulsification state, and is inferior in all the items. It was. The comparative example 2 which did not mix | blend the polyhydroxystearic acid of a component (B) was also a nonuniform emulsification state, and was inferior in all the items. Moreover, comparative example 3 which mix | blended (acrylates / dimethicone) copolymer instead of polyhydroxystearic acid was especially bad with time stability, and was inferior in all the items. Moreover, the comparative example 4 which mix | blended dimethylposilyloxane instead of the non-silicone type | system | group oil agent of the component (C) also became a nonuniform emulsification state, and was inferior in all the items. Moreover, it replaced with the myristoyl methyl taurine sodium of a component (D), the comparative example 5 which mix | blended distearyl dimethyl ammonium chloride which is a cationic surfactant, 2-alkyl-N-carboxymethyl-N which is an amphoteric surfactant. Comparative Example 6 containing hydroxyethyl imidazolinium betaine, Comparative Example 7 containing stearic acid as an anionic surfactant, and Comparative Example 8 containing an increased amount of polyoxyethylene (60) hydrogenated castor oil Was not uniformly dispersed, the stability over time was particularly bad, and other items were also inferior.

Examples 9 to 11 and Comparative Example 9: Oil-in-water emulsified cosmetics Next, oil-in-water emulsified cosmetics containing the fine particle metal oxide dispersion composition having the composition shown in Table 5 were prepared by the following production method. For each sample, “stability with time”, “no stickiness”, and “goodness of spread” were evaluated in the same manner as described above, and the results are also shown in Table 5.

<Manufacturing method>
A. Components (1) to (4) are uniformly mixed and dispersed at 70 ° C.
B. Components (5) to (12) are uniformly mixed and dissolved at 70 ° C.
C. Ingredients (13) and (14) are uniformly mixed and dissolved at 70 ° C.
D. B is uniformly mixed with A and gelled at 70 ° C.
E. C is uniformly mixed and dispersed in D and emulsified at 70 ° C.
F. Cool E.
G. Components (15) to (17) were added to F and mixed and dispersed uniformly to obtain an oil-in-water emulsion cosmetic.

  As shown in Table 5, Examples 9 to 11 in which a fine particle metal oxide dispersion composition was prepared in advance and the fine particle metal oxide dispersion composition was blended were “stable with time” and “no stickiness”. It was excellent in all items of “goodness of spread”. Among them, Examples 9 and 10 in which the component (A) was dispersed and blended in advance only in the non-silicone based oil were further excellent in stability over time. On the other hand, in Comparative Example 9 in which a fine particle metal oxide dispersion composition using a fine particle metal oxide surface-treated with dimethylposilyloxane instead of the component (A) was blended, the fine particle metal oxide was previously dispersed. Despite this, the dispersion of the fine metal oxide was poor and inferior in all items.

Example 12: Oil-in-water sunscreen
(Ingredient) (%)
1. Stearoyl methyl taurine sodium 2
2. Glycerin 20
3. 1,3-butylene glycol 5
4). Sorbitan sesquioleate 0.1
5. Fine particle metal oxide dispersion composition of Production Example 8 10
6). Glyceryl stearate 0.5
7). Cetostearyl alcohol 1
8). Ethyl hexyl methoxycinnamate 3
9. Glyceryl triethylhexanoate 2
10. Xanthan gum 0.2
11. Purified water 19.8
12 Ethanol 2
13. Methylparaben 0.2
14 Purified water balance (production method)
A. Components (1) to (4) are uniformly mixed and dispersed at 70 ° C.
B. Ingredients (5) to (9) are uniformly mixed and dissolved at 70 ° C.
C. Components (10) to (11) are dissolved at 70 ° C.
D. B is uniformly mixed with A and gelled at 70 ° C.
E. C is uniformly mixed and dispersed in D and emulsified at 70 ° C.
F. Cool E.
G. Components (12) to (14) were added to F and mixed and dispersed uniformly to obtain an oil-in-water sunscreen.

  The oil-in-water sunscreen of Example 12 was an oil-in-water sunscreen with excellent stability over time, no stickiness, and good spread.

Example 13: Oil-in-water sunscreen
(Ingredient) (%)
1. Hydroxypropyl starch phosphate (Note 10) 2
2. Purified water balance 3.1,3-butylene glycol 5
4). Polyoxyethylene (4 mol) lauryl ether phosphoric acid (Note 11) 0.1
5. Triethanolamine 0.1
6). Stearoyl methyl taurine sodium 2
7). Fine particle metal oxide dispersion composition of Production Example 8 10
8). Glyceryl stearate 0.5
9. Cetostearyl alcohol 1
10. Ethyl hexyl methoxycinnamate 3
11. Glyceryl triethylhexanoate 2
12 Ethanol 2
13. Methylparaben 0.2
Note 10 STRUCTURE XL (manufactured by Akzo Nobel)
Note 11 HOSTAPHAT KL340D (manufactured by Clariant Japan)
(Production method)
A. Components (1) to (6) are uniformly mixed and dispersed at 70 ° C.
B. Ingredients (7) to (11) are uniformly mixed and dissolved at 70 ° C.
C. B is uniformly mixed and dispersed in A and emulsified at 70 ° C.
D. C is cooled.
E. Components (12) and (13) were added to D and mixed and dispersed uniformly to obtain an oil-in-water sunscreen.

  The oil-in-water sunscreen of Example 13 was an oil-in-water sunscreen with excellent stability over time, no stickiness, and good spread.

Example 14: Oil-in-water cosmetic base material
(Ingredient) (%)
1. Hydrogenated phospholipid (Note 12) 2
2. Glycerin 20
3. 1,3-butylene glycol 5
4). Sorbitan sesquioleate 0.1
5. Fine particle metal oxide dispersion composition of Production Example 8 10
6). Glycerin stearate 0.5
7). Cetostearyl alcohol 1
8). Ethyl hexyl methoxycinnamate 3
9. Glyceryl triethylhexanoate 2
10. Xanthan gum 0.2
11. Purified water 19.8
12 Ethanol 2
13. Methylparaben 0.2
14 Purified water balance
* 12 Nikkor Resinol S-10 (Nikko Chemicals)
(Production method)
A. Components (1) to (4) are uniformly mixed and dispersed at 70 ° C.
B. Ingredients (5) to (9) are uniformly mixed and dissolved at 70 ° C.
C. Components (10) to (11) are dissolved at 70 ° C.
D. B is uniformly mixed with A and gelled at 70 ° C.
E. C is uniformly mixed and dispersed in D and emulsified at 70 ° C.
F. Cool E.
G. Components (12) to (14) were added to F and mixed and dispersed uniformly to obtain an oil-in-water cosmetic base material.

  The oil-in-water cosmetic base material of Example 14 was an oil-in-water cosmetic base material having excellent temporal stability, no stickiness, and good spread.

Claims (6)

The following components (A) to (D);
(A) 3-60 mass% of fine particle metal oxide surface-treated with trialkoxyalkylsilane
(B) Polyhydroxystearic acid (however, the blending mass ratio of component (A) to component (B) (B) / (A) is 0.01 to 0.5)
(C) A hydrocarbon oil having a viscosity at 40 ° C. of 16 mm ² / s or less or an ester oil having 27 or less carbon atoms of 5 to 60% by mass
(D) 0.1 to 5% by mass of a surfactant selected from alkylmethyl taurine salts and / or phospholipids
Is blended,
An oil-in- water emulsified cosmetic, characterized in that the blending amount of silicone oil in all oils is 20% by mass or less .   2. The oil-in-water emulsification according to claim 1, wherein the surface treatment amount of the component (A) by trialkoxyalkylsilane is surface treatment agent / particulate metal oxide = 0.02 to 0.25 in mass ratio. Cosmetics.   The oil-in-water emulsified cosmetic according to claim 1 or 2, wherein the fine metal oxide (A) is further surface-treated with a (dimethicone / methicone) copolymer. The non-silicone oil of component (C) is isododecane, isotetradecane, isohexadecane, liquid paraffin having a viscosity at 40 ° C. of 11 mm ² / s or less, propylene glycol dicaprate, neopentyl glycol dicaprate, isononyl isononanoate, isotridecyl isononanoate The oil-in-water emulsified cosmetic according to any one of claims 1 to 3, which is one or more selected from cetyl 2-ethylhexanoate. Component (A) 3 to 60% by mass of fine particle metal oxide surface-treated with trialkoxyalkylsilane,
Component (B) polyhydroxystearic acid (however, the blending mass ratio of component (A) to component (B) (B) / (A) is 0.01 to 0.5), and component (C) viscosity at 40 ° C. Is 16 mm ² / s or less hydrocarbon oil or carbon number 27 or less ester oil 5 to 90% by mass
To prepare a fine particle metal oxide dispersion composition by dispersion treatment,
Next, the fine particle metal oxide dispersion composition and component (D) 0.1 to 5% by mass of a surfactant selected from alkylmethyl taurate and / or phospholipid are blended,
A method for producing an oil- in- water emulsified cosmetic, wherein the blending amount of a silicone-based oil in all oils is 20% by mass or less . 6. The method for producing an oil-in-water emulsified cosmetic according to claim 5, wherein the compounding amount of the component (A) in the fine particle metal oxide dispersion composition is 30 to 70% by mass.