JP2013107865A - Water-in-oil type emulsified cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil type emulsified cosmetic having no sticky feeing in use and an excellent feeing of grace, and excellent in continuation of the feeing of grace, stability with the elapse of time, skin stability and a feeling of use.SOLUTION: This water-in-oil type emulsified cosmetic includes (A) an organic modified clay mineral, (B) an ester-based nonionic surfactant with ethylene oxide having HLB of 5-8 added thereto, (C) a nonionic surfactant having HLB of <5 which is solid at room temperature, (D) a nonionic surfactant having HLB of <5 which is liquid at room temperature, (E) waxes, (F) a humectant, (G) an oil which is different from the (E) waxes, and (H) water.

Description

  The present invention relates to a creamy water-in-oil emulsified cosmetic that maintains moisture after application for a long time and is excellent in stability over time of emulsification, skin safety, and feel upon use.

  In recent years, the number of people with dry skin has increased due to the effects of climate change, environmental deterioration in urban areas, changes in dietary habits, and mental stress. In addition, the employment rate of women is increasing, and the number of people working outside for a long time is increasing. Against this background, after applying cosmetics, the desire to use cosmetics that last for a long time is increasing.

  It has been reported that the water-in-oil emulsifier type is superior in both occlusive property and water retention (see, for example, Non-Patent Document 1), and the persistence of moisture is also in the oil. It is known from experience that the water emulsifier type is superior.

In this way, the water-in-oil emulsion preparation containing hydrocarbon oil, ester oil, vegetable oil, etc., which are oils having excellent moisturizing feeling as the main oil, despite the expectation of excellent moisturizing feeling and sustainability. At present, almost no creamy products are on the market.
The reason is that it is difficult to maintain the temporal stability of the water-in-oil emulsion particles in the water-in-oil emulsion formulation as compared to the oil-in-water emulsion formulation. In particular, water-in-oil emulsion preparations containing hydrocarbon oils, ester oils, vegetable oils, etc., which are useful as cosmetics and have excellent moisturizing properties as the main oil components, are maintained over time compared to silicone oils and mineral oils. The current situation is much more difficult.

  Conventionally, in order to maintain the stability over time of water-in-oil emulsion preparations, a method has been used to improve the stabilization of an emulsified system by adding a solid oil component at normal temperature such as waxes in addition to a liquid oil component. However, there is a concern that oil content may be separated when stored under high temperature conditions, specifically, near the melting point of waxes. There was a problem of lowering.

In view of such conventional techniques, attempts have been made to improve various emulsification techniques. For example, a technique has been proposed for stabilizing emulsified particles by adding an amino acid and a specific surfactant to a water-in-oil emulsion composition to form a gel (for example, see Non-Patent Document 2). However, the production process is complicated, and high shearing force is required for emulsification, and an expensive mechanical device must be operated under specific conditions, and a stable emulsion can be produced easily and continuously. Has the disadvantage of being difficult.
Further, it has been reported that a stable water-in-oil emulsion preparation is obtained by adding an organically modified clay mineral and a surfactant having a specific HLB value (see, for example, Non-Patent Document 3). Since the resulting water-in-oil emulsion formulation has a low viscosity, in order to obtain a cream-like product, which is the main use of emulsified cosmetics, increase the internal water phase ratio or increase the amount of organically modified clay minerals. It is necessary, and the higher the internal water phase ratio, the more easily moisture is lost, and there are drawbacks in terms of sustaining the moist feeling, and there are drawbacks such as stickiness as the amount of organically modified clay mineral increases. In addition, silicone oil-based technology development using the same technology (see, for example, Patent Document 1) is being performed. Silicone oil is the main component, resulting in a lack of moist feeling. In addition, the viscosity of the organically modified clay mineral has to be thinned by using a bead mill, and it takes time and effort to manufacture. In addition, technical development (for example, see Patent Document 2) in which a specific surfactant and a specific amino acid derivative and a salt thereof are used to increase the internal water phase ratio has been performed. The higher it is, the easier it is to lose moisture, and there is a drawback in terms of maintaining a moist feeling. In addition, technical development (for example, see Patent Document 3) in which a specific surfactant, a specific oil-soluble polymer, and a powder are highly blended has been performed. There is a drawback that it is difficult to obtain a cream-like product having a high moisturizing feeling, such as a dry feeling caused by.

  Journal of Japan Cosmetic Engineers Association Vol. 17, no. 2 (1983) P116-120   Journal of Japan Cosmetic Engineers Association Vol. 11, no. 2 (1977) P58-66   Journal of Japan Cosmetic Engineers Association Vol. 26, no. 4 (1993) P229-237

  JP 2008-63331 A   JP2011-98891A   JP 2010-116354 A

  The object of the present invention made in view of the above situation is that there is no stickiness at the time of use, a moist feeling is good, and the aging stability, skin safety, and feeling of use are excellent. The object is to provide a good water-in-oil emulsified cosmetic.

As a result of intensive studies by the present inventors in view of the above circumstances, hydrocarbon oils, ester oils, vegetable oils and the like are mainly used by combining organically modified clay minerals, specific surfactants and waxes. Even when used as an oil, it has excellent moisturizing feeling, stability over time, skin safety, and feel in use, and it can satisfy consumer's safety orientation and expectation of effect on the skin. It was found that a water-in-oil emulsified cosmetic suitable for use in the present invention was obtained, and the present invention was completed.
That is, the configuration of the present invention is as follows.
<1> (A) an organically modified clay mineral, (B) an ethylene oxide-added ester-based nonionic surfactant of HLB5-8, (C) a nonionic surfactant that is solid at room temperature less than HLB5, and (D) Contains a nonionic surfactant that is liquid at room temperature below HLB5, (E) waxes, (F) a humectant, (G) an oil different from (E) waxes, and (H) water. It is a water-in-oil emulsified cosmetic.
<2> The water-in-oil emulsified cosmetic according to <1>, wherein the (A) organically modified clay mineral is an alkylammonium modified clay mineral.
<3> The ethylene oxide-added ester-based nonionic surfactant of (B) HLB 5 to 8 is isostearic acid hydrogenated castor oil, triisostearic acid hydrogenated castor oil, lauric acid hydrogenated castor oil, glyceryl triisostearate, tristearic acid The water-in-oil emulsion cosmetic according to <1> or <2>, which is at least one selected from the group consisting of glyceryl and POE adducts of glyceryl diisostearate.
<4> The nonionic surfactant that is solid at room temperature below (C) HLB5 is one or more selected from the group consisting of fatty acid sorbitan and fatty acid glyceride, and any one of <1> to <3>. This is a water-in-oil emulsified cosmetic.
<5> The ratio of the inner phase in the water-in-oil emulsified cosmetic is 45% to 70% by mass, and the ratio of the outer phase is 55% to 30% by mass of <1> to <4>. It is a water-in-oil type emulsified cosmetic of any one of Claims.
ADVANTAGE OF THE INVENTION According to this invention, the water-in-oil type emulsified cosmetics which satisfy the effect expectation effect with respect to the cosmetics use of the consumer who has a wide use feeling can be obtained. The water-in-oil emulsified cosmetic of the present invention can be suitably used as a cream type cosmetic (for example, quasi drug).

  According to the present invention, a water-in-oil emulsified cosmetic that has no stickiness during use, has a good moisturizing feeling, and is excellent in the persistence of moisturizing, has excellent stability over time, skin safety, and feel in use. Can be provided.

Hereinafter, the present invention will be described in detail.
The water-in-oil emulsified cosmetic of the present invention (hereinafter sometimes simply referred to as “emulsified cosmetic” or “emulsified cosmetic of the present invention”) is used as the main component of the water phase of the water-in-oil emulsified particles. (H) Water, water-soluble or oil-soluble (F) moisturizer, and (G) oil component that is liquid at room temperature as the main component of the oil phase, and (A) organically modified clay mineral, (B) HLB5 ~ 8 ethylene oxide addition type ester nonionic surfactant, (C) nonionic surfactant solid at room temperature below HLB5, (D) nonionic surfactant liquid at room temperature below HLB5, and (E) waxes Is included.
Hereinafter, each component will be described.

In this specification, polyoxybutylene may be abbreviated as “POB”, polyoxyethylene as “POE”, and polyoxypropylene as “POP”.
Further, when referring to either or both of “acryl” and “methacryl”, it may be described as “(meth) acryl”, and when referring to either or both of “acrylate” and “methacrylate”, “(meth) acrylate” May be described.

(A) Organically modified clay mineral The organically modified clay mineral used in the present invention includes a convertible cation interposed between crystal layers of a clay mineral (for example, montmorillonite, saponite, hectorite, bentonite, smectite, etc.) as an organic polar compound or an organic cation. And the like substituted with.
That is, examples of the organically modified clay mineral that can be used in the present invention include those obtained by treating known clay minerals such as hectorite, montmorillonite, saponite, hectorite, bentonite, and smectite with an organic cation. As a treatment method, a method is preferred in which an organic cation is dissolved or dispersed in a suitable solvent, and after the clay mineral is immersed therein and filtered, the filtrate is dried to prepare an organically modified clay mineral. Examples of the drying method include a method of drying using a kneader, a method of drying using spray drying, and a method of freeze drying. As a drying method, a method of drying using a kneader is preferable from the viewpoint of cost.
In addition, as an organic cation used for modification | denaturation of a clay mineral, 1 or more types chosen from ammonium compounds, such as an alkyl ammonium chloride, are mentioned, Especially, a dimethyl distearyl ammonium chloride is preferable.

  In addition, the (A) organically modified clay mineral in the present invention may be present in the state of the organically modified clay mineral in the emulsified cosmetic, except that the previously described organically modified clay mineral is added to the emulsified cosmetic. For example, an unmodified clay mineral such as synthetic smectite (aluminum magnesium silicate) and a cationic surfactant that is an organic cation capable of organically modifying the clay mineral are separately blended, and in the emulsion composition manufacturing process, The clay mineral may be organically modified. Even in this case, the organically modified clay mineral is present in the obtained emulsified cosmetic.

Specific examples of the organically modified clay mineral that can be used in the present invention include, for example, dimethyl distearyl ammonium hectorite (= quaternium-18 hectorite), dimethyl distearyl ammonium bentonite (= quaternium-18 bentonite), and benzyldimethylstearyl ammonium hector. Examples include lite, dioctadecyldimethylammonium salt-modified montmorillonite, octadecyldimethylbenzylammonium salt-modified montmorillonite, dihexadecyldimethylammonium salt-modified montmorillonite, and dimethyldistearylammonium smectite.
Examples of the organically modified clay mineral used in the present invention include “Benton 38V” (chemical name: quaternium-18 hectorite), “Benton 34” (chemical name: quaternium-18 bentonite), “Benton 27” (chemical name: Benzyldimethylstearylammonium hectorite) (all trade names: all manufactured by Leox Co., Ltd.), “Claytone 40”, “Claytone SO” (all trade names: all manufactured by Southern Clay), etc. It is commercially available.

  The organically modified viscosity mineral used in the emulsified cosmetic of the present invention is preferably one obtained by organically modifying hectorite, and more specifically, from the viewpoint of improving the stability over time, benzyldimethylstearyl ammonium. Nitric hectorite, dimethyl distearyl ammonium hectorite, and the like are preferable, and dimethyl distearyl ammonium hectorite is particularly preferable.

(A) Only 1 type may be used for an organic modified clay mineral with respect to the water-in-oil type emulsified cosmetics whole quantity of this invention, and may use 2 or more types together.
(A) About 0.5-5 mass% is preferable with respect to the whole quantity of the water-in-oil type emulsified cosmetics of this invention, and the compounding ratio of the organic modified clay mineral is the range of 1.0 mass%-3 mass% especially. It is. In addition, when using together 2 or more types of organic modified clay minerals, the said compounding ratio means the compounding ratio of total content.

(B) HLB 5-8 ethylene oxide addition type ester nonionic surfactant HLB5-8 ethylene oxide addition ester nonionic surfactant used in the present invention (hereinafter referred to as (B) surfactant as appropriate) As long as the above HLB and structure are satisfied, they can be appropriately selected and used.
In this specification, when the nonionic surfactant is a commercially available product, the nonionic surfactant HLB adopts the HLB value described in the manufacturer catalog or the IOB value x 10 described in the manufacturer catalog. If it is not a commercial product, the value of [(IOB value described in literature) × 10] in the nonionic surfactant is adopted.

Hereinafter, although HLB5-8 ethylene oxide addition type ester nonionic surfactant used by this invention is mentioned, this invention is not limited to this. In addition, when it describes as "POE (20-30)" in the following compounds, it means that the POE (polyethylene oxide) addition mole number of the said surfactant is the range of 20-30.
The surfactant (B) that can be used in the present invention is preferably a fatty acid ester POE adduct, a fatty acid-hardened castor oil POE adduct, or a fatty acid glyceryl POE adduct having a POE addition mole number of about 3 to 30. Are preferred. Specifically, for example, triisostearic acid POE (20-30) hydrogenated castor oil (HLB: 5.7 to 7.2), isostearic acid POE (10-20) hydrogenated castor oil (HLB: 5.4 to 7) .8), triisostearic acid POE (10-20) glyceryl (HLB: 5.0 to 7.8), isostearic acid POE (3-5) glyceryl (HLB: 6.0 to 7.7), diisostearic acid POE (10) Glyceryl (HLB: 6.9), trioleic acid POE (10-20) glyceryl (HLB: 5.0 to 7.8), isostearic acid POE (3) (HLB: 6.6), POE ( 5-10) hydrogenated castor oil (HLB: 5.1-6.9), stearic acid POE (8) lauryl ether (HLB: 6.6), isostearic POE (8) lauryl ether HLB: 6.6), stearic acid POE (7) cetyl ether (HLB: 5.5), stearic acid POE (9-12) stearyl ether (HLB: 6.3-7.5), dilauric acid POE (5 -6) (HLB: 5.4 to 6.9), distearic acid POE (6-12) (HLB: 5.2 to 7.9), diisostearic acid POE (6-12) (HLB: 5.2) 7.9), dioleic acid POE (6-12) (HLB: 5.2-7.9), triisostearic acid POE (20) trimethylolpropane (HLB: 7.8), and the like.

Among these, fatty acid-hardened castor oil to which POE is added at 10 to 30 or fatty acid glyceryl to which POE is added at 10 to 30 is preferable. More preferred is a compound obtained by adding 10 to 30 moles of POE to glyceryl, glyceryl tristearate, glyceryl diisostearate or the like.
Among the above, triisostearic acid POE (20) hydrogenated castor oil is particularly preferable.

  The blending amount of the HLB5-8 ethylene oxide-added ester-based nonionic surfactant used in the present invention is preferably 0.5 to 7.0 in terms of mass ratio with respect to the blending amount of the organically modified clay mineral. It is particularly preferable to use in the range of 0.7 to 5.0. 1 type, or 2 or more types can be used for the ester nonionic surfactant of HLB5-8 ethylene oxide addition.

(C) Nonionic surfactant that is solid at room temperature below HLB5 Here, “solid at room temperature” indicates that it does not have fluidity at room temperature, that is, at 25 ° C.
Any nonionic surfactant that is solid at room temperature below HLB5 used in the present invention (hereinafter referred to as (C) a surfactant as appropriate) can be used without particular limitation as long as it satisfies this physical property. Examples include solid compounds at room temperature such as glycerides, fatty acid sorbitans, and sucrose fatty acid esters. Specifically, for example, oleic acid monoglyceride (HLB: 2.5), stearic acid monoglyceride (HLB: 3.0), mono- Examples include sorbitan distearate (HLB: 4.2) and decaglycerin pentastearate (HLB: 3.5). Nonionic surfactants that are solid at room temperature and have an HLB of less than 5 are also preferably used. For example, palm oil hydrogenated monoglyceride, rapeseed oil mono-diglyceride, stearic acid mono-diglyceride, sorbitan mono-dipalmitate, decaglycerin pentastearate, decaglycerin decastearate, pentaglycerin hexastearate, 50% acetylated stearin Acid monoglyceride, stearic acid / malic acid monoglyceride, sucrose stearate and the like.
In the above exemplified compounds, stearic acid mono-diglyceride refers to a mixture of stearic acid glyceride and stearic acid diglyceride, mono-distearic acid sorbitan refers to a mixture of sorbitan stearate and sorbitan distearate, stearic acid -Malic acid monoglyceride refers to a mixture of stearic acid monoglyceride and malic acid monoglyceride.

  Among these, at least one selected from a mixture of sorbitan monostearate and sorbitan distearate and monoglyceride stearate is particularly preferable.

  The blending amount of the nonionic surfactant solid at room temperature below HLB5 is preferably about 0.2 to 5% by mass, and particularly preferably about 0.5 to 3% by mass with respect to the total amount of the cosmetic of the present invention. One kind or two or more kinds of nonionic surfactants which are solid at room temperature below HLB5 can be used.

(D) Nonionic surfactant that is liquid at normal temperature less than HLB5 Here, “liquid at normal temperature” indicates that it has fluidity at normal temperature, that is, at 25 ° C.
The nonionic surfactant that is liquid at room temperature below HLB5 used in the present invention (hereinafter referred to as (D) surfactant as appropriate) can be used without particular limitation as long as it satisfies this physical property. Examples include glyceryl monoisostearate (HLB: 4.0), sorbitan monoisodistearate (HLB: 4.5), and sorbitan monooleate (HLB: 4.3). Nonionic surfactants that are liquid at room temperature and have an HLB of less than 5 are also preferably used. For example, diisostearic acid glyceride, dioleic acid glyceride, sorbitan monoisostearate, propylene glycol monooleate, diisostearate diglycerin, pentaoleic acid decaglycerin, dekaoleic acid decaglycerin, (stearic acid / malic acid) glyceride, isostearic acid POE (3 ) Sorbit.

  The blending amount of the nonionic surfactant that is liquid at room temperature below HLB5 is preferably about 0.2 to 5% by mass, and particularly preferably about 0.5 to 3% by mass with respect to the total amount of the cosmetic of the present invention. One kind or two or more kinds of nonionic surfactants which are liquid at room temperature below HLB5 can be used.

(E) Waxes The waxes used in the cosmetic of the present invention can be used without limitation as long as they are oily components that are solid at room temperature (25 ° C.) and are usually used in cosmetics.
As waxes used in the present invention, moles, hardened castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, lobster wax, whale wax, montan wax, nuka wax, kapok wax, sugar cane wax, jojoballow, shellac wax, microcrystalline wax, Wax and paraffin waxes such as ceresin and paraffin, higher alcohols such as behenyl alcohol, stearyl alcohol and cetyl alcohol, higher fatty acids such as behenic acid, stearic acid and myristic acid, cocoa butter, coconut oil, horse fat and hydrogenated coconut oil , Palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork tallow, beef bone fat, owl kernel oil, hardened oil, beef leg oil, hexyl laurate, dextrin palmitate, petrolatum, polyethylene, batyl alcohol Cholesterol esters such as solid oil, cholesterol, phytosterol, cholesteryl 12-hydroxystearate, cholesteryl lanolin fatty acid, cholesteryl isostearate, cholesteryl ricinoleate, macadamia nut oil fatty acid cholesteryl, phytosteryl 12-hydroxystearate, phytosteryl lanolin fatty acid, phytosteryl isostearate Phytosterol esters such as phytosteryl ricinoleate, macadamia nut oil fatty acid phytosteryl, lanolin, lanolin alcohol, hydrogenated lanolin alcohol, lanolin fatty acid, hexa (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, (hydroxystearic acid / isostearic acid) dipentaerythrityl Dipenta etc. Ritoritto, N- lauroyl -L- glutamic acid di (cholesteryl or phytosteryl / behenyl / octyldodecyl), N- lauroyl -L- glutamic acid di (cholesteryl or phytosteryl / octyldodecyl), and the like.
The wax is contained in the oil phase in a molten state when the emulsified cosmetic is prepared by heating, and after the preparation of the emulsified cosmetic is present in the outer phase in a compatible state with the liquid oil, or It exists in a solid dispersion state.

Only one type of wax may be included in the emulsified cosmetic of the present invention, or two or more types may be used in combination.
The blending amount of the wax is preferably about 0.5 to 8% by mass, and particularly preferably about 0.7 to 5% by mass with respect to the total amount of the cosmetic of the present invention.

The water-in-oil emulsified cosmetic of the present invention has (H) water, water-soluble or oil-soluble as a main component of the water phase of the water-in-oil emulsified particles in addition to the components (A) to (E). (F) It is liquid at normal temperature as a moisturizing agent and the main component of the oil phase, and it is necessary to contain (G) an oil component different from the (E) wax.
(F) Moisturizer The moisturizer used in the emulsified cosmetic of the present invention is not particularly limited as long as it is a known moisturizer used in cosmetics. For example, propylene glycol, 1,3-propanediol, 1 , 2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol, hexylene glycol, glycerin, trimethylolpropane and other polyhydric alcohols, dipropylene glycol, polypropylene glycol, polyethylene glycol, diglycerin, triglycerin , Tetraglycerin, polyglycerin and other polyhydric alcohol polymers, dipropylene glycol ethyl ether, polyoxybutylene (hereinafter POB) polyoxyethylene (hereinafter POE) polyoxypropylene (hereinafter POP) glyceryl ether, POP jig Polyhydric alcohol derivatives such as lyseryl ether and POE diglyceryl ether, erythrose, erythrulose, threose, deoxyribose, lyxose, arabinose, ribose, ribulose, xylulose, glucose, talose, psicose, galactose, mannose, tagatose, fucose, fucose, Rhamnose, sedhebutulose, sucrose, maltose, turanose, cellobiose, lactose, trehalose, raffinose, melezitose, maltotriose, acarbose, stachyose, fructooligosaccharide, galactooligosaccharide, mannan oligosaccharide, dextrin saccharide, erythritol, arabinitol, xylitol, sorbitol Sugar alcohols such as maltitol, mannitol and dulcitol, Sugar derivatives such as lucosyl trehalose, ascorbyl glucoside, POE methyl glucoside, POP methyl glucoside, hydroxypropyl-β-cyclodextrin, sugar alcohol derivatives such as sorbitol phosphate, xylitol phosphate, POE maltitol, glycine, threonine Amino acids such as alanine, tyrosine, valine, leucine, arginine, lysine, proline, aspartic acid, glutamic acid, serine, hydroxyproline, pyrrolidone carboxylates such as sodium pyrrolidonecarboxylate, chondroitin sulfate sodium, sodium hyaluronate , Betaine, urea, POE / POP dimethyl ether and the like. It can be used alone or in combination of two or more.
These humectants may be included in the oil phase of the water-in-oil emulsified cosmetic if they are oil-soluble materials, and may be included in the water phase if they are water-soluble materials. Moreover, it may be uniformly dispersed in the system as a fine solid content.
The moisturizing agent is not particularly limited, and may be appropriately selected and used in consideration of the purpose of the cosmetic of the present invention and the affinity with components used in combination.
As a content rate of a moisturizer, it is preferable that it is the range of 2 mass%-30 mass% with respect to all the components used for cosmetics.

(H) Water The emulsified cosmetic of the present invention contains water as the main component of the water phase component. Since the water contained in the emulsified cosmetic preferably contains no impurities, it is preferable to use ion-exchanged water or pure water. The water content is appropriately selected according to the preferred dosage form of the emulsified cosmetic of the present invention, but is determined depending on the preferred content of the inner phase, that is, the water phase constituting the emulsified particles, which will be described later. .

[Other components that can be contained in the aqueous phase]
In addition to water, the water phase (inner phase) may further contain other water phase components.
The components that can be used in combination with water and can be blended in the water phase are not particularly limited as long as they are compatible with water, can be dissolved or uniformly dispersed in water, aqueous organic solvents, various water-soluble substances, In addition, an active ingredient having water dispersibility may be used in combination.
Examples of the component added to the aqueous phase as desired include monohydric alcohols such as ethanol, propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol;
Α-hydroxy acids such as aminocaproic acid, citric acid, lactic acid, glycolic acid and tartaric acid and salts thereof such as sodium and potassium;
Antioxidants such as ascorbic acid and sodium pyrosulfite;
Preservatives such as methylparaben, sodium dehydroacetate, sodium benzoate, phenoxyethanol;
Chelating agent placental extract such as salicylic acid, edetic acid, metaphosphoric acid, nicotinic acid amide, pantotenyl ethyl ether, pantothenic acid, dipotassium glycyrrhizinate, biotin, pyridoxine hydrochloride, adenosine triphosphate, α-lipoic acid, royal jelly, 3 -Drugs such as O-ethyl ascorbic acid, magnesium ascorbate phosphate, arbutin, glucosyl hesperidin, glucosyl rutin;
Etc.

In addition, a water-soluble thickener may be used to improve the stability of the emulsified particles. Examples of the water-soluble thickener include gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, gellan gum, carrageenan and the like. Plant polymers;
Microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, sodium biohyaluronate;
Animal macromolecules such as collagen, casein, albumin, gelatin;
Starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch;
Cellulose polymers such as methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, crystalline cellulose;
Alginate polymers such as sodium alginate, propylene glycol alginate;
Vinyl polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl methyl ether, polyvinyl pyrrolidone, vinyl pyrrolidone and vinyl acetate copolymer, carboxy vinyl polymer;
Acrylic polymers such as sodium polyacrylate, polyethyl acrylate, alkanolamine polyacrylate, alkyl methacrylate and dimethylaminoethyl methacrylate copolymer, poly-2-acrylamido-2-methylpropanesulfonic acid, polymethacryloyloxytrimethylammonium;
A polymer comprising 2-methacryloyloxyethyl phosphorylcholine as a monomer;
Etc.

(G) Oil content different from the (E) wax In the present invention, the (G) oil content different from the (E) wax contained in the oil phase refers to an oily component that is liquid at room temperature (25 ° C.). The oil component (G) that can be used in the present invention is not particularly limited as long as it is liquid at room temperature and can be used in cosmetics. Hydrocarbon oil, ester oil, vegetable oil, animal oil, mineral oil, silicone From the viewpoint that oil and the like can be given, and that the skin feel and moisture can be imparted, one or more selected from hydrocarbon oils, ester oils, and vegetable oils are preferable.
Examples of vegetable oils include avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, maize oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil , Soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, snail oil, Japanese drill oil, jojoba oil, and germ oil.
Examples of animal oils include squalane, turtle oil, mink oil, and egg yolk oil.
Examples of ester oils include glyceryl triisooctanoate, glyceryl triisopalmitate, octyl isopalmitate, isopropyl isostearate, isostearyl isostearate, isocetyl isostearate, hexyl isostearate, myristyl isostearate, isocetyl octanoate, isooctanoic acid Cetyl, isostearyl octoate, isodecyl isononanoate, octyldodecyl dimethyloctanoate, oleyl myristate, isostearyl erucate, isocetyl stearate, octyl stearate, isostearyl palmitate, isocetyl palmitate, octyl palmitate, isomyristate myristate Stearyl, isocetyl myristate, octyldodecyl myristate, decyl myristate, palmiti Isopropyl acid, isopropyl myristate, trimethylolpropane triisostearate, neopentyl glycol dicaprate, dioctyl sebacate, octyldodecyl 12-stearoyloxystearate, dioctyldecyl stearoylglutamate, dioctyl adipate, diisostearyl malate, octyl lactate Examples include dodecyl, isostearyl lactate, and octyl paradimethylaminobenzoate.
Hydrocarbon oils include liquid paraffin, isoparaffin, α-olefin oligomer, polybutene, 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, jojoba alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearin. Examples include acids, oleic acid, linoleic acid, linolenic acid, 2-octyldodecanoic acid and the like.
Examples of the silicone oil include dimethylpolysiloxanes such as decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, and hexadecamethylheptasiloxane;
Cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane;
Examples include methylphenyl polysiloxane. These can be used alone or in combination of two or more.

[Other ingredients that can be contained in the oil phase]
The oil phase may contain various compounds that can be dissolved or dispersed in a liquid oil.
The oil phase preferably contains, for example, active ingredients that are expected to have various effects on moisture and skin. Examples of active ingredients that can be added to the oil phase include ceramides such as ceramide 1, ceramide 2, ceramide 3, ceramide 4, ceramide 5, ceramide 6I, and ceramide 6II;
Lipids such as sphingosine, phytosphingosine, glycosphingolipid, and sphingophospholipid;
Cyclic triterpene compounds such as glycyrrhetinic acid, alkyl glycyrrhetinate, betulinic acid, alkyl betulinate, oleanolic acid, alkyl oleanolate, ursolic acid, alkyl ursolate, benzyl ursolate and their derivatives;
Isoflavans such as grablizine;
Benzoquinone derivatives such as coenzyme Q, enzyme cofactors such as thioctic acid;
carotenoids such as β-carotene, lycopene, astaxanthin;
Retinol derivatives such as retinol, retinol acetate and retinol palmitate;
Derivatives of vitamin B analogues such as riboflavin butyrate, pyridoxine dicaprylate, pyridoxine dipalmitate, pyridoxine dilaurate;
Ascorbic acid derivatives such as ascorbyl dipalmitate and ascorbyl tetrahexyldecanoate;
Vitamin D related compounds such as ergocalciferol and cholecalciferol;
Oil-soluble drugs such as tocopherol derivatives such as tocopherol acetate;
Etc.

Further, for example, preservatives such as ethyl paraben and propyl paraben, oil-soluble ultraviolet absorbers and the like may be blended.
Examples of the oil-soluble ultraviolet absorber include octyl methoxycinnamate, butyl methoxycinnamate, isopropyl methoxycinnamate, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, glyceryl di-2-methoxycinnamate mono-2-ethylhexanoate, 4- tert-butyl-4'-methoxydibenzoylmethane, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine, sodium hydroxymethoxybenzophenonesulfonate, octyl salicylate, salicylic acid Homomenthyl, methylbenzylidene camphor, 2-cyano-3,3-diphenylprop-2-enoic acid-2-ethylhexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl } -6- (4-Methoxyphenyl) 1,3,5-triazine, 2,2′-methylene-bis {6- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol} and the like.

[Other ingredients that can be included in cosmetics]
Other ingredients to be blended in cosmetics include drugs such as silver zeolite, chlorohydroxyaluminum, menthol, titanium oxide, zinc oxide, talc, mica, kaolin, iron oxide, titanium mica, silica, porous silica, nylon, polyethylene, Powders such as polymethyl methacrylate and cellulose, caustic potash, caustic soda, triethanolamine, 2-amino-2-methyl-1-propanol, neutralizing agents such as 2-amino-2-methyl-1,3-propanediol, A plant extract, a fragrance | flavor, a pigment | dye, etc. are mentioned.

  In the water-in-oil emulsified cosmetic of the present invention, the ratio of the inner phase is preferably 45% by mass to 70% by mass, and the ratio of the outer phase is preferably 55% by mass to 30% by mass. Is more preferably 47 mass% to 67 mass%, and the outer phase ratio is more preferably 53 mass% to 33 mass%. The internal phase in the present invention includes components that swell the emulsified particles composed of the aqueous phase contained in the water-in-oil emulsion composition, such as water, water-soluble solvents, water-soluble humectants, and various water-soluble additives. Is included in the internal phase. In addition, the outer phase includes an oil phase such as a liquid oil component, and organic modified viscosity minerals, waxes and the like that are dispersed in the oil phase. The ratio of the internal phase to the external phase can be adjusted as appropriate depending on the type and amount of the component to be contained.

The water-in-oil emulsified cosmetic of the present invention can be produced by a commonly used method.
As a production method, an aqueous phase component in which various water-soluble components are added to water and an oil phase component in which waxes or oil-soluble active ingredients are added to a liquid oil phase are prepared, and these are mixed with a homomixer or the like. A method of preparing a water-in-oil emulsified cosmetic using an emulsifier is mentioned, and this is the simplest production method. However, the method for producing the cosmetic of the present invention is not limited to a preparation method using a general emulsifying apparatus, and may be appropriately determined depending on the intended quality characteristic value and the like.

  The water-in-oil type emulsified cosmetic of the present invention is a cream type with excellent moist feeling immediately after application and a long-lasting moisturizing feeling, and also has excellent use feeling and has a wide use feeling. In particular, it can be suitably used as a cosmetic (quasi-drug).

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Examples 1-2, Comparative Examples 1-2]
In accordance with the prescription described in Table 1 below, 1 to 10 were weighed and mixed to prepare an aqueous phase, which was heated to 70 ° C. 11-25 are weighed and mixed, heated and dissolved at 70 ° C. to prepare an oil phase, the prepared aqueous phase is added to the oil phase, and the emulsifier (Plymix Co., Ltd., homomixer) is used. A shearing force was applied to obtain an emulsified composition. The obtained emulsion was further stirred and cooled to 35 ° C. by stirring for 10 minutes while maintaining the temperature at 70 ° C. in the same emulsifier (Plymix, Homomixer). A whitening moisturizing cream was obtained.
As a result of observation with an optical microscope, water-in-oil type emulsified particles (particle size: 1 μm to 5 μm) were confirmed.

In addition, the detail of each component in following Table 1 is as follows.
15) Olefin oligomer, (2) Hydrogenated poly (C6-12 olefin) (manufactured by Nikko Chemicals, trade name: Synthelan 4S)
16) Sugar wax (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Sugar Wax A-10E)
19) Macadamia nut fatty acid phytostearyl (manufactured by Nippon Seika Co., Ltd., trade name: YOFCO MAS)
22) Triisostearic acid POE (30) hydrogenated castor oil (trade name: EMALEX RWIS-330, manufactured by Nippon Emulsion Co., Ltd.) HLB7.2: (B) an ester-based nonionic surfactant of ethylene oxide addition of HLB5-8 in the present invention .
24) Triisostearic acid POE (20) hydrogenated castor oil (trade name: EMALEX RWIS-320, manufactured by Nippon Emulsion Co., Ltd.) HLB5.7: (B) HB5-8 ethylene oxide addition ester-based nonionic surfactant in the present invention .
21) Triisostearic acid POE (40) hydrogenated castor oil (trade name: EMALEX RWIS-340, manufactured by Nippon Emulsion Co., Ltd.) HLB8.4: Ester-based nonionic surfactant added with ethylene oxide, where HLB is within the scope of the present invention Outside comparative surfactant.
23) Triisostearic acid POE (20) hydrogenated castor oil (trade name: EMALEX RWIS-320, manufactured by Nippon Emulsion Co., Ltd.) HLB5.7: Ester-based nonionic surfactant added with ethylene oxide, where HLB is within the scope of the present invention Outside comparative surfactant.
25) Sorbitan mono-stearate (trade name: Nikkor SS-15V, manufactured by Nikko Chemicals Co., Ltd.) HLB: 4.2: (C) Nonionic surfactant solid at room temperature below HLB5 in the present invention.
26) Diglycerin diisostearate (trade name: Cosmol 42V, manufactured by Nisshin Oilio Co., Ltd.) HLB: 4.0: (D) Nonionic surfactant which is liquid at room temperature below HLB5 in the present invention.

Next, the obtained emulsified cosmetic was evaluated by the evaluation methods and evaluation criteria described below. The results are also shown in Table 1 below.
(1) Long-term stability After storage for 1 month under each temperature condition of 0 ° C, room temperature, 40 ° C and 50 ° C, visually check for changes in appearance such as separation of emulsified cosmetics and follow the criteria below. evaluated. In addition, what was evaluated as (double-circle) and (circle) shows stability sufficient practically.
A: No abnormality such as appearance change, viscosity change, separation, etc. is observed at each temperature.
○: When stored at 50 ° C., slight abnormalities such as changes in appearance, changes in viscosity, and separation are observed.
Δ: Abnormalities such as change in appearance, change in viscosity, separation, etc. are observed when stored at 40 ° C. and 50 ° C.
X: Abnormalities such as changes in appearance, changes in viscosity, and separation are observed at any temperature.

(2) Usability Twelve female panels were allowed to use the emulsified cosmetic immediately after preparation, and were subjected to sensory evaluation on usability immediately after use and a feeling of use after 3 hours, and evaluated according to the following criteria.
[Moisture and sustainability]
◎: More than 10 panelists evaluated that the moist feeling immediately after application was very excellent and the moist feeling after 3 hours was very good ○: Moist feeling immediately after application was very excellent, and the moist feeling after 3 hours was also very high 6 to 9 panels evaluated as being in the surface Δ: Moisture feeling immediately after application is very excellent, and 4 to 5 panels evaluated as having a very moist feeling after 3 hours ×: Moisture feeling immediately after application Less than 3 panelists rated it as excellent and very moist after 3 hours [stickiness]
◎: 10 or more panels evaluated as having no stickiness when applied to the skin and good elongation ○: 6 to 9 panels evaluated as having no stickiness when applied to the skin and good elongation Δ: Applying to the skin 4 to 5 panelists evaluated as having no stickiness when applied and good elongation x: 3 or less panels evaluated as having no stickiness when applied to skin and good stretch

As shown in the results of Table 1, it can be seen that the moisturizing creams of Examples 1 and 2 obtained in the present invention are excellent in stability and are moisturizing and moisturizing excellent in moisturizing feeling.
On the other hand, instead of the surfactant (B) according to the present invention, in Comparative Examples 1 and 2 in which the HLB uses a comparative surfactant outside the scope of the present invention, although the initial moist feeling is somewhat, the sustainability is somewhat It turns out that it is low.

[Example 3, Comparative Examples 3 to 5]
According to the prescription described in Table 2 below, 1 to 10 were weighed and mixed to prepare an aqueous phase, which was heated to 70 ° C. 11 to 25 are weighed and mixed, heated and dissolved at 70 ° C. to prepare an oil phase, and the prepared aqueous phase is added to the oil phase. The emulsion was uniformly and finely emulsified at ℃, and then stirred and cooled to 35 ℃ to obtain a whitening moisturizing cream.
Water-in-oil emulsified particles (particle size: 1 μm to 7 μm) were confirmed by observation with an optical microscope.

In addition, the detail of the component in following Table 2 is as follows.
19) Triisostearic acid POE (20) hydrogenated castor oil (trade name: EMALEX RWIS-320, manufactured by Nippon Emulsion Co., Ltd.) HLB5.7: (B) an ester-based nonionic surfactant of ethylene oxide addition of HLB5-8 in the present invention .
20) Triisostearic acid POE (20) Glyceryl (trade name: EMALEX GWIS-32, manufactured by Nippon Emulsion Co., Ltd.) HLB 7.9: (B) an ester-based nonionic surfactant added with ethylene oxide of HLB 5-8 in the present invention.
21) Stearic acid monoglyceride (trade name: Nikkor MGS-BMV, manufactured by Nikko Chemicals Co., Ltd.) HLB: 3.0, mp: (D) Nonionic surfactant that is liquid at room temperature below HLB5 in the present invention.
22) Sorbitan mono-diisostearate (trade name: Nikkor SI-15RV, manufactured by Nikko Chemicals), HLB: 4.5: (C) Nonionic surfactant that is solid at room temperature below HLB5 in the present invention.

  As shown in Table 2, it can be seen that the whitening moisturizing cream of Example 3 according to the present invention has good stability and is a whitening moisturizing cream excellent in moisturizing feeling and moisturizing feeling during use. On the other hand, in Comparative Example 3 containing no surfactant (B), a stable creamy water-in-oil emulsion composition could not be obtained. In addition, (D) the cosmetic of Comparative Example 4 that does not contain a surfactant is excellent in stability but is inferior in the feeling of use as a cosmetic, and (C) the cosmetic of Comparative Example 5 that does not contain a surfactant. Thus, both the emulsion stability and the feeling of use were inferior to those of the examples.

Claims (5)

(A) an organically modified clay mineral;
(B) HLB 5-8 ethylene oxide addition ester-based nonionic surfactant;
(C) a nonionic surfactant that is solid at room temperature below HLB5;
(D) a nonionic surfactant that is liquid at room temperature below HLB5;
(E) waxes;
(F) a moisturizer;
(G) (E) an oil different from the waxes,
(H) Water-in-oil emulsified cosmetic containing water.   The water-in-oil emulsified cosmetic according to claim 1, wherein the (A) organically modified clay mineral is an alkylammonium modified clay mineral.   (B) HLB 5-8 ethylene oxide addition ester-based nonionic surfactant is isostearic acid hydrogenated castor oil, triisostearic acid hydrogenated castor oil, lauric acid hydrogenated castor oil, glyceryl triisostearate, glyceryl tristearate, and The water-in-oil emulsified cosmetic according to claim 1 or 2, which is one or more selected from the group consisting of POE adducts of glyceryl diisostearate.   The oil according to any one of claims 1 to 3, wherein the (C) nonionic surfactant solid at room temperature less than HLB5 is one or more selected from the group consisting of fatty acid sorbitan and fatty acid glyceride. Water-type emulsified cosmetic.   The ratio of the inner phase in the water-in-oil emulsified cosmetic is 45% by mass to 70% by mass, and the ratio of the outer phase is 55% by mass to 30% by mass. The water-in-oil emulsified cosmetic according to item.