JP6674816B2 - Water-in-oil emulsion composition - Google Patents

Description

  The present invention is a water-in-oil type emulsion composition containing a pigment in a high concentration, in the emulsion composition, color unevenness and white stripes derived from the pigment, a water-in-oil type emulsion composition that does not cause oil separation About.

  As base makeup cosmetics represented by foundations, those which hide skin troubles such as spots and dullness and have a natural skin feeling have come to be preferred. In order to achieve such a natural finish, it is necessary to determine the pigment to be incorporated in consideration of the actual color tone of the skin. Therefore, it has a complex composition in which a plurality of pigments such as coloring pigments (red pigment, yellow pigment, black pigment) such as titanium oxide, talc, and iron oxide, and pearl pigments such as mica titanium are blended. The particle size of these pigments needs to be adjusted to the most effective particle size for scattering visible light in order to recognize as a color. For example, Non-Patent Document 1 states that in order to use rutile-type titanium oxide as a white pigment, it is necessary to adjust the particle diameter to 0.2 to 0.4 μm, which is most effective for scattering visible light. I have. Incidentally, in order to distinguish the pigment adjusted to the particle diameter most effective for scattering of visible light from the fine particle pigment which is a pigment adjusted to the particle diameter most effective for scattering of ultraviolet rays described below, in the present specification, for convenience. Sometimes referred to as normal size pigments.

  In general, in order to provide a cosmetic with an ultraviolet protection function, a method of blending an ultraviolet absorber or a finely divided pigment as an ultraviolet scattering agent is used. The blending of organic UV absorbers into cosmetics is a commonly used technology, but it can cause skin troubles such as rough skin, and tends to be avoided when importance is placed on skin safety. . On the other hand, the compounding of finely divided pigments is becoming mainstream in the formulation of cosmetics with higher safety to the skin because of its low skin irritation. Representative examples of finely divided pigments include fine particle titanium oxide and fine particle zinc oxide. Fine particle titanium oxide is generally used for cutting UVB waves, and fine particle zinc oxide is generally used for cutting UVA waves.

Non-Patent Document 1 discloses that when the particle size of titanium oxide is reduced to a Rayleigh scattering region extremely smaller than the wavelength of light, light scattering decreases in proportion to the sixth power of the particle size. It is described that a transparent coating film can be obtained which has an ultraviolet ray cutting ability and an ultraviolet ray cutting ability. Further, in this document, it is described that the particle diameter of titanium oxide having an ultraviolet ray cutting ability is several nm to several tens nm. Furthermore, nanoparticles of inorganic oxides, such as micronized titanium oxide in order tens m ^{2 /} g to several hundred m ^{2 /} g and the specific surface area is large, aggregation of attempts to decrement the surface energy particles is likely to occur It is described.

  Since the finely divided pigment is liable to agglomerate, some measures are required to ensure the dispersion stability of the finely divided pigment. For example, Patent Literature 1 discloses a technology of an ultraviolet shielding ultrafine particle dispersion in which ultrafine titanium oxide and zinc oxide are stably dispersed.

  In a composition in which various normal-sized pigments are blended with a base makeup cosmetic and, further, a finely divided pigment having an average particle size of 50 nm or less in anticipation of an ultraviolet protection effect is blended, various compositions are included in the composition. Since pigments having a particle size are mixed and agglomeration of powder is more likely to occur, it is more difficult to ensure stability. Finely divided pigment is an important component because it has a high UV scattering effect and low skin irritation, but when aggregated in a base makeup cosmetic adjusted to skin color, it can be recognized as white spots or streaks by the naked eye. In addition, when the cosmetic is discharged from the container, it is not only unpleasant, but when the degree of coagulation progresses, white streaks occur even on the applied skin, which is a serious problem in quality.

  Under such circumstances, various techniques have been proposed for improving the dispersion stability of the finely divided pigment in the emulsion composition. For example, in Patent Document 2, fine particles of titanium oxide and fine particles of zinc oxide are contained in an internal oil phase, and other powders are contained in an external water phase. In a manufacturing process, acyl lactic acid and / or a salt thereof are added immediately before emulsification. There is disclosed a technique of a method for producing an oil-in-water emulsified cosmetic which is characterized by being added to an oil phase. However, this technology is a technology of an oil-in-water emulsion cosmetic, and it is difficult to apply it to a water-in-oil emulsion cosmetic of a different emulsion type.

  Patent Document 3 discloses a water-in-oil type emulsified cosmetic, particularly a makeup cosmetic such as a foundation and a sunscreen cosmetic, in which polyoxyalkylene / alkyl co-modified silicone, sodium glutamate, organically modified clay mineral, diglyceryl diisostearate are disclosed. Describes that a W / O emulsified cosmetic that exhibits characteristic skin friction behavior and is excellent in use feeling and emulsification stability can be obtained by blending. Also, by incorporating sodium glutamate, or an organically modified clay mineral and diglyceryl diisostearate, it is possible to improve the dispersion stability of the powder and the viscosity stability of the composition without impairing the usability and emulsion stability. It states that it can. Patent Literature 3 describes that the generation of color fringes (yellow stripes and red unevenness) caused by agglomeration of powders blended in foundations and sunscreen cosmetics is not sufficient, but is sufficient.

  Further, Patent Document 4 discloses a liquid water-in-oil type emulsifying make which aims to suppress aggregation of an inorganic powder obtained by combining a specific amount of a specific polyoxyalkylenemethyl glucoside, a powder, a liquid oil, a polyhydric alcohol, and water. Although a technique for up cosmetics has been proposed, the use of this technique is not enough to suppress the occurrence of white streaks.

  On the other hand, when imparting a sunburn preventing effect to the base make-up cosmetics, it is designed as a water-in-oil type emulsion which is said to be hard to lose makeup. However, the water-in-oil type emulsion composition may cause an "oil separation" phenomenon which does not occur in the oil-in-water type emulsion composition. The term “oil separation” refers to a phenomenon in which, when stored at a high temperature or for a long period of time, oil contained in an oil phase is discharged and accumulates on the surface or voids of the composition. This oil separation is a phenomenon different from separation caused by so-called poor emulsification, in which water is discharged, and is due to instability of the structure and composition of the oil phase. Oil separation is easily recognized as a defective product and poses a problem in design quality. Prior art for solving oil separation includes, for example, Patent Documents 5 and 6.

Japanese Patent No. 3942767 Japanese Patent No. 5649839 Japanese Patent No. 5814117 Japanese Patent No. 4348251 JP 2007-153812 A JP 2013-107827 A

"Development of Functional Titanium Oxide Material" Production and Technology, Vol. 66, No. 1, 2014, pp. 54-58

  An object of the present invention is to provide a water-in-oil type emulsion composition which does not cause color unevenness, white stripes, and oil separation in a water-in-oil type emulsion composition containing a pigment at a high concentration.

The main configuration of the present invention is as follows.
(1) In a water-in-oil emulsion composition containing 15 to 30% by mass of a pigment,
(A) Organically modified clay mineral (B) (Behenic acid / eicosantioic acid) glyceryl (C) Poly (12-hydroxystearic acid) ester (D) Surfactant (E) Water-in-oil emulsion containing oil agent Stuff.
(2) The water-in-oil emulsion composition according to (1), wherein (C) the poly (12-hydroxystearic acid) ester is PEG-30 dipolyhydroxystearate.
(3) The water-in-oil emulsion composition according to (1) or (2), wherein the pigment is prepared by mixing a plurality of metal oxides to obtain a color of human skin.
(4) Six or more pigments selected from titanium oxide, yellow iron oxide, red iron oxide, black iron oxide, talc, pearl pigment, fine titanium oxide, fine zinc oxide, fine cerium oxide, and fine zirconium oxide (1) The water-in-oil emulsion composition according to any one of (1) to (3).
(5) The water-in-oil emulsion composition according to any one of (1) to (4), which is a base makeup cosmetic or a sunscreen cosmetic.

  Since the water-in-oil emulsion composition of the present invention does not cause oil separation during storage and further does not generate white streaks due to aggregation of pigments, especially pigments having a particle diameter of 50 nm or less, which are finely divided. It is possible to obtain an extremely stable cosmetic. Even when stored under severe conditions of 50 ° C., neither oil release nor white stripes occur. Therefore, when transporting or storing products such as base makeup cosmetics and skin-colored sunscreen cosmetics, which are highly blended with pigments (fine-grained titanium oxide, fine-grained zinc oxide, etc.) that are expected to have an ultraviolet protection effect, Appearance, feeling of use, sunburn prevention effect) No fear of deterioration.

The present application relates to a water-in-oil emulsion composition containing 15 to 30% by mass of a pigment, wherein (A) an organically modified clay mineral, (B) glyceryl (behenic acid / eicosantioic acid), and (C) poly (12-hydroxystearin). The present invention relates to a water-in-oil emulsion composition containing (acid) ester, (D) surfactant, and (E) oil.
Hereinafter, the components of the present invention will be described.
The water-in-oil emulsion composition of the present invention contains 15 to 30% by mass of a pigment. The type of pigment is not particularly limited as long as it is usually used for cosmetics. Since colored pigments and pearl pigments have the effect of correcting skin color and the effect of concealing spots, the water-in-oil emulsion composition is blended to adjust the color tone of human skin. For example, white pigments such as titanium oxide and talc, yellow pigments yellow iron oxide, black pigments black iron oxide, red pigments such as red iron oxide, mica, iron oxide-coated mica, and iron oxide-coated mica titanium. Pearl pigment, gunjou, chromium oxide, kaolin, boron nitride and the like. For example, in the case of titanium oxide, the average particle size is adjusted to 0.15 to 0.4 μm based on Mie's scattering theory in order to make it recognized as white when applied to the skin. As the pigment, a surface-treated powder that has been subjected to a silicone treatment or a fluorine treatment may be used. Alternatively, a commercially available dispersion previously dispersed in silicone oil or the like may be used.

According to the constitution of the present invention, the dispersion stability of the pigment is extremely high, so that a finely divided pigment, which is considered to be difficult to stabilize the dispersion, can be highly blended. Examples of the finely divided pigment include fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and fine particle zirconium oxide. In order to exhibit the effect as an ultraviolet ray protective agent, the average particle size is set to 50 nm or less based on Mie's scattering theory. In particular, it is preferable to use a fine particle titanium oxide and a fine particle zinc oxide having an average particle diameter of 50 nm or less because UVB waves and UVA waves can be protected. Further, it is preferable to use a material that has been surface-treated (coated) with silicone. These finely divided pigments are appropriately determined from commercially available simple substances according to the desired ultraviolet protection effect. Alternatively, a paste-like commercially available product in which a low-order particle is stably formed in a volatile silicone base material may be used. Examples of such commercially available products include Cosmeserve WP-40TK and Cosmeserve WP-TTN (V) manufactured by Dainippon Kasei Co., Ltd.
Cosmeserve WP-40TK contains 30% by mass of fine particle titanium oxide, 50% by mass of cyclopentasiloxane, 10% by mass of PEG-9 polydimethylsiloxyethyl dimethicone, and other components occupying 10% by mass (aluminum hydroxide, silica and (dimethicone / vinyl). Dimethicone) crosspolymer).
Cosmeserve WP-TTN (V) contains 23% by mass of fine-particle titanium oxide, 66% by mass of cyclopentasiloxane, 2% by mass of polyglyceryl-2 diisostearate, and 8% by mass of other components (aluminum hydroxide, stearic acid and (dimethicone) / Vinyl dimethicone) crosspolymer).
The type and amount of the finely divided pigment are appropriately determined according to the desired ultraviolet protection effect. The compounding amount of the fine particle pigment is preferably 4 to 20% by mass, more preferably 4 to 16% by mass as a pure component. If it is less than 4% by mass, a sufficient ultraviolet ray protection effect cannot be obtained. The compounding amount of the fine particle pigment is included in the range of 15 to 30% by mass indicated by the compounding amount of the pigment of the present invention.

The types of pigments selected for making the composition have the color of human skin and the preferred amounts are as follows.
A) White pigment: titanium oxide (average particle diameter 150 to 400 nm) 5 to 10% by mass
I) Yellow pigment: 1-2% by mass of yellow iron oxide
C) Red pigment: red iron oxide (red iron) 0.1 to 0.5% by mass
D) Black pigment: 0.05 to 0.5% by mass of black iron oxide
When talc is blended for adjusting the feeling of use, a part of the blending amount of titanium oxide may be replaced with talc.
Preferred amounts of the fine particle titanium oxide and the fine particle zinc oxide, which are used in combination with the pigment to protect the UVB wave and the UVA wave, are exemplified below.
(Fine particle pigment)
E) Fine particle titanium oxide (average particle diameter 1 to 50 nm) 4 to 16% by mass
F) Fine particle zinc oxide (average particle diameter 1-50 nm) 1-5% by mass
In addition, when fine-particle cerium oxide and fine-particle zirconium oxide are blended, a part of the blending amount of fine-particle titanium oxide may be replaced.
According to the constitution of the present invention, the pigments A to A can be stably blended without generating white stripes.

(A) Organically modified clay mineral In the present invention, an organically modified clay mineral is blended as an essential component. Smectite, which is a swellable layered silicate, is a cationic clay mineral, and the cation replaced with an organic cation such as a quaternary ammonium salt is called an organically modified clay mineral. The minerals contained in smectite include hectorite, montmorillonite, bentonite, saponite, beidellite, nontronite, stevensite, vermiculite, vorconscoite, soconite, magadite, Kenyalite and the like. Examples of the organic cation include dimethyl distearyl ammonium chloride, dimethyl dipalmityl ammonium chloride, stearyl benzyl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, betaine lauryl dimethyl amino acetate, and the like. Examples of the organically modified clay mineral include disteardimonium hectorite, stearalkonium hectorite, and stearalkonium bentonite. As the organically modified clay mineral used in the present invention, disteardimonium hectorite is particularly preferred.

  The amount of the organically modified clay mineral used in the present invention is preferably 0.1 to 5% by mass. If the amount is less than 0.1% by mass, the effect may be insufficient. If the amount is more than 5% by mass, a sticky feeling may be caused.

(B) (Behenic acid / eicosantioic acid) glyceryl The glyceryl (behenic acid / eicosantioic acid) used in the present invention is an oligomer ester composed of behenic acid, eicosantioic acid and glycerin, and is a white to pale yellow wax. It is a solid oily thickener. The blending amount of (behenic acid / eicosane diacid) glyceryl is preferably 1 to 5% by mass.

(C) Poly (12-hydroxystearic acid) ester The poly (12-hydroxystearic acid) ester used in the present invention is a poly (12-hydroxystearic acid) ester. 12-hydroxystearic acid) with an acid chloride prepared by reacting a halogenating agent such as thionyl chloride.
Preferred examples of the polyhydric alcohol include propylene glycol, butanediol, pentanediol, (poly) glycerin, (poly) propylene glycol, and polyethylene glycol, and polyethylene glycol is particularly preferred. In this case, the polyethylene glycol preferably has an average molecular weight of 400 to 6000. On the other hand, it is preferable that the poly (12-hydroxystearic acid) to be a hydrophobic group has an average molecular weight of 1,000 to 3,000.
As the di (12-hydroxystearic acid) ester of polyethylene glycol, those listed under the INCI name PEG-30 dipolyhydroxystearate are preferable, and as commercial products, Alacel P-135 manufactured by Unichema, Clauda Japan And cis-roll DPHS manufactured by K.K. When PEG-30 dipolyhydroxystearate is blended, the content is preferably 0.1 to 3% by mass, particularly preferably 0.5 to 1% by mass. If the amount is less than 0.1% by mass, the effect of the present invention may not be sufficiently exerted. If the amount exceeds 3% by mass, a sticky feeling may be caused.

(D) Surfactant The emulsion type of the present invention is a water-in-oil type. The surfactant used for the emulsification may be any as long as the emulsification type is a water-in-oil type, but is blended separately from the aforementioned poly (12-hydroxystearic acid) ester (surfactant) of (C). I do. As the surfactant used in the present invention, silicone-branched polyether-modified silicone, silicone-branched alkyl co-modified polyether-modified silicone, silicone-branched polyglycerin-modified silicone, polyether-modified silicone, etc. A preferred example is a silicone-based surfactant.
Silicone branched polyether-modified silicone, a polydimethylsiloxane as a scaffold, polyether group of the polydimethylsiloxane skeleton represented by this _{-C 3 H 6 -O- (C 2} H 4 O) n H A plurality is bonded to Si as side chains. _That, -C ₂ H ₄ - is a _{(Si (CH 3) 2 O} ) n-Si (CH 3) compound silicone group represented by ₃ is more bound to Si polydimethylsiloxane backbone as side chains. Commercial products can be used for such a silicone-branched polyether-modified silicone. An example is PEG-9 polydimethylsiloxyethyl dimethicone (trade name: KF-6028) manufactured by Shin-Etsu Chemical Co., Ltd.
The silicone-branched alkyl co-modified polyether-modified silicone has polydimethylsiloxane as a skeleton, and a plurality of alkyl groups having 2 or more carbon atoms are bonded to Si of the polydimethylsiloxane skeleton as side chains. As a side _chain, polyether groups are more bound to Si of the same polydimethylsiloxane skeleton represented by _{-C 3 H 6 -O- (C 2} H 4 O) n H. Commercial products can be used as such a silicone-branched alkyl co-modified polyether-modified silicone. For example, Lauryl PEG-9 polydimethylsiloxyethyl dimethicone (trade name: KF-6038) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
The silicone-branched polyglycerin-modified silicone has polydimethylsiloxane as a skeleton, and a polyether group represented by —C ₃ H ₆ —O— (CH ₂ CH (OH) CH ₂ O) _n H is added to the above-mentioned polyether. It is one bonded to a plurality of Si in the dimethylsiloxane skeleton. Commercial products can be used as such a silicone-branched polyglycerin-modified silicone. For example, polyglyceryl-3 polydimethylsiloxyethyl dimethicone (trade name: KF-6104) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned. Examples of the polyether-modified silicone include PEG-9 dimethicone (trade name: KF-6019) manufactured by Shin-Etsu Chemical Co., Ltd.
Further, a silicone-based surfactant obtained by dissolving a high polymerization and low HLB poly (oxyethylene / oxypropylene) copolymer in cyclopentasiloxane is also preferably exemplified. For example, silicone BY22-008M manufactured by Dow Corning Toray Co., Ltd. may be used. Further, polyglycerin fatty acid esters can also be preferably exemplified. For example, polyglyceryl-2 triisostearate (trade name: EMALEX TISG-2), which is a triester of isostearic acid and diglycerin, may be mentioned.
The surfactants used in the present invention may be used alone or in combination of two or three. Further, the amount can be appropriately set.

(E) Oil agent Examples of the oil agent used in the present invention include oils and fats such as ester oil and vegetable oil, hydrocarbons, and silicone oil. It is preferably liquid at room temperature.
Examples of ester oils include cetyl ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di-2-ethylhexanoate, dipropylene glycol diisononanoate, dipropylene glycol di-2-ethylhexanoate, Examples include isononyl isononanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate, ethylhexyl palmitate, and isostearyl neopentanoate. Examples of oils and fats include liquid oils such as camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, and the like. Examples of the hydrocarbons include liquid paraffin, squalene, squalane, and the like. Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, and cyclic polysiloxanes such as decamethylcyclopentasiloxane and cyclopentasiloxane. Since oil separation does not occur by adopting the configuration of the present invention, (D) a large amount of oil agent can be blended. As a result, a moist feeling of use can be obtained even with a formulation containing a large amount of powder. In the present invention, the oil agent (D) preferably accounts for 20 to 50% by mass, more preferably 30 to 50% by mass.

  The viscosity of the water-in-oil emulsion composition of the present invention is 10,000 to 100,000 mPa when measured with a TV25 viscometer manufactured by Toki Sangyo Co., Ltd. (25 ° C., No. 4 rotor, 12 rpm, 30 seconds). -It is s.

  The water-in-oil emulsified composition of the present invention includes components commonly used in cosmetics, as long as the effects of the present invention are not impaired as optional components, such as organic powders, water-soluble polymers, and polyhydric alcohols. Humectants, salts, pH adjusters, preservatives, sequestering agents, medicinal ingredients, fragrances and the like. In addition, cosmetic ingredients such as ascorbic acid derivatives, ceramides and plant extracts can be added.

  As organic powder, polymer beads such as polymethyl methacrylate resin (PMMA), silicone resin powder such as polysilicone 1 crosspolymer, polyurethane powder, and the like can be blended.

  Water-soluble polymers include gum arabic, tragacanth gum, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, pullulan, carboxymethyl starch, collagen, casein, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, carboxy. Examples thereof include sodium methylcellulose, sodium alginate, and carboxyvinyl polymer.

  Examples of the polyhydric alcohol include glycerin, diglycerin, 1,2-pentanediol, dipropylene glycol, 1,3-butylene glycol and the like.

  Examples of the salts include sodium chloride and magnesium sulfate.

  Examples of the pH adjuster include citric acid, sodium citrate, phosphoric acid, sodium phosphate and the like.

  Examples of the preservative include methyl paraben, ethyl paraben and the like.

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

  Pharmaceutical components include vitamin A oil, vitamin A such as retinol, vitamin B6 such as riboflavin, B6 such as pyridoxine hydrochloride, L-ascorbic acid, L-ascorbic acid phosphate, and L-ascorbic acid monopalmitin. Acid esters, L-ascorbic acid dipalmitate, vitamin Cs such as L-ascorbic acid-2-glucoside, pantothenic acids such as calcium pantothenate, vitamin D6, vitamin Ds such as cholecalciferol, α-tocopherol, Vitamins such as vitamin Es such as tocopherol acetate and DL-α-tocopherol nicotinate can be exemplified.

  The water-in-oil emulsion composition of the present invention is optimally used as a base makeup cosmetic such as a makeup base or a base makeup foundation or a colored sunscreen cosmetic because of its properties. In addition, it can be used as a quasi-drug or pharmaceutical as an external preparation for skin.

Hereinafter, the present invention will be described in more detail by showing test examples using examples and comparative examples.
1. Preparation of Test Product A water-in-oil type milk composition (base makeup cosmetic) having a composition shown in Table 1 (Examples 1 to 6) and Table 2 (Comparative Examples 1 to 11) was prepared by the following preparation method.
Comparative Example 1 is a formulation in which (A) the organically modified clay mineral is not blended. Comparative Examples 2 and 3 are formulations in which (B) behenic acid / eicosantioic acid) glyceryl is not blended. Comparative Example 2 uses dextrin palmitate, which is an oily thickener, instead of glyceryl behenic acid / eicosantioic acid). It is a blended formula. Comparative Examples 4 to 11 are formulations that do not contain (C) poly (12-hydroxystearic acid) ester, whereas Comparative Example 4 increases the amount of surfactant (PEG-9 polydimethylsiloxyethyl dimethicone) originally formulated. Comparative Example 6 is a formulation further blended with an oil agent (polyhydroxystearic acid) which is said to have good powder dispersibility. Comparative Examples 7 to 10 are formulations in which (G) polyglyceryl-3 diisostearate and sorbitan sesquiisostearate are mixed instead of (C) poly (12-hydroxystearic acid) ester. Comparative Example 11 is a formulation in which the amount of the surfactant (polyglyceryl-2 triisostearate) originally formulated was increased.
Further, Pigment 1 and Pigment 2 in the table were separately described according to the particle diameter of the pigment. Pigment 2 was a fine particle pigment having a particle diameter of 50 nm or less, and Pigment 1 was a pigment of a normal size larger than that.

1. Preparation Method The oily component and the powder were mixed at room temperature and mixed for 5 minutes using a homomixer (3000 rpm). While adding the water-soluble component to the mixture, the mixture was mixed with a homomixer (3000 rpm), emulsified for 1 to 2 minutes, and further held for 5 minutes to complete the preparation.

2. Evaluation The water-in-oil emulsion compositions of Tables 1 and 2 were filled in a glass bottle with a lid (6K bottle) and stored in a thermostat at 5 ° C, 25 ° C, 40 ° C, and 50 ° C. It was opened and the filling surface was visually observed for the occurrence of oil separation. Further, the side surface of the glass bottle was observed to confirm whether or not white streaks were generated due to aggregation of the pigment.
Further, the day after the preparation, the viscosity was measured one month later. The viscosity was measured using a TV25 type viscometer manufactured by Toki Sangyo Co., Ltd. in an environment maintained at 25 ± 2 ° C. under conditions of a No. 4 rotor, 12 rpm, and 30 seconds. The unit of the viscosity in the table is mPa · s.
The stability (1. oil release, 2. white stripes) was visually evaluated for appearance according to the following evaluation criteria.
(Visual evaluation criteria)
1. Oil separation ○: No oil separation △: Very little oil separation ×: Clear oil separation White streaks ○: No white streaks △: Very few white streaks ×: White streaks are clear

3. Results The results are shown in Table 3 below.

1. Compositions of Examples 1 to 6 (A + B + C + D + E)
The compositions of the Examples were stable in appearance (white streaks, oil release) on the day after production and after storage for one month in a thermostat at 5 ° C, 25 ° C, 40 ° C, and 50 ° C. No abnormalities were observed.

2. Composition of Comparative Example 1 (B + C + D + E)
The composition of Comparative Example 1 is a formulation that does not contain the A organic modified clay mineral. Under any condition after storage in a thermostat at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for one month, abnormalities were observed in the stability (appearance of white stripes and oil separation) in appearance observation. Oil release and white streaks were observed after 2 weeks.

3. Composition of Comparative Example 2 (A + C + D + E)
The composition of Comparative Example 2 was a formulation in which dextrin palmitate, which is an oily thickener, was added in place of glyceryl B (behenic acid / eicosantioic acid). On the day after production, white streaks were observed after storage at 50 ° C., and then slight white streaks were observed even at 25 ° C. and 40 ° C. In Comparative Example 2, although no oil separation occurred, white stripes were generated, and thus the composition was not a desired composition.

4. Composition of Comparative Example 3 (A + C + D + E)
The composition of Comparative Example 3 was extremely low in viscosity, lower than the measurement limit, and was in the form of a liquid. Oil release and white streaks occurred.

5. Compositions of Comparative Examples 4 to 6 (A + B + D + E)
The composition of Comparative Example 4 did not contain poly (12-hydroxystearic acid) ester, and was one of the surfactants uniformly blended for emulsification in this test, PEG-9 polydimethylsiloxyethyl dimethicone. Was increased from 1% by mass to 2% by mass to test whether generation of white stripes can be suppressed. One month later, white streaks occurred in each temperature zone. Although no oil separation occurred in the composition of Comparative Example 4, the composition was not a desired composition because white streaks were generated.
Although the composition of Comparative Example 5 had no poly (12-hydroxystearic acid) ester, oil separation occurred at 50 ° C., and white stripes were observed in all temperature ranges. White streaks were slightly observed from the day after preparation (25 ° C.).
The composition of Comparative Example 6 contained 1% by mass of an oil agent (polyhydroxystearic acid), which is said to have a good powder dispersion without blending the poly (12-hydroxystearic acid) ester, and prepared a white stripe. The test was conducted to determine whether or not the occurrence of blemishes was suppressed. However, white streaks occurred after storage at 5 ° C., 40 ° C., and 50 ° C. for one month, and white streaks were slightly observed even after storage at 25 ° C. for one month. White streaks were slightly observed from the day after preparation (25 ° C.). Although no oil separation occurred in the composition of Comparative Example 6, the composition was not a desired composition because white streaks occurred.

6. Compositions of Comparative Examples 7 to 11 (A + B + D + E)
Comparative Examples 7 to 10 are formulations in which polyglyceryl-3 diisostearate and sorbitan sesquiisostearate were mixed instead of (C) poly (12-hydroxystearic acid) ester. Comparative Example 11 is a formulation in which polyglyceryl-2 triisostearate, which is one of the surfactants uniformly mixed for emulsification in this test, was increased from 1% by mass to 2% by mass.
In the composition of Comparative Example 7, white streaks were generated after storage at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for one month, and oil release was observed after storage at 50 ° C. for one month. White stripes at 25 ° C. were slightly observed from the day after the preparation, and one month later, white stripes were clearly observed.
The composition of Comparative Example 8 generated white streaks after one month of storage at 5 ° C, 25 ° C, 40 ° C, and 50 ° C. White streaks at 25 ° C were slightly observed from the day after the preparation. No oil separation occurred. This was not the desired composition because white streaks occurred.
In the composition of Comparative Example 9, white streaks were generated after storage at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for one month, and oil release was observed after storage at 50 ° C. for one month. White streaks at 25 ° C were slightly observed from the day after the preparation.
The composition of Comparative Example 10 had white streaks after one month of storage at 5 ° C, 25 ° C, 40 ° C, and 50 ° C. White streaks at 25 ° C were slightly observed from the day after the preparation. No oil separation occurred. This was not the desired composition because white streaks occurred.
In the composition of Comparative Example 11, white streaks occurred after storage at 5 ° C, 25 ° C, 40 ° C, and 50 ° C for one month. White streaks at 25 ° C. were clearly confirmed from the day after the preparation. No oil separation occurred.
From the results of Comparative Examples 4 to 11, it was found that the blending of (C) poly (12-hydroxystearic acid) ester was essential for suppressing the occurrence of white stripes.

Next, Examples 7 and 8 in which the amount of the pigment was further increased were prepared in the same manner, and the viscosity and stability were measured and evaluated. Table 4 shows the composition and the results.

(result)
In the water-in-oil emulsion composition of Example 7, the blending amount of the pigment was higher than Examples 1 to 6 and 8, and was 27% by mass. Further focusing on the blending amounts of the fine particle pigments of Examples 7 and 8, Example 7 has 16% by mass (14% by mass of fine particles of titanium oxide and 2% by mass of fine particles of zinc oxide), and Example 8 has 14% by mass ( 12% by mass of fine titanium oxide particles and 2% by mass of zinc oxide particles). Since Examples 1 to 6 are 7.5% by mass (5.5% by mass in terms of fine particles of titanium oxide and 2% by mass of fine particles of zinc oxide), the composition contains about twice or more of the fine particle pigment. Even with such a composition in which pigment aggregation is particularly likely to occur, Examples 7 and 8 show oil release and white streaks after storage for one month in each temperature zone (5 ° C, 25 ° C, 40 ° C, 50 ° C). Not at all. The viscosity on the day following preparation was 43860 mPa · s in Example 7, and 77700 mPa · s in Example 8.

  As described above, from the evaluation results of the preservation tests of Comparative Examples 1 to 11 and the evaluation results of Examples 1 to 8, in the water-in-oil emulsion composition containing a pigment at a high concentration, (A) the organically modified clay mineral and ( B) glyceryl (behenic acid / eicosantioic acid) and (C) a poly (12-hydroxystearic acid) ester, (D) a surfactant, and (E) a water-in-oil emulsion composition comprising an oil agent. It has been clarified that generation of oil can be prevented and generation of white stripes can be suppressed.

  The water-in-oil emulsion composition having the configuration of the present invention does not cause oil separation during storage, and further has white stripes and color unevenness caused by aggregation of finely divided pigments in a composition in which pigments having various particle diameters are mixed. No cosmetics were generated, and a highly stable cosmetic was obtained. By adopting the constitution of the present invention, even when stored under severe conditions of 50 ° C., oil release does not occur and white streaks and color unevenness do not occur. It is expected that fine particles such as fine particles of titanium oxide and fine particles of zinc oxide can be blended with high reliability. Therefore, the present invention is very useful as a product development technique for base makeup cosmetics and sunscreen cosmetics adjusted to skin color.

Claims (5)

In a water-in-oil emulsion composition containing 15 to 30% by mass of a pigment,
(A) Organically modified clay mineral (B) (Behenic acid / eicosantioic acid) glyceryl (C) Poly (12-hydroxystearic acid) ester (D) Surfactant (E) Water-in-oil emulsion containing oil agent Stuff.   The water-in-oil emulsion composition according to claim 1, wherein the (C) poly (12-hydroxystearic acid) ester is PEG-30 dipolyhydroxystearate.   The water-in-oil emulsion composition according to claim 1 or 2, wherein the pigment is prepared by mixing a plurality of metal oxides to adjust the color of human skin.   The pigment is at least six kinds selected from titanium oxide, yellow iron oxide, red iron oxide, black iron oxide, talc, pearl pigment, fine titanium oxide, fine zinc oxide, fine cerium oxide, and fine zirconium oxide. A water-in-oil emulsion composition according to any one of the above.   The water-in-oil emulsion composition according to any one of claims 1 to 4, which is a base makeup cosmetic or a sunscreen cosmetic.