JP6858510B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

The present invention relates to a water-in-oil emulsified cosmetic.

Conventionally, various surface-treated powders and the like have been used in order to obtain cosmetics having excellent long-lasting makeup.
For example, in Patent Document 1, a water-in-oil emulsified composition containing a siliconeized polysaccharide compound, a polyether-modified silicone, a silicone oil, a hydrophobic powder, ethyl alcohol, and water gives a refreshing feeling after application and is sticky. However, it is stated that it has excellent long-lasting makeup.

Japanese Unexamined Patent Publication No. 2001-278729

The present inventors have found that the water-in-oil emulsified cosmetic containing a siliconeized polysaccharide compound and a hydrophobic coloring pigment has excellent makeup retention, but has a filmy feeling on the skin after application and is further uneven. We found that it is easy, the skin after application is powdery, dry, and the makeup skin does not look beautiful.

By using a specific ester oil in combination with a water-in-oil emulsified cosmetic containing a siliconeized polysaccharide compound and a hydrophobic coloring pigment, the present inventors suppress the feeling of film on the skin after application. The finish of the skin after application is uniform, it looks glossy, the skin does not look powdery, and even after a long period of time, the skin does not look powdery and the makeup skin looks beautiful. I found.

In the present invention, the following components (A), (B) and (C):
(A) Siliconized polysaccharide compound 0.01 to 20% by mass,
(B) Ester oil selected from pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester liquid at 25 ° C. 0.01 to 30% by mass,
(C) Hydrophobicized coloring pigment 0.1 to 20% by mass
Concerning water-in-oil emulsified cosmetics containing.

The water-in-oil emulsified cosmetic of the present invention has no film feeling on the skin after application, the finish of the skin after application is uniform, looks glossy, and does not make the skin look powdery. Furthermore, the skin does not look powdery even after a long period of time has passed after application, and the skin and the makeup film easily follow, so that the makeup skin looks beautiful.

The siliconeized polysaccharide compound of the component (A) used in the present invention includes the following general formula (1).

(In the formula, Glu is a sugar residue of a polysaccharide compound, X is a divalent binding group, Y is a divalent aliphatic group, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² , R. ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms, respectively, or -OSiR ⁵ R ⁶ R ⁷ (R ⁵ , R ⁶ and R ⁷ are monovalent organic groups having 1 to 8 carbon atoms, respectively). Indicates a group, where a indicates 0, 1 or 2)
The ones represented by are mentioned.

In the general formula (1), Glu indicates a sugar residue of a polysaccharide compound, and various known polysaccharide compounds can be used as the polysaccharide compound. For example, cellulose, hemicellulose, arabic gum, tragant gum, tamarind gum, pectin, starch, mannan, guar gum, locust bean gum, quince seed gum, alginic acid, carrageenan, agar, xanthan gum, dextran, pullulan, chitin, chitosan, hyaluronic acid, chondroitin. In addition to sulfuric acid, derivatives of these polysaccharide compounds, such as carboxymethylation, sulfation, phosphorylation, methylation, ethylation, addition of alkylene oxides such as ethylene oxide and propylene oxide, acylation, cationization, and reduction in molecular weight, etc. Examples of the polysaccharide compound derivative obtained in the above. Of these, ethyl cellulose and pullulan are preferable, and pullulan is more preferable.
The average molecular weight of the polysaccharide compound varies depending on the type of the polysaccharide compound, but is usually preferably about 1,000 to 5,000,000.

X represents a divalent bonding group, and examples thereof include a carbamoyl group, -CH ₂ CH (OH)-, a carbonyl group, an amino group, an ether group, and the like, and from the viewpoint of reactivity, a carbamoyl group (-CONH-). ) Is preferable. In this case, the sugar residue of the polysaccharide compound means the remaining portion of the polysaccharide compound excluding the hydrogen atom of the hydroxyl group reacting with the isocyanate group. Also, in the case of other reactions, the sugar residue of the polysaccharide compound means something similar to this.

Examples of the divalent aliphatic group represented by Y include an alkylene group, an alkylene group having an oxygen atom, a nitrogen atom, a sulfur atom and the like in the main chain, and an alkylene group having an arylene group such as a phenylene group in the main chain. , An alkylene group having a carbonyloxy group or an oxycarbonyl group in the main chain and the like can be mentioned. These divalent aliphatic groups can have a substituent such as a hydroxy group, an alkoxy group or an alkyl group, and the terminal atom of the aliphatic group is a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. You may. As Y, for example, − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ −, − (CH ₂ ) ₄ −, − (CH ₂ ) ₆ −, − (CH ₂ ) ₈ −, − [CH ₂ CH (CH ₃ )] −, − (CH ₂ ) ₂ O (CH ₂ ) ₃ −, −CH ₂ CH (OH) −CH ₂ −, etc., preferably indicated by − (CH ₂ ) ₃ −. It is a propylene group.

In the general formula (1), examples of the monovalent organic group having 1 to 8 carbon atoms represented ^{by R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 include a methyl group and an ethyl group.} , Alkyl groups such as propyl group and butyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group; Aralkyl groups such as benzyl group; Alkenyl groups such as vinyl group and allyl group; 3,3 Examples thereof include an alkyl fluoride group such as a 3-torfluoropropyl group.

Further, R ² , R ³ and R ⁴ may be siloxy groups represented by −OSiR ⁵ R ⁶ R ^{7, respectively.} Examples of such a syroxy group include a trimethylsiloxy group, an ethyldimethylsiloxy group, a phenyldimethylsiloxy group, a vinyldimethylsiloxy group, a 3,3,3-trifluoropropyldimethylsiloxy group and the like.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different, but in the siliconeized polysaccharide compound (1) of the component (A), a = 0. Therefore, it is more preferable that R ² , R ³ , and R ^{4 are methyl groups.}

The siliconeized polysaccharide compound can be produced, for example, by the method described in JP-A-11-106310.

The siliconeized polysaccharide compound of the component (A) includes the following general formula (2).

(In the formula, Glu, Y, R ¹ , R ² , R ³ , R ⁴ and a are the same as above)
The one represented by is preferable.
Further, it is preferable that Glu is a glucose residue of pullulan. Further, it is preferable that a = 0 and R ² , R ³ and R ⁴ are methyl groups. Further, it is preferable that Y is a group represented by _{− (CH 2} ) _{3 −.}

As the siliconeized polysaccharide compound of the component (A), a siliconeized pullulan represented by the following general formula (3) is particularly preferable. In the general formula (3), PL represents a glucose residue of pullulan.

More specifically, the siliconeized pullulan is represented by the following general formula (4).

(In the formula, R represents a hydrogen atom or [(CH ₃ ) ₃ SiO] ₃ Si (CH ₂ ) ₃ NHCO group, in which case the degree of substitution is 0.1 to 2.0 and n is 100. The number is ~ 20,000. Here, the degree of substitution is the basic unit:

Substituents attached to [(CH ₃ ) ₃ SiO] ₃ Si (CH ₂ ) ₃ Indicates the average number of NHCO groups added)

This siliconeized pullulan is produced from pullulan, which is a kind of water-soluble polysaccharide, as a raw material. This pullulan is a water-soluble exopolysaccharide biosynthesized by Aureobasidium pullulans, a water-soluble, neutral linear glucan consisting of D-glucopyranose residues. The molecular weight of the pullulan molecule varies depending on the culture conditions of the above-mentioned cells and the strain of the bacteria, but the molecular weight of pullulan that can be used as a raw material for the siliconeized pullulan used in the present invention is 50,000 to 1,000,000. Is desirable.

Siliconized pullulan is produced from pullulan by, for example, the method described in Japanese Patent Application Laid-Open No. 8-134103, that is, by reacting the hydroxyl group of pullulan with an organopolysiloxane containing an isocyanate group. It is possible to manufacture by using the method of. At that time, the degree of substitution of the siliconeized pullulan is 0.1 to 2.0, preferably 1.5 to 1.9.

As such a siliconeized pullulan, for example, commercially available products such as TSPL-30-D5 (manufactured by Shin-Etsu Chemical Co., Ltd.) and TSPL-30-ID (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

As the component (A), one type or two or more types can be used, and the content is such that a sufficient decorative coating film can be obtained, the decorative film after application is soft, and the coating film has excellent followability to the skin. From the viewpoint of suppressing the feeling, it is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, 20% by mass or less, and preferably 12% by mass or less in the total composition. , 6% by mass or less is more preferable. The content of the component (A) is 0.01 to 20% by mass, preferably 0.1 to 12% by mass, and more preferably 1 to 6% by mass in the total composition.

The ester oil of the component (B) is selected from pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester which are liquid at 25 ° C.
The liquid is a fluid, and is a liquid or a paste at 25 ° C. Of these, a liquid at 25 ° C. is preferable.

The fatty acid constituting the pentaerythritol fatty acid ester and the dipentaerythritol fatty acid ester may be either a saturated fatty acid or an unsaturated fatty acid, and may be either a linear fatty acid or a branched chain fatty acid, but has adhesion to the skin and oxidation of the compound. From the viewpoint of stability and the like, it is preferable to use saturated fatty acids. Moreover, these fatty acids may have a hydroxy group. Examples of such fatty acids include caproic acid, caprylic acid, 2-ethylhexanoic acid, isononanic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, and behen. Examples thereof include acids, lignoseric acid, serotic acid, montanic acid, and melisinic acid. Further, among the saturated fatty acids, saturated fatty acids having 16 to 28 carbon atoms are preferable. Examples of such fatty acids include palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid and the like. Further, saturated fatty acids having 16 to 22 carbon atoms are more preferable, and examples thereof include palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, and behenic acid.
Specific examples thereof include dipentaerythrityl tripolyhydroxystearate, dipentaerythrityl pentaisostearate, dipentaerythrityl tetraisostearate, and pentaerythrityl (behenic acid / polyhydroxystearic acid).

The component (B) preferably has a hydroxyl group, and examples thereof include those having hydroxystearic acid, from the viewpoint of suppressing the film feeling of the skin after application and excellent followability between the skin and the cosmetic film.
Specific examples thereof include dipentaerythrityl tripolyhydroxystearate and pentaerythrityl (behenic acid / polyhydroxystearic acid).
Alcohol, which constitutes component (B), makes the skin look uniform after application, glossy, and does not make the skin look powdery, so that it suppresses the feeling of dryness after makeup, and a long time has passed after application. Pentaerythritol and dipentaerythritol are preferred because the skin does not look powdery even afterwards. Among them, dipentaerythritol is preferable.
As the component (B), dipentaerythritol fatty acid ester is preferable, and dipentaerythritol tripolyhydroxystearate is more preferable.

As the dipentaerythrityl tripolyhydroxystearate, commercially available products such as Saracos WO-6 (manufactured by Nisshin Oillio Co., Ltd.) and as the dipentaerythrityl pentaisostearate, Saracos DP-518N (manufactured by Nisshin Oillio Co., Ltd.) can be used.
Further, dipentaerythrityl tetraisostearate and pentaerythrityl (behenic acid / polyhydroxystearic acid) can be produced according to a known method, and can be produced, for example, by the method described in the following production example.

As the component (B), one type or two or more types can be used, and the content is included in the entire composition from the viewpoint that the skin after application looks uniform, glossy, and the skin does not look powdery. It is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 30% by mass or less, preferably 15% by mass or less, and more preferably 4% by mass or less. The content of the component (B) is 0.01 to 30% by mass, preferably 0.1 to 15% by mass, and more preferably 0.3 to 4% by mass in the total composition.

In the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is such that the skin after application looks uniform, glossy, and the skin does not look powdery. 0.1 or more is preferable, and 0.4 or more is preferable, because the dry feeling of the skin is suppressed, the skin does not look powdery even after a long time has passed after application, and the skin and the cosmetic film easily follow. More preferably, 1 or more is further preferable, 50 or less is preferable, 20 or less is more preferable, and 6 or less is further preferable. The mass ratio (A) / (B) of the component (A) to the component (B) is preferably 0.1 to 50, more preferably 0.4 to 20, and even more preferably 1 to 6.

The coloring pigment of the component (C) used in the present invention is hydrophobized.
The coloring pigment to be treated may be any pigment used in ordinary cosmetics, for example, titanium oxide, zinc oxide, yellow iron oxide, red iron oxide, black iron oxide, dark blue, ultramarine blue, chromium oxide, hydroxide. Metal oxides such as chromium; Metal complexes such as manganese violet and cobalt titanate; Inorganic pigments such as carbon black; Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red 205, Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 405, Red 505, Orange 203, Orange 204, Orange 205, Yellow 4 , Blue No. 1 and other synthetic organic pigments; natural organic pigments such as β-carotene, caramel and paprika pigments.
Of these, one or more selected from titanium oxide, yellow iron oxide, red iron oxide, and black iron oxide are preferable.

In order to hydrophobize the coloring pigment, a known hydrophobizing agent and a known hydrophobizing method may be used. For example, a surface treatment agent such as a fluorine compound, a silicone compound, a metal soap or an oil agent is used, and a dry method is used. Treatment, wet treatment, etc. may be performed.
Specific examples of the surface treatment agent include fluorine compounds such as perfluoroalkyl phosphate and perfluoroalkyl alkoxysilane; methylhydrogen polysiloxane, cyclic silicone, and one-terminal or both-terminal trialkoxy group-modified organopolysiloxane. Silicone-based compounds; metal soaps such as aluminum stearate and zinc stearate, and amino acid-based compounds such as lauroyl lysine can be mentioned.
Of these, fluorine compound treatment and silicone treatment are preferable.

As the fluorine compound, tridecafluorooctyltriethoxysilane represented by the following formula is preferable.
F ₃ C − (CF ₂ ) ₅ − (CH ₂ ) _{2 −} Si − (OCH ₂ CH ₃ ) ₃
Among the fluorine compounds that surface-treat the powder, by using the powder that has been surface-treated with tridecafluorooctyltriethoxysilane, it has excellent stability, fits well on the skin, suppresses the feeling of tension and unevenness, and is moist. You can get a good feeling of use. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.

The amount of treatment varies depending on the coloring pigment, but from the viewpoint that water repellency and oil repellency are sufficiently exhibited and the feel is good, 0.05 mass by mass with respect to 100% by mass of the hydrophobized coloring pigment of the component (C). % Or more is preferable, 0.1% by mass or more is more preferable, 50% by mass or less is preferable, and 20% by mass or less is more preferable. When these viewpoints are put together, the treatment amount is preferably 0.05 to 50% by mass, preferably 0.1 to 20% by mass, based on 100% by mass of the hydrophobized coloring pigment of the component (C). More preferred.

As the component (C), one type or two or more types can be used, and the content is 0.1 mass in the entire composition from the viewpoint of appropriate covering power to the skin immediately after application and good familiarity with the skin. % Or more, preferably 1% by mass or more, more preferably 5% by mass or more, 20% by mass or less, preferably 17% by mass or less, more preferably 13% by mass or less, still more preferably 11% by mass or less. The content of the component (C) is 0.1 to 20% by mass, preferably 1 to 17% by mass, more preferably 5 to 13% by mass, still more preferably 5 to 11% by mass in the total composition. ..

In the present invention, the mass ratio (C) / (B) of the component (C) to the component (B) makes the skin look uniform, glossy and smooth after application, and the skin does not look powdery. Therefore, 1 or more is preferable, and 2 or more is preferable because the dry feeling after makeup is suppressed, the skin does not look powdery even after a long time has passed after application, and the skin and the makeup film easily follow. More preferably, 4 or more is further preferable, 80 or less is more preferable, 40 or less is more preferable, and 20 or less is further preferable. The mass ratio (C) / (B) of the component (C) to the component (B) is preferably 1 to 80, more preferably 2 to 40, and even more preferably 4 to 20.

The water-in-oil emulsified cosmetic of the present invention can further contain an oil component that is liquid at 25 ° C. in addition to the component (B). It is an oily component having fluidity at 25 ° C., and as long as it has fluidity, a paste-like oily component is also included.
The oil component liquid at 25 ° C. may be any one used in ordinary cosmetics, for example, liquid paraffin, light isoparaffin, liquid isoparaffin, mineral oil, polybutene, polyisobutene, hydrogenated polydecene, squalane, squalane and the like. Linear or branched hydrocarbon oils; avocado oil, macadamia nut oil, olive oil, rapeseed oil, sesame oil, wheat germ oil, flaxseed oil, cottonseed oil, soybean oil, palm oil, palm oil, caprylic acid, jojoba oil, sunflower oil, Vegetable oils such as camellia oil and corn oil; animal oils such as liquid lanolin; isopropyl myristate, octyldodecyl myristate, isopropyl isostearate, isononyl isononanoate, butyl stearate, oleyl oleate, isotolideyl isononanoate, isostearyl myristate, lysinorain Octyldodecyl acid, octyl hydroxystearate, diglyceryl monoisostearate, ethylhexyl palmitate, cetyl ethylhexanate, octyl methoxycinnamate, tocopherol acetate, propylene carbonate, diisostearyl malate, propylene glycol dicaprylate, neo dicaprate Pentyl glycol, neopentyl glycol diethylhexanoate, diglyceryl diisostearate, propanediol diisostearate, glyceryl monomyristate monoisostearate, glyceryl diisostearate, glyceryl triisostearate, di (capric acid / caprylic acid) propanediol, tri ( Caprylic acid / capric acid) glyceryl, glyceryl tri2-ethylhexanoate, triethylhexanoin, trimethylhexanoate tri-2-ethylhexanoate, trimethylrolpropane triisostearate, pentaerythrityl tetraoctanoate, pentaerythritetraethylhexanoate Slit, pentaerythritol tetraisostearate, polyglyceryl-2 isostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 triisostearate, polyglyceryl-2 tetraisostearate, polyglyceryl octacaprylate-6, ditrimethylol (isostearic acid / sebacic acid) Propane oligoester, di lauroyl glutamate (phytosteryl / octyldodecyl), di lauroyl glutamate (phytosteryl behenyl octyldodecyl), trehalose isostearate, Fatty acid esters such as ethylhexyl hydroxystearate, phytosterol fatty acid ester, cholesterol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, dl-α-tocopherol, dl-α-tocopherol nicotinate; higher alcohols such as octyldodecanol; diphenyl Silicone oils such as dimethicone, dimethylpolysiloxane, methylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane, tris (trimethylsiloxy) methylsilane; fluoropolyether, perfluoroalkyl ether silicone, etc. Fluorine oil; 2-ethylhexyl paramethoxysilicate, propylene carbonate; as cream or paste, trilanolin fatty acid glyceryl, soft lanolin fatty acid, vaseline, branched or hydroxylated fatty acid cholesteryl, isostearic acid-hardened castor oil, monohydroxysteer Acid-cured castor oil, tri (capril, caprin, myristine, stearic acid) glyceride, myristyl lactate, dimer dilinoleic acid hydrogenated castor oil, dimer dilinoleic acid (phytorteryl / isostearyl / cetyl / stearyl / behenyl), phytosteryl oleate , Di (phytosteryl, behenyl, octyldodecyl) lauroyl glutamate and the like.

One or more of these oil components liquid at 25 ° C. can be used, and the content is preferably 5% by mass or more in the total composition from the viewpoint of excellent adhesion between the powder and the skin. 20% by mass or more is more preferable, 30% by mass or more is further preferable, 70% by mass or less is more preferable, 60% by mass or less is more preferable, and 45% by mass or less is further preferable. The content of the oil component liquid at 25 ° C. is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 45% by mass in the total composition.

In the present invention, the content of water in the total composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 70% by mass or less, and more preferably 50% by mass or less. It is preferable, and 30% by mass or less is more preferable. The water content is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass in the total composition.

In addition to the above components, the water-in-oil emulsified cosmetic of the present invention contains components usually used in cosmetics, such as powders other than the above, oily components other than the above, surfactants, water-soluble polymers, and antioxidants. It can contain agents, fragrances, pigments, preservatives, thickeners, pH regulators, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, moisturizers, refreshing agents and the like.

The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and can be made into a liquid, emulsion, paste, cream, gel or other dosage form, liquid, emulsion, etc. Creamy is preferable.
The water-in-oil emulsified cosmetic of the present invention is a makeup base, foundation, concealer; makeup cosmetics such as blusher, eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as an ultraviolet protective cosmetic such as a sunscreen cream. Of these, makeup bases and foundations are more preferable.
The water-in-oil emulsified cosmetic of the present invention can be used alone or in the layering of powder cosmetics such as liquid foundation, powder foundation and white powder.

Production Example 1 (Production of (behenic acid / polyhydroxystearic acid) pentaerythrityl)
(1) 12-Hydroxystearic acid (manufactured by Ogura Synthetic Industry Co., Ltd., trade name "12-hydroic acid HP") in a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a water separator. Purity: 99% by mass) 540 g was charged, 0.1% of the total charged amount of tin chloride was added as a catalyst, and 5% of the total charged amount of xylene was added as a reflux solvent, and the generated water was removed under a nitrogen stream. The reaction was carried out at a temperature of 200 ° C. for 15 hours to obtain a 12-hydroxystearic acid polymer. When the acid value of the obtained polymer was measured, the acid value was 19.4 mgKOH / g, and the average degree of polymerization calculated from the acid value was 10.2. Therefore, the obtained product was 12-hydroxy. It was a stearic acid depolymer.

(2) Next, the 12-hydroxystearic acid polymer obtained as described above (acid value: 19) was placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a water separator. .4 mgKOH / g, 10-mer) 514 g, bechenic acid (manufactured by Unichema, trade name "PRIFRAC2989") 82 g and pentaerythritol (manufactured by Lee Choei Chemical Industry Co., Ltd., trade name "pentaerythritol") 16 g are added under a nitrogen stream. The reaction was carried out at a temperature of 210 ° C. while removing the produced water until the acid value of the product became 1.4 mgKOH / g or less.
After completion of the reaction, the catalyst is filtered off, then decolorized with activated clay, deodorized by a conventional method, and a paste-like esterification reaction product (tetra (poly 12-hydroxystearic acid / behenic acid)) at room temperature. ) Pentaerythrityl) 246 g was obtained.
The acid value of the obtained esterification reaction product was 1.6 mgKOH / g, and the hydroxyl value was 21 mgKOH / g. The molar ratio (%) of the heptameric or higher 12-hydroxystearic acid polymer in the fatty acid residue of the obtained esterification reaction product was 43%, and the molar ratio (%) of behenic acid was 57%. Is.

Production Example 2 (Production of dipentaerythrityl tetraisostearate)
Dipentaerythritol [trade name: Dipentalit, manufactured by Koei Chemical Industries, Ltd.] 58.4 g (0.23 mol) in a 3 L 4-flask equipped with a stirrer, a thermometer, a nitrogen gas blowing pipe and a water separation pipe. 2- (1,3,3-trimethyl) butyl-5,7,7-trimethyloctanoic acid [trade name: isostearic acid, manufactured by Nissan Chemical Industries, Ltd.] 293.9 g (1.03 mol) was charged (raw material preparation). Mass ratio = 10: 50.3). Then, 0.05% by mass of dibutyltin oxide (catalyst) and 5% by mass of xylene (reflux solvent) were added to the total amount charged, and the reaction was carried out at 200 to 250 ° C. for about 21 hours with stirring. After completion of the reaction, xylene, which is a reflux solvent, was distilled off under reduced pressure. The reaction product from which xylene was removed was adsorbed with activated clay, then cooled to about 60 ° C., filtered, and deodorized and distilled by a conventional method to obtain 245 g of dipentaerythrityl tetraisostearate.
The acid value of dipentaerythrityl tetraisostearate was 0.2, the hydroxyl value was 81, the freezing point was -16 ° C, and it did not fog even at -30 ° C. The viscosity at 25 ° C. was 350,000 mPa · s, and it was liquid at 25 ° C. The viscosity was determined by using a Brookfield type viscometer (BH type) at 25 ° C. 6 was used and measured at 2 rpm.

Examples 1-9 and Comparative Examples 1-4
We manufacture water-in-oil emulsified cosmetics (foundations) with the compositions shown in Table 1, "no film feeling after application", "skin looks uniform after application", and "skin after application is glossy". "Looks like", "Skin does not look powdery after application", "Skin does not look powdery after 5 hours of application" and "Easy to follow skin and makeup film after 5 hours of application" Was evaluated. The results are also shown in Table 1.

(Manufacturing method)
The powder phase component was mixed and pulverized, added to the separately mixed oil phase component, and dispersed at a disper (2000 rpm) for 10 minutes. Then, the aqueous phase component was added, and the mixture was stirred with a disper (800 rpm) for 10 minutes, and finally the viscosity was adjusted with a homomixer to obtain a water-in-oil emulsified cosmetic.

(Evaluation method)
When five specialist panelists applied each water-in-oil emulsified cosmetic to their skin, they said, "No film feeling after application,""Skin looks uniform after application," and "Skin after application is glossy.""It looks soft", "Skin does not look powdery after application", "Skin does not look powdery after 5 hours of application" and "Easy to follow the skin and makeup film after 5 hours of application" The sensory evaluation was performed based on the following criteria. The result is shown by the integrated value of 5 people.

(1) No film feeling after application:
5; There is no feeling of film on the skin after application.
4; There is no feeling of film on the skin after application.
3; There is not much feeling of film on the skin after application.
2; There is a slight film feeling on the skin after application.
1; There is a considerable feeling of film on the skin after application.

(2) The skin looks even after application:
5; The skin after application looks fairly uniform.
4; The skin looks even after application.
3; The skin after application looks slightly uniform.
2; The skin after application does not look very uniform.
1; The skin does not look uniform after application.

(3) The skin looks glossy after application:
5; The skin after application looks quite glossy.
4; The skin after application looks glossy.
3; The skin after application looks slightly glossy.
2; The skin after application does not look very glossy.
1; The skin does not look glossy after application.

(4) The skin does not look powdery after application:
5; There is no powdery skin after application.
4; There is no powdery skin after application.
3; There is not much powderiness on the skin after application.
2; The skin is slightly powdery after application.
1; There is considerable powderiness on the skin after application.

(5) The skin does not look powdery after 5 hours of application:
5; There is no powdery skin after the lapse.
4; There is no powdery skin after the lapse.
3; There is not much powderiness of the skin after the lapse.
2; There is a slight powderiness of the skin after the lapse.
1; There is considerable powderiness of the skin after the lapse.

(6) Ease of following the skin and makeup film after 5 hours of application:
5; The followability of the skin and the cosmetic film after the lapse is very good.
4; Good followability of the skin and makeup film after the lapse.
3; The followability of the skin and the cosmetic film after the lapse is slightly good.
2; The followability of the skin and the cosmetic film after the lapse is not very good.
1; The followability of the skin and the cosmetic film after the lapse is not good.

Example 10
A water-in-oil emulsified cosmetic (foundation) having the composition shown in Table 2 was produced in the same manner as in Examples 1 to 9.
The obtained foundation has no film feeling on the skin after application, the finish of the skin after application is uniform, looks glossy, and the skin does not look powdery, and after 5 hours of application, However, the skin does not look powdery, and the skin and the makeup film easily follow, so the makeup skin looks beautiful.

Claims (6)

The following components (A), (B) and (C):
(A) Siliconized polysaccharide compound 0.01 to 20% by mass,
(B) Ester oil selected from pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester liquid at 25 ° C. 0.01 to 30% by mass,
(C) Hydrophobicized coloring pigment 0.1 to 20% by mass
A water-in-oil emulsified cosmetic having a mass ratio (A) / (B) of the component (A) to the component (B) of 0.4 to 20. The component (A) is the following general formula (1)

(In the formula, Glu is a sugar residue of a polysaccharide compound, X is a divalent binding group, Y is a divalent aliphatic group, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² , R. ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms, respectively, or -OSiR ⁵ R ⁶ R ⁷ (R ⁵ , R ⁶ and R ⁷ are monovalent organic groups having 1 to 8 carbon atoms, respectively). Indicates a group, where a indicates 0, 1 or 2)
The water-in-oil emulsified cosmetic according to claim 1, which is a siliconeized polysaccharide compound represented by. The water-in-oil emulsified cosmetic according to claim 2, wherein Glu is a glucose residue of pullulan in the general formula (1). The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the component (B) has a hydroxyl group. The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, wherein the component (B) is a dipentaerythritol fatty acid ester. The water-in-oil emulsified cosmetic according to any one of claims 1 to 5 , wherein the mass ratio (C) / (B) of the component (C) to the component (B) is 1 to 80.