JP6630499B2 - UV protection cosmetics - Google Patents

Description

  The present invention relates to an ultraviolet protection cosmetic.

Sunburn due to ultraviolet rays promotes browning of the skin, lowering of the elasticity of the skin, generation of wrinkles, and the like. To prevent these, cosmetics containing an ultraviolet absorber have been used.
Among the UV absorbers, oil-soluble UV absorbers have an excellent effect of absorbing ultraviolet rays, but when combined with cosmetics as they are, there are problems in terms of usability, such as irritability and stickiness. there were.
For this reason, cosmetics in which an ultraviolet absorber is blended in a fine emulsion or encapsulated and blended have been studied (for example, Patent Literature 1, Patent Literature 2, Patent Literature 3).

JP 2012-31125 A JP-T-2005-504750 JP 2009-167168 A

However, conventional cosmetics containing an ultraviolet absorber have poor storage stability and are not sufficiently satisfactory in terms of feeling of use.
In addition, when a cosmetic containing an ultraviolet absorber was applied to the skin, the ultraviolet absorber did not uniformly adhere to the skin, so that a sufficient ultraviolet protection effect could not be obtained. Even when a large amount of an ultraviolet absorber is blended in order to enhance the ultraviolet protection effect, there have been problems in terms of storage stability and usability.
TECHNICAL FIELD The present invention relates to an ultraviolet protective cosmetic in which an oil agent containing an ultraviolet absorbent is uniformly dispersed, has excellent storage stability, has a high ultraviolet protective effect, has a good feeling in use, and has no skin irritation.

  The present inventors combine a ionic surfactant, a hydrophobic amphiphilic substance, a liquid oil containing an oil-soluble ultraviolet absorber, and a solid oil in a specific ratio, and a cosmetic obtained by a specific method is an oil. It has been found that α-gel particles containing a soluble ultraviolet absorber are dispersed, are excellent in storage stability, have a high ultraviolet protection effect, have a good feeling in use, and have no skin irritation.

The invention comprises the following components (A), (B), (C), (D) and (E):
(A) ionic surfactant 0.18 to 2% by mass,
(B) a hydrophobic amphiphile 1 to 10% by mass,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) solid oil agent 0.01 to 6% by mass,
(E) UV protection cosmetics containing water,
An emulsifying step of mixing the composition containing components (A) to (D) with water under heating (E) to form an emulsion;
The present invention relates to an ultraviolet protection cosmetic obtained by a method including a cooling step of cooling the emulsion formed in the emulsification step at a cooling rate of 0.5 to 5 ° C./sec.

  In the ultraviolet protection cosmetic composition of the present invention, α-gel particles containing an oil-soluble ultraviolet absorber are dispersed and storage stability is good. Further, when applied to the skin, the oil-soluble ultraviolet absorber uniformly adheres to the skin, provides a high UV protection effect, is not sticky, has a good feeling upon use, and has no skin irritation.

It is the schematic which shows the vibration-type stirring mixing apparatus suitable for manufacturing the cosmetics of this invention. FIG. 2 is a schematic view of a vertical cross section of the vibration type stirring and mixing device shown in FIG. 1. FIG. 2 is an enlarged view of a main part of a stirrer in the vibration type stirring and mixing device shown in FIG. 1.

The ionic surfactant of the component (A) used in the present invention is used for ordinary cosmetics, and anionic surfactants, cationic surfactants, amphoteric surfactants, sphingosine and salts thereof can be used.
Examples of the anionic surfactant include fatty acid salts having 12 to 24 carbon atoms such as sodium laurate, potassium palmitate and arginine stearate; alkyl sulfate salts such as sodium lauryl sulfate and potassium lauryl sulfate; polyoxyethylene lauryl sulfate Alkyl ether sulfates such as triethanolamine; N-acyl sarcosine salts such as sodium lauroyl sarcosine; fatty acid amide sulfonates such as N-myristoyl-N-methyltaurine sodium; alkyl phosphates such as sodium monostearyl phosphate Polyoxyethylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether phosphate and sodium polyoxyethylene stearyl ether phosphate; di-2-ethylhexyl sulfosuccinic acid Long-chain sulfosuccinates such as thorium; sodium dilauroylglutamate, monosodium N-lauroylglutamate, sodium N-stearoyl-L-glutamate, N-stearoyl-L-arginine glutamate, sodium N-stearoylglutamate, N-myristoyl-L -Long-chain N-acyl glutamates such as sodium glutamate;
Among these, a long-chain N-acyl glutamate is preferred from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic and improving the feeling of use, particularly reducing stickiness.

  As the cationic surfactant, a quaternary ammonium salt is preferable, and examples thereof include alkyltrimethylammonium chloride salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride; dialkyldimethylammonium, trialkylmethylammonium chloride, and alkylamine salts. Can be

  Examples of the amphoteric surfactant include alkyldimethylamine oxide, alkylcarboxybetaine, alkylsulfobetaine, amide amino acid salts, and alkylamidopropylbetaine, and alkylamidopropylbetaine is preferred.

Examples of sphingosine and its salts include natural sphingosine, dihydrosphingosine, phytosphingosine, sphingdienin, dehydrosphingosine, dehydrophytosphingosine, and N-alkyl compounds (for example, N-methyl compounds) thereof.
These may be either natural extracts or synthetic ones, and commercially available ones can be used. Examples of commercially available natural sphingosine include D-Sphingosine (4-Sphingenine) (SIGMA-ALDRICH), DS-phytosphingosine (DOOSAN), and phytosphingosine (Cosmo Farm).

  Examples of the sphingosine salts include acidic amino acid salts such as glutamic acid and aspartic acid; basic amino acid salts such as arginine; inorganic acid salts such as phosphoric acid and hydrochloric acid; monocarboxylic acid salts such as acetic acid; Dicarboxylates; oxycarboxylates such as citric acid, lactic acid and malic acid; and one or more selected from these are preferred.

As the ionic surfactant of the component (A), at least one selected from an anionic surfactant and sphingosine from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic and improving the feeling of use, particularly reducing stickiness. One type is preferred, and an anionic surfactant is more preferred.
Among the anionic surfactants, it is preferable to include a long-chain N-acyl glutamate, and among the long-chain N-acyl glutamates, sodium dilauroylglutamate, monosodium N-lauroylglutamate, N-stearoyl-L- Sodium glutamate, N-stearoyl-L-glutamate arginine, N-stearoyl sodium glutamate, at least one selected from N-myristoyl-L-sodium glutamate are preferred, and sodium N-stearoyl glutamate, N-stearoyl-L-glutamate are preferred. At least one selected from them is more preferred, and N-stearoyl-L-arginine glutamate is still more preferred.

The component (A) can be used alone or in combination of two or more, and the content is from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic and improving the feeling of use, particularly reducing the stickiness. 0.18% by mass or more in the total composition, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and 0.45% by mass or more. It is still more preferably 2% by mass or less, preferably 1.5% by mass or less, more preferably 1.1% by mass or less, still more preferably 0.9% by mass or less, even more preferably 0.7% by mass or less. . Further, the content of the component (A) is 0.18 to 2% by mass, preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.1% by mass in the whole composition, 0.4-0.9 mass% is still more preferred, and 0.45-0.7 mass% is even more preferred.
In the present invention, the component (A) is a content as an acid.
In addition, a nonionic surfactant can be contained within a range that does not impair the effects of the present invention. However, from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic, the feeling of use is improved, and especially the tackiness is reduced. From the viewpoint, the content of the nonionic surfactant is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and substantially 0% by mass in the whole composition. Even more preferred.

  Examples of the hydrophobic amphiphilic substance of the component (B) used in the present invention include ceramides, alcohols having 10 to 24 carbon atoms, linear saturated fatty acids having 10 to 24 carbon atoms, and 10 to 24 carbon atoms. Mono-fatty acid glycerin esters, mono-alkyl glyceryl ethers having 10 to 24 carbon atoms, mono-fatty acid sorbitan esters having 10 to 24 carbon atoms, mono-fatty acid sorbit esters having 10 to 24 carbon atoms, and the like are exemplified.

  As the ceramides, one or more selected from natural ceramides and pseudo-ceramides can be used. From the viewpoint of improving the storage stability of the ultraviolet protection cosmetic, specifically, ceramides described in JP-A-2013-53146 are preferred.

  Specific examples of natural ceramides include ceramides Type 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine or sphingdienin are amidated (for example, FIG. 2 of J. Lipid Res., 24: 759 (1983), And J. Lipid. Res., 35: 2069 (1994), porcine and human ceramides described in FIG. 4).

Furthermore, these N-alkyl forms (for example, N-methyl forms) are also included.
These ceramides use a natural (D (-) form) optically active substance or an unnatural (L (+) form) optically active substance, and furthermore, a mixture of a natural form and a non-natural form. May be used. The relative configuration of the above compound may be a natural configuration, another non-natural configuration, or a mixture thereof. In particular, a compound of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II (the above, INCI, 8th Edition) and a compound represented by the following formula are preferable.

  These may be either natural extracts or synthetic ones, and commercially available ones can be used. Commercially available such natural ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (all above, Cosmo Farm), Ceramide TIC-001 (Takasago Perfume), CERAMIDE II (Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN) and CERAMIDE2 (Sedama).

  As the pseudo-ceramide, a pseudo-ceramide represented by the following general formula (1) is preferable from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic.

(Wherein, R ¹ represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group or a hydrogen atom having 10 to 22 carbon atoms which may be substituted by a hydroxyl group; X ¹ is a hydrogen atom Represents an acetyl group or a glyceryl group; R ² represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted by a hydroxyl group or an amino group; or the ω-terminal of the hydrocarbon group, those hydroxyl groups are saturated or unsaturated fatty acid, linear or branched chain having 8 to 22 carbon atoms which may be substituted with an ester bond; R ³ is a hydrogen atom Or an alkyl group having a total carbon number of 1 to 30 which may be substituted by a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group.)

  Among these, pseudo-ceramide represented by the following formula is more preferable from the viewpoint of improving the storage stability of the ultraviolet protection cosmetic.

R ¹ is a hexadecyl group, X ¹ is a hydrogen atom, R ² is a pentadecyl group, and R ³ is a hydroxyethyl group; R ¹ is a hexadecyl group, X ¹ is a hydrogen atom, and R ² is a general formula (1). Pseudo-type ceramides in which a nonyl group and R ³ are hydroxyethyl groups are preferable, and R ^{1 in the} general formula (1) is a hexadecyl group, X ¹ is a hydrogen atom, R ² is a pentadecyl group, and R ³ is a hydroxyethyl group ( N- (hexadecyloxyhydroxypropyl) -N-hydroxyethylhexadecanamide) is more preferred. Further, pseudo-ceramides (i) and (ii) represented by the following formulas are also preferable.

  Examples of the alcohol having 10 to 24 carbon atoms include myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol. Among these, those having a straight-chain alkyl group are preferred, alcohols having 16 to 18 carbon atoms are more preferred, and at least one or two or more selected from cetyl alcohol and stearyl alcohol are still more preferred, including cetyl alcohol and stearyl alcohol. Is even more preferred.

  Examples of the straight-chain saturated fatty acid having 10 to 24 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Among these, from the viewpoint of the storage stability of the ultraviolet protection cosmetic and the viewpoint of improving the ultraviolet protection effect, linear saturated fatty acids having 14 to 22 carbon atoms are preferable, and linear saturated fatty acids having 16 to 22 carbon atoms are preferable. More preferably, it further preferably contains at least one selected from palmitic acid and stearic acid.

  Examples of the mono-fatty acid glycerin ester having 10 to 24 carbon atoms include glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate, Glycerin monoisostearate and the like. Of these, at least one or two or more selected from glycerin monobehenate, glycerin monostearate, and glycerin monopalmitate are preferable, and glycerin monobehenate is more preferable.

  Examples of the monoalkyl glyceryl ether having 10 to 24 carbon atoms include monodecyl glyceryl ether, monolauryl glyceryl ether, monomyristyl glyceryl ether, monocetyl glyceryl ether, monostearyl glyceryl ether, and monobehenyl glyceryl ether.

  Examples of the monofatty acid sorbitan ester having 10 to 24 carbon atoms include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monobehenate.

  As the component (B), alcohols having 14 to 22 carbon atoms, monofatty acid glycerin esters having 14 to 22 carbon atoms, and carbon atoms having 14 to 22 carbon atoms, from the viewpoints of storage stability of the ultraviolet protection cosmetic and improving the ultraviolet protection effect. At least one or two or more selected from monoalkyl glyceryl ethers having 22 and sorbitan esters of mono-fatty acids having 14 to 22 carbon atoms are preferable, and selected from alcohols having 16 to 22 carbon atoms and mono-fatty acid glycerin esters having 16 to 22 carbon atoms. At least one kind or two or more kinds are more preferable, and at least one kind or two or more kinds selected from cetyl alcohol, stearyl alcohol, and lipophilic monofatty acid glycerin ester are more preferable.

  Further, from the same viewpoint, as the component (B), an alcohol having 14 to 22 carbon atoms, a monofatty acid glycerin ester having 14 to 22 carbon atoms, a monoalkyl glyceryl ether having 14 to 22 carbon atoms, and a 14 to 22 carbon atoms. It preferably contains at least one kind selected from monofatty acid sorbitan esters, more preferably contains an alcohol having 14 to 22 carbon atoms and a monofatty acid glycerin ester having 14 to 22 carbon atoms, and preferably contains 16 to 22 carbon atoms. More preferably contains an alcohol of the formula (I) and a monofatty acid glycerin ester having 16 to 22 carbon atoms, and still more preferably contains cetyl alcohol and stearyl alcohol, and a monofatty acid glycerin ester having 16 to 22 carbon atoms.

  The component (B) can be used alone or in combination of two or more, and the content is selected from the viewpoints of improving the storage stability of the ultraviolet protective cosmetic, improving the ultraviolet protective effect thereof, and the feeling of use. From the viewpoint of improving the goodness, in particular, from the viewpoint of reducing the stickiness, it is 1% by mass or more, preferably 1.5% by mass or more, more preferably 2% by mass or more, more preferably 2.5% by mass or more in the whole composition. It is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3.8% by mass or less. Moreover, the content of the component (B) is 1 to 10% by mass, preferably 1.5 to 8% by mass, more preferably 2 to 5% by mass, and 2.5 to 3.8% by mass in the whole composition. % Is more preferred.

The component (C) used in the present invention is a liquid oil containing an oil-soluble ultraviolet absorber.
As the oil-soluble ultraviolet absorber, those used in ordinary cosmetics can be used.
Examples of the oil-soluble ultraviolet absorber include salicylic acids such as homomenthyl salicylate, octyl salicylate, and triethanolamine salicylate; Para-aminobenzoic acids such as amyl benzoate and 2-ethylhexyl para-dimethylaminobenzoate; 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF); mono-2-diparamethoxycinnamate Glyceryl ethylhexanoate, methyl 2,5-diisopropylcinnamate, methyl bis (trimethylsiloxy) silyl isopentyl trimethoxycinnamate, isopropyl diisopropyl paramethoxycinnamate Cinnamic acids such as cinnamate mixture, p-methoxyhydrocinnamic acid diethanolamine salt; octocrylene (for example, parasol 340; manufactured by DSM Nutrition Japan), 1- (3,4-dimethoxyphenyl) -4,4 -Dimethyl-1,3-pentanedione, sinoxate, methyl-O-aminobenzoate, 3- (4-methylbenzylidene) camphor; 4- (2-β-glucopyranosyloxy) propoxy-2-hydroxybenzophenone, dihydroxydimethoxy Benzophenone, dihydroxydimethoxybenzophenone sodium disulfonate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-di Benzophenones such as hydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone; , 6-Tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (for example, Ubinal T150; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyl triazine (for example, Tinosorb S; BASF) 2-phenyl-benzimidazole-5-sulfate, 4-isopropyldibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane (for example, parasol 1789; manufactured by DSM Nutrition Japan) Etc. Benzoi 2-methylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (for example, Softshade DH; manufactured by Ajinomoto Co.), hexyl diethylaminohydroxybenzoylbenzoate (for example, Ubinal Aplus; manufactured by BASF), methylenebisbenzotriazolyltetra Methyl butyl phenol (for example, Tinosorb M; manufactured by BASF) and the like.
Some UV absorbers are solid at room temperature. However, in the ultraviolet protection cosmetic of the present invention, since each component is mixed with the component (E) under heating, in the obtained ultraviolet protection cosmetic, the oil-soluble ultraviolet absorber of the component (C) is in a liquid state. It is considered to be present.

Among these, from the viewpoint of improving the ultraviolet protection effect, 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), octocrylene (for example, parasol 340; manufactured by DSM Nutrition Japan), 2, 4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine (for example, Ubinal T150; manufactured by BASF), 4-tert-butyl-4′-methoxydibenzoylmethane ( For example, Parasol 1789; DSM Nutrition Japan Ltd.), 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate (for example, Soft Shade DH; Ajinomoto Co.), hexyl diethylaminohydroxybenzoylbenzoate (for example, Binaru Aplus; manufactured by BASF), bis-ethylhexyloxyphenol methoxyphenyl triazine (e.g., Tinosorb S; 1 kind or more selected from BASF) are preferred. Furthermore, from the same viewpoint, 2-ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), diethylaminohydroxybenzoylbenzoic acid hexyl ester (for example, Ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyl One or more kinds selected from triazines (for example, Tinosorb S; manufactured by BASF) are more preferable.
In addition, from the same viewpoint, as the oil-soluble ultraviolet absorber, one or two selected from the cinnamic acid-based oil-soluble ultraviolet absorber, hexyl diethylaminohydroxybenzoylbenzoate, and the triazine-based oil-soluble ultraviolet absorber. The above is more preferable, and it is still more preferable to include these three oil-soluble ultraviolet absorbers. 2-Ethylhexyl paramethoxycinnamate (for example, Ubinal MC80; manufactured by BASF), diethylaminohydroxybenzoylbenzoic acid hexyl ester (for example, It is more preferable to include Ubinal Aplus (manufactured by BASF) and bisethylhexyloxyphenol methoxyphenyl triazine (for example, Tinosorb S; manufactured by BASF).

Liquid oils other than the oil-soluble ultraviolet absorber have fluidity at 25 ° C. It is not limited as long as it is used in ordinary cosmetics. For example, straight or branched chain hydrocarbon oil such as liquid paraffin, light isoparaffin, squalane, squalene; neopentyl glycol dicaprate, isopropyl palmitate, benzoic acid Ester oils such as fatty acid esters such as alkyl and polyhydric alcohol fatty acid esters such as pentaerythritol tetra-2-ethylhexanoate; dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol Silicone oils such as modified silicone oils; and fluorine oils such as fluoropolyethers and perfluoroalkyl ether silicones. These may be natural oils such as vegetable oils such as jojoba oil and olive oil; animal oils such as liquid lanolin.
Among these, as liquid oils other than the oil-soluble ultraviolet absorber, from the viewpoint of reducing stickiness, from the viewpoint of improving compatibility with the oil-soluble ultraviolet absorber, a linear or branched hydrocarbon oil, ester oil, silicone It preferably contains at least one selected from oils.

In all the liquid oil agents of the component (C), the content of the oil-soluble ultraviolet absorber is preferably 60% by mass or more, more preferably 65% by mass or more, from the viewpoint of improving the UV protection effect and reducing skin irritation. 70 mass% or more is still more preferable, 100 mass% or less is preferable, 95 mass% or less is more preferable, and 85 mass% or less is still more preferable. Further, the content of the oil-soluble ultraviolet absorber in the total liquid oil agent of the component (C) is preferably from 60 to 100% by mass, more preferably from 65 to 90% by mass, and still more preferably from 70 to 85% by mass.
In the oil-soluble ultraviolet absorber, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably from 60 to 100% by mass, and more preferably from 70 to 90% by mass, from the viewpoint of improving the protective effect and reducing skin irritation. preferable. From the same viewpoint, the total content of the triazine-based oil-soluble ultraviolet absorber and hexyl diethylaminohydroxybenzoylbenzoate in the oil-soluble ultraviolet absorber is preferably 0 to 40% by mass, and more preferably 10 to 30% by mass.
In addition, the content ratio of the cinnamic acid-based oil-soluble ultraviolet absorber to the total amount of the triazine-based oil-soluble ultraviolet absorber and diethylaminohydroxybenzoylbenzoic acid hexyl ester in the oil-soluble ultraviolet absorber (cinnamate-based oil-soluble ultraviolet absorber) The ratio of the absorbent / [triazine-based oil-soluble ultraviolet absorber + diethylaminohydroxybenzoylbenzoic acid hexyl ester] is preferably from 9/1 to 5/5, from the viewpoint of improving the ultraviolet protection effect and reducing skin irritation. /1.5 to 6/4 is more preferred, and 8/2 to 6.5 / 3.5 is even more preferred.
In the ultraviolet ray protective cosmetics, the content of the oil-soluble ultraviolet absorbent is preferably 6% by mass or more, more preferably 8% by mass or more, and more preferably 10% by mass, from the viewpoint of improving the ultraviolet ray protective effect and reducing skin irritation. % By mass or more, more preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. In addition, the content of the oil-soluble ultraviolet absorber in the ultraviolet protection cosmetic is preferably 6 to 20% by mass, more preferably 8 to 18% by mass, and still more preferably 10 to 15% by mass in the whole composition.

  The component (C) can be used alone or in combination of two or more. The content is preferably from the viewpoint of improving the UV protection effect, reducing the skin irritating feeling, and further improving the feeling of use, particularly, sticky. From the viewpoint of reducing the content, the total composition is 1% by mass or more, preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, and 40% by mass or less, and 35% by mass or less. Is preferably 25% by mass or less, more preferably 17% by mass or less. Moreover, the content of the component (C) is 1 to 40% by mass, preferably 3 to 35% by mass, more preferably 10 to 25% by mass, and still more preferably 12 to 17% by mass in the whole composition.

  In the present invention, the mass ratio of the component (A) to the component (C) [(A) / (C)] is preferably 0.01 or more, from the viewpoint of improving the storage stability of the ultraviolet protective cosmetic. 015 or more is more preferable, 0.025 or more is still more preferable, 0.034 or more is still more preferable, 0.2 or less is preferable, 0.12 or less is more preferable, 0.06 or less is further preferable, and 0.05 or less is used. Is even more preferred. Further, the mass ratio of the component (A) to the component (C) [(A) / (C)] is preferably 0.01 to 0.2, more preferably 0.015 to 0.12, and 0.025 to 0.06 is more preferred, and 0.034 to 0.05 is even more preferred.

  In the present invention, the mass ratio of the component (B) to the component (C) [(B) / (C)] is determined from the viewpoints of improving the storage stability of the ultraviolet protection cosmetic and improving the usability. From the viewpoint of reducing stickiness, 0.01 or more is preferable, 0.12 or more is more preferable, 0.18 or more is more preferable, 0.19 or more is still more preferable, 0.5 or less is preferable, and 0.39 or less is preferable. The following is more preferable, 0.27 or less is still more preferable, and 0.24 or less is still more preferable. The mass ratio [(B) / (C)] of the component (B) to the component (C) is preferably 0.01 to 0.5, more preferably 0.12 to 0.39, and 0.18 to 0.38. 0.27 is more preferred, and 0.19 to 0.24 is even more preferred.

The solid oil agent of the component (D) is solid at 25 ° C.
Such solid oils are not limited as long as they are used in ordinary cosmetics, and include, for example, candelilla wax (melting point: 66-71 ° C), rice wax (melting point: 77-86 ° C), sunflower wax (Melting point: 65-80 ° C), vegetable wax such as carnauba wax (melting point: 80-86 ° C), wood wax (melting point: 50-56 ° C); beeswax (melting point: 62/65 ° C), whale wax (melting point: Animal waxes such as 42-52 ° C.); mineral waxes such as montan wax (82-95 ° C.) and ozokerite (melting point: 66-78 ° C.); microcrystalline wax (melting point: 60-90 ° C.); paraffin (40 Petroleum waxes such as -70 ° C) and ceresin (60-80 ° C); hardened castor oil (melting point: 85 ° C), hydrogenated jojoba oil (melting point: 66-70 ° C), 12-hydroxy Stearate (melting point: 75-78 ° C.), stearamide (mp: 101 ° C.), a silicone wax (melting point 28-80 ℃), polyethylene wax (melting point: 94-152 ℃) and synthetic waxes, and the like.
In the present invention, the melting point of the solid oil agent is measured by the quasi-drug raw material standard, general test method 70. Melting point measurement method.

As the component (D), a solid oil agent having a melting point of 60 ° C. or more and 80 ° C. or less is preferable and a melting point of 60 ° C. or less from the viewpoint of executing accurate temperature control in a cooling step described below and improving storage stability of the cosmetic. A wax having a temperature of not lower than 80 ° C. and higher is more preferable. For example, Candelilla wax MK-2 (manufactured by Yokoseki Yushi Kogyo Co., Ltd., melting point: 71 ° C.), purified rice wax S-100 (manufactured by Yokoseki Yushi Kogyo Co., Ltd., melting point: 78 ° C.), purified sunflower wax (Yokoseki Yushi Kogyo Co., Ltd., Melting point: 76 ° C), BEES WAX SP (manufactured by Strahl & Pitsch, melting point: 62-65 ° C), WHITE OZOKERITE WAX 1025 (manufactured by Strahl & Pitsch, melting point: 68.3-71.1 ° C), multi-wax ( SONNEBORN, melting point 75 ° C), HNP-3 (Nippon Seiwa, melting point 64 ° C), HNP-9 (Nippon Seiro, melting point, melting point 75 ° C), HNP-11 (Nippon Seiro, melting point) , A melting point of 68 ° C.) and a commercially available product such as Celesin # 810 (manufactured by Nikko Rica, melting point of 74 ° C.).
In addition, as the component (D), a solid oil agent having a melting point of 60 ° C or more and 80 ° C or less, containing at least one selected from ceresin and paraffin, from the viewpoint of improving the storage stability of skin cosmetics and reducing stickiness. More preferred.

  The component (D) can be used alone or in combination of two or more, and the content is reduced from the viewpoint of improving the storage stability of the skin cosmetic and improving the feeling of use, particularly, reducing stickiness. From the viewpoint, and further from the viewpoint of improving the ultraviolet protection effect, it is 0.01% by mass or more, preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the whole composition. Is more preferably 6% by mass or less, preferably 4.5% by mass or less, more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less. Further, the content of the component (D) is 0.01 to 6% by mass, preferably 0.08 to 4.5% by mass, more preferably 0.1 to 2.5% by mass in the whole composition, 0.5-1.5% by mass is even more preferred.

  Further, in the present invention, the mass ratio of the component (D) to the component (C) [(D) / (C)] is intended to improve the storage stability of the ultraviolet protection cosmetic and to improve the feeling of use, and particularly to the stickiness. From the viewpoint of reducing the concentration, 0.01 or more is preferable, 0.02 or more is more preferable, 0.04 or more is more preferable, 0.5 or less is preferable, 0.3 or less is more preferable, and 0.1 or less is more preferable. preferable. In addition, the mass ratio of the component (D) to the component (C) [(D) / (C)] is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and more preferably 0.04 to 0.3. 0.1 is more preferred.

The component (E) used in the present invention is water, which is the remaining amount of each component, and emulsified particles having a stable α-gel structure in the cosmetic by a combination of the components (A) to (C) and (E). It is thought that can be formed. By having an α-gel structure, a liquid oil agent containing an oil-soluble ultraviolet absorber can be included in the α-gel structure. Conventional cosmetics containing emulsified particles having an α-gel structure have higher UV protection effects, while at the same time have good usability and no skin irritation. There was room.
The cosmetic of the present invention contains the component (D) in addition to the components (A) to (C) and (E). It is uniformly dispersed, has excellent storage stability, has a high UV protection effect, has a good feeling in use, and has no skin irritation.
The content of the component (E) is preferably 35% by mass or more, more preferably 45% by mass or more, and more preferably 65% by mass in the total composition, from the viewpoint of improving the storage stability and improving freshness of the ultraviolet protection cosmetic. Or less, more preferably 55% by mass or less. Further, the content of the component (E) is preferably 35 to 65% by mass, and more preferably 45 to 55% by mass in the whole composition.

The ultraviolet protection cosmetic composition of the present invention can further contain (F) a water-soluble polymer, which can improve the storage stability of the ultraviolet protection cosmetic composition and improve the ultraviolet protection effect.
The water-soluble polymer is not limited as long as it is used for ordinary cosmetics, and any of a natural polymer, a semi-synthetic polymer, and a synthetic polymer can be used.
Examples of natural polymers include xanthan gum, carrageenan, alginic acid and the like. Examples of the semi-synthetic polysaccharide polymer include modified polysaccharides such as hydroxycellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, and cationized cellulose. Synthetic polymers include carbomer (cross-linked polyacrylic acid), polyacrylic acid, sodium polyacrylate, acrylic acid / alkyl methacrylate copolymer, polyacrylamide, Na acrylate / acryloyldimethyltaurine Na) copolymer, (hydroxy acrylate) Ethyl / acryloyldimethyltaurine Na) copolymers, (acrylamide / ammonium acrylate) copolymers, acrylic polymers such as acrylic polymers such as polyacrylate-13; polyvinylpyrrolidone, polyvinyl alcohol, and cationized polyvinylpyrrolidone. Among them, acrylic polymers are preferable, and carbomer, acrylic acid / alkyl methacrylate copolymer, polyacrylamide, Na acrylate / acryloyl dimethyl taurine Na) copolymer, (hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymer, ( At least one selected from acrylamide / ammonium acrylate) copolymer and polyacrylate-13 is more preferable, and Na acrylate / acryloyl dimethyl taurine Na) copolymer, (hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymer, (acrylamide / acryl) At least one selected from ammonium acrylate) copolymer and polyacrylate-13.

  Commercially available carbomer products include Carbopol 910, Carbopol 934, Carbopol 940, Carbopol 941, Carbopol 980, and Carbopol 981 (all manufactured by Lubrizol Advanced Materials, Inc.), and acrylic acid / methacrylic acid. Examples of commercially available alkyl acid copolymers include Carbopol 1382, Carbopol ETD2020, PEMULEN TR-1, PEMULEN TR-2 (all manufactured by Lubrizol Advanced Materials, Inc.), and the like, and commercially available polyacrylamide. Include SEPIGEL 305 (manufactured by SEPPIC), and as a commercially available (Na acrylate / acryloyl dimethyl taurine Na) copolymer, SIMULGEL Examples of commercially available (hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymers include SIMULGEL FL, SIMULGEL NS, SEPIPLUS S, SEPINOV EMT 10 (all manufactured by SEPPIC), and the like. No.

  The component (F) can be used alone or in combination of two or more, and the content is preferably 0.3% by mass or more in the entire composition from the viewpoint of improving the storage stability of the emulsified particles. 0.5 mass% or more is more preferable, 1.5 mass% or less is preferable, and 1.0 mass% or less is more preferable. Further, the content of the component (F) is preferably from 0.3 to 1.5% by mass, more preferably from 0.5 to 1.0% by mass in the whole composition.

The ultraviolet protection cosmetic composition of the present invention can further contain an ultraviolet scattering agent, and can further enhance the ultraviolet protection effect. The ultraviolet scattering agent is not limited as long as it is used in ordinary cosmetics, and examples thereof include metal oxides such as titanium oxide, zinc oxide and cerium oxide; and metals such as silicon and aluminum.
The shape of these ultraviolet scattering agents may be spherical or spindle-shaped. Further, the average particle diameter is preferably such that the maximum minor axis is 0.005 to 0.5 μm, more preferably 0.007 to 0.2 μm, and further preferably 0.01 to 0.07 μm. preferable.
Here, the average particle diameter is determined by measuring the maximum minor diameter of 300 particles in an image with a transmission electron microscope (TEM) under the condition of 100,000 magnification, and calculating the average value. It is obtained by calculating. In the present invention, the maximum minor axis means a minor axis having the maximum diameter among minor axes perpendicular to the major axis.

These UV scattering agents are conventionally known surface treatments, for example, a fluorine compound treatment (perfluoroalkyl phosphate ester treatment or the like) from the viewpoint of improving the UV protection effect, improving storage stability, and further reducing stickiness. Perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment is preferred), silicone treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor-phase tetramethyltetrahydrogencyclotetra Siloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicic acid treatment is preferred), pendant treatment (method of adding an alkyl chain etc. after gas phase silicone treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (Preferably alkylsilane or alkylsilazane treatment), oil treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment (preferably stearic acid or myristic acid salt), acrylic resin treatment, metal oxide treatment, etc. It is preferable to use them after surface treatment, and it is more preferable to use a combination of these treatments.
For example, after coating the surface of titanium oxide with a metal oxide such as silane or alumina, surface treatment with an alkylsilane or a fatty acid may be mentioned. It is preferable to treat the surface of titanium oxide with alumina and then with a fatty acid. Further, these ultraviolet scattering agents are preferably surface-treated with a compound having a carboxyl group as a surface treatment, more preferably surface-treated with a fatty acid having 12 to 22 carbon atoms, and 14 to 20 carbon atoms. More preferably, the surface treatment is performed with a fatty acid.

  One or more ultraviolet scattering agents can be used, and the content thereof is preferably 0.1% by mass or more, and more preferably 0.5% by mass, in the entire composition from the viewpoint of improving the ultraviolet protection effect. The above is more preferable, 1% by mass or more is further preferable, 10% by mass or less is preferable, 8% by mass or less is more preferable, and 5% by mass or less is further preferable. Further, the content of the ultraviolet light scattering agent is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, even more preferably from 1 to 5% by mass in the whole composition.

  The ultraviolet protection cosmetic composition of the present invention further includes components other than the components (A) to (F) as components used in ordinary cosmetics, such as a thickener, a bactericide, a humectant, a humectant, and a coloring agent. Agents, preservatives, feel improvers, powders, fragrances, anti-inflammatory agents, whitening agents, antiperspirants, antioxidants, and the like can be appropriately contained.

The ultraviolet protective cosmetic of the present invention comprises an emulsifying step of mixing a composition containing the components (A) to (D) with (E) water under heating to form an emulsion;
It is manufactured by a method including a cooling step of cooling the emulsion formed in the emulsification step at a cooling rate of 0.5 to 5 ° C./sec.
When the ultraviolet protection cosmetic composition of the present invention contains the component (F), the method for producing the ultraviolet protection cosmetic composition includes the steps of: mixing a part of the component (E) with the component (F); It is preferable to include a step of mixing the emulsion obtained in the step with the emulsion.

In the emulsification step, a homomixer, an ultrasonic emulsifier, a high-pressure emulsifier, etc., which are usually used when producing a cosmetic, are mixed under heating, preferably at 60 to 120 ° C, more preferably at 80 to 100 ° C. An emulsion can be obtained by mixing the components.
In the cooling step, the obtained emulsion is mixed with a vibrating stirrer / mixer, a scraping type heat exchanger (Onlator-Sakura Seisakusho), a static mixer (Noritake Co., Ltd.), a general plate type heat exchanger, A method of continuous rapid cooling using a double-tube heat exchanger or the like, or a method of stirring and cooling in a general compounding tank can be used. From the viewpoint of solidification, the temperature is 0.5 ° C./sec or more, preferably 0.8 ° C./sec or more, more preferably 5 ° C./sec or less, and preferably 1.5 ° C./sec or less. Further, the cooling rate of the emulsion is 0.5 to 5 ° C / sec, preferably 0.8 to 1.5 ° C / sec.
By such a cooling step, it is preferable to cool to a temperature lower than the solidification temperature of the oily component.

  In the emulsification step and the cooling step, the emulsification step uses a high-pressure emulsifier or an ultrasonic emulsifier, and the cooling step includes a stirring device including a drive shaft and a stirring blade attached to the drive shaft in a tubular casing. A vibrating agitating and mixing device having a body and the drive shaft vibrating in the axial direction, wherein the agitating blade is provided with one or more openings and / or one or more notches. In the cooling step, the emulsion obtained in the emulsification step is preferably cooled continuously by passing it through a vibrating stirrer / mixer. Cosmetics in which fine emulsified particles are dispersed (fine particle dispersion Thing) can be obtained.

  More specifically, FIG. 1 shows a schematic diagram of a manufacturing apparatus suitably used in the present invention. The production apparatus 100 shown in FIG. 1 includes an emulsifying section 20 that mixes a composition containing the components (A) to (D) with water under heating (E) to form an emulsion, and cools the formed emulsion. And a cooling unit 30 that performs the cooling. Further, the emulsifying section 20 includes a first emulsifying section 21 and a second emulsifying section 22. The first emulsifying unit 21 is used for filling all or a part of the components constituting the fine particle dispersion, and mixing the charged components with water under heating to obtain a pre-emulsion. The second emulsification unit 22 is located downstream of the first emulsification unit 21 and is used to apply high energy to the pre-emulsion obtained in the first emulsification unit 21 to obtain a fine emulsion. . The cooling unit 30 is located downstream of the emulsifying unit 20 and is used to cool the heated and mixed emulsion at 25 ° C. to a solidification temperature of an oily component which is a solid and to obtain a target fine particle dispersion. It is something that can be done.

  The first emulsifying section 21 of the emulsifying section 20 includes a mixing tank 211 as shown in FIG. The mixing tank 211 is heated by a jacket 212 that covers a side portion of the mixing tank 211, and is adjusted to a predetermined temperature. A stirring blade 213 is provided in the mixing tank 211. The stirring blade 213 is connected to a motor 215 provided outside the mixing tank 211 via a shaft 214, and is rotatable. A pipe 216 for taking out the pre-emulsion mixed in the tank 211 is connected to the bottom of the mixing tank 211. The pipe 216 is connected to the second emulsifying section 22 via a valve. Note that a metering pump (not shown) may be interposed in the middle of the pipe 216 as needed for the purpose of quantitatively supplying the preliminary emulsion obtained in the first emulsifying unit 21.

  As the first emulsifying unit 21 having the above-described configuration, TK Combimix (trade name) manufactured by Primix, TK A homomixer (trade name) manufactured by Primix, or the like can be used. These stirrers are mainly used alone, but in some cases, two or more kinds may be used as appropriate.

The second emulsifying unit 22 of the emulsifying unit 20 includes a high energy processing unit 221 as shown in FIG. The high energy processing unit 221 can apply high energy to the preliminary emulsified product obtained in the first emulsifying unit 21 using a high-pressure emulsifier or an ultrasonic emulsifier.
A pipe 222 for taking out an emulsion to which high energy has been added in the high energy processing section 221 is connected to a downstream portion of the high energy processing section 221. The emulsion obtained in the second emulsification unit 22 is supplied to the cooling unit 30 through a pipe 222. In addition, a metering pump (not shown) may be provided in the middle of the pipe 222, if necessary, for the purpose of quantitatively supplying the emulsion obtained in the second emulsifying unit 22.

  When a high-pressure emulsifier is used as the second emulsifier 22 having the above configuration, for example, a high-pressure emulsifier such as Starburst Mini (product number: HJP-25001) (manufactured by Sugino Machine Co., Ltd.) or an Ultimizer (manufactured by Sugino Machine Co., Ltd.) ), Gorin (manufactured by APV Lanie), Microfluidizer (manufactured by Microfluidics), high-pressure jet emulsifier (manufactured by Nippon BEE) and the like can be used.

  When an ultrasonic emulsifier is used as the second emulsifying unit 22, for example, an IKASONIC (product number: U200S) (manufactured by IKA) equipped with an ultrasonic generating horn, an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho), A sonic homogenizer (manufactured by Ultrasonic Industrial Co., Ltd.) or the like can be used. These high-pressure emulsifiers or ultrasonic emulsifiers described above are mainly used alone, but in some cases, two or more of them may be used in combination as appropriate.

  The cooling unit 30 includes a vibrating stirring and mixing device 40. The vibrating agitating / mixing device 40 has a substantially cylindrical structure, and has an inlet 31 connected to a pipe 222 at one end, and a discharge port 32 at the other end. The discharge port 32 is connected to a discharge pipe 33. The emulsified product supplied from the emulsifying unit 20 is supplied into the vibrating stirring and mixing device 40 through the inlet 31, passes through the device 40, and is discharged from the end of the discharge pipe 33 through the discharge port 32. The supplied emulsion is passed through the vibrating stirring and mixing device 40 to be further mixed and continuously cooled at 25 ° C. to the solidification temperature of the solid oily component or lower. In order to perform continuous cooling, the vibration-type stirring and mixing device preferably includes a cooling jacket for circulating cooling water outside a casing 41 described later. Four jackets 34, 35, 36, 37 are attached in this order from the 31 side to the discharge port 32 side. Cooling water circulates through each jacket. The temperature of the cooling water can be appropriately set, and these jackets allow the supplied emulsion to be cooled continuously or stepwise from the inlet 31 to the outlet 32. .

  FIG. 2 is a schematic diagram of a vertical section of the vibration type stirring and mixing device 40. The device 40 includes a stirring body 44 including a drive shaft 42 and a stirring blade 43 attached to the drive shaft 42 in a tubular casing 41. The drive shaft 42 is connected to a vibrator 45a, and is configured to vibrate vertically along the axial direction by the vibrator 45a.

  The casing 41 is a tubular one having a circular cross section, and an inlet 31 is provided near a lower portion thereof. A discharge port 32 is provided near the upper portion of the casing 41. The emulsion flowing from the inlet 31 is mixed while passing through the inside of the casing 41, is continuously cooled, and is discharged from the discharge port 32.

  In the casing 41, the above-described stirring body 44 is disposed. The drive shaft 42 of the stirrer 44 extends in the longitudinal direction (longitudinal direction) of the casing 41. The upper end of the drive shaft 42 is connected to a vibrator 45a via a joint 45b. The vibrator 45a includes a motor (not shown) and a known cam mechanism (not shown) connected to its output shaft. The cam mechanism includes a rotating unit (not shown) and a swinging unit (not shown). The rotating part is mounted eccentrically with respect to the output shaft of the motor. The swing unit swings by eccentric rotation of the rotating unit. Then, the swing of the swing portion is transmitted to the drive shaft 42 as vertical vibration.

  A plurality of annular partitions 46 are provided on the inner wall of the casing 41. The partition portions 46 have the same shape, and protrude horizontally from the inner wall of the casing 41. The drive shaft 42 is inserted into a circular hole formed at the center of the partition 46. The diameter of the circular hole is larger than the diameter of the drive shaft 42. A plurality of mixing chambers 47 are defined inside the casing 41 by two adjacent partitions. The mixing chambers 47 are arranged in series along the longitudinal direction (longitudinal direction) of the casing 41.

  3A and 3B are enlarged views of a main part of the stirring body 44. FIG. The stirrer 44 includes a drive shaft 42 and a stirring blade 43 spirally attached to a peripheral surface of the drive shaft 42. In the figure, the stirring blade 43 is attached in a spiral shape with three turns. A set of the stirring bodies 44 in this state is provided in each mixing chamber 47 in the casing. Therefore, the number of sets of the stirring bodies 44 is the same as the number of the mixing chambers 47. In each set of the stirring bodies 44, the direction of the spiral of the stirring blade 43 is the same.

  One or more openings 48 and / or one or more cutouts 49 are provided in the stirring blades 43 of each set of stirring bodies 44. The opening 48 and the notch 49 are provided so that when the stirring body 44 is viewed from the axial direction of the drive shaft 42 (see FIG. 3A), the formation positions do not match between the stirring blades adjacent vertically. ing. The reason for this is to prevent the generation of a short-circuit flow in the axial direction and enhance the stirring and mixing effect.

  As the vibration-type stirring / mixing device 40 having the above-described configuration, for example, the device described in JP-A-4-235729 can be used. Further, a commercially available product can be used as the vibration type stirring and mixing device 40. As such a commercially available product, for example, there is a device provided with a cooling jacket in a Vibromixer (registered trademark) manufactured by Reika Kogyo Co., Ltd.

  A method for producing a fine particle dispersion using the production apparatus 100 having the above-described configuration will be described. First, the components constituting the target fine particle dispersion are placed in the mixing tank 211 of the first emulsifying unit 21 of the emulsifying unit 20. Fill all or a part (the component to be filled in the mixing tank 211 includes water as a dispersion medium). When filling a part of the components constituting the fine particle dispersion, other components may be supplied from, for example, the high-energy processing unit 221 of the second emulsification unit 22 or the vibration-type stirring and mixing device 40. Good. When two or more first emulsifying units 21 are provided, the first emulsifying unit 21 on the upstream side may be filled with all components constituting the target fine particle dispersion, The emulsifying section 21 may be partially filled with components constituting the target fine particle dispersion. By partially filling, the mixing conditions and the like of each component can be individually and appropriately adjusted.

  The components to be filled in the mixing tank 211 include at least one or more oily components that are solid at 25 ° C. When the filling of the target component into the mixing tank 211 is completed, the mixing tank 211 is heated by the jacket 212 to bring the oil component that is solid at 25 ° C. into a molten state. Then, a pre-emulsion is obtained by mixing and dispersing each component with the stirring blade 213 in the mixing tank 211. The heating temperature can be appropriately set according to the melting point of the solid fat. In general, it is preferable that the temperature is set to be about 10 ° C. higher than the melting point of the solid fat having the highest melting point.

  When the components filled in the mixing tank 211 are stirred and sufficiently mixed, the valve attached to the bottom of the mixing tank 211 is opened, and the pre-emulsion in the mixing tank 211 is taken out. The pre-emulsion is supplied to the high energy processing section 221 of the second emulsification section 22 via the pipe 216.

In the high energy processing section 221, high energy is added to the preliminary emulsion obtained in the first emulsification section 21 using a high-pressure emulsifier or an ultrasonic emulsifier to obtain an emulsion. The drop energy applied by the high-pressure emulsifier or the ultrasonic emulsifier is preferably 5 × 10 ⁴ J / kg or more, and more preferably 2 × 10 ⁵ J / kg, from the viewpoint of reducing the particle size. More preferred. The upper limit value of the drop energy is not particularly limited, and the larger the drop energy is, the more preferable. Here, the “drop energy” is a value that can be calculated by the following formulas (1) to (3) in each emulsifier.

  Further, it is preferable that the number of times of passage through the high energy processing unit 221 is one or more. When passing through the high-energy processing unit 221 a plurality of times, it means the total drop energy of all the drop energy added when passing through each high-energy processing unit 221.

  When the target energy is dropped, the valve attached to the high energy processing unit 221 is opened, and the emulsion in the high energy processing unit 221 is taken out. The emulsion is supplied to the vibrating stirring and mixing device 40 via the tube 222. The transition time from the emulsification step (emulsification section 20) to the cooling step (cooling section 30) is preferably within 60 seconds from the viewpoint of preventing the emulsion obtained in the emulsification section 20 from aggregating. And more preferably within 10 seconds. The lower limit of the transition time is not particularly limited, and the shorter the time, the better. The transition time from the emulsifying unit 20 to the cooling unit 30 is defined as the time when the emulsified product obtained in the second emulsifying unit 22 is transferred from the second emulsifying unit 22 of the emulsifying unit 20 to the vibrating stirring and mixing device 40 of the cooling unit 30 through the pipe 222. Is the time it takes to arrive. The transition time can be adjusted by, for example, the length of the tube 222.

  As described above, the vibration-type stirring and mixing device 40 is provided with four jackets 34, 35, 36, and 37 as cooling jackets. The cooling jackets are arranged outside the casing 41 so as to cover the cylindrical casing 41 shown in FIG. 2, and cooling water at a predetermined temperature is circulated in each jacket. By passing the object through the casing 41, heat exchange for cooling the fluid is performed.

  The upper limit of the total flow rate of the cooling water circulating through the cooling jacket is not particularly limited from the viewpoint of efficiently cooling the emulsified product obtained in the emulsifying section 20 without agglomeration. Specifically, the total flow rate of the cooling water is preferably at least 10 times, more preferably at least 30 times the flow rate of the emulsion. Here, the flow rate of the emulsion means the flow rate when the emulsion obtained in the emulsifying section 20 passes through the inside of the casing 41. In addition, when the total flow rate of the cooling water is equal to the total flow rate of the cooling water circulating through each of the jackets when four jackets 34, 35, 36, and 37 are provided as in the case of the vibration-type stirring and mixing device 40, means.

  The temperature of the cooling water can be appropriately set, and these jackets can continuously or stepwise cool the emulsion from the inlet 31 toward the outlet 32. In this case, the temperature of the cooling water flowing through the four jackets 34, 35, 36, and 37 may be gradually lowered from the entrance side to the exit side of the stirring and mixing device 31, or may be all the same. Is also good.

  In addition, the cooling water of the four jackets 34, 35, 36, and 37 is, for example, the emulsion flowing from the inlet 31 side (upstream side) of the vibrating stirring and mixing device 40 to the discharge port 32 side (downstream side). It may be circulated from the upstream side to the downstream side in accordance with the flow of the emulsion, or from the downstream side to the upstream side against the flow of the emulsion.

  In the vibrating stirring and mixing apparatus 40, the stirring body 44 vibrates up and down along the axial direction, so that the emulsion passing through the casing 41 is provided on the flow along the stirring body 44 and on the stirring blades 43. Further mixing without agglomeration due to turbulence in the flow through the opening 48 and the notch 49. Therefore, it is possible to highly disperse the fine particles of the solid fat.

  When the emulsion is cooled by heat exchange with cooling water, the fluidity of the emulsion decreases. The emulsion is cooled while being mixed by the flow along the stirring body 44 and the turbulence of the flow passing through the opening 48 and the notch 49 provided in the stirring blade 43, so that uneven cooling is less likely to occur. In addition, since there is almost no dead space in the vibration type stirring / mixing device 40, uneven stirring does not easily occur. The vibrating stirring and mixing apparatus 40 can perform good stirring and mixing regardless of whether the fluidity of the emulsion is high or low. These advantages of the vibrating stirrer / mixer 40 have a favorable effect that the emulsified particles containing the solid oil agent (such as a wax component) contained in the emulsion can be uniformly fined. In addition, the vibratory stirring and mixing device 40 has a small heat generation value, is excellent in cooling efficiency, and can be rapidly cooled while uniformly emulsifying the emulsified particles, so that the emulsified particles containing solid fat can be dispersed well. It is possible. A small amount of heat is also advantageous in that temperature control is easy.

  In this way, the emulsion is cooled without continuously agglomerating to or below the solidifying temperature of the solid oil agent, so that the productivity of the fine particle dispersion is high and the fine particle dispersion having excellent quality can be provided. The target dispersion is discharged from the discharge pipe 33 through the discharge port 32 of the vibrating stirring and mixing device 40. The temperature of the target dispersion in this state is about 30 ° C.

  In cooling using the vibrating stirring and mixing device 40, the average cooling rate is preferably set to 0.1 to 8 ° C / sec, more preferably 0.5 to 5 ° C / sec, and more preferably 0.5 to 5 ° C / sec. More preferably, the temperature is set to 8 to 5 ° C / sec. The average cooling rate is a value obtained by dividing the difference between the temperature when the fluid enters the vibrating stirring and mixing device 40 and the temperature when the fluid exits by the residence time. Further, the frequency of the vibration type stirring and mixing device 40 is preferably in the range of 2.5 to 30 Hz, and more preferably in the range of 5 to 25 Hz. It is preferable that the amplitude of the vibration type stirring and mixing device 40 is 4 to 15 mm. Further, the total amount of vibration given during cooling by the vibratory stirring and mixing device 40 is preferably 50 to 100,000 strokes, particularly preferably 200 to 20,000 strokes.

  The fine particle dispersion obtained by the manufacturing apparatus 100 as described above has fluidity at 25 ° C., and includes, for example, paste-like and cream-like ones. Such a fine particle dispersion is applied as the ultraviolet protection cosmetic of the present invention. The fine particle dispersion obtained by the manufacturing apparatus 100 is used because the solid oil is finely uniformized in the high-energy treatment section 221 and cooled in the cooling section 30 while the solid oil is uniformly finely divided. The feeling is good, and in particular, the stickiness is reduced, and the cosmetic effect such as an ultraviolet protection effect is enhanced.

  Although the manufacturing method has been described based on the preferred embodiment, the present invention is not limited to this. For example, in the above-described embodiment, one vibrating agitating / mixing device 40 is used. Alternatively, a plurality of vibrating agitating / mixing devices 40 may be connected in series and used.

The ultraviolet protective cosmetic of the present invention obtained in this manner contains fine emulsified particles because it is manufactured by the above-described steps. In light of improvement in the ultraviolet protection effect and reduction in skin irritation, the volume median diameter of the emulsified particles is preferably 0.1 to 10 μm, more preferably 0.15 to 0.35 μm, and 0.20 to 0.25 μm. Is more preferred.
In addition, from the same viewpoint, the coefficient of variation of the emulsified particles is preferably 18 to 40, more preferably 19 to 30, and still more preferably 20 to 25. The coefficient of variation is a numerical value obtained by dividing the standard deviation in the volume median diameter by the volume median diameter. The lower the numerical value, the sharper the particle size distribution.
As described above, the ultraviolet protection cosmetic composition of the present invention has a small particle size and a sharp particle size distribution, but this particle size distribution has excellent storage stability, a high ultraviolet protection effect, and a good feeling in use. This is considered to be one of the factors that make skin irritationless.
In the present invention, the volume median diameter is measured by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution analyzer (model number: LA-920 manufactured by Horiba, Ltd.).

The ultraviolet protection cosmetic of the present invention can be, for example, a lotion, an emulsion, a cream, a gel, a serum, and the like, and more preferably a cream or a gel. In addition, a sheet-like cosmetic material impregnated or applied to a sheet-like substrate such as a woven fabric and a nonwoven fabric can be used.
The ultraviolet protection cosmetic of the present invention can be used by applying it to the skin, preferably to the scalp, and more preferably to the face, body, limbs or the like.
With respect to the above-described embodiments, the present invention further discloses the following inventions.

<1> The following components (A), (B), (C), (D) and (E):
(A) ionic surfactant 0.18 to 2% by mass,
(B) a hydrophobic amphiphile 1 to 10% by mass,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) solid oil agent 0.01 to 6% by mass,
(E) UV protection cosmetics containing water,
An emulsifying step of mixing the composition containing components (A) to (D) with water under heating (E) to form an emulsion;
An ultraviolet ray protective cosmetic obtained by a method including a cooling step of cooling the emulsion formed in the emulsification step at a cooling rate of 0.5 to 5 ° C./sec.

<2> The ionic surfactant of the component (A) is preferably an anionic surfactant, a cationic surfactant, an amphoteric surfactant, sphingosine and a salt thereof, and is selected from an anionic surfactant and sphingosine. At least one is more preferred, an anionic surfactant is still more preferred, a long-chain N-acyl glutamate is even more preferred, sodium dilauroyl glutamate, monosodium N-lauroyl glutamate, N-stearoyl-L-sodium glutamate, N- At least one member selected from the group consisting of arginine stearoyl-L-glutamate, sodium N-stearoyl glutamate, and sodium N-myristoyl-L-glutamate is more preferable, and sodium N-stearoyl glutamate and N-stearoyl-L-g At least one more preferably more selected from glutamic acid arginine, N- stearoyl -L- glutamic acid arginine is more preferred wherein <1> UV protective cosmetic according.
<3> The content of the component (A) is preferably 0.2% by mass or more in the entire composition, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more. 0.45% by mass or more is more preferable, 1.5% by mass or less is preferable, 1.1% by mass or less is more preferable, 0.9% by mass or less is further preferable, and 0.7% by mass or less is even more preferable. The ultraviolet protection cosmetic according to <1> or <2>.
<4> The content of the nonionic surfactant is preferably 1% by mass or less in the entire composition, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less. 0% by mass is more preferably the ultraviolet protection cosmetic according to any one of the above <1> to <3>.

<5> The hydrophobic amphiphilic substance of the component (B) is preferably a ceramide, an alcohol having 10 to 24 carbon atoms, a linear saturated fatty acid having 10 to 24 carbon atoms, or a monofatty acid having 10 to 24 carbon atoms. A glycerin ester, a monoalkyl glyceryl ether having 10 to 24 carbon atoms, a monofatty acid sorbitan ester having 10 to 24 carbon atoms, or at least one or more selected from monofatty acid sorbite esters having 10 to 24 carbon atoms, At least one or two or more selected from alcohols having 14 to 22 carbon atoms, monofatty acid glycerin esters having 14 to 22 carbon atoms, monoalkyl glyceryl ethers having 14 to 22 carbon atoms, and sorbitan esters having 14 to 22 carbon atoms. More preferably, alcohol having 16 to 22 carbon atoms, glycerin mono-fatty acid having 16 to 22 carbon atoms More preferably ester, cetyl alcohol, stearyl alcohol, at least one or more is even more preferable that the selected lipophilic mono fatty acid glycerides <1> to ultraviolet protective cosmetic as claimed in any one of <4>.
<6> The hydrophobic amphiphilic substance of the component (B) is preferably an alcohol having 14 to 22 carbon atoms, a monofatty acid glycerin ester having 14 to 22 carbon atoms, a monoalkyl glyceryl ether having 14 to 22 carbon atoms, It contains at least one selected from mono-fatty acid sorbitan esters having 14 to 22 carbon atoms, and more preferably contains an alcohol having 14 to 22 carbon atoms and a mono-fatty acid glycerin ester having 14 to 22 carbon atoms. More preferably contains an alcohol having 16 to 22 carbon atoms and a monofatty acid glycerin ester having 16 to 22 carbon atoms, and contains cetyl alcohol and stearyl alcohol, and a monofatty acid glycerin ester having 16 to 22 carbon atoms. The UV protection according to any one of the above <1> to <5>, which is still more preferable. Fee.
<7> The content of the component (B) is preferably 1.5% by mass or more in the entire composition, more preferably 2% by mass or more, still more preferably 2.5% by mass or more, and 8% by mass. The UV protection cosmetic composition according to any one of the above items <1> to <6>, wherein the cosmetic composition is preferably the following, more preferably 5% by mass or less, and still more preferably 3.8% by mass or less.

<8> The oil-soluble ultraviolet absorber of the component (C) is preferably 2-ethylhexyl paramethoxycinnamate, octocrylene, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate, hexyl ester of diethylaminohydroxybenzoyl benzoate (bisethylhexyloxyphenol methoxyphenyl One or two or more selected from triazines, comprising 2-ethylhexyl paramethoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine More preferably, it contains one or more selected from the group consisting of 2-ethylhexyl paramethoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyl triazine. <1> The ultraviolet protective cosmetic according to any one of <7> to <7>.
<9> As the oil-soluble UV absorber, one or more selected from cinnamate-based oil-soluble UV absorbers, diethylaminohydroxybenzoylbenzoic acid hexyl ester, and triazine-based oil-soluble UV absorbers are more preferable. More preferably, it contains oil-soluble ultraviolet absorbers of any kind, more preferably 2-ethylhexyl paramethoxycinnamate, hexyl ester of ethylaminohydroxybenzoylbenzoate, and bisethylhexyloxyphenol methoxyphenyl triazine. 8> The ultraviolet protection cosmetic according to any one of the above.
<10> Any of the above <1> to <9>, wherein the liquid oil agent other than the oil-soluble ultraviolet absorber preferably contains at least one selected from linear or branched hydrocarbon oils, ester oils, and silicone oils. 2. The ultraviolet protective cosmetic according to item 1.

<11> In the entire liquid oil agent of the component (C), the content of the oil-soluble ultraviolet absorber is preferably 60% by mass or more, more preferably 65% by mass or more, even more preferably 70% by mass or more, 100 mass% or less is preferable, 90 mass% or less is more preferable, 85 mass% or less is more preferable, The ultraviolet protection cosmetic of any one of said <1>-<10>.
<12> The content of the oil-soluble UV absorber in the UV protection cosmetic is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, based on the total composition. The UV protection cosmetic according to any one of the above <1> to <10>, preferably at most 18% by mass, more preferably at most 18% by mass, even more preferably at most 15% by mass.
<13> In the oil-soluble ultraviolet absorber, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably from 60 to 100% by mass, and more preferably from 70 to 90% by mass. 12> The ultraviolet protective cosmetic according to any one of the above.
<14> In the oil-soluble ultraviolet absorber, the total content of the triazine-based oil-soluble ultraviolet absorber and hexyl diethylaminohydroxybenzoylbenzoate is preferably 0 to 40% by mass, and more preferably 10 to 30% by mass. The ultraviolet protective cosmetic according to any one of the above <1> to <13>.
<15> In the oil-soluble ultraviolet absorber, the content ratio of the cinnamic acid-based oil-soluble ultraviolet absorber to the total amount of the triazine-based oil-soluble ultraviolet absorber and diethylaminohydroxybenzoylbenzoic acid hexyl ester (cinnamate-based oil-soluble ultraviolet light) Absorbent / [triazine-based oil-soluble ultraviolet absorber + diethylaminohydroxybenzoylbenzoic acid hexyl ester] is preferably 9/1 to 5/5, more preferably 8.5 / 1.5 to 6/4. , 8/2 to 6.5 / 3.5, further preferably, the ultraviolet protection cosmetic according to any one of <1> to <14>.
<16> The content of the component (C) is preferably 3% by mass or more in the entire composition, more preferably 10% by mass or more, still more preferably 12% by mass or more, and preferably 35% by mass or less, The ultraviolet protection cosmetic according to any one of <1> to <15>, wherein the cosmetic is more preferably 25% by mass or less, and even more preferably 17% by mass or less.

<17> The mass ratio of the component (A) to the component (C) [(A) / (C)] is preferably 0.01 or more, more preferably 0.015 or more, and 0.025 or more. More preferably, 0.034 or more is still more preferable, 0.2 or less is preferable, 0.12 or less is more preferable, 0.06 or less is further preferable, and 0.05 or less is further more preferable <1> to <16. > The ultraviolet protection cosmetic according to any one of <1> to <4>.
<18> The mass ratio of the component (B) to the component (C) [(B) / (C)] is preferably 0.01 or more, more preferably 0.12 or more, and 0.18 or more. More preferably, 0.19 or more is still more preferable, 0.5 or less is preferable, 0.39 or less is more preferable, 0.27 or less is further preferable, and 0.24 or less is further more preferable. > The ultraviolet protection cosmetic according to any one of the above items

<19> The solid oil agent of the component (D) is preferably a solid oil agent having a melting point of 60 ° C. or more and 80 ° C. or less, and contains one or more selected from ceresin and paraffin, and has a melting point of 60 ° C. or more and 80 ° C. The ultraviolet protection cosmetic according to any one of <1> to <18>, wherein the following solid oils are more preferable.
<20> The content of the component (D) is preferably 0.08% by mass or more in the whole composition, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more. 0.5 mass% or less is preferable, 2.5 mass% or less is more preferable, 1.5 mass% or less is more preferable, The ultraviolet protection cosmetic of any one of said <1>-<19>.
<21> The mass ratio of the component (D) to the component (C) [(D) / (C)] is preferably 0.01 or more, more preferably 0.02 or more, and 0.04 or more. The UV protection cosmetic composition according to any one of <1> to <20>, further preferably, 0.5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less.

<22> The content of the component (E) is preferably 35% by mass or more in the entire composition, more preferably 45% by mass or more, preferably 65% by mass or less, and more preferably 55% by mass or less. The ultraviolet protection cosmetic according to any one of <1> to <21>.
<23> The ultraviolet protection cosmetic according to any one of <1> to <22>, further comprising (F) a water-soluble polymer.
<24> The component (F) is preferably an acrylic polymer, and is a carbomer, acrylic acid / alkyl methacrylate copolymer, polyacrylamide, Na acrylate / acryloyldimethyltaurine Na) copolymer, (hydroxyethyl acrylate) / Acryloyldimethyltaurine Na) copolymer, (acrylamide / ammonium acrylate) copolymer, at least one selected from polyacrylate-13, more preferably Na acrylate / acryloyldimethyltaurine Na) copolymer, (hydroxyethyl acrylate / acryloyldimethyl acrylate) (23) at least one selected from the group consisting of (taurine Na) copolymer, (acrylamide / ammonium acrylate) copolymer and polyacrylate-13 is more preferable. External protective cosmetic.
<25> The content of the component (F) is preferably 0.3% by mass or more in the entire composition, more preferably 0.5% by mass or more, and preferably 1.5% by mass or less. The ultraviolet protection cosmetic according to <23> or <24>, wherein the content is more preferably 0% by mass or less.

<26> The emulsification step is preferably carried out using a homomixer, an ultrasonic emulsifier, or a high-pressure emulsifier, and mixing the components under heating, preferably at 60 to 120 ° C, more preferably 80 to 100 ° C. The ultraviolet protection cosmetic according to any one of 1> to <25>.
<27> The cooling step is preferably carried out by rapidly and rapidly cooling the obtained emulsion using a vibrating stirring and mixing device, a scraping type heat exchanger, a static mixer, a plate type heat exchanger, and a double tube type heat exchanger. The ultraviolet protective cosmetic according to any one of <1> to <26>, wherein the cosmetic is cooled by a cooling method or a method of stirring and cooling in a general mixing tank.
<28> The ultraviolet protection cosmetic according to any one of <1> to <27>, wherein the cooling rate is preferably 0.8 ° C / sec or more and 1.5 ° C / sec or less.
<29> The volume median diameter of the emulsified particles is preferably 0.1 to 10 μm, more preferably 0.15 to 0.35 μm, and still more preferably 0.20 to 0.25 μm. 28> The ultraviolet protective cosmetic according to any one of the above.
<30> The ultraviolet protection cosmetic according to any one of <1> to <29>, wherein the coefficient of variation of the emulsified particles is preferably 18 to 40, more preferably 19 to 30, and still more preferably 20 to 25. .
<31> An ultraviolet protection cosmetic, which applies the ultraviolet protection cosmetic according to any one of the above <1> to <30> to the skin, preferably excluding the scalp, and more preferably to the face, body, limbs, or the like. Use as a fee.

<32> The following components (A), (B), (C) and (D):
(A) ionic surfactant 0.1 to 2% by mass,
(B) a hydrophobic amphiphile 1 to 10% by mass,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) Solid oil agent 0.01 to 6% by mass
An emulsifying step of forming an emulsion by mixing a composition containing (E) with water under heating;
A method for producing an ultraviolet protective cosmetic, comprising a cooling step of cooling the emulsion formed in the emulsifying step at a cooling rate of 0.5 to 5 ° C./sec.

Examples 1 to 29, Comparative Examples 1 to 5
UV protection cosmetics having the compositions shown in Tables 1 to 3 were produced, and the volume median diameter and the coefficient of variation were measured, and the confirmation of α-gel, SPF value, storage stability, feeling of use, and skin irritation were evaluated. The results are shown in Tables 1 to 3.

(Production method)
(1) Example 1
After dispersing the components (A) to (D), part of the component (E), propanediol, glycerin, arginine and phenoxyethanol with a homomixer under heating at 85 ° C., a high-pressure emulsifier (Starburst, manufactured by Sugino Machine Co., Ltd.) An emulsion was obtained using Mini HJP-25001). The number of passes (number of passes) through the high-pressure emulsifier was one. The emulsified product is supplied to a vibrating stirrer / mixer (manufactured by Reika Kogyo Co., Ltd., vibromixer) with a transition time of 10 seconds while maintaining the emulsified product at 85 ° C., and the emulsified product is stirred by vibrating the stirrer up and down in the device. Then, the temperature was continuously cooled to 40 ° C. or lower (step (1)). A mixture obtained by mixing the cooled emulsion with a part of the component (E), the component (F), and other components shown in the table was mixed at room temperature (25 ° C.) ( Step (2)), an ultraviolet protection cosmetic was obtained.
In the vibratory stirring and mixing apparatus, the flow rate of the emulsion is 1 g / sec, the total flow rate of the cooling water circulating through the cooling jacket is 10 g / sec, and the total flow rate of the emulsion is 10 times that of the emulsion. Cooled by cooling water. The average cooling rate at this time was 1 ° C./sec. The vibration frequency of the vibrating stirring and mixing device was 20 Hz.

(2) Examples 2 to 28, Comparative Examples 1 to 4:
In the same manner as in Example 1, ultraviolet protective cosmetics of Examples 2 to 28 and Comparative Examples 1 to 4 were obtained.

(3) Example 29:
An emulsion was obtained in the same manner as in (1). The obtained emulsion was cooled to 40 ° C. while stirring using an anchor blade (rotation speed: 75 rpm) in a container to obtain an ultraviolet protection cosmetic. The average cooling rate at this time was 1 ° C./sec.

(4) Comparative Example 5:
After performing the same emulsification step as in Example 1, cooling was carried out in a thermostatic bath capable of controlling temperature at a cooling rate of 0.01 ° C./sec without stirring.

(Evaluation method)
(1) Volume median diameter, coefficient of variation:
The volume-based median diameter and variation coefficient were measured at a temperature of 25 ° C. by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution analyzer (manufactured by Horiba, Ltd., model number: LA-920). The coefficient of variation is a value obtained by dividing the standard deviation by the volume-based median diameter.

(2) Confirmation of α-gel:
For each cosmetic, it was confirmed by XRD whether an α-gel structure was formed. Specifically, in the wide-angle X-ray diffraction, "α" is shown in the table on the assumption that a cosmetic material in which at least one sharp diffraction peak appears near Bragg angle = 21 to 22 ° has an α-gel structure.

(3) SPF value:
Each cosmetic was uniformly applied on a PMMA plate so as to be ² mg / cm ² for 1 minute, and dried in a cool and dark place for 15 minutes. After drying, an absorption spectrum (wavelength 350 nm) of a total of 9 points at the midpoint on the square PMMA plate, each vertex, and the midpoint on the side connecting each vertex was measured with an SPF analyzer (SPF 290S plus, manufactured by Optometricus USA). Was measured, and the average of nine locations was determined. The result showed the SPF value (-) obtained from the transmittance (%). (N = 3)

(4) Storage stability:
40 mL of the cosmetic was placed in a 50 mL glass bottle, sealed, stored at -5 ° C for one month, and the appearance and fluidity of the stored cosmetic were visually observed. As for the fluidity, the fluidity when tilted to 45 ° C. was visually confirmed. The criteria are as follows.
4: No change in appearance and / or fluidity.
3: Slight changes are observed in both appearance and fluidity.
2: A slight change is observed in at least one of appearance and fluidity.
1: There is a large change in appearance (separation of oil phase) or a large change in fluidity (gel-like change).

(5) Usability:
Five specialized panelists applied 0.02 mL of each cosmetic to a circle having a diameter of 3 cm on the inner side of the forearm and spread it over 1 minute (25 ° C., 57 RH% lower). Thereafter, the feeling of use (stickiness) was evaluated in increments of 0.1, with 5 when no stickiness was observed and 1 when extremely sticky, and the average score of five persons was determined.

(6) Skin irritation:
Five expert panelists applied 0.02 mL of the cosmetic to the inside of the forearm in a circle of 3 cm in diameter and spread it for 1 minute (at 25 ° C., under 57 RH%). Thereafter, the stimulus sensation was evaluated in increments of 0.1, with 5 when no stimulus was present and 1 when there was a very stimulus, and the average score of five persons was determined.

Example 30
In the same manner as in Examples 1 to 28, ultraviolet protective cosmetics having the compositions shown in Table 4 were produced.
In the obtained ultraviolet protective cosmetic, emulsified particles having a volume median diameter of 0.22 μm were dispersed, and α gel was confirmed.
In addition, the oil agent containing an ultraviolet absorber is uniformly dispersed, has excellent storage stability, has a high ultraviolet protection effect, is not sticky, has a good feeling upon use, and has no skin irritation.

Example 31
In the same manner as in Examples 1 to 28, ultraviolet protective cosmetics having the compositions shown in Table 5 were produced.
In the obtained ultraviolet protection cosmetic, emulsified particles having a volume median diameter of 0.24 μm were dispersed, and α gel was confirmed.
In addition, the oil agent containing an ultraviolet absorber is uniformly dispersed, has excellent storage stability, has a high ultraviolet protection effect, is not sticky, has a good feeling upon use, and has no skin irritation.

Examples 32-34, Comparative Example 6
In the same manner as in Examples 1 to 28, UV protection cosmetics having the compositions shown in Table 6 were produced, and the volume median diameter and the coefficient of variation were measured. Confirmation of α-gel, SPF value, storage stability, feeling of use and skin The irritation was evaluated. The results are shown in Table 6.
In addition, the cooling rates at the time of manufacturing the cosmetics of Examples 32 to 34 and Comparative Example 6 are as shown in Table 6.

REFERENCE SIGNS LIST 100 apparatus 20 emulsifying section 21 first emulsifying section 211 mixing tank 22 second emulsifying section 221 high energy processing section 30 cooling section 34, 35, 36, 37 jacket 40 vibratory stirring and mixing apparatus 41 casing 42 drive shaft 43 stirring blade 44 stirring Body 45a Vibrator 45b Joint 46 Partition 47 Mixing chamber 48 Open hole 49 Notch

Claims (6)

The following components (A), (B), (C), (D) and (E):
(A) ionic surfactant 0.18 to 2% by mass,
(B) a hydrophobic amphiphile 1 to 10% by mass,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) solid oil agent 0.01 to 6% by mass,
(E) A method for producing a UV protective cosmetic containing water,
An emulsifying step of mixing the composition containing components (A) to (D) with water under heating (E) to form an emulsion;
A method for producing an ultraviolet protective cosmetic, comprising a cooling step of cooling the emulsion formed in the emulsifying step at a cooling rate of 0.5 to 5 ° C./sec. The method for producing an ultraviolet protective cosmetic according to claim 1, wherein the content of the oil-soluble ultraviolet absorber in the total liquid oil agent of the component (C) is from 60% by mass to 100% by mass. The ultraviolet protection cosmetic further comprises (F) a water-soluble polymer, and a mixture of a part of component (E) and component (F) previously mixed with the emulsion obtained by the cooling step. The method for producing an ultraviolet protection cosmetic according to claim 1 or 2 , comprising a step of mixing. The method for producing an ultraviolet protective cosmetic according to any one of claims 1 to 3 , wherein a mass ratio (A) / (C) of the component (A) to the component (C) is 0.01 to 0.2. The method according to any one of claims 1 to 4 , wherein a mass ratio (B) / (C) of the component (B) to the component (C) is 0.01 to 0.5. The method according to any one of claims 1 to 5 , wherein a mass ratio (D) / (C) of the component (D) to the component (C) is 0.01 to 0.5.

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