WO2016204124A1 - Cosmetic for protection against ultraviolet radiation - Google Patents

Abstract

Provided is a cosmetic for protection against ultraviolet radiation, wherein the cosmetic has excellent storage stability, provides highly effective protection against ultraviolet radiation, feels good and does not leave a sticky feeling when used, and does not cause skin irritation. The cosmetic for protection against ultraviolet radiation contains components (A), (B), (C), (D) and (E), where (A) is 0.18-2 mass% of an ionic surfactant, (B) is 1-10 mass% of a hydrophobic amphiphilic material, (C) is 1-40 mass% of a liquid oil containing an oil-soluble ultraviolet absorbent, (D) is 0.01-6 mass% of a solid oil, and (E) is water. The cosmetic is obtained by means of a method comprising an emulsification step for mixing a composition containing components (A)-(D) with water (E) under heating to form an emulsion, and a cooling step for cooling the emulsion formed in the emulsification step at a cooling rate of 0.5-5°C/s.

Description

UV protection cosmetics

The present invention relates to an ultraviolet protective cosmetic.

Sunburn by ultraviolet rays promotes browning of the skin, reduction of skin elasticity, generation of wrinkles, and the like. To prevent these, cosmetics containing ultraviolet absorbers are used.
Of the UV absorbers, oil-soluble UV absorbers have an excellent effect of absorbing ultraviolet rays, but if they are added to cosmetics as they are, they may cause irritation and stickiness, and there are problems in terms of feeling of use. there were.
For this reason, cosmetics in which ultraviolet absorbers are blended in a fine emulsion or encapsulated are studied (for example, Patent Documents 1 to 3).

(Patent Document 1) JP 2012-31125 A (Patent Document 2) JP 2005-504750 JP (Patent Document 3) JP 2009-167168 A

The present invention includes the following components (A), (B), (C), (D) and (E):
(A) Ionic surfactant 0.18-2% by mass,
(B) 1-10% by weight of a hydrophobic amphiphile,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) 0.01 to 6% by mass of a solid oil agent,
(E) a UV protection cosmetic containing water,
An emulsification 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 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./second.

It is the schematic which shows the vibration type stirring mixing apparatus suitable in order to manufacture the cosmetics of this invention. It is a schematic diagram of the longitudinal cross-section of the vibration type stirring and mixing apparatus shown in FIG. It is a principal part enlarged view of the stirring body in the vibration type stirring mixing apparatus shown in FIG.

Detailed Description of the Invention

Conventional cosmetics containing UV absorbers are inferior in storage stability and are not sufficiently satisfactory in terms of feeling in use.
Further, when a cosmetic containing an ultraviolet absorber was applied to the skin, the ultraviolet absorber was not uniformly deposited on the skin, so that a sufficient ultraviolet protective 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 are problems in terms of storage stability and usability.
The present invention relates to a UV protective cosmetic in which an oil containing an UV absorber 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 present inventors combined a liquid oil containing an ionic surfactant, a hydrophobic amphiphile, an oil-soluble UV absorber, and a solid oil at a specific ratio, and a cosmetic obtained by a specific method is an oil. The inventors have found that α-gel particles encapsulating a soluble ultraviolet absorber are dispersed, have excellent storage stability, have a high UV protection effect, have a good feeling of use, and have no skin irritation.

The UV protective cosmetic of the present invention is dispersed in α-gel particles encapsulating an oil-soluble UV absorber and has good storage stability. In addition, when applied to the skin, the oil-soluble UV absorber adheres uniformly to the skin, providing a high UV protection effect, being non-sticky and having a good feeling of use. Is low and has no skin irritation.

The ionic surfactant of component (A) used in the present invention is one used in 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 sulfates 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 sodium N-myristoyl-N-methyltaurine; 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 dilauroyl glutamate, monosodium N-lauroyl glutamate, sodium N-stearoyl-L-glutamate, arginine N-stearoyl-L-glutamate, sodium N-stearoyl glutamate, N-myristoyl-L -Long chain N-acyl glutamate such as sodium glutamate.
Of these, long-chain N-acyl glutamates are preferred from the viewpoint of improving the storage stability of UV-protecting cosmetics and improving the feeling of use, particularly reducing stickiness.

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

Examples of the amphoteric surfactant include alkyldimethylamine oxide, alkylcarboxybetaine, alkylsulfobetaine, amide amino acid salt, alkylamidopropylbetaine and the like, and alkylamidopropylbetaine is preferable.

Examples of sphingosine and salts thereof include natural sphingosine, dihydrosphingosine, phytosphingosine, sphingadienin, dehydrosphingosine, dehydrophytosphingosine, and N-alkyl isomers thereof (for example, N-methyl).
These may be any of natural extracts and synthetic products, and commercially available products can be used. Examples of commercially available natural sphingosine include D-Sphingosine (4-Sphingine) (SIGMA-ALDRICH), DS-physphingosine (DOOSAN), and phytosphingosine (Cosmo Farm).

Further, these 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; succinic acid and the like Dicarboxylates; oxycarboxylates such as citric acid, lactic acid, malic acid and the like can be mentioned, and one or more selected from these are preferred.

The ionic surfactant of component (A) is at least selected from anionic surfactants and sphingosine from the viewpoint of improving the storage stability of UV protective cosmetics and improving the feeling of use, particularly reducing stickiness. One is preferable, and an anionic surfactant is more preferable.
Among the anionic surfactants, it is preferable to include a long-chain N-acyl glutamate. Among the long-chain N-acyl glutamates, dilauroyl sodium glutamate, N-lauroyl glutamate monosodium, N-stearoyl-L— At least one selected from sodium glutamate, N-stearoyl-L-glutamic acid arginine, N-stearoyl sodium glutamate, and N-myristoyl-L-glutamic acid sodium is preferable, and from N-stearoyl sodium glutamate and N-stearoyl-L-glutamic acid arginine At least one selected is more preferable, and arginine N-stearoyl-L-glutamate is more preferable.

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 UV protective cosmetic and improving the feeling of use, particularly reducing stickiness. The total composition is 0.18% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, and 0.45% by mass or more. More preferably, it is 2 mass% or less, preferably 1.5 mass% or less, more preferably 1.1 mass% or less, further preferably 0.9 mass% or less, and further preferably 0.7 mass% or less. . The content of component (A) is 0.18 to 2% by mass in the total composition, preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.1% by mass, 0.4 to 0.9% by mass is more preferable, and 0.45 to 0.7% by mass is even more preferable.
In addition, in this invention, a component (A) is content as an acid.
In addition, it can contain a nonionic surfactant as long as it does not impair the effects of the present invention, but it improves the storage stability of the UV protective cosmetic and improves the feeling of use, especially stickiness. 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 total composition. Even more preferred.

Examples of the component (B) hydrophobic amphiphile 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 carbon atoms having 10 to 24 carbon atoms. Examples thereof include mono fatty acid glycerin esters, monoalkyl glyceryl ethers having 10 to 24 carbon atoms, mono fatty acid sorbitan esters having 10 to 24 carbon atoms, and mono fatty acid sorbite esters having 10 to 24 carbon atoms.

As the ceramides, one or more selected from natural ceramides and pseudoceramides can be used. Specifically, from the viewpoint of improving the storage stability of the ultraviolet protective cosmetic, ceramides described in JP2013-53146A are preferable.

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

Further, these N-alkyl compounds (for example, N-methyl compounds) are also included.
These ceramides may be either natural (D (−)) optically active or non-natural (L (+)) optically active, or a mixture of natural and non-natural. May be used. The relative configuration of the above compound may be a natural configuration, a non-natural configuration other than that, or a mixture thereof. In particular, compounds of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II (hereinafter referred to as INCI, 8th Edition) and those represented by the following formula are preferable.

These may be either natural extracts or synthetic products, and commercially available products can be used. Examples of commercially available natural ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (above, Cosmo Farm Company), Ceramide TIC-001 (Takasam RAM ID E), (Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN), CERAMIDE2 (Cederma).

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 protective 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 represents a hydrogen atom; Acetyl group or glyceryl group; R ² is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group; Or an ester bond of a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group at the ω-terminal of the hydrocarbon group; R ³ represents a hydrogen atom Or a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group which may be substituted is an alkyl group having 1 to 30 carbon atoms in total.

Among these, from the viewpoint of improving the storage stability of the UV protective cosmetic, pseudoceramide represented by the following formula is more preferable.

In general formula (1), R ¹ is a hexadecyl group, X ¹ is a hydrogen atom, R ² is a pentadecyl group, R ³ is a hydroxyethyl group; R ¹ is a hexadecyl group, X ¹ is a hydrogen atom, R ² is A pseudo-ceramide having a nonyl group and R ³ having a hydroxyethyl group is preferred, 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, pseudoceramides (i) and (ii) represented by the following formula are also preferable.

Further, examples of the alcohol having 10 to 24 carbon atoms include myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol and the like. Among these, those having a straight chain alkyl group are preferred, alcohols having 16 to 18 carbon atoms are more preferred, at least one or more selected from cetyl alcohol and stearyl alcohol are more preferred, including cetyl alcohol and stearyl alcohol It is even more preferable.

Examples of the linear saturated fatty acid having 10 to 24 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like. Among these, from the viewpoint of storage stability of the ultraviolet protective cosmetic and the viewpoint of improving the ultraviolet protective effect, a linear saturated fatty acid having 14 to 22 carbon atoms is preferable, and a linear saturated fatty acid having 16 to 22 carbon atoms is preferable. More preferably, it contains at least one selected from palmitic acid or stearic acid.

Examples of the monofatty acid glycerin ester having 10 to 24 carbon atoms include glycerin monolaurate, glycerin monomyristic ester, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate, Examples include glycerin monoisostearate. Of these, at least one or more selected from glycerin monobehenate, glycerin monostearate, and glycerin monopalmitate are preferred, and glycerin monobehenate is more preferred.

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, monobehenyl glyceryl ether and the like.

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

As the component (B), from the viewpoint of the storage stability of the ultraviolet protective cosmetic and the viewpoint of improving the ultraviolet protective effect, an alcohol having 14 to 22 carbon atoms, a mono fatty acid glycerol ester having 14 to 22 carbon atoms, and 14 to 14 carbon atoms can be used. Preferred is at least one or more selected from 22 monoalkyl glyceryl ethers and 14 to 22 mono fatty acid sorbitan esters, selected from 16 to 22 alcohols and 16 to 22 mono fatty acid glycerin esters. At least one or more selected from the group consisting of cetyl alcohol, stearyl alcohol, and lipophilic mono fatty acid glycerin ester are more preferable.

Further, from the same viewpoint, the component (B) includes an alcohol having 14 to 22 carbon atoms, a mono fatty acid glycerin ester having 14 to 22 carbon atoms, a monoalkyl glyceryl ether having 14 to 22 carbon atoms, and 14 to 22 carbon atoms. It preferably contains at least one selected from mono fatty acid sorbitan esters, more preferably contains an alcohol having 14 to 22 carbon atoms and a mono fatty acid glycerin ester having 14 to 22 carbon atoms, and has 16 to 22 carbon atoms. It is more preferable to contain the alcohol and mono-fatty acid glycerin ester having 16 to 22 carbon atoms, and it is even more preferable to contain cetyl alcohol and stearyl alcohol and mono-fatty acid glycerin ester having 16 to 22 carbon atoms.

Component (B) can be used singly or in combination of two or more, and the content is improved from the viewpoint of improving the storage stability of the ultraviolet protective cosmetic, the viewpoint of improving the ultraviolet protective effect, and the feeling of use. From the viewpoint of making it favorable, in particular, from the viewpoint of reducing stickiness, it is 1% by mass or more in the total composition, preferably 1.5% by mass or more, more preferably 2% by mass or more, and further more preferably 2.5% by mass or more. Preferably, it is 10 mass% or less, 8 mass% or less is preferable, 5 mass% or less is more preferable, 3.8 mass% or less is further more preferable. Further, the content of the component (B) is 1 to 10% by mass in the total composition, preferably 1.5 to 8% by mass, more preferably 2 to 5% by mass, and 2.5 to 3.8% by mass. % Is more preferable.

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 oil-soluble ultraviolet absorbers include salicylic acid series such as homomenthyl salicylate, octyl salicylate, triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropylparaaminobenzoic acid, glycerylparaaminobenzoic acid, octyldimethylparaaminobenzoic acid, paradimethylamino Paraaminobenzoic acid series such as amyl benzoate and 2-ethylhexyl paradimethylaminobenzoate; 2-ethylhexyl paramethoxycinnamate (eg, ubinal MC80; manufactured by BASF), diparamethoxycinnamate mono-2- Glyceryl ethylhexanoate, methyl 2,5-diisopropylcinnamate, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, isopropyl diisopropyl paramethoxycinnamate Cinnamic acid ester mixture, p-methoxyhydrocinnamic acid diethanolamine salt and other cinnamic acid systems; Octocrylene (eg, 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, sodium dihydroxydimethoxybenzophenone disulfonate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-di Benzophenone series such as hydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone; 2,4 , 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-sulfuric acid, 4-isopropyldibenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane (for example, Parasol 1789; manufactured by DSM Nutrition Japan) Benzoi etc. Dimethanebenzylidenedioxoimidazolidinepropionate 2-ethylhexyl (for example, Softshade DH; manufactured by Ajinomoto Co.), diethylaminohydroxybenzoyl benzoic acid hexyl ester (for example, ubinal Aplus; manufactured by BASF), methylenebisbenzotriazolyltetra Examples thereof include methylbutylphenol (for example, Tinosorb M; manufactured by BASF).
Some ultraviolet absorbers are solid at room temperature. However, since each component of the ultraviolet protective cosmetic of the present invention is mixed with the component (E) under heating, the oil-soluble ultraviolet absorber of the component (C) is liquid in the obtained ultraviolet protective cosmetic. It is considered to exist.

Of these, from the viewpoint of improving the UV protection effect, 2-methoxyhexyl 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; manufactured by DSM Nutrition Japan), 2-methoxyhexyl dimethoxybenzylidenedioxoimidazolidinepropionate (for example, soft shade DH; manufactured by Ajinomoto Co.), diethylaminohydroxybenzoyl hexyl ester (for example, Binaru Aplus; manufactured by BASF), bis-ethylhexyloxyphenol methoxyphenyl triazine (e.g., Tinosorb S; 1 kind or more selected from BASF) are preferred. Further, from the same viewpoint, 2-methoxyhexyl paramethoxycinnamate (for example, ubinal MC80; manufactured by BASF), diethylaminohydroxybenzoylbenzoic acid hexyl ester (for example, ubinal Aplus; manufactured by BASF), bisethylhexyloxyphenol methoxyphenyl One or more selected from triazines (for example, Tinosorb S; manufactured by BASF) are more preferable.
Further, from the same viewpoint, the oil-soluble ultraviolet absorber is one or two selected from the cinnamic acid-based oil-soluble ultraviolet absorber, diethylaminohydroxybenzoyl hexyl hexyl ester, and the triazine-based oil-soluble ultraviolet absorber. More preferably, these three kinds of oil-soluble UV absorbers are further included, and 2-methoxyhexyl paramethoxycinnamate (eg, ubinal MC80; manufactured by BASF), diethylaminohydroxybenzoyl benzoate hexyl ester (eg, 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 oil-soluble ultraviolet absorbers are fluid at 25 ° C. It is not limited as long as it is used in normal cosmetics, for example, liquid or paraffin, light isoparaffin, squalane, squalene, etc. linear or branched hydrocarbon oil; dicaprate neopentyl glycol, isopropyl palmitate, benzoic acid Ester oils such as fatty acid esters such as alkyl and polyhydric alcohol fatty acid esters such as tetra-2-ethylhexanoic acid pentaerythritol; dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol Examples thereof include silicone oils such as modified silicone oils; fluorine oils such as fluoropolyethers and perfluoroalkyl ether silicones. These may be vegetable oils such as jojoba oil and olive oil; natural oils such as animal oils such as liquid lanolin.
Among these, liquid oils other than oil-soluble UV absorbers include linear or branched hydrocarbon oils, ester oils, and silicones from the viewpoint of reducing stickiness and improving compatibility with oil-soluble UV absorbers. It is preferable to include at least one selected from oils.

From the viewpoint of improving the ultraviolet protection effect and reducing the skin irritation feeling in the total liquid oil of component (C), the content of the oil-soluble ultraviolet absorber is preferably 60% by mass or more, more preferably 65% by mass or more, 70 mass% or more is more preferable, 100 mass% or less is preferable, 95 mass% or less is more preferable, and 85 mass% or less is further more preferable. In addition, the content of the oil-soluble ultraviolet absorber in the total liquid oil of component (C) is preferably 60 to 100% by mass, more preferably 65 to 90% by mass, and further preferably 70 to 85% by mass.
In the oil-soluble ultraviolet absorber, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably 60 to 100% by mass and more preferably 70 to 90% by mass from the viewpoint of improving the protective effect and reducing the skin irritation. preferable. From the same viewpoint, the total content of the triazine oil-soluble ultraviolet absorber and diethylaminohydroxybenzoyl hexyl hexyl ester 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 of cinnamate-based oil-soluble UV absorber in the total amount of triazine-based oil-soluble UV absorber and diethylaminohydroxybenzoyl hexyl ester in the oil-soluble UV absorber (cinnamate-based oil-soluble UV Absorber / [triazine-based oil-soluble ultraviolet absorber + diethylaminohydroxybenzoyl benzoic acid hexyl ester] is preferably 9/1 to 5/5 from the viewpoint of improving the ultraviolet protection effect and reducing skin irritation, 8.5 /1.5 to 6/4 is more preferable, and 8/2 to 6.5 / 3.5 is more preferable.
From the viewpoint of improving the UV protection effect and reducing the skin irritation in the UV protection cosmetic, the content of the oil-soluble UV absorber is preferably 6% by mass or more, more preferably 8% by mass or more in the total composition. % By mass or more is more preferable, 20% by mass or less is preferable, 18% by mass or less is more preferable, and 15% by mass or less is more preferable. Further, the content of the oil-soluble ultraviolet absorber in the ultraviolet protective cosmetic is preferably 6 to 20% by mass, more preferably 8 to 18% by mass, and further preferably 10 to 15% by mass in the total composition.

Component (C) can be used singly or in combination of two or more, and the content is particularly improved in terms of improving the UV protection effect, reducing skin irritation, and improving the feeling of use. From the viewpoint of reducing the amount, 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. The following is preferable, 25 mass% or less is more preferable, and 17 mass% or less is further more preferable. The content of component (C) is 1 to 40% by mass in the total composition, preferably 3 to 35% by mass, more preferably 10 to 25% by mass, and still more preferably 12 to 17% by mass.

In the present invention, the mass ratio [(A) / (C)] of the component (A) to the component (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 more preferable, 0.034 or more is 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 preferable. Is even more preferable. The mass ratio [(A) / (C)] of the component (A) to the component (C) is preferably 0.01 to 0.2, more preferably 0.015 to 0.12, and 0.025 to 0.06 is more preferable, and 0.034 to 0.05 is even more preferable.

In the present invention, the mass ratio [(B) / (C)] of the component (B) to the component (C) is the viewpoint of improving the storage stability of the ultraviolet protective cosmetic and the viewpoint of improving the feeling of use, in particular. From the viewpoint of reducing stickiness, it is preferably 0.01 or more, more preferably 0.12 or more, further preferably 0.18 or more, still more preferably 0.19 or more, preferably 0.5 or less, 0.39 The following is more preferable, 0.27 or less is more preferable, and 0.24 or less is 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 0.27 is more preferable, and 0.19 to 0.24 is still more preferable.

The solid oil agent of component (D) is solid at 25 ° C.
Such a solid oil agent is not limited as long as it is used in ordinary cosmetics. For example, candelilla wax (melting point: 66-71 ° C.), rice wax (melting point: 77-86 ° C.), sunflower wax (Melting point: 65-80 ° C.), plant wax such as carnauba wax (melting point: 80-86 ° C.), tree 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), ozokerite (melting point: 66-78 ° C); microcrystalline wax (melting point: 60-90 ° C), paraffin (40 -70 ° C), petroleum waxes such as ceresin (60-80 ° C); hydrogenated 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 is determined by the quasi-drug raw material standard general test method. It is measured by a melting point measurement method.

The component (D) is preferably a solid oil having a melting point of 60 ° C. or higher and 80 ° C. or lower from the viewpoint of performing accurate temperature control in the cooling step described later and improving the storage stability of the cosmetic. More preferred is a wax having a temperature of 80 ° C. or higher. For example, Candelilla wax MK-2 (manufactured by Yokoseki Yushi Kogyo Co., Ltd., melting point: 71 ° C.), refined rice wax S-100 (manufactured by Yokozeki Yushi Kogyo Co., Ltd., melting point: 78 ° C.), 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 Co., Ltd., melting point 64 ° C), HNP-9 (Nippon Seiwa Co., Ltd., melting point, melting point 75 ° C), HNP-11 (Nippon Seiwa Co., Ltd.) , Melting point 68 ° C.) and ceresin # 810 (manufactured by Nikko Rica Co., Ltd., melting point 74 ° C.) can be used.
Moreover, as a component (D), from the viewpoint of improving the storage stability of skin cosmetics and reducing stickiness, a solid oil agent containing at least one selected from ceresin and paraffin and having a melting point of 60 ° C. or higher and 80 ° C. or lower is used. More preferred.

Component (D) can be used alone or in combination of two or more, and the content reduces the stickiness, particularly in terms of improving the storage stability of skin cosmetics and improving the feeling of use. From the viewpoint of further improving the UV protection effect, the total composition is 0.01% by mass or more, preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass or more. Is more preferably 6% by mass or less, preferably 4.5% by mass or less, more preferably 2.5% by mass or less, and further preferably 1.5% by mass or less. The content of the component (D) is 0.01 to 6% by mass in the total composition, preferably 0.08 to 4.5% by mass, more preferably 0.1 to 2.5% by mass, More preferably, it is 0.5 to 1.5% by mass.

Further, in the present invention, the mass ratio [(D) / (C)] of the component (D) to the component (C) is the viewpoint of improving the storage stability of the UV protective cosmetic and improving the feeling of use, in particular, stickiness. Is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.04 or more, preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.1 or less. preferable. The mass ratio [(D) / (C)] of component (D) to component (C) is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and 0.04 to 0.1 is more preferable.

The component (E) used in the present invention is water, which is the remaining amount of each component, and the emulsified particles having a stable α-gel structure in cosmetics by the 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 containing an oil-soluble ultraviolet absorber can be included in the α gel structure. Cosmetics containing conventional emulsified particles having an α-gel structure have a higher UV protection effect, while having a good feeling on use and no skin irritation. There was room.
The cosmetic of the present invention further contains the component (D) in addition to the components (A) to (C) and (E). By producing the cosmetic according to the method described later, an oil agent containing an ultraviolet absorber can be obtained. 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 freshness of the UV protective cosmetic. The following is preferable, and 55 mass% or less is more preferable. Further, the content of the component (E) is preferably 35 to 65% by mass, more preferably 45 to 55% by mass in the total composition.

The ultraviolet protective cosmetic of the present invention can further contain (F) a water-soluble polymer, improve the storage stability of the ultraviolet protective cosmetic, and improve the ultraviolet protective effect.
The water-soluble polymer is not limited as long as it is used in ordinary cosmetics, and any of natural polymers, semi-synthetic polymers, and synthetic polymers can be used.
Examples of natural polymers include xanthan gum, carrageenan, alginic acid and the like. Examples of semi-synthetic polysaccharide polymers 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, acrylic acid Na / acryloyldimethyltaurine Na) copolymer, hydroxy acrylate Examples include acrylic polymers such as ethyl / acryloyldimethyltaurine Na) copolymer, (acrylamide / ammonium acrylate) copolymer, and acrylic acid-based polymers such as polyacrylate-13; polyvinylpyrrolidone, polyvinyl alcohol, cationized polyvinylpyrrolidone, and the like. Of these, acrylic polymers are preferred, including carbomers, acrylic acid / alkyl methacrylate copolymers, polyacrylamide, Na acrylate / acryloyl dimethyl taurine Na) copolymers, (hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymers, ( More preferably, at least one selected from an acrylamide / ammonium acrylate copolymer and polyacrylate-13 is used, such as Na acrylate / acryloyldimethyltaurine Na) copolymer, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, (acrylamide / acrylic). More preferred is at least one selected from (ammonium acid) copolymer and polyacrylate-13.

Examples of commercially available carbomers include carbopol 910, carbopol 934, carbopol 940, carbopol 941, carbopol 980, carbopol 981 (and above, manufactured by Lubrizol Advanced Materials, Inc.), etc., and acrylic acid / methacrylic acid. Examples of commercially available acid alkyl copolymers include Carbopol 1382, Carbopol ETD2020, PEMULEN TR-1, and PEMULEN TR-2 (above, Lubrizol Advanced Materials, Inc.). Includes SEPIGL 305 (manufactured by SEPPIC), and as a commercial product of (Na / acrylic acid dimethyl taurine Na) copolymer, SIMU GEL EG (manufactured by SEPPIC), and the like (commercial products of (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer), such as SIMULGEL FL, SIMULGEL NS, SEPAPLUS SMT, SEPINOV EMT 10 (manufactured by SEPPIC), etc. Is mentioned.

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 total 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 0.3 to 1.5% by mass, more preferably 0.5 to 1.0% by mass in the total composition.

The ultraviolet protective cosmetic of the present invention can further contain an ultraviolet scattering agent, and can further enhance the ultraviolet protective 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; metals such as silicon and aluminum.
These ultraviolet scattering agents may have a spherical shape or a spindle shape. The average particle size is preferably 0.005 to 0.5 μm at the maximum minor axis, 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 short diameter of the particle diameter of 300 particles in an image with a transmission electron microscope (TEM) under the condition of 100,000 magnification. It is obtained by calculating. In the present invention, the maximum minor axis means a minor axis having the largest diameter among the minor axes orthogonal to the major axis.

These ultraviolet scattering agents are conventionally known surface treatments such as a fluorine compound treatment (perfluoroalkyl phosphate treatment or the like) from the viewpoint of improving the ultraviolet protection effect, improving the storage stability, and reducing stickiness. Perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment are preferred, silicone treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, gas phase method tetramethyltetrahydrogencyclotetra Siloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (method of adding an alkyl chain after vapor phase silicone treatment), silane coupling agent, titanium coupling agent treatment, silane treatment (Preferably alkylsilane or alkylsilazane treatment), oil agent 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 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 alkylsilane or fatty acid may be mentioned. It is preferable to treat the surface of titanium oxide with alumina and then with fatty acid. In addition, these ultraviolet light scattering agents are preferably surface-treated with a compound having a carboxyl group as the 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 the fatty acid.

The ultraviolet scattering agent can be used singly or in combination of two or more, and the content thereof is preferably 0.1% by mass or more, preferably 0.5% by mass in the total composition, from the viewpoint of improving the ultraviolet protection effect. The above is more preferable, 1% by mass or more is more preferable, 10% by mass or less is preferable, 8% by mass or less is more preferable, and 5% by mass or less is more preferable. The content of the ultraviolet scattering agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1 to 5% by mass in the total composition.

The ultraviolet protective cosmetic of the present invention is a component other than components (A) to (F) as components used in ordinary cosmetics. For example, thickeners, bactericides, moisturizers, wetting agents, coloring agents Agents, preservatives, feel improvers, powders, fragrances, anti-inflammatory agents, whitening agents, antiperspirants, antioxidants and the like can be contained as appropriate.

The ultraviolet protective cosmetic of the present invention comprises an emulsification step in which an emulsion is formed by mixing a composition containing components (A) to (D) with water under heating (E), and an emulsification formed in the emulsification step. The product is manufactured by a method including a cooling step in which the product is cooled at a cooling rate of 0.5 to 5 ° C./second.
In addition, when the ultraviolet protective cosmetic of the present invention includes the component (F), the method for producing the ultraviolet protective cosmetic includes a liquid mixture obtained by mixing a part of the component (E) and the component (F) in advance, and the cooling. It is preferable to include a step of mixing the emulsion obtained in the step.

In the emulsification step, a homomixer, an ultrasonic emulsifier, a high-pressure emulsifier, etc. that are usually used in the production of cosmetics are used, and heated, 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 process, the obtained emulsion is mixed with a vibratory stirring and mixing device, a scraping heat exchanger (ONTORA Sakai Seisakusho), a static mixer (Noritake Company Limited), a general plate heat exchanger, A continuous rapid cooling method using a double pipe heat exchanger or the like, and a stirring and cooling method in a general compounding tank can be used, and the cooling rate is determined from the viewpoint of forming an α-gel structure and a solid oil agent. From the viewpoint of solidifying, it is 0.5 ° C./second or more, preferably 0.8 ° C./second or more, 5 ° C./second or less, and preferably 1.5 ° C./second or less. The cooling rate of the emulsion is 0.5 to 5 ° C./second, preferably 0.8 to 1.5 ° C./second.
It is preferable to cool to below the solidification temperature of the oil component by such a cooling step.

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 stirring in a tubular casing comprising a drive shaft and a stirring blade attached to the drive shaft. The stirring blade is provided with a body, and the drive shaft is configured to vibrate in the axial direction. The stirring blade is provided with one or more openings and / or one or more notches. It is preferable to continuously cool the emulsion obtained in the emulsification step by passing it through a vibration type stirring and mixing device in the cooling step, and a cosmetic in which fine emulsified particles are dispersed (fine particle dispersion) Product).

More specifically, FIG. 1 shows a schematic diagram of a manufacturing apparatus suitably used in the present invention. The manufacturing apparatus 100 shown in FIG. 1 cools the formed emulsion by mixing the composition containing the components (A) to (D) with water (E) under heating to form an emulsion, and cooling the formed emulsion. The cooling part 30 to be provided. The emulsifying unit 20 includes a first emulsifying unit 21 and a second emulsifying unit 22. The first emulsifying unit 21 is used to fill all or part of the components constituting the fine particle dispersion, and to mix the filled components with water under heating to obtain a preliminary emulsion. The 2nd emulsification part 22 is located in the downstream of the 1st emulsification part 21, and is used in order to add a high energy to the preliminary | backup emulsion obtained by the 1st emulsification part 21, and to obtain a fine emulsion. . The cooling unit 30 is located on the downstream side of the emulsifying unit 20 and is used to cool the heat-mixed emulsion to a temperature equal to or lower than the solidification temperature of the oily component that is solid at 25 ° C. to obtain a desired fine particle dispersion. It is

The 1st emulsification part 21 of the emulsification part 20 is provided with the mixing tank 211 as shown in FIG. The mixing tank 211 is heated by a jacket 212 that covers the side of the mixing tank 211 and is adjusted to a predetermined temperature. A stirring blade 213 is installed in the mixing tank 211. The stirring blade 213 is connected to a motor 215 installed outside the mixing tank 211 via a shaft 214 and is rotatable. A pipe 216 for taking out the preliminary 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 unit 22 through 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 1st emulsification part 21 which has the above structure, TK combi mix (trade name) made by Primex, TK azi homomixer (trade name) made by Primex, etc. can be used. Although these stirring apparatuses are mainly used independently, depending on the case, you may use them suitably combining 2 or more types.

The 2nd emulsification part 22 of the emulsification part 20 is provided with the high energy process part 221 as shown in FIG. The high energy processing unit 221 can apply high energy to the preliminary emulsion obtained in the first emulsification unit 21 using a high-pressure emulsifier or an ultrasonic emulsifier.
A pipe 222 is connected to a downstream portion of the high energy processing unit 221 for taking out the emulsion to which high energy is added in the high energy processing unit 221. The emulsion obtained in the second emulsification unit 22 is supplied to the cooling unit 30 through the pipe 222. Note that a metering pump (not shown) may be interposed in the middle of the pipe 222 as necessary for the purpose of metering the emulsion obtained by the second emulsifying unit 22.

When a high-pressure emulsifier is used as the second emulsifier 22 having the above configuration, for example, a starburst mini (part number: HJP-25001) (manufactured by Sugino Machine) or an optimizer (manufactured by Sugino Machine) is a high-pressure emulsifier ), Gorin (manufactured by APV Runny), microfluidizer (manufactured by Microfluidics), high-pressure jet emulsifier (manufactured by Nippon BEE) and the like.

When an ultrasonic emulsifier is used as the second emulsifier 22, for example, an IKASONIC (part number: U200S) (manufactured by IKA) equipped with an ultrasonic generation 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 kinds may be used as appropriate.

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

FIG. 2 shows a schematic diagram of a longitudinal section of the vibration type stirring and mixing device 40. The apparatus 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 vibrated up and down along the axial direction by the vibrator 45a.

The casing 41 has a tubular shape with a circular cross section, and an inflow port 31 is provided in the vicinity of the lower portion thereof. A discharge port 32 is provided near the upper portion of the casing 41. The emulsion flowing in from the inflow port 31 is mixed while passing through the casing 41, continuously cooled, and discharged from the discharge port 32.

In the casing 41, the above-described stirring body 44 is disposed. The drive shaft 42 of the stirring body 44 extends in the longitudinal direction (vertical direction) of the casing 41. The upper end of the drive shaft 42 is connected to the vibrator 45a through 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 part (not shown) and a swinging part (not shown). The rotating part is attached eccentrically with respect to the output shaft of the motor. The oscillating part is oscillated by the eccentric rotation of the rotating part. Then, the swing of the swing portion is transmitted to the drive shaft 42 as vertical vibration.

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

3 (a) and 3 (b) are enlarged views of the main part of the stirring member 44. FIG. The stirrer 44 includes a drive shaft 42 and a stirring blade 43 spirally attached to the peripheral surface thereof. In the figure, the stirring blades 43 are attached in a spiral shape with three rounds. The stirring bodies 44 in this state are provided as a set, and the stirring bodies 44 are arranged in the mixing chambers 47 in the casing. Therefore, the number of sets of stirring bodies 44 is the same as the number of mixing chambers 47. In each set of stirring bodies 44, the spiral directions of the stirring blades 43 are the same.

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

As the vibratory stirring and mixing device 40 having the above-described configuration, for example, the one described in JP-A-4-235729 can be used. Moreover, a commercial item can also be used as the vibration type stirring and mixing apparatus 40. As such a commercial item, the apparatus provided with the cooling jacket in the Vibro mixer (trademark) by a refrigeration industry company is mentioned, for example.

The production method of the fine particle dispersion using the production apparatus 100 having the above configuration will be described. First, the components constituting the target fine particle dispersion in the mixing tank 211 of the first emulsification unit 21 of the emulsification unit 20 are described. All or a part is filled (water as a dispersion medium is included as a component filled in the mixing tank 211). When a part of the components constituting the fine particle dispersion is filled, 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 types of the first emulsifying unit 21 are provided, the upstream first emulsifying unit 21 may be filled with all of the components constituting the target fine particle dispersion, The emulsifying part 21 may be partially filled with components constituting the target fine particle dispersion. By partially filling, the mixing conditions of each component can be adjusted individually and appropriately.

The components filled in the mixing tank 211 include at least one oily component that is 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 oily component that is solid at 25 ° C. into a molten state. Then, each component is mixed and dispersed by the stirring blade 213 in the mixing tank 211 to obtain a preliminary emulsion. The heating temperature can be appropriately set according to the melting point of the solid fat. Generally, it is preferable to set the temperature higher by about 10 ° C. 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 preliminary emulsion in the mixing tank 211 is taken out. The preliminary emulsion is supplied to the high energy processing unit 221 of the second emulsification unit 22 through the pipe 216.

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

In addition, the number of times the high energy processing unit 221 passes is preferably 1 or more. When passing through the high energy processing unit 221 a plurality of times, it means the total dropped energy of all of the dropped energy added when each high energy processing unit 221 passes.

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 vibratory stirring and mixing device 40 via a tube 222. The transition time from the emulsification step (emulsification unit 20) to the cooling step (cooling unit 30) is preferably within 60 seconds from the viewpoint of preventing the emulsion obtained in the emulsification unit 20 from aggregating. More preferably, it is within 10 seconds. The lower limit value 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 the emulsion obtained in the second emulsifying unit 22 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 to reach. The transition time can be adjusted by the length of the tube 222, for example.

As described above, four jackets 34, 35, 36, and 37 are attached to the vibration type stirring and mixing device 40 as cooling jackets. The cooling jacket is disposed outside the casing 41 so as to cover the cylindrical casing 41 shown in FIG. 2, and cooling water of a predetermined temperature is circulated through each jacket, and the emulsification obtained in the emulsification unit 20 By passing the object through the casing 41, heat exchange for cooling the fluid is performed.

The total flow rate of the cooling water circulating through the cooling jacket is not particularly limited from the viewpoint of efficiently cooling the emulsion obtained in the emulsifying unit 20 without agglomeration, and it is preferable that the upper limit is larger. Specifically, the total flow rate of the cooling water is preferably 10 times or more, more preferably 30 times or more with respect to the flow rate of the emulsion. Here, the flow rate of the emulsion means the flow rate when the emulsion obtained in the emulsification unit 20 passes through the casing 41. Further, the total flow rate of the cooling water is the total flow rate of all the flow rates of the cooling water circulating through each jacket when the four jackets 34, 35, 36, and 37 are provided as in the vibration type stirring and mixing device 40. means.

The temperature of the cooling water can be appropriately set, and these jackets can cool the emulsion continuously or stepwise from the inlet 31 side toward the outlet 32 side. 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 inlet side to the outlet side of the stirring and mixing device 31, or all may be set to the same temperature. Also good.

The cooling water of the four jackets 34, 35, 36, and 37 is, for example, for the emulsion flowing from the inlet 31 side (upstream side) to the outlet 32 side (downstream side) of the vibration type stirring and mixing device 40. Further, it may be circulated from the upstream side to the downstream side in the order of the flow of the emulsion or from the downstream side to the upstream side against the flow of the emulsion.

In the vibration type stirring and mixing device 40, the stirring body 44 vibrates up and down along the axial direction thereof, so that the emulsion passing through the casing 41 is provided in the flow along the stirring body 44 and the stirring blade 43. Further mixing occurs without agglomeration due to turbulence in the flow through the perforations 48 and notches 49. Therefore, it is possible to highly disperse fine particles of solid fat.

And, when the emulsion is cooled by heat exchange with cooling water, its fluidity decreases. The emulsion is cooled while being mixed by the flow along the stirrer 44 and the disturbance of the flow through the opening 48 and the notch 49 provided in the stirring blade 43, so that uneven cooling is less likely to occur. Further, since there is almost no dead space in the vibration type stirring and mixing device 40, uneven stirring is less likely to occur. The vibration type agitation and mixing device 40 can perform good agitation and mixing even when the flowability of the emulsion is high or low. These advantages of the vibration type stirring and mixing device 40 bring about a preferable effect that the emulsified particles containing the solid oil agent (wax component or the like) contained in the emulsion can be uniformly refined. In addition, since the vibration type agitation and mixing device 40 has a small calorific value, it is excellent in cooling efficiency and can be quickly cooled while the emulsion particles are uniformly refined, so that the emulsion particles containing solid fat can be dispersed well. Is possible. A small calorific value is advantageous from the viewpoint of easy temperature control.

In this way, the emulsion is cooled to a solid oil temperature below the solidification temperature without continuously agglomerating, so that the fine particle dispersion is highly productive and can provide a fine particle dispersion with excellent quality. The target dispersion is discharged from the discharge pipe 33 through the discharge port 32 of the vibration type stirring and mixing apparatus 40. The temperature of the target dispersion in this state is about 30 ° C.

In cooling using the vibration type stirring and mixing device 40, the average cooling rate is preferably set to 0.1 to 8 ° C / sec, more preferably set to 0.5 to 5 ° C / sec. More preferably, it 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 it exits by the residence time. Further, the vibration frequency of the vibration type stirring and mixing apparatus 40 is preferably in the range of 2.5 to 30 Hz, and more preferably in the range of 5 to 25 Hz. The amplitude of the vibration type stirring and mixing device 40 is preferably 4 to 15 mm. Further, the total amount of vibration applied while cooling by the vibration type stirring and mixing device 40 is preferably 50 to 100,000 strokes, particularly 200 to 20000 strokes.

Thus, the fine particle dispersion obtained by the production apparatus 100 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 protective cosmetic of the present invention. The fine particle dispersion obtained in the manufacturing apparatus 100 is used because the solid oil agent is uniformly refined in the high energy processing unit 221 and cooled in the cooling unit 30 while the solid oil agent is uniformly refined. The feeling is good, in particular, stickiness is reduced, and cosmetic effects such as UV protection effects are enhanced.

In addition, although the manufacturing method was demonstrated based on preferable embodiment, it is not restrict | limited to this. For example, in the above-described embodiment, one vibration type stirring and mixing device 40 is used, but instead of this, a plurality of vibration type stirring and mixing devices 40 can be connected in series and used.

Since the ultraviolet protective cosmetic of the present invention thus obtained is produced by the process as described above, it contains fine emulsified particles. From the viewpoint of improving the UV protection effect and reducing the feeling of 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 preferable.
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, and the lower the value, the sharper the particle size distribution.
As described above, the ultraviolet protective cosmetic 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 protective effect, and a good feeling of use. This is considered to be one of the factors that cause skin irritation.
In the present invention, the volume median diameter is measured by a laser diffraction / scattering method using a laser diffraction / scattering particle size distribution measuring apparatus (model number: LA-920, manufactured by Horiba, Ltd.).

The ultraviolet protective cosmetic of the present invention can be, for example, lotion, milky lotion, cream, gel, cosmetic liquid, etc., and more preferably cream or gel. Moreover, it can also be set as the sheet-like cosmetics impregnated or apply | coated to sheet-like base materials, such as a woven fabric and a nonwoven fabric.
The UV protective cosmetic of the present invention can be used by applying it to any of skin, preferably scalp, more preferably face, body, limbs and the like.
The present invention further discloses the following inventions with respect to the above-described embodiments.

<1> The following components (A), (B), (C), (D) and (E):
(A) Ionic surfactant 0.18-2% by mass,
(B) 1-10% by weight of a hydrophobic amphiphile,
(C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
(D) 0.01 to 6% by mass of a solid oil agent,
(E) a UV protection cosmetic containing water,
An emulsification step of mixing the composition containing components (A) to (D) with water under heating (E) to form an emulsion;
An ultraviolet 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./second.

<2> The ionic surfactant of component (A) is preferably an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a sphingosine and a salt thereof, and is selected from an anionic surfactant and a sphingosine At least one is more preferred, an anionic surfactant is more preferred, long-chain N-acyl glutamate is still more preferred, sodium dilauroyl glutamate, monosodium N-lauroyl glutamate, sodium N-stearoyl-L-glutamate, N- More preferable is at least one selected from arginine stearoyl-L-glutamate, sodium N-stearoyl glutamate, and sodium N-myristoyl-L-glutamate, 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.
The content of <3> component (A) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, in the total composition, 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 more preferable. The ultraviolet protective cosmetic according to <1> or <2>.
<4> The content of the nonionic surfactant is preferably 1% by mass or less in the total composition, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less. The ultraviolet protective cosmetic according to any one of <1> to <3>, wherein 0% by mass is even more preferable.

<5> The hydrophobic amphiphile of 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 mono fatty acid having 10 to 24 carbon atoms. At least one or more selected from glycerin ester, monoalkyl glyceryl ether having 10 to 24 carbon atoms, mono fatty acid sorbitan ester having 10 to 24 carbon atoms, mono fatty acid sorbite ester having 10 to 24 carbon atoms, At least one 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 monofatty acid sorbitan esters having 14 to 22 carbon atoms More preferably, an alcohol having 16 to 22 carbon atoms and a mono fatty acid glycerin 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 amphiphile of component (B) is preferably an alcohol having 14 to 22 carbon atoms, a mono fatty 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 alcohols having 14 to 22 carbon atoms and mono-fatty acid glycerin esters having 14 to 22 carbon atoms. It is more preferable to contain an alcohol having 16 to 22 carbon atoms and a mono-fatty acid glycerin ester having 16 to 22 carbon atoms, and contains cetyl alcohol and stearyl alcohol, and a mono-fatty acid glycerin ester having 16 to 22 carbon atoms. <1> to <5>, wherein UV protection is more preferable. Fee.
The content of <7> component (B) is preferably 1.5% by mass or more in the total composition, more preferably 2% by mass or more, further preferably 2.5% by mass or more, and 8% by mass. The ultraviolet protective cosmetic according to any one of <1> to <6>, preferably 5% by mass or less, more preferably 3.8% by mass or less.

<8> The oil-soluble ultraviolet absorber of 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, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, diethylaminohydroxybenzoylbenzoic acid hexyl ester, bisethylhexyloxyphenol methoxyphenyltriazine One or more selected from the group consisting of 2-methoxyhexyl paramethoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine, It is more preferable to include one or more selected from the above, and it is more preferable to include 2-methoxyhexyl paramethoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate and bisethylhexyloxyphenol methoxyphenyl triazine <1> The ultraviolet protective cosmetic according to any one of <7>.
<9> As the oil-soluble UV absorber, one or more selected from cinnamic acid-based oil-soluble UV absorbers, diethylaminohydroxybenzoyl hexyl benzoate, triazine-based oil-soluble UV absorbers are more preferable. It is more preferable to include an oil-soluble ultraviolet absorber of some kinds, and it is more preferable to include 2-methoxyhexyl paramethoxycinnamate, hexyl ethylaminohydroxybenzoylbenzoate, and bisethylhexyloxyphenol methoxyphenyl triazine. 8> UV protection cosmetics given in any 1 paragraph.
<10> Any of the above <1> to <9>, wherein the liquid oil other than the oil-soluble ultraviolet absorber preferably contains at least one selected from linear or branched hydrocarbon oils, ester oils, and silicone oils Or UV protective cosmetics according to claim 1.

<11> In the total liquid oil of component (C), the content of the oil-soluble ultraviolet absorber is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more. The ultraviolet protective cosmetic according to any one of <1> to <10>, preferably 100% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
<12> In the UV protective cosmetic, the content of the oil-soluble UV absorber is preferably 6% by mass or more, more preferably 8% by mass or more, more preferably 10% by mass or more, in the total composition, 20 The ultraviolet protective cosmetic according to any one of the above items <1> to <10>, preferably at most mass%, more preferably at most 18 mass%, further preferably at most 15 mass%.
<13> In the oil-soluble ultraviolet absorber, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably 60 to 100% by mass, and more preferably 70 to 90% by mass. 12> UV protection cosmetics given in any 1 paragraph.
<14> In the oil-soluble ultraviolet absorber, the total content of the triazine oil-soluble ultraviolet absorber and diethylaminohydroxybenzoyl hexyl benzoate is preferably 0 to 40% by mass, more preferably 10 to 30% by mass. The ultraviolet protective cosmetic according to any one of the above items <1> to <13>.
<15> The content ratio of the cinnamic acid-based oil-soluble UV absorber to the total amount of the triazine-based oil-soluble UV absorber and diethylaminohydroxybenzoyl hexyl ester in the oil-soluble UV absorber (cinnamate-based oil-soluble UV light Absorber / [Triazine oil-soluble UV absorber + diethylaminohydroxybenzoyl hexyl benzoate] is preferably 9/1 to 5/5, more preferably 8.5 / 1.5 to 6/4 The ultraviolet protective cosmetic according to any one of <1> to <14>, more preferably 8/2 to 6.5 / 3.5.
The content of <16> component (C) is preferably 3% by mass or more in the total composition, more preferably 10% by mass or more, further preferably 12% by mass or more, and preferably 35% by mass or less, The UV protective cosmetic according to any one of <1> to <15>, wherein 25% by mass or less is more preferable, and 17% by mass or less is more preferable.

<17> The mass ratio [(A) / (C)] of the component (A) to the component (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 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 more preferable. <1> to <16 > UV protective cosmetics according to any one of
<18> The mass ratio [(B) / (C)] of the component (B) to the component (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 more preferable, 0.5 or less is preferable, 0.39 or less is more preferable, 0.27 or less is more preferable, and 0.24 or less is more preferable. <1> to <17 > UV protective cosmetics according to any one of

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

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

<26> The emulsification step is preferably performed using a homomixer, an ultrasonic emulsifier, and a high-pressure emulsifier, and the blended components are mixed under heating, preferably at 60 to 120 ° C., more preferably at 80 to 100 ° C. The ultraviolet protective cosmetic according to any one of 1> to <25>.
<27> The cooling step is preferably performed by rapidly and rapidly using the obtained emulsion using a vibration type stirring and mixing device, a scraping type heat exchanger, a static mixer, a plate type heat exchanger, and a double pipe type heat exchanger. The ultraviolet protective cosmetic according to any one of <1> to <26>, wherein the cosmetic is cooled by a method of cooling or a method of stirring and cooling in a general mixing tank.
<28> The ultraviolet protective cosmetic according to any one of <1> to <27>, wherein the cooling rate is preferably 0.8 ° C./second or more and preferably 1.5 ° C./second 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 further preferably 0.20 to 0.25 μm. 28> The ultraviolet protective cosmetic according to any one of 28>.
<30> The ultraviolet protective 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 further preferably 20 to 25. .
<31> An ultraviolet protective makeup wherein the ultraviolet protective cosmetic according to any one of the above <1> to <30> is applied to the skin, preferably excluding the scalp, more preferably any one of the face, body, limbs, etc. Use as a fee.

<32> The following components (A), (B), (C) and (D):
(A) Ionic surfactant 0.1-2% by mass,
(B) 1-10% by weight of a hydrophobic amphiphile,
(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 emulsification step in which an emulsion is formed by mixing a composition containing
A method for producing an ultraviolet protective cosmetic comprising a cooling step of cooling the emulsion formed in the emulsification step at a cooling rate of 0.5 to 5 ° C / second.

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

(Production method)
(1) Example 1:
Components (A) to (D), a part of component (E), propanediol, glycerin, arginine and phenoxyethanol are dispersed with a homomixer under heating at 85 ° C., and then a high-pressure emulsifier (Sugino Machine, Starburst) An emulsion was obtained using Mini HJP-25001). The number of passes (number of passes) of the high-pressure emulsifier was one. The emulsion is supplied to a vibration type stirring and mixing apparatus (Cooling Kogyo Co., Ltd., Vibro mixer) with a transition time of 10 seconds while maintaining the emulsion at 85 ° C., and the emulsion is stirred by vibrating the stirring body up and down in the apparatus. While continuously cooling to 40 ° C. or lower (step (1)). This cooled emulsion and a mixture obtained by mixing a part of component (E), component (F) and the other components described in the table are mixed at room temperature (25 ° C.) ( Step (2)), an ultraviolet protective cosmetic was obtained.
In the vibration type 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 is 10 times the flow rate of the emulsion. Cooled by cooling water. The average cooling rate at this time was 1 ° C./sec. Moreover, the vibration frequency of the vibration type stirring and mixing apparatus was 20 Hz.

(2) Examples 2 to 28 and Comparative Examples 1 to 4:
In the same manner as in Example 1, UV 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 (1). The obtained emulsion was cooled to 40 ° C. with stirring using an anchor blade (rotation speed: 75 rpm) in a container to obtain an ultraviolet protective 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 performed without stirring at a cooling rate of 0.01 ° C./second in a thermostat capable of temperature control.

(Evaluation methods)
(1) Volume median diameter, coefficient of variation:
The volume-based median diameter and coefficient of variation were measured at a temperature of 25 ° C. by a laser diffraction / scattering method using a laser diffraction / scattering 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, cosmetics in which at least one sharp diffraction peak appears in the vicinity of a Bragg angle = 21 to 22 ° have an α-gel structure, and “α” is shown in the table.

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

(4) Storage stability:
A 50 mL glass bottle was charged with 40 mL of cosmetic, sealed, and stored at −5 ° C. for 1 month. The appearance and fluidity of the cosmetic after storage were visually observed. As for the fluidity, the fluidity when tilted to 45 ° C. was visually confirmed. The standards are as follows.
4: No change in appearance and / or fluidity.
3: Slight changes are observed in both appearance and fluidity.
2: Slightly large 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) Feeling of use:
Five professional panelists applied 0.02 mL of each cosmetic material to a 3 cm diameter circle 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, assuming that there was no stickiness at all, and 1 when there was very stickiness, and the average score of five people was obtained.

(6) Skin irritation:
Five specialist panelists applied 0.02 mL of cosmetic material with 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 sense of irritation was evaluated in increments of 0.1, assuming 5 when there was no irritation and 1 when there was a very irritation, and the average score of 5 people was obtained.

[Supplement under rule 26 29.07.2016]

[Supplement under rule 26 29.07.2016]

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

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

Examples 32-34, Comparative Example 6
In the same manner as in Examples 1 to 28, UV protective cosmetics having the compositions shown in Table 6 were produced, volume median diameter and coefficient of variation were measured, α gel confirmation, SPF value, storage stability, feeling of use and skin Irritation was evaluated. The results are also shown in Table 6.
The cooling rates for producing the cosmetics of Examples 32 to 34 and Comparative Example 6 are as shown in Table 6.

Example 35 and Comparative Example 7
In the same manner as in Examples 1 to 28, ultraviolet protective cosmetics having the compositions shown in Table 7 were produced, and the transdermal absorbability of the ultraviolet absorber was evaluated.

Evaluation of transdermal absorbability of UV absorber
Test procedure The test procedure is as follows. The human excised skin stored frozen at −80 ° C. was thawed at room temperature for about 30 minutes to remove excess fat attached to the skin, and then cut into about 2 cm squares and used for measurement. The sample was applied to the skin thus obtained and subjected to a permeation test.
The permeation test was performed using a Franz type diffusion cell (formulation application area 1 cm ² , receptor phase 16 mL). 10 μL of the prepared sample was put in the donor phase and kept at 37 ° C. for 24 hours. After 24 hours, the skin surface sample was cleanly removed with purified water, and then separated into epidermis and dermis. Each was ultrasonically treated with 5 mL of methanol for 20 minutes, filtered through a membrane filter (PTFE 0.45 μm ADVANTEC), and then the concentration of the ultraviolet absorber was measured with an ultraviolet-visible spectrophotometer UV3600 (Shimadzu Corporation).

Test Results The samples of Table 7 were evaluated for transdermal absorbability. The results are shown in Table 8 below.

It can be seen that the sample of Example 35 encapsulating the UV absorber has a much lower transdermal absorbability of the UV absorber than the sample of Comparative Example 7 not encapsulating the UV absorber.

DESCRIPTION OF SYMBOLS 100 Apparatus 20 Emulsification part 21 1st emulsification part 211 Mixing tank 22 2nd emulsification part 221 High energy processing part 30 Cooling part 34,35,36,37 Jacket 40 Vibrating stirring 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 (8)

1. The following components (A), (B), (C), (D) and (E):
   (A) Ionic surfactant 0.18-2% by mass,
   (B) 1-10% by weight of a hydrophobic amphiphile,
   (C) 1 to 40% by mass of a liquid oil containing an oil-soluble ultraviolet absorber,
   (D) 0.01 to 6% by mass of a solid oil agent,
   (E) a UV protection cosmetic containing water,
   An emulsification step of mixing the composition containing components (A) to (D) with water under heating (E) to form an emulsion;
   An ultraviolet 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./second.
2. The ultraviolet protective cosmetic according to claim 1, further comprising (F) a water-soluble polymer.
3. The ultraviolet protective cosmetic according to claim 1 or 2, wherein the mass ratio (A) / (C) of the component (A) to the component (C) is 0.01 to 0.2.
4. The ultraviolet protective cosmetic according to any one of claims 1 to 3, wherein the mass ratio (B) / (C) of the component (B) to the component (C) is 0.01 to 0.5.
5. The ultraviolet protective cosmetic according to any one of claims 1 to 4, wherein the mass ratio (D) / (C) of the component (D) to the component (C) is 0.01 to 0.5.
6. The ultraviolet protective cosmetic according to any one of claims 1 to 5, further comprising (F) a water-soluble polymer.
7. The ultraviolet protective cosmetic according to any one of claims 1 to 6, wherein the emulsified particles have a volume median diameter of 0.1 to 10 µm.
8. The following components (A), (B), (C) and (D):
   (A) Ionic surfactant 0.1-2% by mass,
   (B) 1-10% by weight of a hydrophobic amphiphile,
   (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 emulsification step in which an emulsion is formed by mixing a composition containing
   A method for producing an ultraviolet protective cosmetic comprising a cooling step of cooling the emulsion formed in the emulsification step at a cooling rate of 0.5 to 5 ° C / second.

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