TWI739747B - Manufacturing method of UV protection cosmetics - Google Patents

Abstract

The ultraviolet protective cosmetics provided by the present invention have excellent storage stability, high ultraviolet protective effect, non-sticky, good use feeling, and no skin irritation.

The ultraviolet protective cosmetic of the present invention contains the following components (A), (B), (C), (D) and (E): (A) 0.18-2% by mass of ionic surfactant, (B) Hydrophobic amphiphilic substance 1-10% by mass, (C) liquid oil containing oil-soluble ultraviolet absorber 1-40% by mass, (D) solid oil 0.01-6% by mass, (E) water Ultraviolet protection cosmetics, which are obtained by a method including the following steps: an emulsification step of mixing a composition containing ingredients (A) to (D) with (E) water under heating to form an emulsified product; The emulsified product formed in the above emulsification step is subjected to a cooling step of cooling at a cooling rate of 0.5 to 5°C/sec.

Description

Manufacturing method of UV protection cosmetics

The present invention relates to UV protection cosmetics.

Sun exposure by ultraviolet rays promotes skin browning, reduced skin elasticity, and wrinkles. Therefore, in order to prevent these phenomena, cosmetics mixed with ultraviolet absorbers are used.

Among the ultraviolet absorbers, oil-soluble ultraviolet absorbers are excellent in absorbing ultraviolet rays, but if they are directly blended into cosmetics, irritation and stickiness may be felt, and there are problems in terms of the feeling of use.

Therefore, reviews have been conducted on cosmetics in which the ultraviolet absorber is formed into a fine emulsion and then blended or encapsulated and blended (for example, Patent Documents 1 to 3).

(Patent Document 1) Japanese Patent Laid-Open No. 2012-31125

(Patent Document 2) Japanese Patent Publication No. 2005-504750

(Patent Document 3) Japanese Patent Laid-Open No. 2009-167168

The ultraviolet protection cosmetics related to the present invention contain the following ingredients (A), (B), (C), (D) and (E): (A) ionic surfactant 0.18-2% by mass, (B) hydrophobic amphiphilic substance 1-10% by mass, (C) oil-soluble ultraviolet absorber Liquid oil 1-40% by mass, (D) solid oil 0.01-6% by mass, (E) water UV protection cosmetics, which are obtained by a method including the following steps: The composition of A)~(D) is mixed with (E) water under heating to form an emulsification step of emulsification; the emulsification formed in the above emulsification step is cooled at a cooling rate of 0.5-5°C/sec. The cooling step.

20‧‧‧Emulsification Department

21‧‧‧Part 1 Emulsification Department

22‧‧‧Second Emulsification Department

30‧‧‧Cooling Department

31‧‧‧Inlet

32‧‧‧Exit

33‧‧‧Exhaust tube

34, 35, 36, 37‧‧‧ Jacket

40‧‧‧Vibrating mixing device

41‧‧‧Shell

42‧‧‧Drive shaft

43‧‧‧Mixing blade

44‧‧‧Agitator

45a‧‧‧Vibrator

45b‧‧‧Connector

46‧‧‧Compartment Department

47‧‧‧Mixing Room

48‧‧‧Opening

49‧‧‧Gap

100‧‧‧Manufacturing equipment

211‧‧‧Mixing tank

212‧‧‧Jacket

213‧‧‧Mixing blade

214‧‧‧Axis

215‧‧‧Motor

216‧‧‧tube

221‧‧‧High Energy Processing Department

222‧‧‧tube

Fig. 1 is a schematic diagram showing a vibration-type stirring and mixing device suitable for manufacturing the cosmetic of the present invention.

Fig. 2 is a schematic diagram of a longitudinal section of the vibratory stirring and mixing device shown in Fig. 1.

Fig. 3 is an enlarged view of an important part of a stirring body of the vibratory stirring and mixing device shown in Fig. 1.

Conventional cosmetics blended with ultraviolet absorbers have poor storage stability and are not sufficiently satisfactory in terms of feeling in use.

Furthermore, when applying cosmetics containing ultraviolet absorbers to the skin, the ultraviolet absorbers are not uniformly attached to the skin, and therefore, sufficient UV protection effects cannot be obtained. fruit. Even if a large amount of ultraviolet absorbers are blended in order to improve the ultraviolet protection effect, there are still problems in terms of storage stability, feeling of use, and the like.

The present invention relates to an ultraviolet protection cosmetic that uniformly disperses an oil agent containing an ultraviolet absorber, has excellent storage stability, has a high ultraviolet protection effect, has a good feeling of use, and has no skin irritation.

The inventors of the present invention found that a cosmetic obtained by combining ionic surfactants, hydrophobic amphiphilic substances, liquid oils containing oil-soluble ultraviolet absorbers, and solid oils in a specific ratio and according to a specific method The material is dispersed with α gel particles containing oil-soluble ultraviolet absorbers, and has excellent storage stability, high ultraviolet protection effect, good use feeling, and no skin irritation.

The ultraviolet protection cosmetic of the present invention is dispersed with α gel particles containing an oil-soluble ultraviolet absorber, and has excellent storage stability. In addition, when applied to the skin, the oil-soluble UV absorber is uniformly attached to the skin, and can obtain a high UV protection effect, is non-sticky, and has a good feeling of use, and the transdermal absorbability of the UV absorber is low. Skin irritation.

The ionic surfactant of the component (A) used in the present invention is generally used by cosmetics users, and anionic surfactants, cationic surfactants, amphoteric surfactants, neuraminol and salts thereof can be used.

Examples of anionic surfactants include: sodium laurate, potassium palmitate, arginine stearate and other fatty acid salts with carbon numbers 12-24; sodium lauryl sulfate, potassium lauryl sulfate and other alkyl sulfate ester salts; Ethylene lauryl sulfate triethanolamine and other alkyl ether sulfates; Sodium cinnamyl sarcosinate and other N-lactyl sarcosinates; N-myristyl-N-methyl taurate sodium and other fatty acid amide sulfonates; sodium monostearyl phosphate and other alkyl phosphates Salts; polyoxyethylene alkyl ether phosphates such as polyoxyethylene oleyl ether sodium phosphate, polyoxyethylene stearyl ether sodium phosphate; long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate; Sodium dilaurate glutamate, monosodium N-laurel glutamate, sodium N-stearyl-L-glutamate, N-stearyl-L-glutamate arginine, Sodium N-stearyl glutamate, sodium N-myristyl-L-glutamate and other long-chain N-glutamate, etc.

Among them, from the standpoint of improving the preservation stability of the ultraviolet protective cosmetics, and from the standpoint of improving the feeling of use, especially reducing the stickiness, the long-chain N-glycylglutamate is preferred.

The cationic surfactant is preferably a quaternary ammonium salt, such as: stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride and other alkyl trimethyl ammonium chloride salts; dialkyl dimethyl ammonium, Trialkyl methyl ammonium chloride, alkyl amine salt, etc.

、烷基磺基甜菜

、醯胺胺基酸鹽、烷基醯胺丙基甜菜

等，較佳係烷基醯胺丙基甜菜

。 Amphoteric surfactants include, for example: alkyl dimethyl amine oxide, alkyl carboxyl beet

Alkyl Sulfobeet

, Amide amino acid salt, alkyl amide propyl beet

Etc., preferably alkylamidopropyl beet

.

Neuraminol and its salts can include, for example: natural neuraminol, dihydroneuraminol, autonomic neuraminol, sphingosine dienol, dehydrosphingosine (dehydrosphingosine), dehydrophytosanol, And these N-alkyl bodies (for example, N-methyl bodies) and the like.

These can be any of natural extracts and synthetics, and commercially available ones can be used. Things. Examples of commercially available natural-type sphingosines include D-sphingenine (4-Sphingenine) (SIGMA-ALDRICH), DS-sphingosine (DOOSAN), and phytosphingenine (COSMO FARM).

Furthermore, the salts of these neuraminols include, for example, acidic amino acid salts such as glutamine and aspartic acid; basic amino acid salts such as arginine; inorganic acid salts such as phosphoric acid and hydrochloric acid; acetic acid, etc. Monocarboxylates; dicarboxylates such as succinic acid; oxycarboxylates such as citric acid, lactic acid, and malic acid, etc. It is preferable to select one or two or more from these.

The ionic surfactant of component (A) is preferably an anionic surfactant and neuraminol from the viewpoint of improving the preservation stability of UV-protective cosmetics, improving the feeling of use, and particularly reducing stickiness. Among them, at least one, more preferably an anionic surfactant is selected.

Among the anionic surfactants, it is preferred to contain long-chain N-glutamate; and among the long-chain N-glutamate, it is preferred to be from sodium dilaurate glutamate, N -Sodium lauryl glutamate, sodium N-stearyl-L-glutamate, N-stearyl-L-glutamate arginine, sodium N-stearyl glutamate , Choose at least one of N-myristyl-L-glutamate sodium, more preferably from N-stearyl glutamate sodium, N-stearyl-L-glutamate spermine Choose at least one of the acids, especially N-stearyl-L-glutamate arginine.

Component (A) can be used singly or in combination of two or more. From the standpoint of improving the storage stability of UV-protective cosmetics, improving the feeling of use, and particularly reducing stickiness, its content is the total 0.18% by mass or more in the composition, preferably 0.2 Mass% or more, particularly preferably 0.3 mass% or more, more preferably 0.4 mass% or more, still more preferably 0.45 mass% or more, and 2 mass% or less, preferably 1.5 mass% or less, more preferably 1.1 mass% or less, and still more The best system is 0.9 mass% or less, and the more preferable system is 0.7 mass% or less. In addition, the content of the component (A) in the total composition is 0.18 to 2% by mass, preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.1% by mass, still more preferably 0.4 to 0.9% by mass, and still more The best system is 0.45~0.7% by mass.

In addition, in the present invention, the component (A) is the content in terms of acid.

Furthermore, within a range that does not impair the effects of the present invention, non-ionic surfactants may also be included. From the viewpoint of improving the storage stability of the ultraviolet protective cosmetics, and improving the feeling of use, especially reducing the stickiness. The content of the nonionic surfactant in the total composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, and still more preferably substantially 0% by mass.

The hydrophobic amphiphilic substance of the component (B) used in the present invention includes, for example, brain amines, alcohols with 10 to 24 carbons, linear saturated fatty acids with 10 to 24 carbons, and 10 to 24 carbon atoms. 24 monoglycerides of fatty acids, monoalkyl glycerides with 10-24 carbons, sorbitan monofatty acids with 10-24 carbons, sorbitan monofatty acids with 10-24 carbons, etc.

Cerebral amines can use one or two or more types selected from natural ceramide and pseudo-cerebral amine. From the viewpoint of improving the preservation stability of the ultraviolet protective cosmetics, specifically, the brain amines described in Japanese Patent Laid-Open No. 2013-53146 are preferable.

Specific examples of natural ceramides include, for example, brains that are aminated by ceramide, dihydroceramide, autonomic ceramide, or sphingadienine (sphingadienine). Amide Type1~7 (e.g.: Figure 2 in J. Lipid Res., 24: 759 (1983), and the pig and human body described in Figure 4 in J. Lipid. Res., 35: 2069 (1994) Brain amine).

Furthermore, these N-alkyl forms (such as N-methyl forms) are also included.

These brain amines can use natural (D(-) form) optically active form, non-natural form (L(+) form) optical active form, and natural and non-natural form mixture. The relative three-dimensional configuration of the above compound may be a natural three-dimensional configuration, other non-natural three-dimensional configurations, or a mixture of these. Especially good series of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II compounds (the above are INCI, 8th Edition) and the following formula:

For these systems, any of natural extracts and synthetics can be used, and commercially available products can also be used. Such commercially available natural brain amines include, for example: Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (all above are COSMO FARM); Ceramide TIC-001 (Takasago Fragrances) CERAMIDE II (Quest International); DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN); CERAMIDE2 (Sederma).

(式中，R¹係表示亦可被羥基取代的碳數10~22之直鏈、分支鏈、或環狀的飽和或不飽和烴基、或氫原子；X¹係表示氫原子、乙醯基或甘油基；R²係表示亦可被羥基或胺基取代的碳數5~22之直鏈、分支鏈或環狀的飽和或不飽和烴基，或者在該烴基的ω末端，酯鍵結著亦可被羥基取代的碳數8~22之直鏈或分支鏈的飽和或不飽和脂肪酸；R³係表示氫原子、或者亦可被羥基、羥烷氧基、烷氧基或乙醯氧基取代的總碳數1~30之烷基。) Pseudo-cerebral amine is preferably a pseudo-cerebral amine represented by the following general formula (1) from the viewpoint of improving the preservation stability of the ultraviolet protective cosmetics:

(In the formula, R ¹ represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group with 10 to 22 carbons that may be substituted by a hydroxyl group, or a hydrogen atom; X ¹ represents a hydrogen atom, an acetyl group Or glyceryl; R ² represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group with carbon number of 5 to 22 that can be substituted by a hydroxyl group or an amino group, or at the ω end of the hydrocarbon group, an ester bond Straight or branched saturated or unsaturated fatty acids with 8 to 22 carbons that may be substituted by hydroxyl; R ³ represents a hydrogen atom, or may be substituted by hydroxyl, hydroxyalkoxy, alkoxy or acetoxy Substituted alkyl group with 1 to 30 carbon atoms.)

Among them, from the viewpoint of improving the preservation stability of the ultraviolet protective cosmetics, it is more preferable to be pseudocerebral amine represented by the following formula: [化4]

In general formula (1), preferably, 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, or R ¹ is a hexadecyl group and X ¹ is Hydrogen atom, R ² is a nonyl group, R ³ is a hydroxyethyl pseudo-type brain amine, more preferably R ¹ of the general formula (1) is a hexadecyl group, X ¹ is a hydrogen atom, and R ² is a ten Pentaalkyl and R ³ is hydroxyethyl [N-(hexadecyloxyhydroxypropyl)-N-hydroxyethylhexadecylamide]. In addition, it is preferable to have pseudocephalin (i) and (ii) represented by the following formulas.

In addition, examples of alcohols having 10 to 24 carbon atoms include myristyl alcohol, cetyl alcohol, stearyl alcohol, docosadiol, and oleyl alcohol. Among them, those with straight-chain alkyl groups are preferred, and alcohols with 16 to 18 carbon atoms are more preferred, and at least one or more than two types are selected from cetyl alcohol and stearyl alcohol. The most preferred one is Contains cetyl alcohol and stearyl alcohol.

Examples of linear saturated fatty acids having 10 to 24 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, and arinolic acid. Among them, from the viewpoint of the preservation stability of the UV protection cosmetics and the viewpoint of enhancing the UV protection effect, the straight-chain saturated fatty acid with 14 to 22 carbon atoms is more preferable, and the one with 16 to 22 carbon atoms is more preferable. The straight-chain saturated fatty acid particularly preferably contains at least one selected from palmitic acid or stearic acid.

Examples of monoglycerides of fatty acids with carbon number 10-24 include: glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monostearate, and glycerol mono-oil Acid esters, glycerol monoisostearate, etc. Among these, it is preferable to select at least one or more kinds from glycerol monostearate, glycerol monostearate, and glycerol monopalmitate, and more preferably glycerol monostearate.

Examples of monoalkyl glyceryl ethers with carbon numbers of 10-24 include: monodecyl glyceryl ether, monolauryl glyceryl ether, monomyristyl glyceryl ether, monocetyl glyceryl ether, monostearyl glyceryl ether, and monodecyl glyceryl ether. Dialkyl glycerol ether and so on.

Examples of sorbitan monofatty acid esters with carbon number of 10-24 include: sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, and sorbitan monostearate. , Sorbitan and so on.

Component (B) is from the viewpoint of the preservation stability of the UV protection cosmetics and the viewpoint of enhancing the UV protection effect, preferably from the alcohols with 14 to 22 carbons, monoglycerides with 14 to 22 carbons, Choose at least one or more of monoalkyl glycerol ethers with 14-22 carbons and sorbitan mono-fatty acid with 14-22 carbons, more preferably from the number of carbons Choose at least one or more of the 16-22 alcohols and the monoglycerides of fatty acids with carbon numbers 16-22, especially preferably at least one from cetyl alcohol, stearyl alcohol, and lipophilic monoglycerides One or more than two.

Furthermore, from the same point of view, component (B) preferably contains alcohols with 14 to 22 carbons, monoglycerides of fatty acids with 14 to 22 carbons, monoalkyl glycerides with 14 to 22 carbons, Choose at least one of sorbitan monofatty acid esters with 14 to 22 carbon atoms, more preferably an alcohol with 14 to 22 carbon atoms, and a monoglyceride with 14 to 22 carbon atoms, and particularly preferably a monoglyceride with 14 to 22 carbon atoms. Alcohols of 16-22, and monoglycerides of fatty acids with carbon numbers of 16-22, the best containing cetyl alcohol, stearyl alcohol, and monoglycerides of fatty acids with carbon numbers of 16-22.

Component (B) can be used singly or in combination of two or more, and its content is based on the viewpoint of improving the storage stability of UV protection cosmetics, the viewpoint of enhancing the UV protection effect, the viewpoint of improving the feeling of use, especially From the viewpoint of reducing stickiness, the total composition is 1% by mass or more, preferably 1.5% by mass or more, more preferably 2% by mass or more, still more preferably 2.5% by mass or more, and 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3.8% by mass or less. In addition, the content of the component (B) in the total composition is 1 to 10% by mass, preferably 1.5 to 8% by mass, more preferably 2 to 5% by mass, and still more preferably 2.5 to 3.8% by mass.

The component (C) used in the present invention is a liquid oil containing an oil-soluble ultraviolet absorber.

酯、水楊酸辛酯、水楊酸三乙醇胺等水楊酸系；對胺基苯甲酸、乙基二羥丙基對胺基苯甲酸、甘油 對胺基苯甲酸、辛基二甲基對胺基苯甲酸、對二甲胺基苯甲酸戊酯、對二甲胺基苯甲酸-2-乙基己酯等對胺基苯甲酸系；對甲氧基桂皮酸-2-乙基己酯(例如Uvinul® MC80；BASF公司製)、二對甲氧基桂皮酸單-2-乙基己酸甘油酯、2,5-二異丙基桂皮酸甲酯、三甲氧基桂皮酸甲酯雙(三甲基矽烷氧基)矽烷基異戊酯、對甲氧基桂皮酸異丙酯．桂皮酸二異丙酯混合物、對甲氧基氫化桂皮酸二乙醇胺鹽等桂皮酸系；奧克立林(octocrylene)(例如PARSOL® 340；DSM Nutrition Japan公司製)、1-(3,4-二甲氧苯基)-4,4-二甲基-1,3-戊二酮、辛諾賽(cinoxate)、甲基-O-胺基苯甲酸酯、3-(4-甲基苯亞甲基)樟腦；4-(2-β-吡喃葡萄糖基氧基)丙氧基-2-羥二苯基酮、二羥二甲氧基二苯基酮、二羥二甲氧基二苯基酮二磺酸鈉、2-羥-4-甲氧基二苯基酮、2-羥-4-甲氧基二苯基酮-5-硫酸、2,2'-二羥-4-甲氧基二苯基酮、2,4-二羥二苯基酮、2,2'4,4'-四羥二苯基酮、2,2'-二羥-4,4'-二甲氧基二苯基酮、2-羥-4-N-辛氧基二苯基酮等二苯基酮系；2,4,6-參[4-(2-乙基己氧羰基)苯胺基]-1,3,5-三

(例如Uvinul® T150；BASF製)、雙乙基己氧基酚甲氧苯基三

(例如TINOSORB S；BASF製)等三

系；2-苯基-苯并咪唑-5-硫酸、4-異丙基二苯甲醯基甲烷、4-第三丁基-4'-甲氧基二苯甲醯基甲烷(例如PARSOL® 1789；DSM Nutrition Japan公司製)等苯甲醯基甲烷系；二甲氧基苯亞甲基二氧基咪唑啶丙酸-2-乙基己酯(例如SOFT SHADE DH；Ajinomoto公司製)、二乙胺基羥苯甲醯基苯甲酸己酯(例如Uvinul® Aplus；BASF製)、亞甲基雙苯并三唑基四甲基丁基酚(例如TINOSORB M；BASF製)等。 The oil-soluble ultraviolet absorber can be used by ordinary cosmetics. Examples of oil-soluble UV absorbers include: high salicylic acid

Ester, octyl salicylate, salicylic acid triethanolamine and other salicylic acid series; p-aminobenzoic acid, ethyldihydroxypropyl p-amino benzoic acid, glycerol p-amino benzoic acid, octyl dimethyl p-amine P-aminobenzoic acid, p-dimethylaminobenzoic acid, pentyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl ester and other p-aminobenzoic acid series; p-methoxycinnamic acid-2-ethylhexyl ester ( For example, Uvinul® MC80; manufactured by BASF Corporation), di-p-methoxycinnamate mono-2-ethylhexanoic acid glyceride, 2,5-diisopropyl cinnamate methyl ester, trimethoxycinnamate bis( Trimethylsilyloxy) silyl isoamyl ester, isopropyl p-methoxycinnamate. Cinnamic acid series such as diisopropyl cinnamic acid mixture, p-methoxy hydrogenated cinnamic acid diethanolamine salt; octocrylene (for example, PARSOL® 340; manufactured by DSM Nutrition Japan), 1-(3,4- Dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, cinoxate, methyl-O-aminobenzoate, 3-(4-methylbenzene Methylene) camphor; 4-(2-β-glucopyranosyloxy) propoxy-2-hydroxydiphenyl ketone, dihydroxydimethoxydiphenyl ketone, dihydroxydimethoxydi Sodium phenyl ketone disulfonate, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone-5-sulfuric acid, 2,2'-dihydroxy-4- Methoxy diphenyl ketone, 2,4-dihydroxy diphenyl ketone, 2,2'4,4'-tetrahydroxy diphenyl ketone, 2,2'-dihydroxy-4,4'-dimethyl Diphenyl ketones such as oxybenzophenone and 2-hydroxy-4-N-octyloxybenzophenone; 2,4,6-see [4-(2-ethylhexyloxycarbonyl)anilino ]-1,3,5-Three

(E.g. Uvinul® T150; made by BASF), diethylhexyloxyphenol methoxyphenyl three

(Eg TIINOSORB S; BASF system) etc.

System; 2-Phenyl-benzimidazole-5-sulfuric acid, 4-isopropyl dibenzyl methane, 4-tertiary butyl-4'-methoxy dibenzyl methane (such as PARSOL® 1789; manufactured by DSM Nutrition Japan) and other benzyl methane systems; dimethoxybenzylidene dioxyimidazolidinium propionate-2-ethylhexyl (for example, SOFT SHADE DH; manufactured by Ajinomoto), two Ethylamino parabens hexyl benzoate (for example, Uvinul® Aplus; manufactured by BASF), methylene bisbenzotriazolyl tetramethylbutylphenol (for example, TIINOORB M; manufactured by BASF), and the like.

In addition, some of the ultraviolet absorbers themselves are solid at room temperature. but, Since each component of the ultraviolet protective cosmetic of the present invention is mixed with the component (E) under heating, it can be considered that the oil-soluble ultraviolet absorber of the component (C) exists in a liquid state in the obtained ultraviolet protective cosmetic.

(例如Uvinul® T150；BASF公司製)、4-第三丁基-4'-甲氧基二苯甲醯基甲烷(例如PARSOL® 1789；DSM Nutrition Japan公司製)、二甲氧基苯亞甲基二氧基咪唑啶丙酸-2-乙基己酯(例如SOFT SHADE DH；Ajinomoto公司製)、二乙胺基羥苯甲醯基苯甲酸己酯(例如Uvinul® Aplus；BASF公司製)、雙乙基己氧基酚甲氧苯基三

(例如TINOSORB S；BASF公司製)之中選擇1種或2種以上。又，從同樣的觀點而言，更佳係從對甲氧基桂皮酸-2-乙基己酯(例如Uvinul® MC80；BASF公司製)、二乙胺基羥苯甲醯基苯甲酸己酯(例如Uvinul® Aplus；BASF公司製)、雙乙基己氧基酚甲氧苯基三

(例如TINOSORB S；BASF公司製)之中選擇1種或2種以上。 Among them, from the viewpoint of enhancing the effect of UV protection, it is preferable to use p-methoxycinnamic acid-2-ethylhexyl ester (for example, Uvinul® MC80; manufactured by BASF), octocrelin (for example, PARSOL). ®340; manufactured by DSM Nutrition Japan), 2,4,6-ginseng [4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tri

(E.g. Uvinul® T150; manufactured by BASF), 4-tert-butyl-4'-methoxydibenzamethane (e.g. PARSOL® 1789; manufactured by DSM Nutrition Japan), dimethoxybenzylidene 2-ethylhexyl dioxyimidazolidinium propionate (for example, SOFT SHADE DH; manufactured by Ajinomoto), diethylamino hydroxybenzyl hexyl benzoate (for example, Uvinul® Aplus; manufactured by BASF), Diethylhexyloxyphenol methoxyphenyl three

(E.g. TIINOSORB S; made by BASF) Choose one or two or more types. Also, from the same point of view, it is more preferable to use p-methoxycinnamic acid-2-ethylhexyl ester (for example, Uvinul® MC80; manufactured by BASF Corporation), diethylamino parabens hexyl benzoate (E.g. Uvinul® Aplus; manufactured by BASF), bis-ethylhexyloxyphenol methoxyphenyl three

(E.g. TIINOSORB S; made by BASF) Choose one or two or more types.

系油溶性紫外線吸收劑之中選擇1種或2種以上，特佳係含有該等3種油溶性紫外線吸收劑，最佳係含有：對甲氧基桂皮酸-2-乙基己酯(例如Uvinul® MC80；BASF公司製)、二乙胺基羥苯甲醯基苯甲酸己酯(例如Uvinul® Aplus；BASF公司製)、及雙乙基己 氧基酚甲氧苯基三

(例如TINOSORB S；BASF公司製)。 Furthermore, from the same point of view, the oil-soluble ultraviolet absorber is more preferably selected from the above-mentioned cinnamic acid-based oil-soluble ultraviolet absorber, diethylaminoparaben hexyl benzoate, and the above-mentioned three

Choose one or more than two kinds of oil-soluble ultraviolet absorbers, particularly preferably those containing these three kinds of oil-soluble ultraviolet absorbers, and the most preferable one contains: 2-ethylhexyl p-methoxycinnamic acid (e.g. Uvinul® MC80; manufactured by BASF Corporation), diethylamino hydroxybenzyl hexyl benzoate (for example, Uvinul® Aplus; manufactured by BASF Corporation), and diethylhexyloxyphenol methoxyphenyl three

(For example, TIINOSORB S; made by BASF).

In addition, liquid oils other than oil-soluble ultraviolet absorbers have fluidity at 25°C. There are no restrictions on the users of general cosmetics, for example: flowing paraffin, light isoalkanes, squalane, squalene and other linear or branched chain hydrocarbon oils; neopentyl glycol dicaprate, Fatty acid esters such as isopropyl palmitate and alkyl benzoate; ester oils such as polyol fatty acid esters such as pentaerythritol tetra-2-ethylhexanoate; dimethyl polysiloxane, dimethyl cyclopolysiloxane Polysiloxane oils such as oxane, methyl phenyl polysiloxane, methyl hydrogen polysiloxane, higher alcohol modified polysiloxane oil; fluorine oil such as fluoropolyether, perfluoroalkyl ether polysiloxane, etc. Wait. These can also be vegetable oils such as jojoba oil and olive oil; natural oils such as animal oils such as liquid lanolin.

Among them, liquid oils other than oil-soluble ultraviolet absorbers are preferably linear or branched chain hydrocarbons from the viewpoint of reducing stickiness and improving compatibility with oil-soluble ultraviolet absorbers. Choose at least one of oil, ester oil, and silicone grease.

In the total liquid oil, 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 enhancing the UV protection effect and reducing skin irritation. , It is more preferably 70% by mass or more, and more preferably 100% by mass or less, more preferably 95% by mass or less, and still more preferably 85% by mass or less. In addition, the content of the component (C) in the total liquid oil agent is preferably 60-100% by mass, more preferably 65-90% by mass, and still more preferably 70-85% by mass.

系油溶性紫外線吸收劑與二乙胺基羥苯甲醯基苯甲酸己酯的合計含有量，較佳係0~40質量%、更佳係10~30質量%。 Among the oil-soluble ultraviolet absorbers, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably 60-100% by mass, more preferably 70-90% by mass from the viewpoint of enhancing the defense effect and reducing skin irritation. From the same point of view, among the oil-soluble UV absorbers, three

The total content of the oil-soluble ultraviolet absorber and diethylamino parabens hexyl benzoate is preferably 0-40% by mass, more preferably 10-30% by mass.

系油溶性紫外線吸收劑與二乙胺基羥苯甲醯基苯甲酸己酯合計量的含有比例(桂皮酸系油溶性紫外線吸收劑/[三

系油溶性紫外線吸收劑+二乙胺基羥苯甲醯基苯甲酸己酯]，係從提升紫外線防禦效果與減輕皮膚刺激感的觀點而言，較佳為9/1~5/5、更佳8.5/1.5~6/4、再更佳8/2~6.5/3.5。 Furthermore, among the oil-soluble ultraviolet absorbers, cinnamic acid-based oil-soluble ultraviolet absorbers are relative to three

The content ratio of the total amount of oil-soluble ultraviolet absorber and diethylamino paraben hexyl benzoate (cinnamic acid-based oil-soluble ultraviolet absorber/[三

Oil-soluble UV absorber + diethylamino parabens hexyl benzoate], from the viewpoint of enhancing the UV protection effect and reducing skin irritation, it is preferably 9/1~5/5, more Best 8.5/1.5~6/4, even better 8/2~6.5/3.5.

In the UV protection cosmetics, from the viewpoint of enhancing the UV protection effect and reducing skin irritation, the content of the oil-soluble UV absorber is based on the total composition, preferably 6% by mass or more, more preferably 8% by mass or more, It is still more preferably 10% by mass or more, and more preferably 20% by mass or less, more preferably 18% by mass or less, and still more preferably 15% by mass or less. In addition, in the ultraviolet protection cosmetics, the content of the oil-soluble ultraviolet absorber is preferably 6-20% by mass, more preferably 8-18% by mass, and still more preferably 10-15% by mass in the total composition.

Component (C) can be used singly or in combination of two or more. The content is from the viewpoint of enhancing the UV protection effect, reducing the skin irritation, and the feeling of use, especially from the viewpoint of reducing the stickiness. In the composition, 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, preferably 35% by mass or less, more preferably 25% by mass or less , And even better 17% by mass or less. In addition, the content of the component (C) in the total composition 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 present invention, the mass ratio of component (A) to component (C) [(A)/(C)] is from the viewpoint of improving the storage stability of the ultraviolet protective cosmetic, preferably 0.01 or more, more preferably 0.015 or more, still more preferably 0.025 or more, still more preferably 0.034 or more, and preferably 0.2 or less, more preferably 0.12 or less, still more preferably 0.06 or less, still more preferably 0.05 or less. In addition, the mass ratio of component (A) to component (C) [(A)/(C)] is preferably 0.01~0.2, more preferably 0.015~0.12, still more preferably 0.025~0.06, and still more preferably 0.034~ 0.05.

In the present invention, the mass ratio of component (B) to component (C) [(B)/(C)] is from the viewpoint of improving the preservation stability of the UV-protective cosmetics, and the viewpoint of good usability, especially from the viewpoint of From the viewpoint of reducing stickiness, it is preferably 0.01 or more, more preferably 0.12 or more, still more preferably 0.18 or more, still more preferably 0.19 or more, and preferably 0.5 or less, more preferably 0.39 or less, still more preferably 0.27 or less, and More preferably, it is below 0.24. In addition, the mass ratio of component (B) to component (C) [(B)/(C)] is preferably 0.01 to 0.5, more preferably 0.12 to 0.39, still more preferably 0.18 to 0.27, and still more preferably 0.19 ~0.24.

The solid oil agent of component (D) is one that is solid at 25°C.

If the solid oil agent is used by ordinary cosmetics, there are no restrictions. For example, candelilla wax (melting point: 66-71°C), rice wax (melting point: 77-86°C), sunflower Seed wax (melting point: 65-80°C), carnauba wax (melting point: 80-86°C), wood wax (melting point: 50-56°C) and other vegetable waxes; beeswax (melting point: 62/65°C), sperm wax (Melting point: 42-52°C) and other animal waxes; montan wax (82-95°C), ozokerite (melting point: 66-78°C) and other mineral waxes; microcrystalline wax (melting point: 60-90°C), paraffin wax (40-70℃), ozokerite (60-80℃) and other petroleum waxes; hardened sesame oil (melting point: 85℃), hydrogenated jojoba oil (melting point: 66-70℃), 12-hydroxystearic acid (Melting point: 75-78℃), amide stearate (melting point: 101℃), polysiloxane wax (melting point: 28-80 ℃), polyethylene wax (melting point: 94-152℃) and other synthetic waxes.

In the present invention, the melting point of the solid oil agent is measured in accordance with the General Test Method 70. Melting Point Measurement Method for Quasi-Drug Raw Material Specifications.

Component (D) is a solid oil agent having a melting point of 60°C or more and 80°C or less, and more preferably a solid oil agent having a melting point of 60°C or more and 80°C or less, from the viewpoint of performing accurate temperature control in the cooling step described below and improving the storage stability of the cosmetics Wax above 60°C and below 80°C. For example, candelilla wax (candelilla wax) MK-2 (manufactured by Yokosen Oil & Fat Co., Ltd., melting point: 71°C), refined rice wax S-100 (manufactured by Hengseki Oil & Fat Co., Ltd. melting point: 78°C), refined Sunflower wax (manufactured by Yokosen Oil Industry 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), MULTIWAX (manufactured by SONNEBORN, melting point 75°C), HNP-3 (manufactured by Nippon Seiki Wax Corporation, melting point 64°C), HNP-9 (manufactured by Nippon Seiki Wax Corporation, melting point 75°C), HNP-11 (Japan Commercially available products such as Refined Wax Co., Ltd., melting point 68°C), ozokerite #810 (Nikko Rica Co., Ltd., melting point 74°C) and the like.

Furthermore, from the viewpoints of improving the storage stability of skin cosmetics and reducing stickiness, component (D) preferably contains one or more selected from ozokerite and paraffin, and has a melting point of 60°C or higher and Solid state oil below 80°C.

Component (D) can be used singly or in combination of two or more. The content is from the viewpoint of improving the storage stability of skin cosmetics and the feeling of use, especially from the viewpoint of reducing stickiness, and further improving the UV protection From the viewpoint of effects, in the total composition, it is 0.01% by mass or more, preferably 0.08% by mass or more, more preferably 0.1% by mass or more, It is still more preferably 0.5% by mass or more, and 6% by mass or less, more preferably 4.5% by mass or less, more preferably 2.5% by mass or less, and still more preferably 1.5% by mass or less. In addition, the content of the component (D) in the total composition is 0.01 to 6% by mass, preferably 0.08 to 4.5% by mass, still more preferably 0.1 to 2.5% by mass, and still more preferably 0.5 to 1.5% by mass.

Furthermore, in the present invention, the mass ratio of the component (D) to the component (C) [(D)/(C)] is based on the viewpoint of improving the preservation stability of the UV-protective cosmetics and improving the feeling of use. From the viewpoint of reducing stickiness, it is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.04 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less. In addition, the mass ratio [(D)/(C)] of the component (D) to the component (C) is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and still more preferably 0.04 to 0.1.

The component (E) water used in the present invention becomes the remaining amount of each component. It is considered that the combination of components (A) to (C) and (E) can form a stable α gel structure in cosmetics Of emulsified particles. By having an α gel structure, a liquid oil containing an oil-soluble ultraviolet absorber can be contained in the α gel structure. The conventional cosmetics containing emulsified particles with an alpha gel structure have higher UV protection effects, good feeling in use, and no skin irritation. There is room for improvement in recent years.

The cosmetic of the present invention contains ingredient (D) in addition to ingredients (A) to (C) and (E), and is manufactured by the method described below, so that the ultraviolet absorber-containing oil can be uniformly dispersed and stored Excellent stability, high UV protection effect, good use feeling, and no skin irritation.

The content of ingredient (E) is preferably 35% by mass or more in the total composition from the viewpoints of improving the preservation stability of the UV protection cosmetics and enhancing the moisture feeling, and more preferably 45% by mass or more, more preferably 65% by mass or less, and still more preferably 55% by mass or less. In addition, 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) water-soluble polymer, which can improve the storage stability of the ultraviolet protective cosmetic and can enhance the ultraviolet protective effect.

The water-soluble polymer is not limited as long as it is used by ordinary cosmetics, and any one of natural polymer, semi-synthetic polymer, and synthetic polymer can be used.

Examples of natural polymers include sanxian gum, carrageenan, and alginic acid. Examples of semisynthetic polysaccharide-based polymer systems include modified polysaccharides such as hydroxycellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and cationized cellulose. Synthetic polymers can include, for example: carbomer (crosslinked polyacrylic acid), polyacrylic acid, sodium polyacrylate, acrylic acid/alkyl methacrylate copolymer, polypropylene amide, (acrylic acid Na/acrylic acid Dimethyl taurine Na) copolymer, (hydroxyethyl acrylate/acryloyl dimethyl taurine Na) copolymer, (acrylamide/ammonium acrylate) copolymer, acrylic acid such as polyacrylate-13 Acrylic polymers such as polymers; polyvinylpyrrolidone, polyvinyl alcohol, cationized polyvinylpyrrolidone, etc. Among them, acrylic polymers are preferred, and carbomers, acrylic acid/alkyl methacrylate copolymers, polypropylene amides, (acrylic acid Na/acrylic acid dimethyl taurine Select at least one of Na) copolymer, (hydroxyethyl acrylate/acryloyl dimethyl taurine Na) copolymer, (acrylamide/ammonium acrylate) copolymer, and polyacrylate-13, especially preferred From (acrylic acid Na/acrylic dimethyl taurine Na) copolymer, (hydroxyethyl acrylate/acrylic dimethyl taurine Na) copolymer, (acrylamide/ammonium acrylate) copolymer Polypropylene At least one of the acid esters-13 is selected.

Commercial products of Carbomer include, for example: Carbopol® 910, Carbopol® 934, Carbopol® 940, Carbopol® 941, Carbopol® 980, Carbopol® 981 (all of the above are manufactured by Lubrizol Advanced Materials, Inc.), etc.; acrylic/ Commercial products of alkyl methacrylate copolymers include, for example: Carbopol® 1382, Carbopol® ETD2020, PEMULEN TR-1, PEMULEN TR-2 (all of the above are manufactured by Lubrizol Advanced Materials, Inc.), etc.; Examples of commercially available amines include: SEPIGEL 305 (manufactured by SEPPIC); commercially available products of (acrylic acid Na/acryloyl dimethyl taurine Na) copolymer include, for example: SIMULGEL EG (manufactured by SEPPIC) Etc.; (Hydroxyethyl acrylate/acryloyl dimethyl taurine Na) copolymer commercially available products include, for example: SIMULGEL FL, SIMULGEL NS, SEPIPLUS S, SEPINOV EMT 10 (all of the above are made by SEPPIC), etc. .

Component (F) can be used singly or in combination of two or more. From the viewpoint of improving the storage stability of emulsified particles, the content is preferably 0.3% by mass or more, more preferably 0.5% by mass in the total composition. Above, it is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. In addition, the content of the component (F) in the total composition is preferably 0.3 to 1.5% by mass, more preferably 0.5 to 1.0% by mass.

The ultraviolet defense cosmetics of the present invention may further contain an ultraviolet scattering agent, which can further enhance the ultraviolet defense effect. The ultraviolet scattering agent is not limited as long as it is used by ordinary cosmetics, and examples include metal oxides such as titanium oxide, zinc oxide, and cerium oxide; metals such as silicon and aluminum.

The shape of these ultraviolet scattering agents may be spherical or spun-shaped. In addition, the average particle diameter is preferably 0.005 to 0.5 μm, more preferably 0.007 to 0.2 μm, and particularly preferably 0.01 to 0.07 μm.

Here, the average particle diameter is obtained by measuring the maximum short diameter of 300 particles in the image using a transmission electron microscope (Transmission Electron Microscope: TEM) under 100,000 magnification conditions, and calculating the average value. In the present invention, the "largest short diameter" refers to the short diameter having the largest diameter among the short diameters orthogonal to the long diameter.

These UV-scattering agents are from the viewpoint of enhancing the UV protection effect and improving the storage stability and reducing the stickiness. It is better to use a conventionally known surface treatment, such as fluorine compound treatment (preferably all Fluoroalkyl phosphate treatment, perfluoroalkyl silane treatment, perfluoropolyether treatment, fluoropolysiloxane treatment, fluorinated polysiloxane resin treatment), silicone treatment (preferably methyl hydrogen polysiloxane Treatment, dimethylpolysiloxane treatment, gas phase method tetramethyltetrahydrocyclotetrasiloxane treatment), polysiloxane resin treatment (preferably trimethylsiloxy silicic acid treatment), drape treatment ( The method of adding alkyl chains after gas phase polysiloxane treatment), silane coupling agent, titanium coupling agent treatment, silane treatment (preferably alkyl silane, alkyl silazane treatment), oil treatment , N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment (preferably stearic acid, myristate), acrylic resin treatment, metal oxide treatment and other surface treatments, more preferably used in combination Such processing.

For example, after coating the surface of titanium oxide with metal oxides such as silane and alumina, surface treatment is performed with alkyl silanes and fatty acids. Preferably, after the surface of the titanium oxide is treated with aluminum oxide, the surface treatment is performed with fatty acid. In addition, the surface treatment of the ultraviolet scattering agents is preferably performed by using a compound having a carboxyl group, and more preferably by using Fatty acids with 12 to 22 carbons are surface-treated, and particularly preferably fatty acids with 14 to 20 carbons are used for surface treatment.

One or more kinds of ultraviolet scattering agents can be used, and the content is from the viewpoint of enhancing the effect of ultraviolet protection. In the total composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass Above, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. In addition, the content of the ultraviolet scattering agent in the total composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass.

The ultraviolet protection cosmetic of the present invention may further suitably contain ingredients other than ingredients (A) to (F), which are commonly used in cosmetics, such as thickeners, bactericides, moisturizers, humectants, colorants, and preservatives. , Tactile enhancers, powders, fragrances, anti-inflammatory agents, whitening agents, perspiration agents, antioxidants, etc.

The ultraviolet protective cosmetic of the present invention is manufactured by a method including the following steps: an emulsification step of mixing a composition containing components (A) to (D) with (E) water under heating to form an emulsified product ; And the emulsification formed according to the above emulsification step is subjected to a cooling step of cooling at a cooling rate of 0.5 to 5° C./sec.

In addition, when the ultraviolet protective cosmetic of the present invention contains the component (F), the method of manufacturing the ultraviolet protective cosmetic preferably includes: mixing a part of the component (E) with the component (F) in advance The step of mixing the liquid and the emulsion obtained in the above-mentioned cooling step.

In the emulsification step, the homomixer, ultrasonic emulsifier, high pressure emulsifier, etc. usually used in the manufacture of cosmetics are used. By mixing, an emulsion can be obtained.

Furthermore, in the cooling step, the obtained emulsion can be used to use a vibration-type stirring and mixing device, a scraper type heat exchanger (Onlator Sakura Manufacturing Co., Ltd.), a static mixer (Noritake Co., Ltd.), a general plate type heat exchanger, Double-tube heat exchanger, etc., a continuous rapid cooling method; or a method of stirring and cooling in a general mixing tank, and the cooling rate is from the viewpoint of forming an α-gel structure and solidifying the solid oil From the viewpoint of, it is 0.5°C/sec or more, more preferably 0.8°C/sec or more, and 5°C/sec or less, preferably 1.5°C/sec or less. In addition, the cooling rate of the emulsion is 0.5 to 5°C/sec, preferably 0.8 to 1.5°C/sec.

Preferably, it is cooled to below the solidification temperature of the oily component by such a cooling step.

In the above-mentioned emulsification step and cooling step, the emulsification step uses a high-pressure emulsifier or ultrasonic emulsifier, and the cooling step uses a stirring consisting of a drive shaft and a stirring blade mounted on the drive shaft in a tubular housing. Body, a vibrating stirring and mixing device that makes the drive shaft vibrate in the axial direction, and the stirring blade is provided with more than one opening and/or more than one notch; the emulsion obtained according to the emulsification step is preferably used In the cooling step, cooling is continuously performed by passing through the inside of the vibrating stirring and mixing device, and a cosmetic material (fine particle dispersion) in which fine emulsified particles are dispersed can be obtained.

More specifically, FIG. 1 shows a schematic diagram of a manufacturing apparatus suitable for use in the present invention. The manufacturing apparatus 100 shown in FIG. 1 includes an emulsifying part 20 and a cooling part 30. The emulsifying part 20 is formed by mixing a composition containing components (A) to (D) with (E) water under heating Into an emulsion. The cooling part 30 cools the formed emulsion. In addition, the emulsification unit 20 includes a first emulsification unit 21 and a second emulsification unit 22. The first emulsification part 21 is filled with all or a part of the components constituting the fine particle dispersion, and the filled components are mixed with water under heating to obtain a pre-emulsion. The second emulsification section 22 is located on the downstream side of the first emulsification section 21, and applies high energy to the pre-emulsion obtained by the first emulsification section 21 to obtain a fine emulsion. The cooling unit 30 is located on the downstream side of the emulsification unit 20 and cools the heated and mixed emulsion to a solidification temperature of the oily component that is solid at 25° C. to obtain a target fine particle dispersion.

As shown in FIG. 1, the first emulsification section 21 of the emulsification section 20 includes a mixing tank 211. The mixing tank 211 is heated by a jacket 212 covering the side of the mixing tank 211 and 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. At the bottom of the mixing tank 211, a pipe 216 for taking out the pre-emulsion mixed in the tank 211 is connected. The pipe 216 is connected to the second emulsification part 22 via a valve. In addition, for the purpose of quantitatively supplying the pre-emulsion obtained by the first emulsification part 21, a metering pump (not shown) may be set in the middle of the tube 216 if necessary.

For the first emulsification part 21 having the above configuration, TK COMBIMIX (trade name) manufactured by PRIMIX Corporation, TK AGI HOMO MIXER (trade name) manufactured by PRIMIX Corporation, etc. can be used. These stirring devices are mainly used alone, but they can also be used in combination of two or more types depending on the situation.

The second emulsification section 22 of the emulsification section 20 is shown in FIG. 1 and is equipped with high-energy processing 部221. The high-energy processing unit 221 is configured to be capable of applying high energy to the pre-emulsion obtained by the first emulsifying unit 21 using a high-pressure emulsifier or an ultrasonic emulsifier.

The downstream part of the high energy processing part 221 is connected with a pipe 222 for taking out the emulsion to which the high energy is applied in the high energy processing part 221. It is structured so that the emulsion obtained by the 2nd emulsification part 22 may pass through the tube 222 and be supplied to the cooling part 30. In addition, for the purpose of quantitatively supplying the emulsion obtained by the second emulsification unit 22, a metering pump (not shown) may be set in the middle of the tube 222 if necessary.

When a high-pressure emulsifier is used in the second emulsification section 22 having the above configuration, for example, Star Burst minimo (product model: HJP-25001) (manufactured by Sugino Machine) and ULTIMAIZER (manufactured by Sugino Machine) belonging to the high-pressure emulsifier can be used. , Gaulin (manufactured by APV Rannie), micro-jet homogenizer (manufactured by Microfluidics), high-pressure jet emulsifier (manufactured by Japan BEE), etc.

In addition, when the second emulsification unit 22 uses an ultrasonic emulsifier, for example, IKASONIC (product model: U200S) (manufactured by IKA Corporation) equipped with an ultrasonic generator amplifier, or ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) can be used. ), ultrasonic homogenizer (manufactured by Ultrasonic Industry Co.), etc. The above-mentioned high-pressure emulsifiers or ultrasonic emulsifiers are mainly used alone, but two or more types can be appropriately combined for use depending on the situation.

The cooling unit 30 is provided with a vibration-type stirring and mixing device 40. The vibration-type stirring and mixing device 40 has a substantially cylindrical structure, and an inflow port 31 connected to a pipe 222 is provided on one end side, and a discharge port 32 is provided on the other end side. The discharge port 32 is connected to the discharge tube 33. The emulsion system supplied from the emulsification unit 20 is supplied to the vibratory stirring and mixing through the inlet 31 The inside of the device 40 passes through the inside of the device 40 and then discharges from the end of the discharge tube 33 through the discharge port 32. The supplied emulsion is further mixed by passing through the vibratory stirring and mixing device 40, and is continuously cooled to the solidification temperature of the oily component that is solid at 25°C. In order to perform continuous cooling, it is preferable to use a vibrating stirring and mixing device. A cooling jacket for circulating cooling water is provided on the outside of the housing 41 described later. On the vibrating stirring and mixing device 40, from the side of the inlet 31 Four jackets 34, 35, 36, 37 are installed in sequence toward the discharge port 32 side. Cooling water is circulated in each jacket respectively. The temperature of the cooling water can be appropriately set, and the supplied emulsion can be cooled continuously or stepwise from the side of the inflow port 31 toward the side of the discharge port 32 by using these jackets.

FIG. 2 shows a schematic longitudinal cross-sectional view of the vibration-type stirring and mixing device 40. The device 40 is provided with a stirring body 44 constituted by 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 the vibrator 45a, and is configured to vibrate up and down in the axial direction by the vibrator 45a.

The housing 41 is a tube with a circular cross section, and an inflow port 31 is provided near the lower portion. A discharge port 32 is provided near the upper part of the housing 41. The emulsion flowing in from the inflow port 31 is mixed and continuously cooled while passing through the housing 41, and then discharged from the discharge port 32.

The aforementioned stirring body 44 is arranged in the housing 41. The drive shaft 42 of the stirring body 44 extends in the longitudinal direction (longitudinal direction) of the housing 41. The upper end of the drive shaft 42 is connected to the vibrator 45a via a joint 45b. The vibrator 45a is equipped with a motor (not shown) and a well-known cam mechanism (not shown) connected to its output shaft. The cam mechanism consists of a rotating part (not shown) (Shown) and a swing part (not shown). The rotating part is eccentrically mounted on the output shaft of the motor. The swinging part swings by eccentric rotation of the rotating part. Then, the swing of the swing part is transmitted to the drive shaft 42 in the form of up and down vibration.

A plurality of annular compartments 46 are provided on the inner wall of the housing 41. The compartments 46 all have the same shape and protrude in the horizontal direction from the inner wall of the housing 41. The drive shaft 42 is inserted into a circular hole formed in the center of the compartment 46. The diameter of the circular hole is larger than the diameter of the drive shaft 42. The inside of the housing 41 is divided into a plurality of mixing chambers 47 by two adjacent compartments. The mixing chamber 47 is arranged in series along the longitudinal direction (longitudinal direction) of the casing 41.

3(a) and (b) show an enlarged view of the main part of the stirring body 44. The stirring body 44 is provided with the drive shaft 42 and the stirring blade 43 helically attached to the peripheral surface. In the same figure, the stirring blade 43 is installed in a spiral shape with 3 turns. The stirring bodies 44 in this state are set as a set, and the stirring bodies 44 are arranged in each mixing chamber 47 in the casing. Therefore, the number of groups of the stirring body 44 is the same as the number of the mixing chamber 47. In the stirring bodies 44 of each group, the spiral directions of the stirring blades 43 are the same.

In the stirring blades 43 of the stirring bodies 44 of each group, more than one opening 48 and/or more than one notch 49 are provided. The opening 48 and the notch 49 are designed so that when the agitating body 44 is viewed from the axial direction of the drive shaft 42 (see FIG. 3(a)), the formation positions of the agitating blades adjacent to each other up and down do not match. The reason is to prevent short-circuit flow in the axial direction to improve the mixing effect.

The vibration-type stirring and mixing device 40 having the above-mentioned structure can be used, for example, from Japan Those described in Japanese Patent Laid-Open No. 4-235729, etc. In addition, a commercially available product may also be used for the vibration-type stirring and mixing device 40. Such a commercially available product includes, for example, a device in which a cooling jacket is provided in a vibration mixer (registered trademark) manufactured by Refrigerating Industry Co., Ltd.

The method of manufacturing a fine particle dispersion using the manufacturing apparatus 100 having the above configuration will be described. First, the mixing tank 211 of the first emulsification section 21 of the emulsification section 20 is filled with all the components constituting the target fine particle dispersion. Or a part of it (the component filled in the mixing tank 211 contains water which is 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 section 221 of the second emulsification section 22 or the vibration-type stirring and mixing device 40. In addition, when the first emulsification section 21 is provided with two or more types, the first emulsification section 21 on the upstream side may be filled with all the components constituting the target fine particle dispersion, or each of the first emulsification sections 21 may be filled successively It is filled with a part of the components constituting the target fine particle dispersion. By filling a part of them one by one, the mixing conditions of each component can be adjusted appropriately.

The component filled in the mixing tank 211 contains at least one or more oily components that are solid at 25°C. After 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 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 pre-emulsion. The heating temperature can be set appropriately according to the melting point of the solid fat. Generally, it is best to set it to be about 10°C higher than the melting point of the solid fat with the highest melting point.

After the ingredients filled in the mixing tank 211 are stirred and thoroughly mixed, turn on the A valve is installed at the bottom of the mixing tank 211, and the pre-emulsion in the mixing tank 211 is taken out. The pre-emulsion system is supplied to the high-energy processing part 221 of the second emulsification part 22 via the tube 216.

In the high-energy treatment part 221, a high-pressure emulsifier or an ultrasonic emulsifier is used to apply high energy to the pre-emulsion obtained by the first emulsification part 21 to obtain an emulsion. The drop energy applied by a high-pressure emulsifier or an ultrasonic emulsifier is preferably 5×10 ⁴ J/kg or more, more preferably 2×10 ⁵ J/kg or more from the viewpoint of particle size reduction. The upper limit of the energy dropped is not particularly limited, but the greater the energy dropped, the better. The so-called "drop energy" here refers to the value that can be calculated according to the following formulas (1) to (3) in each emulsifier.

V=81.6d．πd²/4

V=81.6d. πd ² /4

In the formula, Q: volume flow, △P: operating pressure, ρ: density, V: micro-jet space volume, t: time, d: inner diameter.

In the formula, p: density, W: output, A: amplifier area, V: mixing volume, t: time.

In the formula, p: density, Np: power number, n: rotation number, d: blade diameter, V: mixing volume, t: time.

Furthermore, the number of passes of the high-energy processing part 221 is preferably one or more. When passing through the high-energy processing part 221 multiple times, it refers to the total drop energy of all the drop energy applied when passing through each high-energy processing part 221.

After the target energy is dropped, the valve attached to the high-energy treatment part 221 is opened, and the emulsion in the high-energy treatment part 221 is taken out. The emulsion is supplied to the vibration-type stirring and mixing device 40 via the pipe 222. The migration time from the emulsification step (emulsification part 20) to the cooling step (cooling part 30) is from the viewpoint of preventing aggregation of the emulsion obtained in the emulsification part 20, and is preferably within 60 seconds, more preferably 10 seconds. Within seconds. The lower limit of the migration time is not particularly limited, and the shorter the time, the better. The migration time from the emulsification part 20 to the cooling part 30 refers to the emulsification obtained by the second emulsification part 22 from the second emulsification part 22 of the emulsification part 20 through the tube 222 to the vibration-type stirring and mixing device 40 of the cooling part 30 Of time. The migration time is adjustable by using the length of the tube 222, for example.

The vibration-type stirring and mixing device 40 is equipped with four jackets 34, 35, 36, and 37 as cooling jackets as described above. The cooling jacket covers the cylindrical shell 41 shown in Figure 2 The method is arranged on the outside of the shell 41, and cooling water of a predetermined temperature is circulated in each jacket, and the emulsion obtained by the emulsification part 20 is passed through the shell 41 to perform heat exchange for cooling the fluid .

The total flow rate of the cooling water circulating in the cooling jacket is from the viewpoint of efficiently cooling the emulsion obtained by the emulsification part 20 without agglomeration, and the upper limit is not particularly limited, and the more the better. Specifically, the total flow rate of the cooling water is relative to the flow rate of the emulsion, and is preferably 10 times or more, more preferably 30 times or more. Here, the “flow rate of the emulsion” refers to the flow rate when the emulsion obtained by the emulsification unit 20 passes through the housing 41. In addition, the "total flow rate of cooling water" refers to the total flow rate of all the flow rates of cooling water circulating in each jacket when there are four jackets 34, 35, 36, and 37 like the vibratory stirring and mixing device 40.

The temperature of the cooling water can be appropriately set, and by using these jackets, the emulsion can be cooled continuously or stepwise from the side of the inflow port 31 toward the side of the discharge port 32. In this case, the temperature of the cooling water circulating in the four jackets 34, 35, 36, 37 may gradually decrease from the inlet side of the stirring and mixing device 40 toward the outlet side, or all of them may be at the same temperature.

In addition, the cooling water system of the four jackets 34, 35, 36, 37 is for the emulsion flowing from the inlet 31 side (upstream side) of the vibratory stirring and mixing device 40 to the discharge outlet 32 side (downstream side), for example, According to the flow sequence of the emulsion, it circulates from the upstream side to the downstream side, or it may circulate from the downstream side to the upstream side in the opposite direction to the flow of the emulsion.

In the vibratory stirring and mixing device 40, the emulsification passing through the casing 41 flows along the stirring body 44 due to the up and down vibration of the stirring body 44 in the axial direction, and the flow of the emulsion through the stirring body 44 on the stirring blade 43 is used. The flow of the openings 48 and the gaps 49 is messy, so that they do not agglomerate and are further mixed. Therefore, the fine particles of solid fat can be highly dispersed.

Then, if the emulsion is cooled due to heat exchange with the cooling water, the fluidity will decrease. Since the emulsion is cooled while being mixed by the flow along the stirring body 44 and the mess of the flow passing through the opening 48 and the notch 49 provided in the stirring blade 43, uneven cooling is unlikely to occur. In addition, since there is almost no dead space in the vibration-type stirring and mixing device 40, uneven stirring is unlikely to occur. The vibration type stirring and mixing device 40 can perform good stirring and mixing regardless of the case where the fluidity of the emulsion is high or low. These advantages possessed by the vibratory stirring and mixing device 40 can obtain the better effect of uniformly miniaturizing the emulsified particles with the solid oil (wax component, etc.) contained in the emulsion. In addition, because the vibrational stirring and mixing device 40 has a small heat generation, it has excellent cooling efficiency, and can be cooled rapidly in a state where the emulsified particles are uniformly and micronized, so that the emulsified particles containing solid fat can be well dispersed. It is also advantageous from the viewpoint of easier temperature control to generate less heat.

According to this, since the emulsion is continuously cooled to the solidification temperature of the solid oil agent without agglomeration, it is possible to provide a fine particle dispersion with high productivity and excellent quality. The target dispersion is discharged from the discharge tube 33 through the discharge port 32 of the vibration-type stirring and mixing device 40. The target dispersion temperature in this state is about 30°C.

When the vibration type stirring and mixing device 40 is used for cooling, it is preferable to set the average cooling rate Set it to 0.1~8°C/sec, more preferably 0.5~5°C/sec, and even more preferably 0.8~5°C/sec. The average cooling rate is a value obtained by dividing the temperature when the fluid enters the vibratory stirring and mixing device 40 and the temperature difference when going out by the residence time. In addition, the vibration number of the vibratory 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. The amplitude of the vibrating stirring and mixing device 40 is preferably 4 to 15 mm. In addition, the total amount of vibration imparted during cooling by the vibratory stirring and mixing device 40 is preferably 50 to 100,000 strokes, and more preferably 200 to 20,000 strokes.

Accordingly, the fine particle dispersion obtained by the manufacturing apparatus 100 has fluidity at 25° C., and includes, for example, a paste form and a cream form. Such a fine particle dispersion is used as the ultraviolet protective cosmetic of the present invention. The fine particle dispersion obtained by the manufacturing device 100 is uniformly refined in the high-energy processing section 221, and the solid state oil is maintained in a uniformly refined state in the cooling section 30, and is cooled, so the feeling of use is good. , Specially reduce stickiness, and improve the make-up effect such as UV protection effect.

In addition, the manufacturing method has been described based on the preferred embodiment, but it is not limited to this. For example, in the above-mentioned 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 may be connected in series.

The ultraviolet protective cosmetic of the present invention obtained in this way is produced by the aforementioned steps, and thus contains fine emulsified particles. From the viewpoint of enhancing the UV protection effect and reducing skin irritation, the volume median particle size of the emulsified particles is preferably 0.1-10 μm, more preferably 0.15-0.35 μm, and even more preferably 0.20-0.25 μm.

Furthermore, from the same viewpoint, the coefficient of variation of the emulsified particles is preferably 18-40, more preferably 19-30, and even more preferably 20-25. In addition, the so-called "coefficient of variation" refers to the value obtained by dividing the standard deviation of the volume median particle size by the volume median particle size, and the lower the value, the sharper the particle size distribution.

The ultraviolet protection cosmetics of the present invention have a small particle size and a sharp particle size distribution as described above, and this particle size distribution can be considered to be one of the factors for excellent storage stability, high ultraviolet protection effect, good use feeling, and no skin irritation.

In the present invention, the volume median particle size is measured in accordance with the laser diffraction scattering method using a laser diffraction/scattering particle size distribution measuring device (Model: LA-920 manufactured by Horiba Manufacturing Co., Ltd.).

The ultraviolet protection cosmetics of the present invention can be formed into, for example, lotions, emulsions, creams, gels, beauty liquids, etc., and are preferably formed into creams and gels. In addition, it is also possible to form a sheet-like cosmetic that is moisturized or coated on a sheet-like substrate such as a woven fabric or a non-woven fabric.

The ultraviolet protective cosmetic of the present invention can be used by applying it to the skin, preferably excluding the scalp, more preferably any place such as the face, body, hands and feet.

In relation to the foregoing embodiments, the present invention further discloses the following inventions.

<1> An ultraviolet protective cosmetic containing the following components (A), (B), (C), (D) and (E): (A) 0.18-2% by mass of ionic surfactant, (B ) Hydrophobic amphiphilic substance 1-10% by mass, (C) Liquid oil containing oil-soluble ultraviolet absorber 1-40% by mass, (D) Solid oil 0.01-6% by mass, (E) Water The UV protection cosmetics are obtained by a method including the following steps: an emulsification step of mixing a composition containing ingredients (A) to (D) with (E) water under heating to form an emulsified product; The emulsion formed in the emulsification step is subjected to a cooling step of cooling at a cooling rate of 0.5 to 5°C/sec.

<2> The ultraviolet protection cosmetics as described in the above <1>, wherein the ionic surfactant of the component (A) is preferably an anionic surfactant, a cationic surfactant, an amphoteric surfactant, neuraminol, and The salt is more preferably selected from at least one of anionic surfactants and neuraminol, more preferably an anionic surfactant, more preferably long-chain N-glycylglutamate, and still more preferably from two Sodium lauryl glutamate, monosodium lauryl glutamate, sodium N-stearyl-L-glutamate, N-stearyl-L-glutamate arginine, N -Select at least one of sodium stearyl glutamate and sodium N-myristyl-L-glutamate, and more preferably from sodium N-stearyl glutamate and N-stearic acid At least one of arginine-L-glutamic acid is selected, and N-stearyl-L-glutamic acid arginine is more preferable.

<3> The ultraviolet protection cosmetic as described in the above <1> or <2>, wherein the content of the component (A) in the total composition is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more It is preferably 0.4% by mass or more, more preferably 0.45% by mass or more, and more preferably 1.5% by mass or less, more preferably 1.1% by mass or less, still more preferably 0.9% by mass or less, and still more preferably 0.7% by mass or less.

<4> The ultraviolet protection cosmetic as described in any one of the above <1> to <3>, wherein the content of the nonionic surfactant in the total composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, even better, 0.1% by mass or less, and better Quality 0% by mass.

<5> The ultraviolet protection cosmetics described in any one of the above <1> to <4>, wherein the hydrophobic amphiphilic substance of the component (B) is preferably selected from brain amines, carbon number 10~ 24 alcohols, linear saturated fatty acids with carbon numbers 10-24, monoglycerides of fatty acids with carbon numbers 10-24, monoalkyl glycerides with carbon numbers of 10-24, sorbitol monofatty acids with 10-24 carbons Select at least one or more of anhydride esters and sorbitan monofatty acid esters with carbon numbers 10-24, more preferably from alcohols with 14-22 carbons, monoglycerides with 14-22 carbons, and carbon numbers Choose at least one or more of 14-22 monoalkyl glycerol ethers and 14-22 sorbitan monofatty acid esters, and more preferably alcohols with 16-22 carbons and 16-22 carbons The monoglycerides of fatty acids are more preferably selected from at least one or more of cetyl alcohol, stearyl alcohol, and lipophilic monoglycerides.

<6> The ultraviolet protection cosmetic as described in any one of the above <1> to <5>, wherein the hydrophobic amphiphilic substance of the component (B) preferably contains an alcohol having 14 to 22 carbon atoms 、Choose at least one of monoglycerides of fatty acids with 14 to 22 carbons, monoalkyl glycerides with 14 to 22 carbons, and sorbitan esters of fatty acids with 14 to 22 carbons, more preferably containing 14 carbons ~22 alcohols, and monoglycerides of fatty acids with 14-22 carbons, more preferably, alcohols with 16-22 carbons, and monoglycerides with 16-22 carbons, and more preferably cetyl alcohol , Stearyl alcohol, and monoglycerides of fatty acids with carbon number 16-22.

<7> The ultraviolet protection cosmetic as described in any one of the above <1> to <6>, wherein the content of the component (B) in the total composition is preferably 1.5% by mass or more, more preferably 2 mass % Or more, more preferably 2.5% by mass or more, and more preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3.8% by mass or less.

、4-第三丁基-4'-甲氧基二苯甲醯基甲烷、二甲氧基苯亞甲基二氧基咪唑啶丙酸-2-乙基己酯、二乙胺基羥苯甲醯基苯甲酸己酯、雙乙基己氧基酚甲氧苯基三

之中選擇1種或2種以上，更佳係含有從對甲氧基桂皮酸-2-乙基己酯、二乙胺基羥苯甲醯基苯甲酸己酯、雙乙基己氧基酚甲氧苯基三

之中選擇1種或2種以上，再更佳係含有對甲氧基桂皮酸-2-乙基己酯、二乙胺基羥苯甲醯基苯甲酸己酯及雙乙基己氧基酚甲氧苯基三

。 <8> The ultraviolet protection cosmetics according to any one of the above <1> to <7>, wherein the oil-soluble ultraviolet absorber of the component (C) preferably contains from p-methoxycinnamic acid-2- Ethylhexyl ester, octocrelin, 2,4,6-ginseng [4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-tris

, 4-tertiary butyl-4'-methoxydibenzylmethane, dimethoxybenzylidene dioxyimidazolidinium propionate-2-ethylhexyl, diethylaminohydroxybenzene Formyl hexyl benzoate, diethylhexyloxyphenol methoxyphenyl three

Choose one or two or more of them, more preferably containing 2-ethylhexyl p-methoxycinnamic acid, hexyl diethylamino paraben, and diethylhexyloxyphenol Methoxyphenyl three

Choose one or more than two, and more preferably contain 2-ethylhexyl p-methoxycinnamic acid, hexyl diethylaminohydroxybenzyl benzoate and diethylhexyloxyphenol Methoxyphenyl three

.

系油溶性紫外線吸收劑之中選擇1種或2種以上，特佳係含有該等3種油溶性紫外線吸收劑，再更佳係含有對甲氧基桂皮酸-2-乙基己酯、二乙胺基羥苯甲醯基苯甲酸己酯、雙乙基己氧基酚甲氧苯基三

。 <9> The ultraviolet protection cosmetics according to any one of the above <1> to <8>, wherein the oil-soluble ultraviolet absorber is more preferably a cinnamic acid-based oil-soluble ultraviolet absorber, diethylaminohydroxybenzene Methylhexyl benzoate, three

One or two or more types of oil-soluble ultraviolet absorbers can be selected. Especially preferred ones contain these three kinds of oil-soluble ultraviolet absorbers, and even more preferred ones contain 2-ethylhexyl p-methoxycinnamic acid and two Ethyl hydroxybenzyl hexyl benzoate, diethylhexyloxyphenol methoxyphenyl three

.

<10> The ultraviolet protection cosmetics according to any one of the above <1> to <9>, wherein the liquid oil agent other than the oil-soluble ultraviolet absorber preferably contains a linear or branched chain hydrocarbon oil, Choose at least one of ester oil and silicone oil.

<11> The ultraviolet protective cosmetic as described in any one of the above <1> to <10>, wherein the component (C) is in the total liquid oil, and the content of the oil-soluble ultraviolet absorber is preferably 60 Mass% or more, more preferably 65% by mass or more, particularly preferred 70% by mass or more, and more preferably 100% by mass or less, more preferably 90% by mass or less, particularly superior 85% by mass or less.

<12> The ultraviolet protective cosmetic as described in any one of the above <1> to <10>, wherein the content of the oil-soluble ultraviolet absorber in the ultraviolet protective cosmetic is preferably 6 in the total composition % By mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less.

<13> The ultraviolet protective cosmetics according to any one of the above <1> to <12>, wherein, in the oil-soluble ultraviolet absorber, the content of the cinnamic acid-based oil-soluble ultraviolet absorber is preferably 60~ 100% by mass, more preferably 70~90% by mass.

系油溶性紫外線吸收劑與二乙胺基羥苯甲醯基苯甲酸己酯的合計含有量，較佳係0~40質量%、更佳係10~30質量%。 <14> The ultraviolet protective cosmetic as described in any one of the above <1> to <13>, wherein, in the oil-soluble ultraviolet absorber, three

The total content of the oil-soluble ultraviolet absorber and diethylamino parabens hexyl benzoate is preferably 0-40% by mass, more preferably 10-30% by mass.

系油溶性紫外線吸收劑與二乙胺基羥苯甲醯基苯甲酸己酯合計量的含有比例[桂皮酸系油溶性紫外線吸收劑/(三

系油溶性紫外線吸收劑+二乙胺基羥苯甲醯基苯甲酸己酯)]，較佳係9/1~5/5、更佳係8.5/1.5~6/4、再更佳係8/2~6.5/3.5。 <15> The ultraviolet protective cosmetic as described in any one of the above <1> to <14>, wherein, in the oil-soluble ultraviolet absorber, the cinnamic acid-based oil-soluble ultraviolet absorber is relative to three

The content ratio of the total amount of oil-soluble ultraviolet absorber and diethylamino paraben hexyl benzoate [cinnamic acid-based oil-soluble ultraviolet absorber/(three

Oil-soluble UV absorber + diethylamino parabens hexyl benzoate)], preferably 9/1~5/5, more preferably 8.5/1.5~6/4, and even more preferably 8 /2~6.5/3.5.

<16> The ultraviolet protection cosmetics described in any one of the above <1> to <15>, wherein the content of the component (C) in the total composition is preferably 3% by mass or more, more preferably 10% by mass % Or more, more preferably 12% by mass or more, and more preferably 35% by mass or less, more preferably 25% by mass or less, still more preferably 17% by mass or less.

<17> The ultraviolet protection cosmetics described in any one of the above <1> to <16>, wherein the mass ratio of component (A) to component (C) [(A)/(C)] is relatively Preferably it is 0.01 or more, more preferably 0.015 or more, still more preferably 0.025 or more, still more preferably 0.034 or more, and more preferably 0.2 or less, more preferably 0.12 or less, even more preferably 0.06 or less, and even more preferably 0.05 the following.

<18> The ultraviolet protection cosmetics described in any one of the above <1> to <17>, wherein the mass ratio of the component (B) to the component (C) [(B)/(C)] is relatively Preferably it is 0.01 or more, more preferably 0.12 or more, still more preferably 0.18 or more, still more preferably 0.19 or more, and more preferably 0.5 or less, more preferably 0.39 or less, even more preferably 0.27 or less, and even more preferably 0.24 the following.

<19> The ultraviolet protection cosmetic as described in any one of the above <1> to <18>, wherein the solid oil agent of the component (D) is preferably a solid oil having a melting point of 60°C or more and 80°C or less The agent, more preferably, contains one or more solid oil agents with a melting point of 60°C or more and 80°C or less selected from ozokerite and paraffin wax.

<20> The ultraviolet protection cosmetic as described in any one of the above <1> to <19>, wherein the content of the component (D) is based on the total composition, preferably 0.08% by mass or more, more preferably 0.1 % By mass or more, more preferably 0.5% by mass or more, and more preferably 4.5% by mass or less, more preferably 2.5% by mass or less, still more preferably 1.5% by mass or less.

<21> The ultraviolet protection cosmetic as described in any one of the above <1> to <20>, wherein the mass ratio of the component (D) to the component (C) [(D)/(C)] is relatively Preferably it is 0.01 or more, more preferably 0.02 or more, still more preferably 0.04 or more, and more preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less.

<22> The ultraviolet protection cosmetics according to any one of the above <1> to <21>, wherein the content of the component (E) in the total composition is preferably 35% by mass or more, more preferably 45 mass% % Or more, and preferably 65% by mass or less, more preferably 55% by mass or less.

<23> The ultraviolet protection cosmetic as described in any one of the above <1> to <22>, which further contains (F) a water-soluble polymer.

<24> The ultraviolet protection cosmetic as described in the above <23>, wherein the component (F) is preferably an acrylic polymer, and more preferably is selected from carbomer, acrylic acid/alkyl methacrylate copolymer, and polymer Acrylic amide, (acrylic acid Na/acrylic acid dimethyl taurine Na) copolymer, (hydroxyethyl acrylate/acrylic acid dimethyl taurine Na) copolymer, (acrylic acid amide/ammonium acrylate) Select at least one of copolymers and polyacrylate-13, particularly preferably from (acrylic acid Na/acrylic acid dimethyl taurine Na) copolymer, (hydroxyethyl acrylate/acrylic acid dimethyl taurine) At least one selected from among sodium sulfonate copolymer, (acrylamide/ammonium acrylate) copolymer, and polyacrylate-13.

<25> The ultraviolet protection cosmetic as described in the above <23> or <24>, wherein the content of the component (F) is based on the total composition, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, And it is preferably 1.5% by mass or less, more preferably 1.0% by mass or less.

<26> The ultraviolet defense cosmetics as described in any one of the above <1> to <25>, wherein the emulsification step preferably uses a homomixer, ultrasonic emulsifier, or high-pressure emulsifier, preferably under heating Mix the blending ingredients at 60~120℃, more preferably 80~100℃.

<27> The ultraviolet protection cosmetics as described in any one of the above <1> to <26>, wherein the cooling step is preferably to use a vibration-type stirring and mixing device, a scraper type heat exchanger, and the obtained emulsion in the cooling step. , Static mixer, plate heat exchanger, double The layered tube heat exchanger adopts continuous rapid cooling method, or adopts agitation cooling method in a general mixing tank for cooling.

<28> The ultraviolet protective cosmetic as described in any one of the above <1> to <27>, wherein the cooling rate is preferably 0.8°C/sec or more, and more preferably 1.5°C/sec or less.

<29> The ultraviolet protective cosmetic as described in any one of the above <1> to <28>, wherein the volume median particle size of the emulsified particles is preferably 0.1 to 10 μm, more preferably 0.15 to 0.35 μm, and further More preferably, it is 0.20~0.25μm.

<30> The ultraviolet protection cosmetics described in any one of the above <1> to <29>, wherein the coefficient of variation of the emulsified particles is preferably 18-40, more preferably 19-30, and even more preferably 20 ~25.

<31> The use of an ultraviolet protective cosmetic, which is to apply the ultraviolet protective cosmetic described in any one of the above <1> to <30> to the skin, preferably excluding the scalp, and more preferably the face and body , Hands and feet, etc. anywhere.

<32> A manufacturing method of ultraviolet protection cosmetics, including: containing the following ingredients (A), (B), (C) and (D): (A) 0.18-2% by mass of ionic surfactant , (B) Hydrophobic amphiphilic substance 1-10% by mass, (C) Liquid oil containing oil-soluble ultraviolet absorber 1-40% by mass, (D) Solid oil 0.01-6% by mass The emulsification step of mixing with (E) water under heating to form an emulsified product; and cooling the emulsified product formed by the above emulsification step at a cooling rate of 0.5~5°C/sec Perform the cooling step of cooling.

[Example] [Examples 1 to 29, Comparative Examples 1 to 5]

The ultraviolet protection cosmetics with the compositions shown in Table 1 to Table 3 were produced, the volume median particle size and the coefficient of variation were measured, the α gel and the SPF value were confirmed, and the storage stability, feeling of use, and skin irritation were evaluated. The results are combined in Table 1~Table 3.

(Production method)

(1) Example 1:

After the ingredients (A) to (D), part of the ingredient (E), propylene glycol, glycerin, arginine, and phenoxyethanol are dispersed in a homomixer under heating at 85°C, a high-pressure emulsifier (manufactured by Sugino Machine) is used. , Star Burst minimo HJP-25001) to obtain an emulsion. The number of passes of the high-pressure emulsifier (pass number) is set to one. The emulsion was kept at 85°C and was supplied to a vibratory stirring and mixing device (manufactured by Ryo Kagyo Kogyo Co., Ltd., vibrating mixer) according to the migration time for 10 seconds. The stirring body was stirred up and down in the device. The emulsion is continuously cooled to 40°C or lower while continuously (step (1)). This cooled emulsion and a mixed solution obtained by mixing a part of component (E), component (F) and other components described in the table are mixed at room temperature (25°C) (step (2) )), to obtain UV protection cosmetics.

In the vibratory stirring and mixing device, the flow rate of the emulsion is 1 g/sec, and the total flow rate of cooling water circulating in the cooling jacket is 10 g/sec, and cooling is performed with the total flow rate of cooling water that is 10 times the flow rate of the emulsion. The average cooling rate at this time is 1°C/sec. In addition, the vibration number of the vibratory stirring and mixing device is 20 Hz.

(2) Examples 2-28, Comparative Examples 1-4:

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

(3) Example 29:

According to (1), an emulsion was obtained. The obtained emulsion was cooled to 40°C while stirring with an anchor (number of rotations: 75 rpm) in a container to obtain an ultraviolet protective cosmetic. The average cooling rate at this time is 1°C/sec.

(4) Comparative example 5:

After performing the same emulsification step as in Example 1, cooling was performed at a cooling rate of 0.01° C./sec without stirring in a temperature-controllable thermostatic bath.

(Evaluation method)

(1) Volume median particle size and coefficient of variation:

According to the laser diffraction scattering method using a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, model: LA-920), the volume-based median particle size and coefficient of variation are measured at a temperature of 25°C . The coefficient of variation is the value of the standard deviation divided by the median particle size on the volume basis.

(2) Confirmation of α gel:

For each cosmetic, XRD was used to confirm whether an α-gel structure was formed. Specifically, in wide-angle X-ray diffraction, Bragg angle = 21~22° At least one cosmetic with a sharp diffraction peak is judged to have an α-gel structure, and is marked with "α" in the table.

(3) SPF value:

Apply evenly on the PMMA board so that each cosmetic material becomes 2mg/cm ^{2 for} 1 minute, and dry for 15 minutes in a dark place. After drying, use an SPF analyzer (SPF 290S plus, manufactured by Optometricus USA) to measure the absorption spectrum (wavelength 350nm) at 9 points in total on the midpoint, each vertex, and the midpoint of the side connecting each vertex on the square PMMA board. Transmittance (%), take the average of 9 points. The result represents the SPF value (-) obtained from the transmittance (%). (N=3)

(4) Preservation stability:

Put 40mL cosmetics in a 50mL glass bottle, seal it and store it at -5°C for 1 month, visually observe the appearance and fluidity of the cosmetics after storage. The fluidity is to visually confirm the fluidity when tilted at 45°C. The reference system is as follows.

4: There is no change in appearance and/or fluidity.

3: A slight change was found in both appearance and fluidity.

2: At least one of appearance and fluidity is slightly changed.

1: There is a large change in appearance (oil phase separation), or a large change in fluidity (a gel-like change).

(5) Feeling of use:

Five professional examiners applied 0.02 mL of each cosmetic material into a circle with a diameter of 3 cm on the inside of the forearm, and spread the application (at 25°C, 57RH%) over a period of 1 minute. Then, make The feeling of use (sticky feeling) is rated as 5 when it is completely non-sticky, and 1 when it is very sticky, and the evaluation is performed on a scale of 0.1, and the average score of the 5 digits is obtained.

(6) Skin irritation:

Five professional examiners applied 0.02 mL of each cosmetic material into a circle with a diameter of 3 cm on the inside of the forearm, and spread the application (at 25°C, 57RH%) over a period of 1 minute. Then, the irritation system rated the case where there was no irritation at all, and the case where the irritation was very irritating was rated as 1, and the evaluation was performed on a scale of 0.1, and the average score of 5 places was obtained.

[Example 30]

According to the same manner as in Examples 1 to 28, ultraviolet protective cosmetics having the composition shown in Table 4 were produced.

In the obtained ultraviolet protection cosmetic system, emulsified particles having a volume median diameter of 0.22 μm were dispersed, and an α gel was confirmed.

Furthermore, the oil agent containing the ultraviolet absorber is uniformly dispersed, has excellent storage stability, has a high ultraviolet protection effect, is not sticky, has a good feeling of use, and has no skin irritation.

[Example 31]

In the same manner as in Examples 1 to 28, the composition shown in Table 5 was produced to protect against ultraviolet rays. Makeup.

In the obtained ultraviolet protection cosmetic system, emulsified particles having a volume median diameter of 0.24 μm were dispersed, and α gel was confirmed.

Furthermore, the oil containing the ultraviolet absorber is uniformly dispersed, has excellent storage stability, has a high ultraviolet protection effect, is not sticky, has a good feeling of use, and has no skin irritation.

[Examples 32 to 34, Comparative Example 6]

According to the same methods as in Examples 1 to 28, the ultraviolet protection cosmetics with the composition shown in Table 6 were produced, the volume median particle size and the coefficient of variation were measured, the α gel and the SPF value were confirmed, and Evaluate storage stability, feeling of use and skin irritation. The results are combined in Table 6.

In addition, when manufacturing the cosmetics of Examples 32 to 34 and Comparative Example 6, the cooling rate is 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 composition shown in Table 7 were produced, and the transdermal absorbability of the ultraviolet absorber was evaluated.

Evaluation of transdermal absorbability of ultraviolet absorbers

Test sequence

The test sequence is as follows. The excised skin of the human body that has been cryopreserved at -80°C is thawed at room temperature for about 30 minutes, after removing excess fat from the skin, it is cut into approximately 2 cm squares and used for measurement. The skin samples obtained in this way were used for penetration tests.

The penetration test was performed using a Franz-type diffusion cell (1 cm ² area of the formulation and 16 mL of the receptor phase). Put 10 μL of the prepared sample in the donor phase and keep it at 37°C for 24 hours. After 24 hours, purified water was used to cleanly remove the sample on the skin surface, and then the epidermis and the dermis were separated. Ultrasonic treatment was performed with 5 mL of methanol for 20 minutes, and after filtration with a membrane filter (PTFE 0.45 μm ADVANTEC), the concentration of the ultraviolet absorber was measured using an ultraviolet-visible spectrophotometer UV3600 (Shimadzu Corporation).

test results

The transdermal absorbability was evaluated for the samples in Table 7. The results are shown in Table 8 below.

It can be seen that the transdermal absorbability of the sample of Example 35 containing the ultraviolet absorbent is greatly reduced compared with the sample of Comparative Example 7 that does not contain the ultraviolet absorbent.

20‧‧‧Emulsification Department

21‧‧‧Part 1 Emulsification Department

22‧‧‧Second Emulsification Department

30‧‧‧Cooling Department

31‧‧‧Inlet

32‧‧‧Exit

33‧‧‧Exhaust tube

34, 35, 36, 37‧‧‧ Jacket

40‧‧‧Vibrating mixing device

41‧‧‧Shell

100‧‧‧Manufacturing equipment

211‧‧‧Mixing tank

212‧‧‧Jacket

213‧‧‧Mixing blade

214‧‧‧Axis

215‧‧‧Motor

216‧‧‧tube

221‧‧‧High Energy Processing Department

222‧‧‧tube

Claims (7)

A method for manufacturing an ultraviolet protective cosmetic, the ultraviolet protective cosmetic contains the following ingredients (A), (B), (C), (D) and (E): (A) Ionic surfactant 0.18~ 2% by mass; (B) 1~10% by mass of hydrophobic amphiphilic substance; (C) 1~40% by mass of liquid oil containing oil-soluble ultraviolet absorber; (D) 0.01~6 mass of solid oil %; (E) water; the manufacturing method includes the following steps: an emulsification step of mixing a composition containing components (A) to (D) with (E) water under heating to form an emulsified product; emulsifying the above The emulsion formed in the step is subjected to a cooling step of cooling 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 of the component (C) is 60% by mass or more and 100% by mass or less. For example, the method of manufacturing an ultraviolet protective cosmetic of claim 1 or 2, wherein the ultraviolet protective cosmetic further contains (F) a water-soluble polymer; F) The step of mixing the mixed liquid and the emulsion obtained in the above cooling step. Such as Claim 1 or 2 of the manufacturing method of ultraviolet protection cosmetics, wherein the mass ratio (A)/(C) of component (A) to component (C) is 0.01 to 0.2. Such as claim 1 or 2 of the manufacturing method of ultraviolet protection cosmetics, wherein the ingredients (B) The mass ratio (B)/(C) relative to the component (C) is 0.01 to 0.5. For example, the method for manufacturing an ultraviolet protective cosmetic of claim 1 or 2, wherein the mass ratio (D)/(C) of the component (D) to the component (C) is 0.01 to 0.5. Such as claim 1 or 2, the manufacturing method of the ultraviolet defense cosmetics, wherein the volume median diameter of the emulsified particles is 0.1-10 μm.

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