WO2011108583A1 - 日焼け止め用組成物 - Google Patents
日焼け止め用組成物 Download PDFInfo
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- WO2011108583A1 WO2011108583A1 PCT/JP2011/054755 JP2011054755W WO2011108583A1 WO 2011108583 A1 WO2011108583 A1 WO 2011108583A1 JP 2011054755 W JP2011054755 W JP 2011054755W WO 2011108583 A1 WO2011108583 A1 WO 2011108583A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/068—Microemulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
Definitions
- the present invention relates to a sunscreen composition used as a sunscreen cosmetic. More specifically, the sunscreen composition is excellent in UV protection and stability, and further has a good spread on the skin, excellent coating uniformity, good familiarity, and a transparent bicontinuous microemulsion phase. About.
- sunscreen compositions are blended with UV absorbers or UV scattering agents (zinc oxide, titanium dioxide, etc.) in order to block UV irradiation and obtain high SPF (Sun Protection Factor) values.
- UV absorbers or UV scattering agents Zinc oxide, titanium dioxide, etc.
- SPF Sun Protection Factor
- examples of the type of sunscreen composition include various oil-in-water emulsion types and water-in-oil emulsion types.
- an oil-in-water emulsion type as shown in Patent Documents 1 and 2 is preferably used.
- an oil component serving as an inner phase cannot be blended in a large amount due to the stability of the emulsion system.
- sticking occurs when a large amount of oil is blended, so that usually a large amount of oil is not blended. Therefore, in an oil-in-water emulsion composition, it is difficult to blend a large amount of an oil-soluble ultraviolet absorber while maintaining the refreshing and fresh feel that is characteristic. Therefore, other emulsion type sunscreen compositions Higher UV protection ability cannot be obtained.
- the oil-soluble UV absorber is added to the oil-soluble one without increasing the blending amount.
- a water-soluble ultraviolet absorber is blended (see, for example, Patent Document 4).
- a salt neutralized salt
- the salt concentration in the emulsified composition is increased, the electrostatic repulsion of the emulsified particles is canceled, and the emulsion stability may be extremely deteriorated.
- the oil phase is a continuous phase (outer phase). Therefore, compared with the oil-in-water emulsification type sunscreen composition, a large amount of oil and oil-soluble UV absorber can be blended, and high UV protection ability can be obtained. Furthermore, in use, an oil film with low moisture permeability is left on the surface of the skin and the like to protect it from drying for a long time, and it hardly causes re-emulsification even when it comes into contact with water by water bath, water work or sweating. Therefore, it is used in sunscreen compositions as an excellent sweat / water resistant base.
- an emulsified composition is a non-equilibrium system in which water is dispersed in oil by a surfactant or oil is dispersed in water as emulsion particles, whereas a microemulsion has water in oil by a surfactant. Or it is an isotropic low viscosity solution of an equilibrium system in which oil is solubilized in water.
- microemulsions There are three types of microemulsions: a micellar aqueous phase in which oil is solubilized in water, a reverse micellar oil phase in which water is solubilized in oil, and a bicontinuous microemulsion phase in which both water and oil have a continuous structure. There are types.
- the aqueous micelle phase has a continuous state of water, and spherical or rod-like aggregates with the lipophilic group of the surfactant facing inward are dispersed.
- the size of the aggregate is at most about 100 nm, and it is optically isotropic and has a transparent to slightly bluish translucent appearance.
- reverse micelle oil solution phase spherical or rod-like aggregates with the hydrophilic group of the surfactant facing inward are dispersed.
- the reverse micro oil solution phase is utilized as a sunscreen composition, a large amount of water cannot be solubilized, and therefore, stickiness and oiliness are large and a satisfactory use feeling cannot be obtained.
- the bicontinuous microemulsion phase is generally generated under conditions where the hydrophilic-hydrophobic balance is balanced, the oil-water interfacial tension is minimized, the number of associations of the surfactant increases, and the infinite association occurs.
- the solubilization amount of water and oil is dramatically improved, and the solubilization system has a unique structure in which water and oil form continuous channels.
- Non-Patent Document 1 polyoxyethylene lauryl ether (4EO) is used as a surfactant, and isohexadecane is used as an oil.
- 4EO polyoxyethylene lauryl ether
- Non-Patent Document 3 didecyldimethylammonium salt is used as a surfactant, and dodecane is used as an oil.
- non-patent document 4 it is reported that a bicontinuous microemulsion phase can be obtained by using soybean phospholipid as a surfactant, propanol as a surfactant, and triglyceride as an oil.
- Patent Document 6 uses polyethylene glycol monolaurate (12EO) as a surfactant, lauryl alcohol and ethanol as a surfactant aid, and liquid isoparaffin as an oil component.
- Patent Document 7 discloses POE (8 as a surfactant).
- Patent Document 8 discloses imidazolinium betaine and POE lauryl ether sulfate as surfactants, mono fatty acid monoglycerin ester and monoalkyl monoester as oil components. It has been reported that a bicontinuous microemulsion phase can be obtained by using glyceryl ether.
- the bicontinuous microemulsion phase has a unique structure in which both water and oil are continuous, it can contain a larger amount of oil and oily components than the micelle phase. Moreover, compared with a reverse micelle phase, a large amount of water and an aqueous component can be mix
- Patent Documents 6 to 10 There are many report examples (see, for example, Patent Documents 6 to 10). However, the industrial use other than the purpose of cleaning has not been sufficiently used, and its use as a sunscreen composition such as a sunscreen cosmetic is not known.
- JP 2002-284638 A JP 2005-255669 A JP-A-5-97644 JP 2008-162930 A JP-A-9-255544 JP 2004-217640 A JP 2005-194249 A JP 2007-77302 A Patent Publication No. 3684144 JP 2009-196909 A
- the problem to be solved by the present invention is to provide a sunscreen composition that is excellent in UV protection ability and stability and further in use feeling by utilizing a bicontinuous microemulsion phase. .
- the present invention comprises (a) a surfactant, (b) water, (c) an oil component, (d) a water-soluble UV absorber and / or an oil-soluble UV absorber, and a bicontinuous microemulsion phase at 25 ° C.
- a sunscreen composition characterized by the above is provided.
- the present invention also provides the sunscreen composition described above, wherein the component (a) surfactant is an ionic and / or nonionic surfactant.
- the present invention is characterized in that the component (a) surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant, or a combination of an anionic surfactant and a cationic surfactant.
- the component (a) surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant, or a combination of an anionic surfactant and a cationic surfactant.
- the present invention also provides the sunscreen composition described above, wherein the component (a) surfactant is a nonionic surfactant, and the HLB is between 5 and 14. To do.
- the component (d) water-soluble ultraviolet absorber is phenylbenzimidazole sulfonate, hydroxymethoxybenzophenone sulfonate, 4- (2- ⁇ -glucopyranosyloxy) propoxy-2-hydroxybenzophenone. 1 or 2 or more types selected from phenylene-1,4-bis (2-benzimidazolyl) -3,3′-5,5′-tetrasulfonic acid bis-sodium salt A stop composition is provided.
- the component (d) oil-soluble ultraviolet absorber is selected from the group consisting of 2-ethylhexyl-p-methoxycinnamate, 4-tert-4′-methoxydibenzoylmethane, octocrylene, 2,4-bis-[ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, methylenebisbenzotriazolyltetramethylbutylphenol, 2,4,6- One or more selected from tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine, diethylaminohydroxybenzoyl hexyl benzoate, oxybenzone, dihydroxydimethoxybenzophenone,
- the sunscreen composition is provided.
- the bicontinuous microemulsion phase by using the bicontinuous microemulsion phase, it is possible to obtain a sunscreen composition that exhibits an extremely excellent ultraviolet protection ability and that is excellent in use feeling. Furthermore, it is possible to provide a sunscreen cosmetic comprising a sunscreen composition using a transparent bicontinuous microemulsion phase, which has good spreading on the skin at the time of application, excellent uniformity of the coating film, good familiarity, and transparency.
- FIG. 1 is a phase diagram for determining the amounts of the essential components (a) to (d) in order to produce a sunscreen composition that is a bicontinuous microemulsion phase.
- FIG. 2 shows the absorbance spectra of Test Examples 1-1, 1-3, 1-4, and 1-5.
- FIG. 3 is a phase diagram showing the compositions of Test Examples 4-1 and 4-2 on FIG.
- FIG. 4 is a phase diagram showing the compositions of Test Examples 5-1 to 4 on FIG.
- FIG. 5 is a phase diagram for determining the blending amounts of the essential components (a) to (d) in order to produce a sunscreen composition that is a bicontinuous microemulsion phase.
- 4 is a phase diagram showing the composition of FIG.
- FIG. 6 is a phase diagram showing the compositions of Test Examples 7-1 to 3 on FIG.
- FIG. 7 shows the absorbance spectra of Examples 1 to 4.
- the (a) surfactant used in the present invention is an ionic and / or nonionic surfactant.
- An ionic surfactant is a surfactant that is charged by being ionized in an aqueous solution, and is classified into an amphoteric surfactant, a cationic surfactant, and an anionic surfactant depending on the type of the charge.
- the amphoteric surfactant has at least one cationic functional group and one anionic functional group, becomes cationic when the solution is acidic, and anionic when the solution is alkaline, and is close to a nonionic surfactant near the isoelectric point. It has properties.
- Amphoteric surfactants are classified into carboxylic acid type, sulfate ester type, sulfonic acid type and phosphate ester type depending on the type of anionic group.
- the carboxylic acid type, sulfate type and sulfonic acid type are preferred in the present invention.
- Carboxylic acid types are further classified into amino acid types and betaine types. Particularly preferred is a betaine type.
- imidazoline-based amphoteric surfactants for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide) 1-carboxyethyloxy disodium salt
- betaine surfactants for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfone) Betaine
- cationic surfactant examples include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammonium methylsulfate. Can be mentioned.
- stearic acid diethylaminoethylamide stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethyl Aminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenine Amidoamino such as dimethylaminopropylamide Compounds
- Anionic surfactants include fatty acid soap, N-acyl glutamate, carboxylate type such as alkyl ether acetic acid, sulfonic acid type such as ⁇ -olefin sulfonate, alkane sulfonate, alkylbenzene sulfonic acid, higher alcohol sulfate It is classified into a sulfate ester salt type such as a salt and a phosphate ester salt type. Carboxylate type, sulfonic acid type and sulfate ester type are preferred, and sulfate ester type is particularly preferred.
- fatty acid soap eg, sodium laurate, sodium palmitate, etc.
- higher alkyl sulfate ester salt eg, sodium lauryl sulfate, potassium lauryl sulfate
- alkyl ether sulfate ester salt eg, POE- Lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.
- N-acyl sarcosine acid eg, sodium lauroyl sarcosine, etc.
- higher fatty acid amide sulfonate eg, sodium N-myristoyl-N-methyltaurine, coconut oil fatty acid
- phosphoric acid ester salts POE-oleyl ether sodium phosphate, POE-stearyl ether phosphoric acid etc.
- sulfosuccinate eg, di-2-ethy
- an anionic surfactant and an amphoteric surfactant decrease the interfacial tension with respect to oil when mixed in an aqueous solution. Therefore, it is easy to produce a bicontinuous microemulsion phase having a minimum oil-water interfacial tension, which is a suitable combination in the present invention.
- the interfacial tension is not sufficiently lowered, and a bicontinuous microemulsion phase cannot be obtained or obtained. Even in such a case, the generation region is narrow, and the stability may not be sufficiently satisfied in practical use.
- a nonionic surfactant is a surfactant that is not ionized in an aqueous solution and has no electric charge.
- a type using alkyl and a type using dimethyl silicone are known.
- the former for example, glycerin fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene oxide derivative of propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyethylene glycol alkyl ether, Examples include polyethylene glycol alkylphenyl ether, polyethylene glycol castor oil derivatives, polyethylene glycol hydrogenated castor oil derivatives, and the like. Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone.
- a type using alkyl as a hydrophobic group is preferred.
- sorbitan fatty acid esters for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate), glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, glyceryl monoerucate, sesquiolein) Acid glycerin, glyceryl monostearate, ⁇ , ⁇ '-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.), propylene glycol fatty acid ester And the like (
- hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate).
- POE-sorbitan fatty acid esters for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate.
- POE sorbite fatty acid esters eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.
- POE-glycerin fatty acid esters eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate
- POE-fatty acid esters for example, POE-distearate, OE-monodiolate, ethylene glycol distearate, etc.
- POE-alkyl ethers for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core
- Stanol ether etc.
- the nonionic surfactant preferably has an HLB of between 5 and 14.
- HLB when HLB is 7, it is known that the solubility in water and the solubility in oil are balanced. That is, the surfactant suitable in the present invention has an intermediate oil / water solubility. If the HLB is less than 5 or exceeds 14, a bicontinuous microemulsion phase cannot be obtained, or even if it is obtained, its formation region is narrow, and the stability is sufficiently satisfied in practical use. May not be possible.
- a component called cosurfactant that functions as a surfactant aid can be blended.
- a monoglycerol derivative and / or a diglycerol derivative are mentioned.
- monoglycerin derivatives monooctanoic acid monoglycerin ester, monooctyl monoglyceryl ether, monononanoic acid monoglycerin ester, monononyl monoglyceryl ether, monodecanoic acid monoglycerin ester, monodecyl monoglyceryl ether, monoundecylene Acid monoglycerin ester, monoundecylenyl monoglyceryl ether, monododecanoic acid monoglycerin ester, monododecyl monoglyceryl ether, monotetradecanoic acid monoglycerin ester, monohexadecanoic acid monoglycerin ester, monooleic acid monoglycer
- the blending amount of the surfactant is appropriately determined according to the phase diagram, but is preferably from 0.1 to 50% by mass, more preferably from 0.3 to 30% by mass, based on the total amount of the sunscreen composition.
- the water contained in the sunscreen composition of the present invention is not particularly limited, and examples thereof include purified water, ion exchange water, and tap water.
- the amount of water is appropriately determined depending on the phase diagram, but is preferably 1 to 95% by mass with respect to the total amount of the sunscreen composition.
- the oily component contained in the sunscreen composition of the present invention includes hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid fats, solid fats, waxes, and the like that are usually used in cosmetics, quasi drugs, etc. 1 type, or 2 or more types of oily components can be used.
- hydrocarbon oil examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
- higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) ) And the like.
- higher alcohols examples include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol), branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol)) -2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol, etc.).
- linear alcohols eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol
- branched chain alcohols eg, monostearyl glycerin ether (batyl alcohol)) -2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, is
- Synthetic ester oils include, for example, octyl octoate, nonyl nonanoate, cetyl octanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethyloctane Hexyldecyl acid, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl monoisostearate Glycol, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisosteary
- silicone oil examples include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane etc.) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones forming a three-dimensional network structure Etc.
- linear polysiloxanes for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
- liquid oils and fats examples include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanca oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
- solid fat examples include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.
- waxes examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin.
- the blending amount of the oil is appropriately determined according to the phase diagram, but is preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass with respect to the total amount of the sunscreen composition.
- Water-soluble UV absorber and / or oil-soluble UV absorber examples include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,2′-dihydroxy-4,4′-dimethoxy.
- Benzophenone ultraviolet rays such as sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone Absorber, phenylbenzimida Benzo-5-sulfonic acid and salts thereof, benzimidazole-based UV absorbers such as phenylene-bis-benzimidazole-tetrasulfonic acid and salts thereof, 3- (4′-methylbenzylidene) -d, l-camphor, 3- Examples include benzylidene-d, l-camphor, uroca
- oil-soluble ultraviolet absorber contained in the sunscreen composition of the present invention examples include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N Benzoic acid ultraviolet absorbers such as N, N-dimethyl PABA ethyl ester and N, N-dimethyl PABA butyl ester; Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomentil Salicylic acid UV absorbers such as salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl -2,
- the water-soluble ultraviolet absorber includes phenylbenzimidazole sulfonate, hydroxymethoxybenzophenone sulfonate, 4- (2- ⁇ -glucopyranosyloxy) propoxy-2- One or more selected from hydroxybenzophenone and phenylene-1,4-bis (2-benzimidazolyl) -3,3′-5,5′-tetrasulfonic acid bis-sodium salt are preferred.
- the oil-soluble ultraviolet absorber contained in the sunscreen composition of the present invention includes 2-ethylhexyl-p-methoxycinnamate, 4-tert-4′-methoxydibenzoylmethane, octocrylene, 2,4-bis-[ ⁇ 4 -(2-Ethylhexyloxy) -2-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine, methylenebisbenzotriazolyltetramethylbutylphenol, 2,4,6-tris [4- (2-Ethylhexyloxycarbonyl) anilino] 1,3,5-triazine, diethylaminohydroxybenzoyl hexyl benzoate, oxybenzone, dihydroxydimethoxybenzophenone is preferably one or more.
- the blending amount of the water-soluble UV absorber and / or the oil-soluble UV absorber is appropriately determined according to the phase diagram, but is preferably 0.1 to 20% by mass, more preferably 0, based on the total amount of the sunscreen composition. 3 to 15% by mass.
- sunscreen composition in the sunscreen composition according to the present invention, other components generally used in skin preparations for cosmetics and quasi-drugs, such as water-soluble alcohols and thickeners, are generally used within the range not impairing the effects of the present invention.
- powders such as inorganic pigments and extender pigments, moisturizers, chelating agents, preservatives, dyes, and fragrances can be appropriately blended as desired.
- Water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, One or more selected from oligosaccharides, polysaccharides and derivatives thereof.
- lower alcohols examples include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
- polyhydric alcohol examples include dihydric alcohols (eg, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.), trihydric alcohol (eg, glycerin, trimethylolpropane, etc.), tetrahydric alcohol (eg, diglycerin, 1,2, , 6-hexanetriol, etc.), pentahydric alcohol (eg, xylitol, triglycerin, etc.), hexahydric alcohol (eg, sorbitol, mannitol, etc.), polyhydric alcohol polymer (eg, diethylene glycol) Dipropylene glycol-triethylene glycol, polypropylene glycol, tetra
- monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.), tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.), pentose sugars (eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc., hexose (eg, D-glucose, D-talose, D -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.), pentose sugar (eg, aldheptose, heprose, etc.), octose sugar (eg
- Oligosaccharides include, for example, sucrose, guntianose, umbelliferose, lactose, planteose, isoliquinoses, ⁇ , ⁇ -trehalose, raffinose, lycnose, umbilicin, stachyose verbus courses, and the like.
- polysaccharide examples include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate-tragacanth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, etc. Is mentioned.
- polyols include polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and the like.
- thickener examples include gum arabic, carrageenan, colored gum, tragacanth gum, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, silicate A1Mg (vee gum), Examples thereof include laponite and silicic anhydride.
- natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid), microbial polymers (eg, xanthan gum, dextran, succinoglucan, pullulan, etc.), animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.
- plant-based polymers for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid),
- semi-synthetic water-soluble polymers include starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.), cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate). Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.), alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.
- starch polymers eg, carboxymethyl starch, methylhydroxypropyl starch, etc.
- cellulose polymers methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate. Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.
- alginic acid polymers for example, sodium alginate
- Examples of the synthetic water-soluble polymer include vinyl polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.) and polyoxyethylene polymers (for example, polyethylene glycol 20,000, 40). , 000, 60,000, etc.), acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.), polyethyleneimine, cationic polymers and the like.
- vinyl polymers for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.
- polyoxyethylene polymers for example, polyethylene glycol 20,000, 40. , 000, 60,000, etc.
- acrylic polymers for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
- polyethyleneimine for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
- the powder component examples include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
- inorganic powders for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
- Organic pigment Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203 , Green No. 3 and Blue No. 1
- natural pigments for example, chlorophyll, ⁇ -carotene, etc.
- humectant examples include chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, DL-pyrrolidone carboxylate, short chain soluble collagen, Diglycerin (EO) PO adduct, Izayoi rose extract, Achillea millefolium extract, Merirot extract and the like can be mentioned.
- EO Diglycerin
- sequestering agent examples include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate.
- amino acids examples include neutral amino acids (eg, threonine, cysteine, etc.), basic amino acids (eg, hydroxylysine, etc.), and the like.
- amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl ⁇ -alanine sodium, glutathione and the like.
- organic amine examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis (2-hydroxypropyl) ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino Examples include -2-methyl-1-propanol.
- polymer emulsion examples include acrylic resin emulsion, polyethyl acrylate emulsion, acrylic resin liquid, polyacryl alkyl ester emulsion, polyvinyl acetate resin emulsion, natural rubber latex, and the like.
- pH adjuster examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
- vitamins examples include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.
- antioxidants examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
- antioxidant assistant examples include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.
- ingredients that can be blended include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.), anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.), Whitening agents (for example, Yukinosita extract, arbutin, etc.), various extracts (for example, agate, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, red pepper, chimney, seaweed, etc., activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.), blood circulation promoter (
- the sunscreen composition of the present invention contains the above-mentioned components (a) to (d), and other components are added as necessary within a range not impairing the effects of the present invention. It is a microemulsion phase.
- the bicontinuous microemulsion phase which is a requirement of the present invention, is in a thermodynamic equilibrium state and is generated regardless of the order of addition. Therefore, any order of addition can be produced.
- water, a surfactant, a water-soluble UV absorber, a salt or other water-soluble substance is mixed to prepare an aqueous solution with a sufficiently reduced interfacial tension, and then the oil content. It is desirable to gradually add an oil-soluble substance such as an oil-soluble ultraviolet absorber with stirring.
- each vertex of the phase diagram in FIG. 1 is an A component, a B component, and water, and the composition of the A component and the B component is as follows.
- ⁇ A component Imidazolinium betaine 35.0 Sodium polyoxyethylene lauryl ether sulfate 15.0 2-Ethylhexyl monoglyceryl ether 30.0 Phenylbenzimidazolesulfonic acid 12.5 Triethanolamine 7.5 ⁇ B component> Octyl octoate 75.0 2-Ethylhexyl-p-methoxycinnamate 25.0
- the method for creating the phase equilibrium diagram of FIG. 1 is shown below. 1: First, the A component, the B component, and water are weighed into a screw test tube, shaken vigorously, and then left in a constant temperature bath to observe the state of the solution. If it is not turbid and completely transparent, it is one phase. If turbidity is present, leave it for a longer period of time and wait for separation of each phase. In rare cases, when the phase separation is very slow and there is a concern about deterioration of components, a centrifugal separator is used. In this case, it is necessary to use a type capable of temperature control.
- the bicontinuous microemulsion phase of the present invention generally has a lighter specific gravity than the aqueous phase and the micelle aqueous solution phase, and a higher specific gravity than the oil phase and the reverse micelle oil solution phase. It depends on. Although the specific gravity of the bicontinuous microemulsion phase and the lamellar liquid crystal phase are close to each other, both can be distinguished by optical isotropy. 4: A phase equilibrium diagram is completed by preparing a large number of solutions according to the above procedure, identifying phases appearing in each composition, and determining the regions.
- the bicontinuous microemulsion phase is a solution in which surfactants are infinitely associated, and means an optically isotropic transparent low-viscosity solution in which both water and oil are continuous. It is also referred to as a middle phase microemulsion phase, bicontinuous phase, sponge phase, L3 phase, D phase, etc., and in the present invention, it provides an excellent UV protection ability and a feeling of use. In appearance, the bicontinuous microemulsion is a transparent low-viscosity one-phase region and is optically isotropic. The following method is further effective for distinguishing from other micelle aqueous solutions, reverse micelle oil solutions, and liquid crystal phases, which are other isotropic one-phase regions.
- the sunscreen composition containing the components (a) to (d) is in a bicontinuous microemulsion phase is determined by (1) judgment by appearance, (2) creation of a phase equilibrium diagram, (3) electrical conduction (4) measurement of self-diffusion coefficient by NMR, (5) electron microscope observation of a replica prepared using the freeze fracture method. It may be determined by any method.
- the bicontinuous microemulsion phase is a transparent low-viscosity one-phase region and is optically isotropic.
- the liquid crystal phase having optical anisotropy can be distinguished by holding the sample while combining two polarizing plates with a phase difference of 90 degrees and confirming that there is no light transmission.
- phase equilibrium diagram a three-component phase equilibrium diagram consisting of water / oil component / surfactant (oil component includes cosurfactant surfactant) isotropic. It can be identified by having a characteristic such as a transparent low viscosity one-phase region and a region that is not continuous from any of the top of water and oil, but this feature varies depending on the system (component) to be constructed .
- a compounding quantity represents the mass%.
- the sunscreen cosmetics of each test example were produced by a conventional method, and the association state (whether or not a bicontinuous microemulsion phase was exhibited at 25 ° C.) and the effect as a sunscreen cosmetic were compared.
- test examples (a) a surfactant, (b) water, (c) an oil component, (d) a water-soluble UV absorber and / or an oil-soluble UV absorber,
- the numbers of the test examples of the sunscreen compositions showing the nuclide microemulsion phase and being examples of the present invention are the test examples 1-1, 1-2, 2-1, 3-1, 4-1, 5-1 -4, 6-1 to 4, 7-1.
- Other test examples other than the above do not show a bicontinuous microemulsion phase at 25 ° C. and do not constitute examples of the present invention.
- Evaluation (1) Association State The association state of the sunscreen composition of the present invention was evaluated. The method described in “0081” was used for the determination of the bicontinuous microemulsion phase.
- L3 The bicontinuous microemulsion phase is in a single-phase association state.
- L1 The micelle aqueous solution phase is in one-phase association state.
- L2 The reverse micelle oil solution phase is in one phase of association. II: Water separation, oil separation, etc. are occurring.
- O / W An oil-in-water type emulsified state is taken.
- W / O Water-in-oil type emulsified state.
- Evaluation (2) UV protection effect The UV protection effect of the sunscreen composition of the present invention was evaluated. A certain amount of the sunscreen composition of each test example was applied to a polymethylmethacrylate plate, and the ultraviolet protection effect was evaluated by measuring the absorption spectrum. In the table, the absorbance value at a wavelength of 310 nm of each sunscreen composition is shown. The larger the value, the better the UV protection effect.
- Evaluation (3) Familiarity Familiarity with the skin being used was subjected to an actual use test of each test example by 10 professional panels.
- the evaluation criteria are as follows. ⁇ ... 8 or more panelists recognized that familiarity was good during use. ⁇ : 6 or more panelists and less than 8 panelists recognized that familiarity was good during use. ⁇ : 3 or more panelists and less than 6 panelists recognized that familiarity was good during use. X: Less than 3 panelists recognized that familiarity was good during use.
- Evaluation (4) No stickiness
- the actual use test of each test example was conducted by 10 professional panels on the non-stickiness on the skin during and after use.
- the evaluation criteria are as follows. A: More than 8 panelists recognized that there was no stickiness during and after use. ⁇ : 6 or more and less than 8 panelists recognized that there was no stickiness during and after use. ⁇ : 3 or more and less than 6 panelists recognized that there was no stickiness during and after use. X: Less than 3 panelists recognized that there was no stickiness during and after use.
- Test Example 2-2 O which takes a micellar aqueous phase even though the blending concentration of the ultraviolet absorber (phenylbenzimidazolesulfonic acid) is the same.
- the UV protection effect was inferior and the feel in use was slightly inferior.
- Test Examples 2-2 and 2-4 the uniformity of the coating film tended to be poor.
- Test Example 2-1 formed a bicontinuous microemulsion phase and was excellent in any of the evaluations (1) to (5).
- Test Example 3-2 in which no surfactant was blended could not be in either a solubilized state or an emulsified state, and was in a separated state and could not be evaluated.
- Test Example 3-1 containing a surfactant formed a bicontinuous microemulsion phase and was excellent in any of the evaluations (1) to (5).
- FIG. 3 shows the compositions of Test Examples 4-1 and 4-2 on the phase diagram of FIG. Test Examples 4-1 and 4-2 contain the same concentration of B component (oil content and oil-soluble UV absorber), but Test Example 4-1 forms a bicontinuous microemulsion phase, and Test Example 4-2 Indicates that it is polymorphic.
- the concentration of the water-soluble UV absorber is less than 4-1, and the difference is corrected by adding it later.
- Test Example 4-2 which does not form a bicontinuous microemulsion phase and takes an O / W emulsified state, was inferior in UV protection effect and in use feeling.
- Test Example 4-3 in which 2-ethylhexyl monoglyceryl ether, which is a surface active aid, was not blended, also formed an O / W emulsified state without forming a bicontinuous microemulsion phase, and was inferior in UV protection effect. It was somewhat inferior to the feeling of use.
- Test Example 4-1 for forming a bicontinuous microemulsion phase was excellent in any of the evaluations (1) to (5).
- FIG. 4 shows the compositions of Test Examples 5-1 to 5-4 on the phase diagram of FIG.
- Test Examples 5-1 to 5-4 formed a bicontinuous microemulsion phase, and contained UV absorbers (phenylbenzimidazole sulfonic acid and 2-ethylhexyl-p-methoxycinnamate). Depending on the amount, the UV protection effect was high, and all were excellent in use feeling and coating uniformity.
- UV absorbers phenylbenzimidazole sulfonic acid and 2-ethylhexyl-p-methoxycinnamate
- sunscreen compositions containing various concentrations of surfactant, oil and UV absorbers Obtainable.
- FIG. 5 shows a phase diagram of the prepared nonionic surfactant system and the compositions of Test Examples 6-1 to 6-4 therein.
- Test Examples 6-1 to 6-4 formed a bicontinuous microemulsion phase, and UV protection was performed according to the blending amount of the blended UV absorber (2-ethylhexyl-p-methoxycinnamate). The effects were high, and all were excellent in use feeling and uniformity of the coating film.
- Sunscreen compositions containing surfactants, oils and UV absorbers at various concentrations by utilizing the bicontinuous microemulsion phase of various compositions generated on the phase diagram of nonionic surfactant systems Can be obtained.
- FIG. 6 shows the compositions of Test Examples 7-1 to 7-3 on the same phase diagram as FIG. Test Examples 7-1 to 7-3 contain the same concentration of oil and oil-soluble UV absorber, but Test Example 7-1 forms a bicontinuous microemulsion phase, and Test Examples 7-2 and 7 -3 indicates that it is multiphase.
- Test Example 7-2 which does not form a bicontinuous microemulsion phase and takes an O / W emulsified state, was inferior in UV protection effect and in use feeling. Further, Test Example 7-3 in a multiphase state including a bicontinuous microemulsion phase was slightly inferior in the ultraviolet protection effect and inferior in the feeling in use. On the other hand, Test Example 7-1 for forming a bicontinuous microemulsion phase was excellent in any of the evaluations (1) to (5).
- the obtained sunscreen composition exhibited a bicontinuous microemulsion phase at 25 ° C., had good safety and use feeling, and had high base stability.
- the absorption spectrum measurement results of Examples 1 to 3 are shown in FIG.
- Example 1 Sunscreen lotion
- Imidazolinium betaine 7.0 POE (2.5) sodium lauryl ether sulfate 3.0 2-Ethylhexyl monoglyceryl ether 6.0 Phenylbenzimidazolesulfonic acid 2.5 Triethanolamine 1.5 Citric acid 0.01 Sodium citrate 0.09
- Chelating agent Appropriate amount of ion-exchanged water Residual octyl octanoate 11.3 2-Ethylhexyl-p-methoxycinnamate 3.8 Diethylaminohydroxybenzoyl hexyl benzoate 0.5 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] 1,3,5-triazine 0.5 4-tert-4'-methoxydibenzoylmethane 0.5
- Example 2 Sunscreen mist
- Imidazolinium betaine 7.0 POE (2) sodium lauryl ether sulfate 1.5 POE (3) sodium lauryl ether sulfate 1.5 2-ethylhexyl monoglyceryl ether 5.9 Phenylbenzimidazolesulfonic acid 2.5 Triethanolamine 1.5 Citric acid 0.01 Sodium citrate 0.09
- Chelating agent Appropriate amount of ion-exchanged water Residual nonyl nonanoate 11.3 2-Ethylhexyl-p-methoxycinnamate 3.75 2,4-bis-[ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 1.0 Octocrylene 1.0
- Example 3 Sunscreen lotion
- Phytantriol 28.5 Citric acid 0.01 Sodium citrate 0.09
- Chelating agent Appropriate amount of ion exchange water Residual dimethylpolysiloxane 61.0 2-Ethylhexyl-p-methoxycinnamate 5.0 Diethylaminohydroxybenzoyl hexyl benzoate 0.5
- Example 4 Sunscreen liquid
- Chelating agent Appropriate amount of ion-exchanged water Residual residual isododecane 45.0 Octocrylene 2.2
- 4-tert-4'-methoxydibenzoylmethane 1.1 2,4-bis-[ ⁇ 4- (2-ethylhexyloxy) -2-hydroxy ⁇ -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine
- 2-Ethylhexyl-p-methoxycinnamate 1.6 Diethylaminohydroxybenzoyl hexyl benzoate 0.5
- the present invention provides a sunscreen composition utilizing a transparent bicontinuous microemulsion phase.
- the novel sunscreen composition of the present invention uses the bicontinuous microemulsion phase to provide extremely excellent UV protection, excellent stability, and good spreading to the skin during application. It is useful as a sunscreen cosmetic with excellent coating film uniformity and excellent skin familiarity. Furthermore, since the sunscreen composition of the present invention is excellent in UV protection, it is also usefully used in various industrial products.
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Abstract
Description
また、使用感を重視するという化粧料の特異性に鑑み、油分を多量に配合するとべたつきが生じるため、通常、油分を多量に配合することはしない。したがって、水中油型乳化組成物においては、特徴であるさっぱりとしたみずみずしい感触を維持しながら油溶性紫外線吸収剤を多量に配合することは困難であることから、その他の乳化タイプの日焼け止め組成物と比較して高い紫外線防御能を得ることができない。
さらに皮膚外用剤としての使用性に関しても、水中油型タイプの日焼け止め組成物に比較し、べたつきや油性感があり、のびが悪いという問題点を有していた。
本発明に用いる(a)界面活性剤は、イオン性および/または非イオン性界面活性剤である。
イオン性界面活性剤は、水溶液中で電離して電荷を有する界面活性剤であり、その電荷の種類によって両性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤に分類される。
両性界面活性剤は、アニオン基の種類により、カルボン酸型、硫酸エステル型、スルホン酸型およびリン酸エステル型に分類される。本発明に好ましくはカルボン酸型、硫酸エステル型およびスルホン酸型である。カルボン酸型はさらにアミノ酸型とベタイン型に分類される。特に好ましくはベタイン型である。
具体的には、例えば、イミダゾリン系両性界面活性剤(例えば、2-ウンデシル-N,N,N-(ヒドロキシエチルカルボキシメチル)-2-イミダゾリンナトリウム、2-ココイル-2-イミダゾリニウムヒドロキサイド-1-カルボキシエチロキシ2ナトリウム塩等);ベタイン系界面活性剤(例えば、2-ヘプタデシル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、ラウリルジメチルアミノ酢酸ベタイン、アルキルベタイン、アミドベタイン、スルホベタイン等)等が挙げられる。
具体的には、例えば、脂肪酸石鹸(例えば、ラウリン酸ナトリウム、パルミチン酸ナトリウム等)、高級アルキル硫酸エステル塩(例えば、ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等)、アルキルエーテル硫酸エステル塩(例えば、POE-ラウリル硫酸トリエタノールアミン、POE-ラウリル硫酸ナトリウム等)、N-アシルサルコシン酸(例えば、ラウロイルサルコシンナトリウム等)、高級脂肪酸アミドスルホン酸塩(例えば、N-ミリストイル-N-メチルタウリンナトリウム、ヤシ油脂肪酸メチルタウリッドナトリウム、ラウリルメチルタウリッドナトリウム等)、リン酸エステル塩(POE-オレイルエーテルリン酸ナトリウム、POE-ステアリルエーテルリン酸等)、スルホコハク酸塩(例えば、ジ-2-エチルヘキシルスルホコハク酸ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等)、アルキルベンゼンスルホン酸塩(例えば、リニアドデシルベンゼンスルホン酸ナトリウム、リニアドデシルベンゼンスルホン酸トリエタノールアミン、リニアドデシルベンゼンスルホン酸等)、高級脂肪酸エステル硫酸エステル塩(例えば、硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等)、N-アシルグルタミン酸塩(例えば、N-ラウロイルグルタミン酸モノナトリウム、N-ステアロイルグルタミン酸ジナトリウム、N-ミリストイル-L-グルタミン酸モノナトリウム等)、硫酸化油(例えば、ロート油等)、POE-アルキルエーテルカルボン酸、POE-アルキルアリルエーテルカルボン酸塩、α-オレフィンスルホン酸塩、高級脂肪酸エステルスルホン酸塩、二級アルコール硫酸エステル塩、高級脂肪酸アルキロールアミド硫酸エステル塩、ラウロイルモノエタノールアミドコハク酸ナトリウム、N-パルミトイルアスパラギン酸ジトリエタノールアミン、カゼインナトリウム等が挙げられる。
両性界面活性剤、カチオン性界面活性剤およびアニオン性界面活性剤の1種類のみ用いた場合には、界面張力の低下が十分でなく、バイコンティニュアスミクロエマルション相が得られないか、あるいは、得られた場合であってもその生成領域が狭く、実質上の使用にあたって安定性を十分に満たすことができない場合がある。
界面活性剤の配合量は相図により適宜決定されるが、日焼け止め組成物全量に対して0.1~50質量%が好ましく、さらに好ましくは、0.3~30質量%である。
本発明の日焼け止め組成物に含まれる水は特に限定されず、具体的に示すとすれば精製水、イオン交換水、水道水等が挙げられる。
水の配合量は相図により適宜決定されるが、日焼け止め組成物全量に対して1~95質量%が好ましい。
本発明の日焼け止め組成物に含まれる油性成分は、通常化粧品、医薬部外品等に使用される炭化水素油、高級脂肪酸、高級アルコール、合成エステル油、シリコーン油、液体油脂、固体油脂、ロウ類などが挙げられ、一種または二種以上の油性成分を用いることができる。
油分の配合量は相図により適宜決定されるが、日焼け止め組成物全量に対して0.1~90質量%が好ましく、さらに好ましくは、0.5~80質量%である。
本発明の日焼け止め組成物に含まれる水溶性紫外線吸収剤は、例えば2,4-ジヒドロキシベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-4’-メチルベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン-5-スルホン酸塩、4-フェニルベンゾフェノン、2-エチルヘキシル-4’-フェニル-ベンゾフェノン-2-カルボキシレート、2-ヒドロキシ-4-n-オクトキシベンゾフェノン、4-ヒドロキシ-3-カルボキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤、フェニルベンズイミダゾール-5-スルホン酸およびその塩、フェニレン-ビス-ベンゾイミダゾール-テトラスルホン酸およびその塩等のベンゾイミダゾール系紫外線吸収剤、3-(4’-メチルベンジリデン)-d,l-カンファー、3-ベンジリデン-d,l-カンファー、ウロカニン酸、ウロカニン酸エチルエステル等が挙げられる。
水溶性紫外線吸収剤および/または油溶性紫外線吸収剤の配合量は、相図により適宜決定されるが、日焼け止め組成物全量に対して0.1~20質量%が好ましく、さらに好ましくは、0.3~15質量%である。
水溶性アルコールは、低級アルコール、多価アルコール、多価アルコール重合体、2価のアルコールアルキルエーテル類、2価アルコールアルキルエーテル類、2価アルコールエーテルエステル、グリセリンモノアルキルエーテル、糖アルコール、単糖、オリゴ糖、多糖およびそれらの誘導体から選ばれる1種または2種以上である。
増粘剤としては、例えば、アラビアガム、カラギーナン、カラーヤガム、トラガカントガム、キャロブガム、クインスシード(マルメロ)、カゼイン、デキストリン、ゼラチン、ペクチン酸ナトリウム、アラギン酸ナトリウム、メチルセルロース、エチルセルロース、CMC、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、PVA、PVM、PVP、ポリアクリル酸ナトリウム、カルボキシビニルポリマー、ローカストビーンガム、グアガム、タマリントガム、ジアルキルジメチルアンモニウム硫酸セルロース、キサンタンガム、ケイ酸アルミニウムマグネシウム、ベントナイト、ヘクトライト、ケイ酸A1Mg(ビーガム)、ラポナイト、無水ケイ酸等が挙げられる。
酸化防止助剤としては、例えば、リン酸、クエン酸、アスコルビン酸、マレイン酸、マロン酸、コハク酸、フマル酸、ケファリン、ヘキサメタフォスフェイト、フィチン酸、エチレンジアミン四酢酸等が挙げられる。
<A成分>
イミダゾリニウムベタイン 35.0
ポリオキシエチレンラウリルエーテル硫酸ナトリウム 15.0
2-エチルヘキシルモノグリセリルエーテル 30.0
フェニルベンズイミダゾールスルホン酸 12.5
トリエタノールアミン 7.5
<B成分>
オクタン酸オクチル 75.0
2-エチルヘキシル-p-メトキシシンナメート 25.0
1:まず、A成分、B成分、および水をねじ口試験管に秤量し、激しく振とうしたのち恒温水槽中に静置し溶液の状態を観察する。濁りがなく完全に透明であれば1相である。濁りがある場合にはさらに長期間静置しそれぞれの相の分離を待つ。まれに相分離が非常に遅く、成分の劣化などが懸念される場合には遠心分離装置を用いる。この場合、温度コントロールが可能なタイプを用いることが必要である。
2:次に溶液が1相の場合にはバイコンティニュアスミクロエマルション相、ミセル水溶液相、液晶相、逆ミセル油溶液相などの可能性があるため、どの相であるかを決定する。決定の方法は、粘度による判定、光学的等(異)方性、電気伝導度測定、偏光顕微鏡観察、X線構造解析等の手法を用いる。
3:溶液が多相の共存状態である場合には、完全な相分離後に各相の光学的等(異)方性を確認する。また、この共存するいくつかの相のうち1つは、近接する1相領域の相である。確実に確認するためには、溶液の組成を近接する1相の領域に向かって徐々に変化させたいくつかの溶液を調製する、多相共存溶液のうち当該相の全溶液に占める容積が徐々に増加し、ついには1相となることから確認が可能である。また、比重を考慮し各相の試験管内の存在位置からの確認も可能である。本発明のバイコンティニュアスミクロエマルション相は、水相およびミセル水溶液相よりも比重が軽く、油相および逆ミセル油溶液相よりも比重が重いことが一般であるが、これは構成成分(系)によって異なる。バイコンティニュアスミクロエマルション相とラメラ液晶相の比重は近いが、両者は光学的等方性により判別が可能である。
4:上記の手順により、多数の溶液を調製し、それぞれの組成において出現する相を特定し、領域を決定することにより、相平衡図が完成する。
外観的にはバイコンティニュアスミクロエマルションは、透明な低粘度1相領域であり光学的には等方性である。これが他の等方性1相領域であるミセル水溶液、逆ミセル油溶液や、液晶相との区別にはさらに次の方法が有効である。
(1)外観による判定では、バイコンティニュアスミクロエマルション相は透明な低粘度1相領域であり光学的には等方性である。光学的異方性のある液晶相との区別は偏光板2枚を90度の位相差で組み合わせた間にサンプルを保持し、光の透過がないことを確認することで可能である。バイコンティニュアスミクロエマルション相と他の等方性1相領域であるミセル水溶液、逆ミセル油溶液との区別には、さらに(2)~(5)の方法が有効である。
(2)相平衡図の作成では、水/油性成分/界面活性剤(油性成分にはコサーファクタントの界面活性助剤を含む)で構成される3成分系の相平衡図を作成すると、等方性透明低粘度1相領域で、かつ水および油頂点のいずれからも連続する領域でない等の特徴を有していることで同定可能であるが、この特徴は構成される系(成分)によって異なる。
(3)電気伝導度測定では、バイコンティニュアスミクロエマルション相の伝導度は同じ系で得られるミセル水溶液相の約2/3の値をとることが知られている。
(4)NMRによる自己拡散係数測定は、LindmanらによりJ. Colloid Interface Sci.,1981,83,569等に詳しく記載されている方法である。
(5)フリーズフラクチャー法を用いて調製した相サンプルの電子顕微鏡観察によれば、バイコンティニュアスミクロエマルション相の水および油の両方が連続となった像を得ることが可能である。この像によれば水あるいは油が連続のミセル水溶液相で得られる球状の会合体像との区別が容易である。この方法については、今栄らによる文献Colloid polym. Sci.,1994,272,604に詳しく記載されている。
各試験例の日焼け止め化粧料を常法により製造し、会合状態(25℃においてバイコンティニュアスミクロエマルション相を示すか否か)と日焼け止め化粧料としての効果について比較検討した。
なお、以下の試験例において、(a)界面活性剤、(b)水、(c)油分、(d)水溶性紫外線吸収剤および/または油溶性紫外線吸収剤を含有し、25℃においてバイコンティニュアスミクロエマルション相を示し、本発明の実施例となる日焼け止め組成物の試験例の番号は、試験例1-1、1-2、2-1、3-1、4-1、5-1~4、6-1~4、7-1である。上記以外のその他の試験例は、25℃においてバイコンティニュアスミクロエマルション相を示さず、本発明の実施例とならない。
本発明の日焼け止め組成物の会合状態を評価した。バイコンティニュアスミクロエマルション相の判定には「0081」に述べた方法をとった。
L3:バイコンティニュアスミクロエマルション相一相の会合状態をとっている。
L1:ミセル水溶液相一相の会合状態をとっている。
L2:逆ミセル油溶液相一相の会合状態をとっている。
II:水分離、油分離などが起こっている。
O/W:水中油型の乳化状態をとっている。
W/O:油中水型の乳化状態をとっている。
本発明の日焼け止め組成物の紫外線防御効果を評価した。各々の試験例の日焼け止め組成物をポリメチルメタクリレート板に一定量塗布し、吸収スペクトルを測定することにより紫外線防御効果を評価した。表中には各日焼け止め組成物の波長310nmにおける吸光度の値を示す。値が大きいほど紫外線防御効果に優れることを示す。
使用中の肌へのなじみのよさを、専門パネル10名により各々の試験例の実使用試験を実施した。評価基準は以下の通りである。
◎…パネル8名以上が、使用中なじみがよいと認めた。
○…パネル6名以上8名未満が、使用中なじみがよいと認めた。
△…パネル3名以上6名未満が、使用中なじみがよいと認めた。
×…パネル3名未満が、使用中なじみがよいと認めた。
使用中及び使用後の肌へのべたつきのなさを、専門パネル10名により各々の試験例の実使用試験を実施した。評価基準は以下の通りである。
◎…パネル8名以上が、使用中及び使用後べたつき感がないと認めた。
○…パネル6名以上8名未満が、使用中及び使用後べたつき感がないと認めた。
△…パネル3名以上6名未満が、使用中及び使用後べたつき感がないと認めた。
×…パネル3名未満が、使用中及び使用後べたつき感がないと認めた。
油相に蛍光物質を配合して、試料を調製した。これをスライドグラス上に塗布し、15分間乾燥した後、塗膜を顕微鏡観察し、油相(白い蛍光を発する)と水相の面積割合から、塗膜の均一性を評価した。
◎…塗膜の均一性がきわめて高い。
○…塗膜の均一性が高い。
△…塗膜がやや不均一である。
×…塗膜が不均一である。
以下の表1に記載した配合組成よりなる試験例の日焼け止め組成物を製造し、上記の評価(1)~(5)について評価試験を行った。
一方、成分(a)としてイオン性界面活性剤を配合した試験例1-1、非イオン性界面活性剤を配合した試験例1-2は、いずれもバイコンティニュアスミクロエマルション相を形成し、評価(1)~(5)のいずれの評価にも優れるものであった。
以下の表2に記載した配合組成よりなる試験例の日焼け止め組成物を製造し、評価(1)~(5)について評価試験を行った。
一方、試験例2-1はバイコンティニュアスミクロエマルション相を形成し、評価(1)~(5)のいずれの評価にも優れるものであった。
一方、界面活性剤を配合した試験例3-1はバイコンティニュアスミクロエマルション相を形成し、評価(1)~(5)のいずれの評価にも優れるものであった。
一方、バイコンティニュアスミクロエマルション相を形成する試験例4-1は、評価(1)~(5)のいずれの評価にも優れるものであった。
また、本試験を実施するにあたり、作成した非イオン性界面活性剤系の相図およびその中に試験例6-1~6-4の組成を示したものを図5に示す。図5中の相図の各頂点はPOE(8)グリセリンモノイソステアレート(HLB=10、日本エマルジョン社製、製品名:EMALEX GWIS-108)、B成分、水であり、B成分の組成は下記の通りである。
<B成分>
オクタン酸オクチル 75.0
2-エチルヘキシル-p-メトキシシンナメート 25.0
一方、バイコンティニュアスミクロエマルション相を形成する試験例7-1は、評価(1)~(5)のいずれの評価にも優れるものであった。
イミダゾリニウムベタイン 7.0
POE(2.5)ラウリルエーテル硫酸ナトリウム 3.0
2-エチルヘキシルモノグリセリルエーテル 6.0
フェニルベンズイミダゾールスルホン酸 2.5
トリエタノールアミン 1.5
クエン酸 0.01
クエン酸ナトリウム 0.09
キレート剤 適 量
イオン交換水 残 余
オクタン酸オクチル 11.3
2-エチルヘキシル-p-メトキシシンナメート 3.8
ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル 0.5
2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]1,3,5-トリアジン
0.5
4-tert-4’-メトキシジベンゾイルメタン 0.5
イミダゾリニウムベタイン 7.0
POE(2)ラウリルエーテル硫酸ナトリウム 1.5
POE(3)ラウリルエーテル硫酸ナトリウム 1.5
2-エチルヘキシルモノグリセリルエーテル 5.9
フェニルベンズイミダゾールスルホン酸 2.5
トリエタノールアミン 1.5
クエン酸 0.01
クエン酸ナトリウム 0.09
キレート剤 適 量
イオン交換水 残 余
ノナン酸ノニル 11.3
2-エチルヘキシル-p-メトキシシンナメート 3.75
2,4-ビス-[{4-(2-エチルヘキシルオキシ)-2-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン
1.0
オクトクリレン 1.0
フィタントリオール 28.5
クエン酸 0.01
クエン酸ナトリウム 0.09
キレート剤 適 量
イオン交換水 残 余
ジメチルポリシロキサン 61.0
2-エチルヘキシル-p-メトキシシンナメート 5.0
ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル 0.5
モノイソステアリン酸グリセリル 44.4
クエン酸 0.01
クエン酸ナトリウム 0.09
キレート剤 適 量
イオン交換水 残 余
イソドデカン 45.0
オクトクリレン 2.2
4-tert-4’-メトキシジベンゾイルメタン 1.1
2,4-ビス-[{4-(2-エチルヘキシルオキシ)-2-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン
0.5
2-エチルヘキシル-p-メトキシシンナメート 1.6
ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル 0.5
本発明の新規な日焼け止め組成物は、バイコンティニュアスミクロエマルション相を利用することにより、きわめて優れた紫外線防御能を発揮し、安定性に優れ、さらには、塗布時の皮膚へののびがよく塗膜均一性に優れ、皮膚に対するなじみに優れた日焼け止め化粧料として有用に利用される。さらに、本発明の日焼け止め組成物は紫外線防御能に優れるため、各種工業製品にも有用に利用される。
Claims (6)
- (a)界面活性剤
(b)水
(c)油分
(d)水溶性紫外線吸収剤および/または油溶性紫外線吸収剤
を含有し、25℃においてバイコンティニュアスミクロエマルション相であることを特徴とする日焼け止め組成物。 - 前記成分(a)界面活性剤が、イオン性および/または非イオン性界面活性剤であることを特徴とする、請求項1記載の日焼け止め組成物。
- 前記成分(a)界面活性剤が、アニオン性界面活性剤および両性界面活性剤の組み合わせ、または、アニオン性界面活性剤およびカチオン性界面活性剤の組み合わせから選ばれることを特徴とする、請求項1または2記載の日焼け止め組成物。
- 前記成分(a)界面活性剤が、非イオン性界面活性剤であって、そのHLBが5から14の間であることを特徴とする、請求項1または2記載の日焼け止め組成物。
- 前記成分(d)水溶性紫外線吸収剤が、フェニルベンズイミダゾールスルホン酸塩、ヒドロキシメトキシベンゾフェノンスルホン酸塩、4-(2-β-グルコピラノシロキシ)プロポキシ-2-ヒドロキシベンゾフェノン、フェニレン-1,4-ビス(2-ベンズイミダジル)-3,3’-5,5’-テトラスルホン酸ビス-ナトリウム塩から選ばれる1種または2種以上であることを特徴とする、請求項1~4の何れか1項記載の日焼け止め組成物。
- 前記成分(d)油溶性紫外線吸収剤が、2-エチルヘキシル-p-メトキシシンナメート、4-tert-4’-メトキシジベンゾイルメタン、オクトクリレン、2,4-ビス-[{4-(2-エチルヘキシルオキシ)-2-ヒドロキシ}-フェニル]-6-(4-メトキシフェニル)-1,3,5-トリアジン、メチレンビスベンゾトリアゾリルテトラメチルブチルフェノール、2,4,6-トリス[4-(2-エチルヘキシルオキシカルボニル)アニリノ]1,3,5-トリアジン、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル、オキシベンゾン、ジヒドロキシジメトキシベンゾフェノンから選ばれる1種または2種以上であることを特徴とする、請求項1~5の何れか1項記載の日焼け止め組成物。
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US20140294904A1 (en) * | 2011-12-13 | 2014-10-02 | Otto Glatter | Water-in-oil emulsions and methods for their preparation |
CN112062878A (zh) * | 2020-08-25 | 2020-12-11 | 南方科技大学 | 水溶性光吸收剂及其制备方法和3d打印材料 |
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CN102844015B (zh) | 2015-09-09 |
EP2543356A4 (en) | 2014-01-01 |
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US20120321576A1 (en) | 2012-12-20 |
JP4834775B2 (ja) | 2011-12-14 |
EP2543356B1 (en) | 2017-01-04 |
KR20120057665A (ko) | 2012-06-05 |
KR101197910B1 (ko) | 2012-11-05 |
JP2011178769A (ja) | 2011-09-15 |
CN102844015A (zh) | 2012-12-26 |
EP2543356A1 (en) | 2013-01-09 |
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