CN1636550A - Water-in-oil emulsion composition - Google Patents
Water-in-oil emulsion composition Download PDFInfo
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- CN1636550A CN1636550A CN 200410087096 CN200410087096A CN1636550A CN 1636550 A CN1636550 A CN 1636550A CN 200410087096 CN200410087096 CN 200410087096 CN 200410087096 A CN200410087096 A CN 200410087096A CN 1636550 A CN1636550 A CN 1636550A
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Abstract
To obtain a W/O-type emulsion composition having high emulsion stability with time in a system compounded with a salicylic acid derivative (e.g. an alkoxysalicylic acid) without deteriorating the function of the component and having excellent usability. This W/O-type emulsion composition contains (a) the salicylic acid derivative (e.g. a methoxysalicylic acid salt or an ethoxysalicylic acid salt), (b) a salt and (c) a polyethylene glycol having a molecular weight of 1,000-200,000 in the water phase (inner phase) and optionally further contains a silicone oil exhibiting liquid state at normal temperature (25[deg.]C) in the oil phase (outer phase) in an amount of >=30 mass% based on the oil phase (outer phase).
Description
Technical field
The present invention relates to Water-In-Oil (W/O) type emulsification composition mainly as the skin preparations for extenal use use.In more detail, relate to and contain the good water-in-oil emulsion composition of salicyclic acid derivatives, ageing stability and usability.
Background technology
In recent years, when in water-in-oil emulsion composition, cooperating salicylic acid,, as a result of there is the problem that produces on the layering equistability because the process certain hour produces merging, the system instabilityization of emulsified particle.So,, take to increase the method for lipophilic emulsifier or in foreign minister's (oil phase), cooperate method such as wax to reach stabilisation in order to prevent layering.Therefore, when use has cooperated the water-in-oil emulsifier of salicyclic acid derivatives, be stretch bad, the usability that highly is clamminess is arranged, can not gratifying product aspect hobby property.
On the other hand, find that salicyclic acid derivatives has and can improve unusual calm, the whitening function (patent documentation 1) that prevents dermal melanin with excellence, the expectation exploitation cooperates this material as whitening agent, the water-in-oil emulsion composition of ageing stability and use sense of touch excellence.
Patent documentation 1: No. 27222309 communique of Japan Patent
Summary of the invention
The present invention is in order to solve the invention of above-mentioned prior art problems point, it is a kind of in having cooperated the water-in-oil emulsion system of salicyclic acid derivatives that its purpose is to provide, do not damage salicyclic acid derivatives functional performance, along with the time change, emulsion stability is good, and the water-in-oil emulsion composition of usability excellence.
In order to solve above-mentioned problem, the invention provides a kind of water-in-oil emulsion composition, it is characterized in that, in water (inner phase), contain (a) salicyclic acid derivatives and (b) salt and (c) Polyethylene Glycol of molecular weight 1,000～200,000.
In addition, the invention provides above-mentioned water-in-oil emulsion composition, (a) composition is the alkoxyl salicylic acid shown in the following general formula (I) or its salt.
(in the formula (I), R represents alkyl)
In addition, the invention provides above-mentioned water-in-oil emulsion composition, in the above-mentioned general formula (I), R is the alkyl of carbon number 1～6.
In addition, the invention provides above-mentioned water-in-oil emulsion composition, in the above-mentioned general formula (I), R is a methyl.
In addition, the invention provides above-mentioned water-in-oil emulsion composition, in the above-mentioned general formula (I), R is an ethyl.
In addition, the invention provides above-mentioned water-in-oil emulsion composition, in oil phase (foreign minister), contain with respect to this oil phase (foreign minister) 30 quality % or be down the silicone oil of liquid at room temperature (25 ℃) more than it.
According to the present invention,, also can provide and not damage its performance function, ageing stability and the good water-in-oil emulsion composition of usability even cooperated situation with the salicyclic acid derivatives that destroys water-in-oil emulsion character.
Water-in-oil emulsion composition of the present invention in the system that contains known salicyclic acid derivatives as whitening composition, can be used as ageing stability excellence and the external agent of usability advantages of good skin and uses.
Specific embodiments
Salicyclic acid derivatives as (a) composition that uses among the present invention, if spendable salicyclic acid derivatives in fields such as cosmetics, medicine, cosmeceutical, then have no particular limits, but preferably especially use the alkoxyl salicylic acid shown in the following general formula (I), promptly salicylic 3,4 or 5 s' arbitrary hydrogen atom alkoxy (OR) the salicylic acid based compound of Qu Daiing or its salt.
In above-mentioned general formula (I), (alkyl OR) (R) is though have no particular limits, and preferred carbon number is 1～6 low alkyl group to constitute alkoxyl.Comprise any of straight chain, side chain.Specifically, methoxyl group), ethyl (corresponding alkoxyl-OR: ethyoxyl), propyl group (corresponding alkoxyl-OR: propoxyl group), isopropyl (corresponding alkoxyl-OR: isopropoxy), butyl (corresponding alkoxyl-OR: butoxy), isobutyl group (corresponding alkoxyl-OR: isobutoxy) etc., but be not limited in these can enumerate methyl (corresponding alkoxyl-OR:.
As the alkoxyl salicylic acid shown in the above-mentioned general formula (I), specifically, can enumerate 3-methoxyl group salicylic acid (2-hydroxy 3-methoxybenzene formic acid), 3-ethyoxyl salicylic acid (2-hydroxyl-3-ethoxybenzoic acid), 4-methoxyl group salicylic acid (2-hydroxyl-4-methoxybenzoic acid), 4-ethyoxyl salicylic acid (2-hydroxyl-4-ethoxybenzoic acid), 4-propoxyl group salicylic acid (2-hydroxyl-4-propoxy benzoic acid), 4-isopropoxy salicylic acid (2-hydroxyl-4-isopropoxy benzoic acid), 4-butoxy salicylic acid (2-hydroxyl-4-butyl phenyl ether formic acid), 5-methoxyl group salicylic acid (2-hydroxy-5-methyl p-methoxybenzoic acid), 5-ethyoxyl salicylic acid (2-hydroxyl-5-ethoxybenzoic acid), 5-propoxyl group salicylic acid (2-hydroxyl-5-propoxy benzoic acid) etc.
The alkoxyl salicylic acid is a known substances, and for example, 5-methoxyl group salicylic acid is with in " Beil ", 10227, and the method for putting down in writing respectively in the 4-methoxyl group salicylic acid " Beil ", 10379 can be easy to synthesize.In addition, Aldrich company (Germany) etc. sells as reagent it on market, also can use it.
The alkoxyl salicylic acid that can cooperate in emulsification composition of the present invention also comprises its salt.If the kind of this salt admissible salt on galenic pharmacy then has no particular limits, for example can enumerate, alkali metal salts such as sodium salt, potassium salt, perhaps alkali earth metal salt such as calcium salt in addition, also can be enumerated the salt of ammonium salt or amino acid salts etc.
(a) composition can cooperate a kind or 2 kinds or more than it.(a) use level of composition should be taken into account the concrete dosage form of skin preparations for extenal use or the selection that other gradation composition suits, though have no particular limits, but generally with respect to the emulsification composition total amount, use as (a) composition shown in the above-mentioned general formula (I) as the alkoxyl salicylic acid of whitening composition or its salt the time, be preferably 0.001～20.0 quality %, be preferably 0.01～10.0 quality % especially.During less than 0.001 quality %, be difficult to give full play to the functional effect that (a) composition has, whitening effect particularly, on the other hand, even surpassing 20.0 quality % cooperates, also be difficult to the raising of affirmation, can see on the contrary and encourage the tendency that produces the usability that is clamminess, so not preferred along with the increase whitening effect of use level.
As the salt of (b) composition among the present invention, owing to be the material that cooperates as buffer agent, if therefore the salt that at room temperature is dissolved in easily in the water gets final product.For example can enumerate inorganic salts such as sodium chloride, magnesium sulfate, magnesium chloride; Organic acid salts such as L-arginine monohydrochloride, L-aspartic acid 1 hydrate, L-glutamic acid hydrochloride, L-histidine hydrochloride 1 hydrate, L-dlornithine hydrochloride, L-NaAsp 1 hydrate, L-potassium aspartate 2 hydrates, L-sodium glutamate 1 hydrate, L-Kaglutam 1 hydrate, lactate, citrate, edetate, ethylenediamine ethoxy triacetate, hexametaphosphate etc.
(b) composition can use a kind or 2 kinds or more than it.(b) use level of composition is preferably 0.01～10.0 quality % with respect to the emulsification composition total amount, is preferably 0.01-5.0 quality % especially.During less than 0.01 quality %, owing to, on the other hand, cooperate when surpassing 10.0 quality % easy instabilityization when high temperature is preserved along with the time changes the merging of generation emulsion particles, easy instabilityization.
As the Polyethylene Glycol of (c) composition, the use molecular weight is 1,000～200,000 material.This molecular weight is preferably 1,000～20, and 000.Specifically, can enumerate cetomacrogol 1000, Macrogol 1540, Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, Polyethylene Glycol 11000, Macrogol 2000 0 etc.
(c) composition can use a kind or 2 kinds or more than it.(c) use level of composition is preferably 0.01～5.0 quality %, is preferably 0.1～3.0 quality % especially with respect to the emulsification composition total amount.During less than 0.01 quality %, owing to, on the other hand, cooperate when surpassing 5.0 quality % easy instabilityization when high temperature is preserved along with the time changes the merging of generation emulsion particles, easy instabilityization.
Above-mentioned (a)～(c) composition cooperates in water (inner phase).At aqueous phase, beyond dewatering, can be in the scope of not damaging effect of the present invention cooperate water soluble polymer, the water soluble medicament generally spendable water composition in cosmetics, medicine, cosmeceutical field that becomes to grade arbitrarily.
Water of the present invention (inner phase) is preferably the use level of 5～95 quality % with respect to the emulsification composition total amount, more preferably 10～90 quality %.
In oil phase of the present invention (foreign minister), except that the oiliness composition, the emulsifying agent that can suit to cooperate is 7 or its following emulsifying agent but this emulsifying agent preferably uses HLB.As HLB is 7 or emulsifying agent below it, can enumerate sorbitan fatty ester classes such as mono laurate sorbitan esters, single oleic acid sorbitan esters, single isostearic acid sorbitan esters, three stearic acid sorbitan esters; Glycerine fatty acid esters such as glyceryl monostearate, glyceryl monooleate, glyceryl isostearate, two isostearic acid double glycerides, five isostearic acids, ten glyceride; Polyoxyethylene hardened castor oils such as POE (5), POE (7.5), POE (10) hardened castor oil; Dimerization hydroxy stearic acid esters; ア ラ セ Le 135) dimerization hydroxy stearic acid polyglycerin ester-2 (コ グ ニ ス corporate system: PGPH), PEG30 dimerization hydroxy stearic acid ester (ユ ニ ケ マ corporate system: high molecular lipophile activating agent such as; The poly-oil of the cetyl polydimethylsiloxane [siloxanes of for example " ABIL EM90 " (go one Le De シ ユ ミ Star ト corporate system), polyether modified siloxane [for example " SC 9450 " (chemical industrial company of SHIN-ETSU HANTOTAI system)], cross-linking type polyether modified siloxane polyethers such as [for example " KSG " シ リ one ズ (chemical industrial company of SHIN-ETSU HANTOTAI system)] system; The siloxanes of polyglycereol such as polyglycerol-modified siloxanes, alkyl co-modified polyglycerol-modified siloxanes system etc.Can use a kind or 2 kinds or its above HLB among the present invention is 7 or its following emulsifying agent.Especially preferably use the silicone emulsifiers of polyethers system, polyglycereol system.
HLB be 7 or its following emulsifying agent preferably cooperate 0.01～10.0 quality %, more preferably cooperate 0.1～5.0 quality % with respect to the emulsification composition total amount.The use level of this emulsifying agent is during less than 0.01 quality %, owing to along with the time changes the merging that produces emulsion particles, instabilityization easily, on the other hand, when cooperating above 10.0 quality %, be easy to generate the thick and heavy usability that is clamminess and feels.
In addition, in foreign minister of the present invention (oil phase),, preferably contain with respect to being the silicone oil of liquid under this oil phase (foreign minister) 30 quality % or its above room temperature (25 ℃) from forming the viewpoint of salubrious usability.As this silicone oil, specifically for example can enumerate chain silicone oil such as dimethyl polysiloxane, methyl phenyl silicone, hydrogenated methyl diene polysiloxanes; Ring-type silicone oil such as octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten dimethyl annulars, six polysiloxanes, tetramethyl tetrahydro diene cyclic polysiloxanes, the alkyl modified silicon oil of room temperature liquid state such as capryl first polysiloxanes, capryl front three polysiloxanes, stearyl first polysiloxanes; The fluorine modified silicon oil of dimethyl siloxane diphenyl siloxane methyl (perfluoroalkyl) silicone copolymers etc. etc.
As the oiliness composition that in oil phase (foreign minister), cooperates (the oiliness composition beyond the above-mentioned silicone oil), have no particular limits, can enumerate for example oils and fats, wax class, hydrocarbon ils, higher fatty acids, higher alcohol, synthetic ester oil, type siloxane etc.
As oils and fats, can enumerate liquid fat such as American Avocado Tree oil, Camellia oil, Radix Oenotherae erythrosepalae oil, Oleum Testudinis, macadimia nut oil, Semen Maydis oil, ermine oil, olive oil, Oleum Brassicae campestris, egg oil, Oleum sesami, basswood oil, Semen Tritici aestivi germ oil, Flos Camelliae Japonicae caul-fat, Oleum Ricini, oleum lini, safflower oil, Oleum Gossypii semen, perilla oil, soybean oil, Oleum Arachidis hypogaeae semen, Oleum Camelliae, cocos nucifera oil, Testa oryzae oil, Oleum Verniciae fordii, Japanese tung oil, Jojoba oil, germ oil, triglycerin, tricaprylin, three different tripalmitins; Solid greases such as cocoa butter, cocos nucifera oil, horse fat, hardened castor oil, Petiolus Trachycarpi oil, Adeps Bovis seu Bubali, Adeps caprae seu ovis, sclerosis Adeps Bovis seu Bubali, palm kernel oil, leaf fat, Os Bovis seu Bubali fat, vegetable wax kernel oil, fixed oil, cattle foot fat, vegetable wax, hardened castor oil etc.
As the wax class, can enumerate Cera Flava, candelilla wax, cotton wax, Brazil wax, laurel wax, Chinese wax, spermaceti, montan wax, bran wax, lanoline, kapok wax, acetic acid lanoline, liquid lanolin, Caulis Sacchari sinensis fat, lanolin fatty acid isopropyl ester, lauric acid hexyl ester, reduction lanoline, Simmondsin. haze tallow, hard lanoline, shellac wax, POE lanoline alcohol ether, POE lanoline acetic acid alcohol ester, POE cholesterol ether, lanolin fatty acid Polyethylene Glycol, POE hydrogenated lanolin alcohol ether etc.
As hydrocarbon ils, can enumerate oil contents such as liquid paraffin, ceresine, squalane, Lin Risi alkane, paraffin, ceresin, Squalene, vaseline, microwax.
As higher fatty acids, can enumerate lauric acid, myristic acid, Palmic acid, stearic acid, behenic acid, oleic acid, 12-hydroxy stearic acid, 9-undecylenic acid, the acid of appropriate that, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexenoic acid (DHA) etc.
As high fatty alcohol, can enumerate the straight chain alcohol of lauryl alcohol, spermol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, 16/octadecanol etc.; Branched-chain alcohos such as single stearyl glycerin ether (batilol), 2-decyl four decanol, lanolin alcohol, cholesterol, plant sterol, hexyl dodecanol, isooctadecanol, octyldodecanol.
As synthetic ester oil, can enumerate isopropyl myristate; Octanoic acid, hexadecyl ester; myristic acid octyl group dodecyl ester; isopropyl palmitate; butyl stearate; lauric acid hexyl ester; myristyl myristate; decyl oleate; the sad hexyl dodecyl ester of dimethyl; the lactic acid cetyl; Tetradecyl lactate; the acetic acid lanoline; Standamul 7061; the different cetyl of isostearic acid; 12-hydroxy stearic acid gallbladder steroid ester; two-2 ethyl hexanoic acid second diester; the dipentaerythritol fatty acid ester; single isostearic acid-N-alkyl diol ester; two capric acid DOPCP; malic acid two isooctadecanol esters; two-2-heptyl hendecanoic acid glyceride; three-2 ethyl hexanoic acid trimethylolpropane; three isostearic acid trihydroxymethylpropanyl esters; four-2 ethyl hexanoic acid pentaerythritol ester; three-2 ethyl hexanoic acid glyceride; three isostearic acid trihydroxymethylpropanyl esters; the 2 ethyl hexanoic acid cetyl; Palmic acid 2-ethylhexyl fat; myristin; three-2-heptyl hendecanoic acid glyceride; the Castor Oil Fatty Acid methyl ester; oleic acid oil base ester; aceto-glyceride; Palmic acid-2-heptyl undecyl ester; diisobutyl adipate; N-lauroyl-L-glutamic acid-2-octyl group dodecyl ester; adipic acid two-2-heptyl undecyl ester; the lauric acid ethyl ester; Diisooctyl Sebacate; myristic acid-2-hexyl dodecyl ester; Palmic acid-2-hexyl dodecyl ester; adipic acid-2-hexyl dodecyl ester; Dermol DIPS; succinic acid-2-Octyl Nitrite; ethyl acetate; butyl acetate; pentyl acetate; triethyl citrate; crotamiton (C
13H
17NO) etc.
As type siloxane, can enumerate the alkyl and the oxyalkylsiloxane wax of stearoyl modified dimethyl polysiloxane, docosyl modified dimethyl polysiloxane etc., form 3 yuan of cancellated organic siliconresins, silicone rubber etc.
In the present invention, height cooperates solid oil contents such as wax in oil phase unlike prior art, and the elapsed time does not produce separation, can obtain excellent in stability and usability good emulsifying compositions.
In water-in-oil emulsion composition of the present invention, except that above-mentioned gradation composition, in the scope of not damaging effect of the present invention, also can suitably cooperate the general composition that in cosmetics, medicine etc., uses as required, for example UV absorbent, surfactant (except above-mentioned HLB7 or its following emulsifying agent), wetting agent, thickening agent, polyhydric alcohol, powder composition, synthetic resin Emulsion, aminoacid, organic amine, blocking metal agent, medicament, saccharide etc. still are not limited in these illustrative compositions.
As UV absorbent, for example can enumerate, para-amino benzoic acid, para-amino benzoic acid monoglyceride, N, N-dipropoxy ethylaminobenzoate, N, benzoic acid such as N-dimethyl ethylaminobenzoate are UV absorbent; All menthyl-ortho-aminobenzoic acids such as N-acetyl group o-aminobenzoa are UV absorbent; Salicylic acid such as salicylic acid amyl group ester, the equal menthyl ester of salicylic acid, salicylic acid octyl group ester, salicylic acid phenylester, salicylic acid benzyl ester, salicylic acid p-isopropyl alcohol phenylester are UV absorbent; Octyl methoxycinnamate, di-p-methoxy cinnamic acid-list-2 ethyl hexanoic acid glyceride, the octyl group cinnamate, Ethyl 4-isopropylcinnamate., methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl group-p-Methoxycinnamate, isopropyl-p-Methoxycinnamate, isopentyl-p-Methoxycinnamate, octyl group-p-Methoxycinnamate, (2-ethylhexyl-p-Methoxycinnamate), 2-ethoxyethyl group-p-Methoxycinnamate, cyclohexyl-p-Methoxycinnamate, ethyl-alpha-cyano-beta-phenyl cinnamate, 2-ethylhexyl-alpha-cyano-beta-phenyl cinnamate, glyceryl list-2-ethyl hexanoyl base di-p-methoxy cinnamate, 3,4,5-trimethoxy cinnamic acid-3-methyl-4-[methyl two (trimethylsiloxy) silicyl] butyl ester, cinnamic acid such as trimethoxy cinnamic acid methyl two (trimethylsiloxy) silicyl isopentyl ester are UV absorbent; 2,4-dihydroxy benaophenonel, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxy benzophenone-5-sulfonate, 4-phenyl benzophenone, 2-ethylhexyl-4 '-phenyl benzophenone-benzophenone series UV absorbent such as 2-carboxylate; 3-(4 '-methyl benzal)-d; l-Camphora, 3-benzal-d; l-Camphora, urocanic acid, urocanic acid ethyl ester, 2; 2 '-hydroxy-5-methyl base phenyl benzotriazole, 2-(2 '-hydroxyl-5 '-uncle-octyl phenyl) benzotriazole, dibenzylidene azine, two anisoyl methane, 4-methoxyl group-4 '-tert-butyl group dibenzoyl methane, 5-(3,3-dimethyl-2-norborene subunit)-3-pentane-2-ketone, dimorpholino radical pyridazine ketone etc.
As the hydrophilic nonionic surfactant, for example can enumerate polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monoleate, polyoxyethylene sorbitan monostearate; Polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monoleate, polyoxyethylene sorbitol monostearate; Polyoxyethylene fatty acid glycerides such as polyoxyethylene glyceryl monostearate, polyoxyethylene list glyceryl isostearate, polyoxyethylene three glyceryl isostearates, polyoxyethylene fatty acid ester classes such as polyoxyethylene monooleate, polyoxyethylene distearate; Polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl base ether, polyoxyethylene-2-octyl group lauryl ether, polyoxyethylene cholestane base ether; Polyoxyethylene alkyl phenyl ether classes such as NONIN HS 240, polyoxyethylene nonylplenyl ether, polyoxyethylene dinonyl phenyl ether; Pu Lunuonike type surfactants such as Pu Lunuonike; Polyoxyethylene polyoxy-propylene classes such as polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene-2-decyl myristyl ether, polyoxyethylene polyoxypropylene monobutyl ether, polyoxyethylene polyoxypropylene, hydrogenated lanolin, polyoxyethylene polyoxypropylene glycerin ether; Oxozone ethylene oxozone propylene and ethylene diamidogen condensation substance classes such as テ ト ロ ニ Star Network; Castor oil derivatives or polyoxyethylene hardened castor oil derivants such as polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene hardened castor oil list isostearate, polyoxyethylene hardened castor oil three isostearates, polyoxyethylene hardened castor oil list pyroglutamic acid list isostearic acid diester, polyoxyethylene hardened castor oil maleate; Alkylolamideses such as fatty acid distribution of coconut oil diglycollic amide, lauric monoethanolamide, fatty acid isopropanol amide, in addition, can enumerate polyoxyethylene methyl glycol fatty acid ester class, polyoxyethylene alkyl amine class, polyoxyethylene fatty acid amide, sucrose fatty acid ester, polyoxyethylene nonyl phenyl formaldehyde condensation products, alkyl ethoxy dimethylamine oxide, three oleyl alcohol phosphate esters etc.
As the anionic surfactant, for example can enumerate senior alkyl sulfate salt such as fatty acid soaps such as sodium laurate, sodium palmitate, sodium lauryl sulfate, lauryl potassium sulfate; Alkyl ether sulphate salts such as polyoxyethylene triethanolamine lauryl sulfate, polyoxyethylene sodium lauryl sulfate; Senior fatty acid amide sulfonates such as N-acyl group sarcosine acid such as sodium N-lauroyl sarcosinate, N-myristoyl-N methyl taurine sodium, N-stearyl-N methyl taurine sodium, fatty acid distribution of coconut oil methylamino ethyl sulfonic acid sodium, lauryl methyl taurine sodium; Phosphate ester salts such as polyoxyethylene oleyl ether sodium phosphate, polyoxyethylene stearyl base ether phosphoric acid sodium; Sulfosuccinates such as two-2-ethylhexyl sodium sulfosuccinate, single lauroyl single ethanol amide polyoxyethylene sodium sulfosuccinate, lauryl polypropylene glycol sodium sulfosuccinate; Alkylbenzenesulfonates such as linear dodecylbenzene sodium sulfonate, linear DBSA triethanolamine; N-acyl glutamic acids such as N-lauroyl glutamate list sodium, N-stearyl disodium glutamate; Senior fatty acid ester sulfuric acids such as sclerosis coconut oil fat acid glyceride sodium sulfate; in addition, can enumerate polyoxyethylene alkyl ether carboxylate, alpha-alkene sulfonate, higher fatty acids sulfonated ester, dihydroxylic alcohols sulfuric acid, higher fatty acids alkanolamide sulfuric acid, lauroyl single ethanol amide sodium succinate, N-palmityl aspartic acid, two triethanolamine, fatty acid distribution of coconut oil collagen hydrolysate alkali metal salt etc.
As cationic surfactant, for example can enumerate dialkyl dimethyl ammonium salts such as alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, VARISOFT TA100; Chlorination gathers (N, N '-dimethyl-3, the 5-methylenepiperidines), alkyl salt such as hexadecylpyridinium chloride, in addition, can enumerate alkyl quaternary ammonium salts, alkyl dimethyl benzyl ammonium salt, alkyl isoquinolinium salt, dialkyl group alkylbenzyldimethylasaltsum saltsum, polyoxyethylene alkyl amine, alkylamine salt, polyamine derivative of fatty acid, amylalcohol derivative of fatty acid, benzalkonium chloride, benzethonium chloride, cationic polymer, propenoic acid beta-N-N-dimethyl-N-ethyl ammonium ethyl chloride vinylpyrrolidone copolymer etc.
As amphoteric surfactant, for example can enumerate, 2-undecyl-N, N, N-(hydroxyethyl-carboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazoline hydroxide-imidazolines such as 1-carboxyl hydroxy ethoxy 2 sodium salts are amphoteric surfactant; Betanins such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betanin, lauryl dimethyl aminoacetic acid betanin, alkyl betaine, amide betaine, sulfonyl betanin be amphoteric surfactant etc.,
As wetting agent, for example can enumerate, cholest-12-hydroxy stearic acid ester, sodium lactate, dl-pyrrolidone carboxylic acid salt, carbamide, two glycerol oxirane propylene oxide adducts etc. have particularly cooperated acid mucopolysaccharide time-likes such as chondroitin sulfate or hyaluronic acid, have had potentiation for the whitening effect of alkoxyl salicylic acid and/or its salt.
As viscosifier, for example can enumerate arabic gum, carrageenin, Tragacanth, Fructus cydoniae oblongae, casein, casein sidium, dextrin, gelatin, sodium alginate, methylcellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl-cellulose, hydroxypropyl cellulose, polyvinyl alcohol, sodium polyacrylate, carboxy vinyl polymer, guar gum, HANSHENGJIAO, aluminium-magnesium silicate, bentonite, Strese Hofmann's hectorite. etc.
As the organo-clay mineral, can enumerate the aluminium-magnesium silicate of Dimethyl Ammonium Strese Hofmann's hectorite., benzyl dimethyl stearyl ammonium Strese Hofmann's hectorite., VARISOFT TA100 processing etc.As commercially available product the ベ Application ト Application 38 (Montmorillonitum that VARISOFT TA100 is handled is arranged; Na シ ヨ Na Le レ Star De company) etc.
As polyhydric alcohol, for example can enumerate ethylene glycol, propylene glycol, dipropylene glycol, 1,3 butylene glycol, glycerol, erithritol, trimethylolpropane, tetramethylolmethane, Sorbitol, maltol, diglycerol, Polyethylene Glycol etc.
As the powder composition, for example can enumerate inorganic powders such as Talcum, Kaolin, Muscovitum, sericite, phlogopite, synthetic mica, magnesium carbonate, calcium carbonate, aluminium silicate, silicon dioxide, zeolite, barium sulfate, sintering calcium sulfate (bassanite), calcium phosphate, fluoridated apatite, hydroxyapatite, ceramic powders, metallic soap (Grillocin P 176, calcium palmitate, aluminium stearate etc.), boron nitride; Organic dusts such as polyamide powder (nylon powder), polyethylene powders, polyisobutylene acid methyl ester powder, polystyrene powder, styrene and acrylic acid copolymer resin powder, poly-sesquialter methylsiloxane (Port リ メ チ シ Le セ ス キ オ キ サ Application) powder, cellulose powder; Titanium dioxide, zinc oxide, ferrum oxide (iron oxide red), iron titanate, yellow iron oxide, black iron oxide, white carbon black, rudimentary titanium oxide, Fructus Mangifera Indicae purple, cobalt violet, chromium oxide, ultramarine, inorganic pigment such as dark purple; Titanium oxide covers pigments, mica, titanium oxide covers pearl pigments such as bismuth oxychloride, painted titanium oxide covering pigments, mica, bismuth oxychloride, guanin; Metallic powdery pigments such as aluminium powder; Organic pigments such as No. 201, redness, redness No. 202, orange No. 203, orange No. 205, No. 401, yellow, No. 404, blueness, organic pigments such as zirconium, barium, aluminum color lake such as No. 3, redness, No. 4, yellow, No. 3, green, No. 1, blueness, natural pigment such as chlorophyll, beta-carotene etc.
As synthetic resin Emulsion, for example can enumerate allyl resin Emulsion, polyvinyl acetate resins Emulsion etc.
As aminoacid; can enumerate glycine, leucine, phenylalanine, tyrosine, aspartic acid, glutamic acid, sodium glutamate, arginine, histidine, lysine, cystine, cysteine, acyl group sodium sarcosinate (sodium N-lauroyl sarcosinate), acyl glutamate, glutathion, 2-pyrrolidone-5-carboxylic acid etc.
As organic amine, for example can enumerate monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1, ammediol, 2-amino-2-methyl-1-propanol etc.
In addition, can also suitably cooperate caffeine, tannin, isoptin, tranexamic acid and derivant, Radix Glycyrrhizae extract, (3-(2 ' for glabridin, 4 '-dihydroxy phenyl)-8-dimethyl-pyrans [8,7-e] benzodihydropyran also), the hot water extract of firethorn fruit, various crude drug, tocopheryl acetate, glycyrrhetinic acid and medicaments such as derivant or its salt thereof; Other whitening agents such as vitamin C, magnesium ascorbyl phosphate, ascorbic acid glucosides, arbutin; Saccharides such as glucose, fructose, mannose, sucrose, trehalose etc. are particularly cooperating vitamin-e ester time-like such as tocopheryl acetate, have the effect of the whitening effect that strengthens alkoxyl salicylic acid and/or its salt.
Embodiment
Below, enumerate embodiment the present invention is described in further detail, but the present invention is not limited in following embodiment.In addition, use level is not if specify that this composition is represented with quality % with respect to the system that will cooperate.
Before embodiment, the evaluation methodology of using is described in each embodiment.
[usability (expansion on skin)]
60 of one group of triers (men and women each 30) are used the emulsification composition (sample) of each embodiment, comparative example,, estimate by following standard to the unfolded quality on skin.
(evaluation)
◎: 30 or its above trier feel that the expansion on skin is good
Zero: 10～29 triers feel that the expansion on skin is good
△: 5～9 triers feel that the expansion on skin is good
*: 4 or its following trier feel that the expansion on skin is good
[usability (tender and lovely sense)]
60 of one group of triers (men and women each 30) are used the emulsification composition (sample) of each embodiment, comparative example,, estimate by following standard to the tender and lovely sense of skin.
(evaluation)
◎: feel that the trier who bears a pretty, delicate skin is 30 or more than it
Zero: feel that the trier who bears a pretty, delicate skin is 10～29
△: feel that the trier who bears a pretty, delicate skin is 5～9
*: feel that the trier who bears a pretty, delicate skin is 4 or below it
[usability (nothing is clamminess)]
60 of one group of triers (men and women each 30) are used the emulsification composition (sample) of each embodiment, comparative example, be clamminess, estimate by following standard about the nothing of skin.
(evaluation)
◎: feel that it is 30 or more than it that skin does not have the trier of being clamminess
Zero: feel that it is 10～29 that skin does not have the trier of being clamminess
△: feel that it is 5～9 that skin does not have the trier of being clamminess
*: feel that it is 4 or below it that skin does not have the trier of being clamminess
[usability (salubrious sense)]
60 of one group of triers (men and women each 30) are used the emulsification composition (sample) of each embodiment, comparative example,, estimate by following standard about the salubrious sense of skin.
(evaluation)
◎: the trier who feels the salubrious sense of skin is 30 or more than it
Zero: the trier who feels the salubrious sense of skin is 10～29
△: the trier who feels the salubrious sense of skin is 5～9
*: the trier who feels the salubrious sense of skin is 4 or below it
[stability]
Each sample that embodiment, comparative example are obtained is filled in the sample cell (vial) of 50ml, after room temperature, 50 ℃ placed for 2 weeks down, with the naked eye with the microscopic examination emulsified state, estimates by following standard.
(evaluation)
Zero: all do not separate, emulsified particle is also stable
△: though do not separate, an emulsified particle part is destroyed
▲: though do not separate, emulsified particle is destroyed
*: separate, emulsified particle is also destroyed
(comparative example 1～6)
Preparation has the water-in-oil emulsion composition that comparative example shown in the following table 1 is formed, and it as sample, according to following evaluation criterion, is carried out the evaluation of usability, stability.The result is shown in table 1 in the lump.
(method for making)
The oil phase part of (1) in the mixture table 1～(3) and (12) equably.On the other hand, in (13), add (4)～(11), dissolving fully, preparation aqueous portion.This aqueous portion is slowly added in the oil phase part, carry out homodisperse, obtain W/O Emulsion part (water-in-oil emulsion composition).In addition, in table 1, " cetyl polydimethylsiloxane polyhydric alcohol
(* 1)" use " ABILEM90 " (go one Le De シ ユ ミ Star ト corporate system).
(embodiment 1～6)
Preparation has the water-in-oil emulsion composition that embodiment shown in the following table 2 forms, and it as sample, according to following evaluation criterion, is carried out the evaluation of usability, stability.The result is shown in table 2 in the lump.
(method for making)
The oil phase part of (1) in the mixture table 2～(4) and (15) equably.On the other hand, in (16), add (5)～(14), dissolving fully, preparation aqueous portion.This aqueous portion is slowly added in the oil phase part, carry out homodisperse, obtain W/O Emulsion part (water-in-oil emulsion composition).In addition, in table 2, " cetyl polydimethylsiloxane polyhydric alcohol
(* 1)" use " ABILEM90 " (go one Le De シ ユ ミ Star ト corporate system), " five isostearic acids, ten glyceride " use " Decaglyn 5-IS " (daylight ケ ミ カ Le ズ corporate system).
Table 1
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| (1) ring-type silicone oil | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 2.0 |
| (2) squalane | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 18.0 |
| (3) cetyl polydimethylsiloxane polyhydric alcohol (*1) | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| (4) 1,3 butylene glycol | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (5) glycerol | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (6) 4-methoxyl group potassium salicylate | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (7) PEG400 | - | - | - | 3.0 | 3.0 | 3.0 |
| (8) cetomacrogol 1000 | - | 3.0 | - | - | - | 1.0 |
| (9) sodium chloride | - | - | 2.0 | - | 2.0 | - |
| (10) p-Hydroxybenzoate | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| (11)EDTA·3Na·2H 2O | 0.1 | - | 0.1 | - | 0.1 | - |
| (12) spice | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| (13) ion exchange water | Remaining | Remaining | Remaining | Remaining | Remaining | Remaining |
| Usability (expansion on skin) | ○ | ○ | ○ | ○ | ○ | ○ |
| Usability (tender and lovely sense) | ○ | ○ | ○ | ○ | ○ | ○ |
| Usability (nothing is clamminess) | ○ | ○ | ○ | △ | ○ | △ |
| Usability (salubrious sense) | ○ | ○ | ○ | ○ | ○ | ○ |
| 50 ℃ of stability room temperatures (2 week) (2 week) | × × | △ × | × × | × × | △ × | × × |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| (1) ring-type silicone oil | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 2.0 |
| (2) squalane | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 18.0 |
| (3) cetyl polydimethylsiloxane polyhydric alcohol (*1) | 3.0 | 3.0 | 3.0 | 3.0 | 1.5 | 3.0 |
| (4) five isostearic acids ten glyceride (*2) | - | - | - | - | 1.5 | - |
| (5) 1,3 butylene glycol | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (6) glycerol | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (7) 4-methoxyl group potassium salicylate | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| (8) cetomacrogol 1000 | 2.0 | - | - | 0.1 | 2.0 | 2.0 |
| (9) polyethylene glycol 6000 | - | 2.0 | - | - | - | - |
| (10) Macrogol 2000 0 | - | - | 2.0 | - | - | - |
| (11) sodium chloride | 2.0 | 2.0 | 2.0 | 2.0 | - | 2.0 |
| (12) L-sodium glutamate | - | - | - | - | 2.0 | - |
| (13) p-Hydroxybenzoate | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| (14)EDTA·3Na·2H 2O | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| (15) spice | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| (16) ion exchange water | Remaining | Remaining | Remaining | Remaining | Remaining | Remaining |
| Usability (stretching out on skin) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Usability (tender and lovely sense) | ◎ | ◎ | ◎ | ◎ | ○ | ○ |
| Usability (nothing is clamminess) | ○ | ◎ | ◎ | ◎ | ◎ | ○ |
| Usability (salubrious sense) | ◎ | ◎ | ◎ | ◎ | ○ | ○ |
| 50 ℃ of stability room temperatures (2 week) (2 week) | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ |
By table 1, result shown in 2 can be clear and definite, usability of the present invention, stable both's excellence.On the other hand, comparative example is compared with embodiment, and usability is poor and stability is also poor.
(embodiment 7: whitening emulsion) (quality %)
(1) decamethyl ring-type four polysiloxanes 20.0
(2) three (capryl/capric acid) glyceride 10.0
(3) (Dimethicone/Vinyl Dimethicone) cross-linked polymeric 3.0
Thing (" ト レ Off イ Le E506 "; レ ダ ウ コ one ニ Application グ corporate system)
(4) cetyl polydimethylsiloxane polyhydric alcohol (" ABIL EM90 " go one Le 2.0 De シ ユ ミ Star ト corporate systems)
(5) 1,3 butylene glycol 5.0
(6) Polyethylene Glycol 11,000 2.0
(7) glycerol 5.0
(8) p-Hydroxybenzoate is an amount of
(9) 4-methoxyl group potassium salicylate 5.0
(10) citric acid is an amount of
(11) sodium citrate 0.1
(12) sodium chloride 1.0
(13)EDTA·3Na·2H
2O????????????????????????????????0.05
(14) spice is an amount of
(15) ion exchange water remnants
(method for making)
In the material of (1)～(4), (14), be added on the material that adds (5)～(13) uniform dissolution in (15) at homodisperse, carry out homodisperse, obtain whitening emulsion.
(embodiment 8: daily whitening emulsion) (quality %)
(1) decamethyl ring-type four polysiloxanes 10.0
(2) ten dimethyl annulars six polysiloxanes 5.0
(3) Jojoba oil 3.0
(4) octyl methoxycinnamate 2.0
(5) the cross-linking type polyether modified siloxane 2.0
(" KSG21 "; Chemical industrial company of SHIN-ETSU HANTOTAI system)
(6) cetyl polydimethylsiloxane polyhydric alcohol 2.0
(" ABIL EM90 " go one Le De シ ユ ミ Star ト corporate system)
(7) alkyl-modified organic siliconresin lining titanium oxide 1.0
(8) the organo-clay mineral 0.5
(" ベ Application ト Application 38 "; Na シ ヨ Na Le レ Star De corporate system)
(9) 1,3 butylene glycol 5.0
(10) ethanol 7.0
(11) 4-methoxyl group potassium salicylate 5.0
(12) polyethylene glycol 6000 2.0
(13) p-Hydroxybenzoate is an amount of
(14) retinol is an amount of
(15)EDTA·3Na·2H
2O????????????????????????0.1
(16) sodium chloride 1.0
(17) spice is an amount of
(18) ion exchange water remnants
(method for making)
In the material of (1)～(8), (14), (17), be added on the material that adds (9)～(13), (15), (16) uniform dissolution in (18) at homodisperse, carry out homodisperse, obtain daily whitening emulsion.
(embodiment 9: whitening sunscreen agent) (quality %)
(1) decamethyl ring-type four polysiloxanes 10.0
(2) ten dimethyl annulars six polysiloxanes 10.0
(3) methyl phenyl silicone 4.0
(4) octyl methoxycinnamate 10.0
(5) tert-butyl group methoxy dibenzoyl methylmethane 3.0
(6) polydimethylsiloxane is handled silicic acid anhydride lining zinc oxide 10.0
(7) dimethyl distearyl ammonium Strese Hofmann's hectorite. 1.0
(ベ Application ト Application 38V; Na シ ヨ Na Le レ Star De corporate system)
(8) Dehymuls PGPH Polyglycerin 12-hydroxystearate 2.0
(" DEHYMULS PGPH "; コ グ ニ ス corporate system)
(9) the polydimethylsiloxane polyhydric alcohol 1.0
(" siloxanes SC 9450 "; Chemical industrial company of SHIN-ETSU HANTOTAI system)
(10) Stearyl dimethicone 0.5
(" DC 2503 "; ダ ウ コ one ニ Application グ corporate system)
(11) 1,3 butylene glycol 5.0
(12) ethanol 7.0
(13) 4-methoxyl group potassium salicylate 5.0
(14) p-Hydroxybenzoate is an amount of
(15)EDTA·3Na·2H
2O?????????????????????????????0.1
(16) Macrogol 4000 2.0
(17) Sal 1.0
(18) sodium hexameta phosphate 0.1
(19) pigment is an amount of
(20) spice is an amount of
(21) ion exchange water remnants
(method for making)
In the material of (1)～(10), (20), be added on the material that adds (10)～(19) uniform dissolution in (21) at homodisperse, carry out homodisperse, obtain whitening sunscreen agent.
(embodiment 10: whitening cream) (quality %)
(1) decamethyl ring-type four polysiloxanes 10.0
(2) ten dimethyl annulars six polysiloxanes 10.0
(3) squalane 5.0
(4) the cross-linking type polyether modified siloxane 2.0
(" KSG21 "; Chemical industrial company of SHIN-ETSU HANTOTAI system)
(5) cetyl polydimethylsiloxane polyhydric alcohol 2.0
(" ABIL EM90 " go one Le De シ ユ ミ Star ト corporate system)
(6) the spermaceti polydimethylsiloxane 1.0
(7) the organo-clay mineral 1.0
(" ベ Application ト Application 38 "; Na シ ヨ Na Le レ Star De corporate system)
(8) 1,3 butylene glycol 5.0
(9) ethanol 7.0
(10) 4-methoxyl group potassium salicylate 5.0
(11) polyethylene glycol 6000 2.0
(12) p-Hydroxybenzoate is an amount of
(13) arbutin is an amount of
(14) the ethyl vitamin C is an amount of
(15) the ascorbic acid glucosides is an amount of
(16) sodium succinate 0.1
(17)EDTA·3Na·2H
2O?????????????????????????0.1
(18) magnesium sulfate 1.0
(19) spice is an amount of
(20) ion exchange water remnants
(method for making)
In the material of (1)～(7), (19), be added on the material that adds (8)～(18) uniform dissolution in (20) at homodisperse, carry out homodisperse, obtain whitening cream.
(embodiment 11: whitening cream) (quality %)
(1) decamethyl ring-type four polysiloxanes 10.0
(2) ten dimethyl annulars six polysiloxanes 5.0
(3) Jojoba oil 3.0
(4) vaseline 2.0
(5) microwax 2.0
(6) cetyl polydimethylsiloxane polyhydric alcohol 2.0
(" ABIL EM90 " go one Le De シ ユ ミ Star ト corporate system)
(7) Parleam 5.0
(8) the polydimethylsiloxane polyhydric alcohol 2.0
(" ABIL EM97 " go one Le De シ ユ ミ Star ト corporate system)
(9) 1,3 butylene glycol 5.0
(10) glycerol 15.0
(11) 4-methoxyl group potassium salicylate 5.0
(12) polyethylene glycol 6000 2.0
(13) p-Hydroxybenzoate is an amount of
(14) sodium carboxymethyl cellulose 0.5
(15) hexa metaphosphoric acid alkali 0.1
(16) magnesium sulfate 0.5
(17) spice is an amount of
(18) ion exchange water remnants
(method for making)
In the material of (1)～(8), (17), be added on the material that adds (9)～(16) uniform dissolution in (18) at homodisperse, carry out homodisperse, obtain daily whitening emulsion.
Claims (6)
1. a water-in-oil emulsion composition is characterized in that, contains the Polyethylene Glycol of (a) salicyclic acid derivatives, (b) salt, (c) molecular weight 1,000～200,000 in the water (inner phase).
2. water-in-oil emulsion composition as claimed in claim 1, (a) composition is the alkoxyl salicylic acid shown in the following general formula (I) or its salt.
(in the formula (I), R represents alkyl)
3. water-in-oil emulsion composition as claimed in claim 2, in the above-mentioned general formula (I), R is that carbon number is 1～6 alkyl.
4. water-in-oil emulsion composition as claimed in claim 2, in the above-mentioned general formula (I), R is a methyl.
5. water-in-oil emulsion composition as claimed in claim 2, in the above-mentioned general formula (I), R is an ethyl.
6. as the water-in-oil emulsion composition of each record of claim 1～5, in oil phase (foreign minister), contain with respect to this oil phase (foreign minister) 30 quality % or be the silicone oil of liquid at room temperature (25 ℃) more than it.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP373590/2003 | 2003-10-31 | ||
| JP2003373590A JP4073389B2 (en) | 2003-10-31 | 2003-10-31 | Water-in-oil emulsion composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1636550A true CN1636550A (en) | 2005-07-13 |
| CN1636550B CN1636550B (en) | 2010-06-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410087096 Active CN1636550B (en) | 2003-10-31 | 2004-10-26 | Water-in-oil emulsion composition |
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| Country | Link |
|---|---|
| JP (1) | JP4073389B2 (en) |
| CN (1) | CN1636550B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228260A (en) * | 2010-11-26 | 2013-07-31 | 株式会社爱茉莉太平洋 | Cosmetic makeup composition having an excellent moisture-ustaining capability |
| CN103717197A (en) * | 2011-08-12 | 2014-04-09 | 株式会社资生堂 | Water-in-oil-type skin-whitening cosmetic |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155274A (en) * | 2007-12-27 | 2009-07-16 | Shiseido Co Ltd | Water-in-oil type cosmetic for pore-masking use |
| JP5547123B2 (en) * | 2011-03-30 | 2014-07-09 | 株式会社 資生堂 | Water-in-oil emulsified cosmetic |
| JPWO2016084615A1 (en) * | 2014-11-27 | 2017-05-25 | 株式会社マンダム | Liquid skin preparation |
| JP6893758B2 (en) * | 2015-09-02 | 2021-06-23 | ライオン株式会社 | W / O type emulsified composition |
| CN112451403B (en) * | 2020-12-11 | 2022-09-23 | 华熙生物科技股份有限公司 | Application of combination of ectoin and 4-methoxy potassium salicylate in cosmetics |
| JP2022099546A (en) * | 2020-12-23 | 2022-07-05 | 株式会社 資生堂 | Water-in-oil emulsion cosmetic |
-
2003
- 2003-10-31 JP JP2003373590A patent/JP4073389B2/en not_active Expired - Lifetime
-
2004
- 2004-10-26 CN CN 200410087096 patent/CN1636550B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103228260A (en) * | 2010-11-26 | 2013-07-31 | 株式会社爱茉莉太平洋 | Cosmetic makeup composition having an excellent moisture-ustaining capability |
| CN103228260B (en) * | 2010-11-26 | 2016-08-10 | 株式会社爱茉莉太平洋 | There is the cosmetic composition of good lasting performance of keeping humidity |
| CN103717197A (en) * | 2011-08-12 | 2014-04-09 | 株式会社资生堂 | Water-in-oil-type skin-whitening cosmetic |
| CN103717197B (en) * | 2011-08-12 | 2015-04-01 | 株式会社资生堂 | Water-in-oil-type skin-whitening cosmetic |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005132807A (en) | 2005-05-26 |
| CN1636550B (en) | 2010-06-16 |
| JP4073389B2 (en) | 2008-04-09 |
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