CN1331459C - Skin care composition comprising first and second emulsions - Google Patents
Skin care composition comprising first and second emulsions Download PDFInfo
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- CN1331459C CN1331459C CNB2004800030707A CN200480003070A CN1331459C CN 1331459 C CN1331459 C CN 1331459C CN B2004800030707 A CNB2004800030707 A CN B2004800030707A CN 200480003070 A CN200480003070 A CN 200480003070A CN 1331459 C CN1331459 C CN 1331459C
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- activating agent
- oily components
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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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
- A61K8/72—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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Abstract
Disclosed is a skin care composition comprising: (a) a first emulsion comprising: a first surfactant system comprising nonionic surfactants; a first oily component is selected from the group consisting of emollients, silicone oils, and mixtures thereof; and a first aqueous carrier; wherein the weight ratio of the first surfactant system to the first oily component is from about 5:1 to about 1:1; (b) a second emulsion comprising: a second surfactant system comprising nonionic surfactants; a second oily component is selected from the group consisting of perfumes, hydrophobic plant extracts containing terpene compounds, hydrophobic vitamins, and mixtures thereof; and a second aqueous carrier; wherein the second oily component comprises and wherein the weight ratio of the second surfactant system to the second oily component is from about 20:1 to about 3:1; and (c) a third aqueous carrier.
Description
Invention field
The present invention relates to comprise the skin care compositions of first emulsion and second emulsion.The invention particularly relates to transparent or semitransparent skin care compositions, said composition provides aesthstic beneficial effect and/or extra conditioning beneficial effect when not destroying the transparency and skin condition beneficial effect (for example, moisture retention, slickness and flexibility).
Background of invention
Consumer's obtainable many personal care articles at present relates generally to health and/or the physical appearance that improves skin.In these skin-protection products, many products relate to delay, farthest reduce or even eliminate wrinkle of skin and other histology changes, described histology changes typically relevant to the injury of human skin with skin aging or environment.
In order to keep or skin to be got well and/or young state, typically use wetting agent to come nursing skin.Known wetting agent comprises, for example, and water-soluble wetting agent (as glycerol).It is reported that it also is favourable adding oily components, this is because they can provide flexibility, smoothness and additional iuntercellular lipoid.
For moisture retention, slickness and flexibility are provided to skin, known in the art is the clear state distillate medicinal water and the emulsion of mixing water-soluble wetting agent and oils, and for example, PCT announces WO99/49841, WO00/37029, WO00/61098 and WO00/61083.This transparent appearance can cause the interest of consumer, just as believing that to use skin that these compositionss will make them transparent and seem young.If these products also provide other beneficial effect except that moisture retention, slickness and flexibility are provided, for example, aesthstic beneficial effect and/or extra conditioning beneficial effect, this will more can cause the interest of consumer.These aesthstic beneficial effects and/or extra conditioning beneficial effect can be available from for example components such as spice, hydrophobicity plant extract and hydrophobic vitamin.
Be desirably under the condition of the not transparency, moisture retention, slickness and the flexibility of destroying compositions, will mix in the distillate medicinal water and emulsion of clear state such as materials such as spice, hydrophobicity plant extract and hydrophobic vitamin.
Described based on preamble, need a kind of transparent or semitransparent skin care compositions, said composition can provide aesthstic beneficial effect and/or extra conditioning beneficial effect when not destroying the transparency and skin condition beneficial effect (for example, moisture retention, slickness and flexibility).
Can provide whole advantage of the present invention and beneficial effect without any prior art.
Summary of the invention
The present invention relates to skin care compositions, said composition comprises:
(a) first emulsion, this emulsion comprise first surface activating agent system, first oily components and first aqueous carrier; Wherein this first surface activating agent system comprises two or more non-ionic surface active agents, and this non-ionic surface active agent is selected from an alkyl or the trialkyl glyceride of polyoxyalkylene alkyl, polyoxyalkylene castor oil hydrogenated and straight or branched with C12-18 alkyl substituent; Wherein this first oily components is selected from emollient, silicone oil and their mixture; And wherein the weight ratio of the first surface activating agent system and first oily components is about 5: 1 to about 1: 1;
(b) second emulsion, this emulsion comprise second surface activating agent system, second oily components and second aqueous carrier; Wherein this second surface activating agent system comprises one or more non-ionic surface active agents, this non-ionic surface active agent is selected from the polyoxyalkylene castor oil hydrogenated, has the polyglycereol Arrcostab of C10-20 alkyl substituent, polysorbate, polyoxyethylene sterol, polyethylene glycol hydrogenated sterol, hydroxylated lecithin, polyoxyethylene alkyl ether phosphate ester and salt thereof, and glycerin polyether-25PCA isostearate; Wherein this second oily components is selected from spice, comprises hydrophobicity plant extract, hydrophobic vitamin and their mixture of terpenoid; And wherein the weight ratio of the second surface activating agent system and second oily components is about 20: 1 to about 3: 1; With
(c) the 3rd aqueous carrier.
By reading following description and appending claims, can understand these and other feature, aspect and advantage of the present invention better.
The relevant portion of the document of all references is incorporated herein by reference; Any document quote the approval that may not be interpreted as it be can be used as prior art of the present invention.
Detailed Description Of The Invention
Though this description it is believed that by following explanation to understand the present invention better by particularly pointing out and clearly claimed claims of the present invention are drawn a conclusion.
In this article, " comprise " and be meant and add other step of not influencing final result and other composition.This term comprise term " by ... form " and " basically by ... composition ".
Except as otherwise noted, all percent than, umber and ratio all in the gross weight of the present composition.All relate to the above-mentioned weight of ingredients listed all in content of active substance, and therefore do not comprise the carrier or the by-product that may be included in the commercially available material.
Herein, " mixture " is intended to comprise the simple combination of material and by their the issuable any chemical compound of combination.
Though this description be believed by following explanation and will understand the present invention better by particularly pointing out and clearly claimed claims of the present invention are drawn a conclusion.
In this article, " comprise " and be meant and add other step of not influencing final result and other composition.This term comprise term " by ... form " and " basically by ... composition ".
Except as otherwise noted, all percentage ratio, umber and ratio are all in the gross weight of compositions of the present invention.All relate to the above-mentioned weight of ingredients listed all in activity substance content, and therefore do not comprise the carrier or the by-product that may be included in the commercially available material.
Compositions
Compositions of the present invention is suitable for local coating to human body skin, is particularly useful for skin of face.Said composition has transparent or semitransparent outward appearance, therefore is particularly useful for transparent distillate medicinal water product.Typically, described coating with every day frequency approximately once in these extended periods, use, its coating rate can be up to about three times or more times of every day.
The present composition can provide aesthstic beneficial effect and/or extra conditioning beneficial effect when not destroying the transparency and skin condition beneficial effect (for example, moisture retention, slickness and flexibility).
" base composition " of the present composition has high transparent." base composition " is meant the present composition that only contains solvent, that is, and and the compositions of forming by first emulsion, second emulsion and the 3rd aqueous carrier basically.The absorbance of base composition less than about 2, is preferably about 1 to about 1.5 under identical wavelength under wavelength 340nm.In this article, absorbance can be measured with the microplate reader of TECAN Co.Ltd..
First emulsion
The present composition comprises first emulsion.First emulsion comprises first surface activating agent system, first oily components and first aqueous carrier.This first emulsion also can comprise antiseptic, for example, and benzylalcohol.
Preferably, the mean diameter of first emulsion is less than about 100nm; Be more preferably less than about 80nm.The size of droplet can use the laser light scattering particle size distribution analyser LA-910 of Horiba (Japan) to measure.After emulsion was mixed 30 seconds and temperature when being 25 ℃+/-1 ℃, measure the size of droplet.This first emulsion has the microemulsion form.Herein, " microemulsion " is meant the emulsion that comprises as the aqueous carrier of continuous phase, and water-msoluble ingredients is dispersed in wherein as droplet so that its outward appearance is a transparency emulsion, and described water-msoluble ingredients is opaque outward appearance in other cases.It is transparent to those skilled in the art will appreciate that some oily components may look like, even also is like this when they disperse with bigger droplet size.In the present invention, the droplet size of oily components is very crucial to the transparent appearance that base composition is provided, and when droplet size is big, they will be no longer transparent.Be not bound by theory, it is believed that the dispersion oily components that is chosen as of surfactant system kind and quantity provides suitable microemulsion.The weight ratio of the first surface activating agent system and first oily components is about 5: 1 to about 1: 1.
First surface activating agent system
First surface activating agent system comprises two or more non-ionic surface active agents, and described non-ionic surface active agent is selected from an alkyl or the trialkyl glyceride of polyoxyalkylene alkyl, polyoxyalkylene castor oil hydrogenated and straight or branched with C12-C18 alkyl substituent.
Be applicable to polyoxyalkylene alkyl of the present invention be oxyalkylene and fatty acid and aliphatic alcohol condensation product (for example, an end fatty acid esterification of polyalkylene oxides part wherein, and at the other end with aliphatic alcohol etherificate (for example, by the ehter bond connection)).These materials have formula R
1CO (X
1) zOR
2, R wherein
1And R
2Independently for having about 12 alkyl to about 18 carbon atoms; X
1For-OCH
2CH
2(its derived from, for example ethylene glycol) or-OCH
2CHCH
3-(derived from propylene glycol or oxide); Z is about 6 to about 50 integer.
Non-limiting example derived from this oxyalkylene of non-ionic surface active agent comprises spermaceti polyoxyethylene ether-6, spermaceti polyoxyethylene ether-10, spermaceti polyoxyethylene ether-12, cetearyl polyoxyethylene ether-6, cetearyl polyoxyethylene ether-10, cetearyl polyoxyethylene ether-12, cetearyl polyoxyethylene ether-20, cetearyl polyoxyethylene ether-30, stearyl polyoxyethylene ether-6, stearyl polyoxyethylene ether-10, stearyl polyoxyethylene ether-12, stearyl polyoxyethylene ether-20, PEG-100 stearyl polyoxyethylene ether, the PEG-6 stearate, the PEG-10 stearate, the PEG-12 stearate, the PEG-100 stearate, the PEG-10 tristerin, the PEG-20 tristerin, the PEG-30 glyceryl cocoate, the PEG-80 glyceryl cocoate, PEG-80 tallow acid glyceride, PEG-200 tallow acid glyceride, the PEG-8 dilaurate, PEG-10 distearate and their mixture; Preferred cetearyl polyoxyethylene ether-12, cetearyl polyoxyethylene ether-20 and cetearyl polyoxyethylene ether-30.Commercially available surfactant comprises that trade name is the cetearyl polyoxyethylene ether-12 of Eumulgin B1, the cetearyl polyoxyethylene ether-20 of commodity Eumulgin B2 by name and the cetearyl polyoxyethylene ether-30 of commodity Eumulgin B3 by name, and these materials all can be buied from Henkel company.
The embodiment that is applicable to the polyoxyalkylene castor oil hydrogenated of this paper comprises polyoxyethylene hydrogenated Oleum Ricini, preferred polyoxyethylene (20) castor oil hydrogenated.
The embodiment that is applicable to an alkyl of the present invention or trialkyl glyceride comprises glyceryl monostearate, olein and two isostearic acid triglyceride, preferred two isostearic acid triglyceride.
Comprise first surface activating agent system in compositions of the present invention, its content is preferably about 0.02% to about 3% by described composition weight meter, and more preferably from about 0.1% to about 2%.
The hydrophil lipophil balance (HLB) of this first surface activating agent system is selected according to the value volume and range of product of first oily components by the technical staff.Preferably, the HLB of first surface activating agent system is as a whole greater than about 10.Preferably, at the surfactant that is used for first surface activating agent system, the HLB of at least a surfactant is greater than 10, and the HLB of at least a surfactant is lower than 10.More preferably, the quantity of higher HLB surfactant is greater than the quantity of low HLB surfactant.Be not bound by theory,, can make the stable emulsion that contains the lower content surfactant by surfactant that uses higher HLB and the surfactant that hangs down HLB.In an especially preferred embodiment, used 3 kinds of surfactants at least, these surfactants have different HLB respectively.
In the method for optimizing of the preparation present composition, first surface activating agent system is at first mixed with first oily components, then this mixture is joined in first aqueous carrier.Amount first oil component and first surface activating agent system gross weight about 0.5 to about 10 times preferably that are used for first aqueous carrier of this step, more preferably from about 1 to about 7 times.Be not bound by theory, by mixing surfactant system by this way, can make the stable emulsion of surfactant with the low content of most probable.
First oily components
This first oily components comprises that one or more are selected from (i) emollient, (ii) silicone oil and their the ingredients of a mixture.First oily components that is used for this paper offers the effect of skin moisture-keeping.
This first oiliness composition preferably can be heat-resisting under 80 ℃." under 80 ℃ can heat-stable oiliness composition " be meant at 80 ℃, and preferred 82 ℃, more preferably meet the oiliness composition of following condition under 85 ℃: (i) this oily components is nonvolatile; (ii) this oily components is not irreversible thermal denaturation.
Be included in first oily components in described first emulsion by the weight of described compositions with preferred about 0.02% to about 2%, more preferably from about 0.05% to about 2% content is included in the described compositions.
(i) emollient
Be applicable to that soothing oil of the present invention is that fusing point is no more than about 25 ℃ and those materials of skin moistening beneficial effect are provided for skin.Can be used for soothing oil of the present invention and comprise ester and hydrocarbon.The soothing oil of highly preferred low viscosity, low-molecular-weight or branched structure.Be surprised to find, being clamminess of skin felt and greasy feeling by using these oil to alleviate.
Can be used for soothing oil of the present invention and be ester, especially have an ester of branched alkyl and alkenyl.These esters comprise, for example, 2 ethyl hexanoic acid cetyl, different n-nonanoic acid tridecyl ester, the isostearyl isostearate ester, the different cetyl of isostearic acid, the isostearic acid isopropyl ester, different n-nonanoic acid isodecyl, Octanoic acid, hexadecyl ester, isononyl isononanoate, the myristic acid diisopropyl ester, the different cetyl of myristic acid, myristic acid isotridecyl ester, isopropyl myristate, myristic acid myristyl ester, Palmic acid isooctadecanol ester, the different cetyl of Palmic acid, Palmic acid isodecyl ester, isopropyl palmitate, myristic acid iso stearyl ester, Palmic acid octyl group ester, caprylic/capric triglyceride, glyceryl three-2-ethylhexoate, dimethyltrimethylene glycol two (2-ethylhexoate), dimethyltrimethylene glycol two caprates, diisopropyl dimer salt, three hot glyceride, three different tripalmitins, isopropyl myristate, octyl group dodecyl lactate and their mixture.Also can use triglyceride such as caprylic/capric triglyceride, PEG-6 caprylic/capric triglyceride and PEG-8 caprylic/capric triglyceride.Also can use the crude mixture of these triglyceride of CTFA Limnanthes Alba Seed Oil by name.Commercially available oils comprises that for example, commodity are called Salacos 99, available from Nisshin Oil Mills or trade name Lanol 99, available from the isononyl isononanoate of Seppic; With trade name Crodamol TN available from Croda, with trade name Hexalan available from the different n-nonanoic acid tridecyl ester of Nisshin Seiyu with the Limnanthes Alba Seed Oil of trade name Cropure MDF available from Croda.
Be applicable to that also soothing oil of the present invention is the hydrocarbon of various grades and kind.Mineral oil is the liquid mixture that derives from the hydrocarbon of oil.The specific embodiment of the hydrocarbon that is fit to comprises paraffin oil (comprising those materials that are called as pumice wax or isoparaffin), mineral oil, isotriacontane, dodecane, Fancol ID, hexadecane, 2-Methylpentadecane, eicosylene, different eicosylene, tridecane, the tetradecane, Parleam, docosane and their mixture.Be applicable to that commercially available hydrocarbon of the present invention comprises that commodity are called PERMETHYL 99A, PERMETHYL 101A and PERMETHYL1082 Fancol ID, 2-Methylpentadecane and the different eicosylene available from Presperse (South Plainfield New Jersey, the U.S.); Commodity BENOL by name is available from the mineral oil of Witco; Commodity ISOPAR by name is called the isoparaffin of Amsco Mineral Spirits available from Ashland available from Exxon Chemical Co. (Houston Texas, the U.S.), commodity Isoparaffin 2028 by name available from Idemitsu and commodity.
(ii) silicone oil
Can be used for silicone components of the present invention and comprise the insoluble silicone that is applicable to skin.The so-called insoluble siloxanes that is meant forms and the isolating discontinuous phase of carrier, for example the siloxanes droplet of emulsion or form of suspension.Silicone components can comprise the emulsion polymerisation effect by any suitable method preparation known in the art herein.Silicone components can also emulsion form mix this compositions, wherein emulsion is made by mechanical mixture, or make via the emulsion polymerisation effect by building-up process, this preparation process can or not have to carry out under its auxiliary situation the down auxiliary of surfactant, and described surfactant is selected from anion surfactant, non-ionic surface active agent, cationic surfactant and their mixture.High-molecular weight silicone components can be prepared by the emulsion polymerisation effect.
Be applicable to that silicone components of the present invention comprises the poly-aryl siloxanes of poly-alkyl, silicone resin, the amino siloxanes that replaces and their mixture.Silicone components is preferably selected from the poly-aryl siloxanes of poly-alkyl, silicone resin and composition thereof, more preferably is selected from the poly-aryl siloxanes of one or more poly-alkyl.
Be applicable to that the poly-aryl siloxanes of poly-alkyl of the present invention comprises those materials with following array structure (I):
Wherein R is an alkyl or aryl, and x is about 7 to about 8,000 integer.The group of " A " representative sealing siloxane chain end.As long as it is mobile that the gained siloxanes at room temperature keeps, can disperse, non-stimulated in the time of on being coated to skin, nontoxic do not have other illeffects yet, with other component compatibility of compositions, routine use and condition of storage under chemically stable and can be deposited on the skin and regulate skin, go up or can have arbitrary structures at siloxane chain (R) so at the alkyl or aryl of the end replacement of siloxane chain (A).The A group that is fit to comprises hydroxyl, methyl, methoxyl group, ethyoxyl, propoxyl group and aryloxy group.Two R groups on silicon atom can be represented identical or different group.Preferably, two identical groups of R group representative.The R group that is fit to comprises methyl, ethyl, propyl group, phenyl, aminomethyl phenyl and phenyl methyl.Preferred silicone compounds is polydimethylsiloxane, poly-di-ethyl siloxane and PSI.Polydimethylsiloxane is also referred to as dimethicone, is especially preferred.Spendable poly-alkylsiloxane comprises, for example, and polydimethylsiloxane.These silicone compounds can be for example with trade name Viscasil and SF96 series available from GeneralElectric Company and with trade name Dow Corning 200 series available from DowCorning.For example, be applicable to the present invention from the commodity of General Electric Company SF1075 aminomethyl phenyl fluid by name or from the commodity of the Dow corning fluidic PSI of 556 cosmetics-stages by name.
The poly-aryl siloxanes of the poly-alkyl of the another kind of particularly suitable is a siloxanes natural gum.Term used herein " siloxanes natural gum " is meant that viscosity under 25 ℃ is more than or equal to the polysiloxane material of 1m2/s (1,000,000 centistoke).Will be appreciated that polysiloxanes natural gum of the present invention also can have some repetitions with above-mentioned silicone compounds.This repeats not to be intended to any of these material is limited.Polysiloxanes natural gum is described in Petrarch and other document, be included in the United States Patent (USP) of announcing on May 1st, 1,979 4 of authorizing people such as Spitzer, 152,416, and Noll, the Chemistry and Technologyof Silicones of Walter, New York:Academic Press, 1968.General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE76 have also described polysiloxanes natural gum.All these documents are incorporated herein by reference.The weight average molecular weight of " polysiloxanes natural gum " is typically about more than 200,000, usually about 200,000 to about 1,000, between 000.Its specific embodiment comprises polydimethylsiloxane, poly-(dimethyl siloxane ethylene methacrylic radical siloxane) copolymer, poly-(dimethyl siloxane diphenyl siloxane ethylene methacrylic radical siloxane) copolymer and their mixture.
The method for preparing these silicone components can be referring to " Encyclopedia of PolymerScience and Engineering ", the 15th volume, second edition, 204-308 page or leaf, JohnWiley﹠amp; Sons, Inc., 1989.
In a preferred embodiment, silicone components is the mixture of high-viscosity silicone chemical compound and siloxy group carrier.Herein, the high-viscosity silicone chemical compound comprises that molecular weight is about 200,000 to about 540, those chemical compounds that are selected from above-mentioned substance of 000, be preferably selected from dimethiconol, fluorosilicone polydimethylsiloxane and their mixture, more preferably be essentially dimethiconol.Especially preferred dimethiconol is to have dimethyl siloxane and with those hydroxy-end capped materials, and wherein the dimethyl siloxane part constitutes to about 4500 repetitives by about 2700.The siloxy group carrier comprises that viscosity is extremely about 100mPas of about 6mPas, is selected to have than the ring-type polymethyl siloxane (cyclomethicone) of low repetitive and those materials of polydimethylsiloxane.
Be applicable to that commercially available silicone components of the present invention comprises the dimethiconol available from Dow CorningCorporation of commodity DC345 by name available from polydimethylsiloxane, the polydimethylsiloxaneresins resins solution available from General Electric of commodity SE 30, SE33, SE 54 and SE 76 by name, commodity DCQ2-1403 by name and the DCQ2-1401 of Dow Corning Corporation, with be described in UK Patent Application 2 available from Toshiba Silicone company, the dimethiconol of the emulsion polymerisation in 303,857.
Second emulsion
The present composition comprises second emulsion.Second emulsion comprises second surface activating agent system, second oily components and second aqueous carrier.Preferably, this second emulsion also comprises the polyhydric alcohol carrier.The second particle size of emulsion scope is preferably about 50nm or still less, more preferably from about 30nm or still less.
The weight ratio of the second surface activating agent system and the second oiliness composition is about 20: 1 to about 3: 1, preferred about 15: 1 to 5: 1.
Second surface activating agent system
Second surface activating agent system comprises one or more non-ionic surface active agents, and described non-ionic surface active agent is selected from the polyoxyalkylene castor oil hydrogenated, has the polyglycereol Arrcostab of C10-C20 alkyl substituent, polysorbate, polyoxyethylene sterol, polyethylene glycol hydrogenated sterol, hydroxylated lecithin, polyoxyethylene alkyl ether phosphate ester and salt thereof and glycerin polyether-25 PCA isostearate.Preferably, this second surface activating agent system comprises the non-ionic surface active agent that two or more are selected from mentioned kind.
Can be used for polyoxyalkylene castor oil hydrogenated of the present invention comprises, for example, polyoxyethylene hydrogenated Oleum Ricini with 20 to 100 moles of ethylene oxide, for example, polyethylene (20) castor oil hydrogenated, polyethylene (40) castor oil hydrogenated and polyoxyethylene (100) castor oil hydrogenated.
The polyglycereol Arrcostab that can be used for the C10-20 of having alkyl substituent of the present invention comprises, for example, have 6 to 10 mole of glycerin unitary those, for example, lauric acid polyglycereol-6 ester, lauric acid polyglycereol-10 ester and stearic acid polyglycereol-10 ester.
Can be used for polysorbate of the present invention and comprise, for example, have those of 20 to 80 moles of ethylene oxide, for example, polysorbate-20, polysorbate-40, polysorbate-60 and polysorbate-80.
Can be used for polyethylene sterol of the present invention and polyethylene hydrogenation sterol comprises, for example, have those of 10 to 30 moles of ethylene oxide, for example, polyethylene (10) plant sterol, polyethylene (30) plant sterol and polyethylene (20) cholesterol.
Can be used for polyoxyethylene alkyl ether phosphate ester of the present invention and comprise for example, having those of one or more polyoxyethylene alkyl ethers, wherein said moieties have about 10 to about 20 carbon atoms.These polyoxyethylene alkyl ether phosphate esters preferably are included in the compositions of the present invention with the form of salt.The salt that can be used for polyoxyethylene alkyl ether phosphate ester of the present invention comprises for example sodium salt, ammonium salt and potassium salt.Two two oleyl alcohol ether-8 phosphoric acid ester sodiums of two lauryl ether-10 phosphoric acid ester sodiums of polyoxyethylene and polyoxyethylene for example preferably.
Comprise second surface activating agent system in compositions of the present invention, its content is preferably about 0.003% to about 3% by described composition weight meter, and more preferably from about 0.01% to about 2%.
The hydrophil lipophil balance (HLB) of this second surface activating agent system is selected according to the value volume and range of product of second oily components by the technical staff.Preferably, the HLB of second surface activating agent system is generally greater than about 8, more preferably greater than about 10.Preferably, this second surface activating agent system is 8 or higher value by the HLB that is had substantially, more preferably 10 or the non-ionic surface active agent of higher value form.Be not bound by theory,, this second emulsion can be included in the present composition, do not destroy its transparency simultaneously by only using the surfactant of higher HLB.
In a method for optimizing of the preparation present composition, second surface activating agent system is at first mixed with second oily components, then this mixture is joined in second aqueous carrier.Amount second oil component and second surface activating agent system gross weight about 0.5 to about 20 times preferably that are used for second aqueous carrier of this step, more preferably from about 1 to about 10 times.Be not bound by theory,, can make the stable emulsion of surfactant with most probable low content by mixing surfactant system by this way.
Second oily components
This second oily components comprises one or more compositions, and described composition is selected from spice, comprises the hydrophobicity plant extract of terpenoid, hydrophobic vitamin and their mixture.
In this compositions, with this second oily components (being different from first oily components) emulsifying, and preferred emulsifying under about 20 ℃ to 40 ℃ temperature.Preferably, in this compositions, second oily components, especially spice, only the form with second emulsion exists.It is believed that said composition can have improved stability by second oily components is mixed in the described compositions with the form of second emulsion.It has been observed by the present inventors that, if preparation does not comprise second emulsion of second oily components, and with second oily components, especially spice, when mixing in the described compositions, this oily components can destroy the transparency or the translucence of described compositions, promptly, compositions can become opaque or be emulsus, when especially storing under 50 ℃ or higher temperature.
Can be used for the mixture that spice of the present invention comprises a kind of perfume composition and two or more perfume compositions.Can be used for these perfume compositions of the present invention and comprise natural perfume material component and synthetic perfume component.Be applicable to that highly synthetic perfume of the present invention comprises, for example, terpenes (for example, menthol, Camphora and limonene); And aldehyde (as, γ-Geng Jidingneizhi and strawberry aldehyde.
Can be used for the hydrophobicity plant extract that comprises terpenoid of the present invention and comprise, for example, comprise the tea tree oil and the chamomile extract that comprises bisabolol (bisarol) of the pure and mild γ-terpinene of terpinene-4-.
Can be used for hydrophobic vitamin of the present invention and comprise, for example, vitamin A and its derivant (for example, vitamin A palmitate and vitamin A propionic ester) and vitamin D and its derivant.
Can comprise second oily components in said composition, its content is preferably about 0.001% to about 1% by described composition weight meter, and more preferably from about 0.01% to about 0.5%.
The polyhydric alcohol carrier
Preferably, this second emulsion also comprises the polyhydric alcohol carrier.Can be used for polyhydric alcohol carrier of the present invention and comprise, for example, 1,3 butylene glycol, glycerol, pentanediol and propylene glycol.In these polyhydric alcohol carriers some also can be used as " water-soluble wetting agent " described below.
This polyhydric alcohol can be preferably to be included in the compositions by described composition weight meter about 0.01% to about content of 10%, more preferably from about 0.1% to about 6%.The weight ratio of polyhydric alcohol carrier and second surface activating agent system is preferably about 5: 1 to about 1: 5, more preferably from about 3: 1 to about 1: 3.
It is believed that the polyhydric alcohol carrier by dissolving second surface activating agent system, helps second emulsion to form.In a method for optimizing of the preparation present composition, the polyhydric alcohol carrier at first mixes with the second surface activating agent system and second oily components, then this mixture is joined in second aqueous carrier.
Aqueous carrier
Compositions of the present invention comprises aqueous carrier.According to selecting the content and the kind of carrier with required other characteristic of the compatibility of other component and product.
Be used for the aqueous solution that carrier of the present invention comprises water and lower alkyl alcohol.Being used for lower alkyl alcohol of the present invention is the monohydric alcohol with 1 to 6 carbon atom, more preferably ethanol and isopropyl alcohol.
Preferably, aqueous carrier is water basically.The preferred deionized water that uses.The characteristic required according to product also can be used the water of the natural origin that comprises mineral cation.
Usually, the present composition adds up to by described composition weight meter and comprises about 10% to about 99%, preferred about 50% to about 95%, more preferably from about 60% to about 90% aqueous carrier.
The pH of this compositions is preferably about 4 to about 8, more preferably from about 5 to about 7.In this pH scope, the viscosity skin treatment agents that is fit to is especially effective.For obtaining required pH, can comprise buffer agent and other pH regulator agent.
Carboxylic acid/carboxylate copolymer
The present composition comprises about 0.01% to about 5%, preferred about 0.04% to about 1% carboxylic acid/carboxylate copolymer.
Be not bound by theory, it is believed that carboxylic acid/carboxylate copolymer provides shear thinning character for this compositions.Shear thinning character is meant and is present in typically and can be administered to yield point in the shear pressure on the skin by hands, and the composition viscosity that surpasses yield point significantly is decreased to the degree that can be arrived by the consumer alert.In a preferred embodiment, before using shearing, compositions of the present invention has suitable viscosity, and preferably about 100mPa.s is to about 6000mPa.s, and more preferably from about 500mPa.s is to about 4500mPa.s, also 700mPa.s about 4000mPa.s extremely more preferably from about.In the time of 25 ℃,, can suitably measure the viscosity of this paper with any (this depends on the viscosity and the characteristic of compositions) among the axle #4,5,6 or 7 by the rotating speed of Brookfield LV with 2rad/s (20rpm).In a highly preferred embodiment, the viscosity that surpasses yield point is similar to the viscosity in the water.After use, shear thinning character can directly provide low viscosity compositions, provides thus water is coated to sensation on the skin.
Carboxylic acid/carboxylate copolymer also can make compositions keep transparent relatively and have suitable viscosity, and can compositions be become to be clamminess or greasy.
In addition, carboxylic acid/carboxylate copolymer can disperse and stable oily components in aqueous environment, so that these components can not separated.When except in first emulsion, comprising a certain amount of first oily components, when also mixing first oily components in the described compositions, can be by disperseing that with carboxylic acid/carboxylate copolymer the first extra oily components is mixed described compositions.The first extra oily components is silicone oil preferably.With the dispersive first extra oily components of carboxylic acid/carboxylate copolymer, can be by described composition weight meter with about 0.05% to about 5%, preferred about 0.5% to about 3% content is included in the described compositions.
Carboxylic acid/carboxylate copolymer of the present invention is through the carboxylic acid of hydrophobically modified and the cross-linked copolymer of alkyl carboxylates, and has amphipathic characteristic.It is believed that carboxylic acid/carboxylate copolymer can not make compositions have the viscosity of not expecting owing to comprise alkyl in the copolymer.
Suitable carboxylic acid/carboxylate copolymer of the present invention is the acrylic acid/alkyl acrylate copolymer with following formula:
R wherein
51Be hydrogen or alkyl, wherein at least one R independently with 1 to 30 carbon atom
51Be hydrogen, R
52As above definition, n, n ', m and m ' are integer, wherein n+n '+m+m ' is about 40 to about 100, n, and " be 1 to about 30 integer, and l is restricted to: the molecular weight of copolymer is about 500,000 to about 3,000,000.
Being used for commercially available carboxylic acid/carboxylate copolymer of the present invention comprises: the CTFA name is called acrylate/C10-30 alkyl acrylate cross-linked copolymer, its commodity are called Pemulen TR-1, Pemulen TR-2, Carbopol 1342, Carbopol 1382 and Carbopol ETD 2020, these materials all can be available from B.F.Goodrich Company.
Can comprise nertralizer with the carboxylic acid/carboxylate copolymer of the present invention that neutralizes.The non-limiting example of these nertralizers comprises sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine (DIPA), amino methyl propanol, tromethane, tetrahydroxypropyl ethylenediamine and their mixture.
Additional water-soluble polymer
The present composition can also comprise additional water-soluble polymer, and preferably its content is about 0.01% to about 5%, more preferably from about 0.04% to about 1%.Additional herein water-soluble polymer is polymer water miscible or can be miscible with water, and is compatible with carboxylic acid/carboxylate copolymer.Be not bound by theory, it is believed that the additional water-soluble polymer of controlled quatity in the compositions provides humidification and the slickness improved for skin, but can not produce undesirable be clamminess sense or sticking sense.
In a preferred embodiment, select additional water-soluble polymer so that the present composition has and be preferably the appropriate viscosity of about 100mPas, as mentioned above to about 6000mPa.s.
Be applicable to that other water-soluble polymer of the present invention comprises anionic polymer and non-ionic polymers.Can be used for water-soluble polymer of the present invention and comprise, for example, ethene polymers, as, the CTFA name is called the crosslinked acrylic acid polymer of carbomer; The cellulosic polymer of cellulose derivative and modification, as, methylcellulose, ethyl cellulose, hydroxyethyl-cellulose, hydroxyethyl ethylcellulose, hydroxypropyl emthylcellulose; Polyvinylpyrrolidone; Polyvinyl alcohol; Natural gum, as, guar gum, hydroxypropyl guar gum and xanthan gum; Microbial polymer, as, glucosan and succinoglucan; Based on the polymer of starch, as, carboxymethyl starch and methyl hydroxypropyl starch; Acrylates (ester) polymer, as, sodium polyacrylate, polyethyl acrylate and polyacrylamide.Molecular weight also can be used for the present invention greater than about 1000 poly alkylene glycol.Can be used for additional water soluble polymer of the present invention and comprise amphiphilic polymers, as polyquaternary ammonium salt 22, polyquaternary ammonium salt 39, polyquaternary ammonium salt 47 and octyl acrylamide/acrylates (ester)/methacrylic acid fourth amino ethyl ester copolymer.
Be applicable to that highly commercially available additional water soluble polymer of the present invention comprises xanthan gum, commodity are called Keltrol series, available from Kelco; Carbomer, commodity are called Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980 and Carbopol 981, all available from B.F.Goodr ich Company; Acrylate/stearyl polyoxyethylene ether-20 methacrylate ester copolymer, commodity are called ACRYSOL22, available from Rohm and Hass; The ninth of the ten Heavenly Stems oxygen ethylhydroxyethylcellulose, commodity are called AMERCELL POLYMER HM-1500, available from Amerchol; Methylcellulose, commodity are called BENECEL, hydroxyethyl-cellulose, and commodity are called NATROSOL, hydroxypropyl cellulose, and commodity are called KLUCEL, cetyl hydroxyethyl-cellulose, and commodity are called POLYSURF 67, provide by Herculus; Scleroglycan, commodity are called Clearogel SCll, available from Michel Mercier Products Inc. (NJ, USA)); Oxirane and/or propylene oxide based polyalcohol, commodity are called CARBOWAX PEG, POLYOX WASR and UCON FLUIDS, provide by Amerchol.
Water-soluble wetting agent
The present composition comprises about 1% to about 20%, preferred about 5% to about 15% water-soluble wetting agent.Be applicable to that water-soluble wetting agent of the present invention comprises polyhydric alcohol such as glycerol, sorbitol, propylene glycol, butanediol, hexanediol, ethoxylated glucose, 1,2-hexanediol, 1,2-pentanediol, hexanetriol, dipropylene glycol, erithritol, trehalose, two glycerol, xylitol, maltose alcohol, maltose, glucose, fructose, sodium chondroitin sulfate, hyaluronate sodium, adenylic acid sodium, sodium lactate, ketopyrrolidine carbonate, glucamine, cyclodextrin and their mixture.
Be applicable to that water-soluble wetting agent of the present invention comprises the Polyethylene Glycol and the polypropylene glycol of water soluble alkoxylated non-ionic polymers such as molecular weight the most about 1000, be called those materials of PEG-200, PEG-400, PEG-600, PEG-1000 and their mixture as the CTFA name.
Be applicable to that highly commercially available wetting agent of the present invention comprises: butanediol, commodity are called 1,3 butylene glycol, available from ASAHI DENKA Co.Ltd.; Glycerol, commodity are called CRODEROLGA7000, available from Croda Universal Ltd., PRECERIN series, identical with this chemical name available from Unichema with a kind of trade name, available from NOF; Propylene glycol, commodity are called LEXOLPG-865/855, available from Inolex, 1,2-propylene glycol USP is available from BASF; Dipropylene glycol, trade name is identical, available from BASF; Diglycerol, commodity are called DIGLYCEROL, available from SolvayGmbH; Polyethylene Glycol, commodity are called CARBOWAX series, available from Union Carbide and polymethyl acid glyceride, the mixture of propylene glycol and PVM/MA copolymer, commodity are called Lubrajel Oil, available from Guardian Lab.
The sebum absorbent
The present composition can comprise about 0.1% to about sebum absorbent of 10%, preferred about 1% to about 5%.Being applicable to that sebum absorbent of the present invention comprises in fact can absorb from the oozy sebum of pore and those materials compatible with Aquo-composition of the present invention.Water solublity, hydroexpansivity or the component with higher emulsifying capacity are unsuitable for the present invention, because when being formulated in it in this compositions, they no longer have the sebum absorbability.
The preferred sebum absorbent of the present invention comprises porous spherical cellulose powder, Trefil 506C, surface modification porous silica powder, porous nylon powder, porous propylene acid ester copolymer and their mixture.The type of sebum absorbent and quantity are selected according to the required character of product.
Be applicable to that highly commercially available porous spherical cellulose powder of the present invention comprises the material of commodity Celluflow series by name, for example, Celluflow C025 is available from Chisso Corp.Be applicable to that highly commercially available Trefil 506C of the present invention comprises vinyldimethicone/methylsiloxane silsesquioxane cross linked polymer, commodity are called KSP series, available from Tokyo ShinEtsu Chemical Co., Ltd..Other commercially available sebum absorbent comprises the porous propylene acid ester copolymer, and commodity are called Polytrap, available from Dow Corning.
The viscosity skin-care agent
The present composition can comprise about 0.5% to about 10%, preferred about 1% to about 5% viscosity skin treatment agents.Be applicable to that skin-care agent of the present invention helps to repair and additional epidermis natural water divides the barrier function, so they can improve for skin provides beneficial effect such as skin texture.Usually be known that these reagent are the beneficial effect that skin provides usefulness when these reagent of life-time service, but when they apply separately, also be easy to the dermal sensation that provides relatively poor.
Be applicable to that viscosity skin treatment agents of the present invention has nicotiamide, nicotinic acid and ester thereof, nicotinyl alcohol, pantothenylol, pantoyl benzyl ethyl ether, positive acetylcysteine, positive acetyl-L-serine, phosphodiesterase inhibitor, trimethyl glycine, carbamide, gelatin, soluble collagen, Lac regis apis, tocopheryl nicotinate and vitamin D3 and analog or derivant and their mixture.Especially preferred nicotiamide because when it uses with pharmacy effective dose, can reduce or alleviate the intensity of chronic speckle.Nicotiamide is adapted to pass through at first to be dissolved in the water and mixes in the compositions.Pantothenylol also is especially preferred because when it when using at least about 1% amount, the beneficial effect that can provide skin texture to improve.Nicotiamide and pantothenylol can be commercially available from for example Roche.
Sebum suppresses plant extract
The present composition also comprises about 0.001% to about 5%, and more preferably from about 0.05% to about 1% sebum suppresses plant extract.Be applicable to that plant extract of the present invention has the astringent type effect that reduces pore size, or have the inhibition of 5-5 alpha-reductases, and compatible with this compositions of moisture form, the preferred transparent or semitransparent outward appearance that can not change this compositions.Preferred water soluble plant extract.Be applicable to that plant extract of the present invention comprises Flos Caryophylli (choji) extract, Semen Coicis (yokuinin) extract, Radix Hamamelidis Mollis (hamamerisu) extract and their mixture.These plant extracts are available from Iwase.
Ultraviolet protective agent
The present composition also comprises about 1% to about 10%, more preferably from about 3% to about 9.5% ultraviolet protective agent.Ultraviolet protective agent prevents to change owing to cuticular excessively the peeling off with skin texture that ultraviolet radiation causes usually, and can be added in the emulsion of the present invention.The ultraviolet protective agent that is fit to can be Organic substance or inorganic matter.Can use the hydrophobic and water-insoluble ultraviolet protective agent of controlled quatity.
The wide variety of conventional ultraviolet protective agent is applicable to the present invention.These ultraviolet protective agents that can be used in the emulsion are preferably selected from 2-ethylhexyl-p-methoxycinnamic acid ester (PARSOLMCX is commercially available with trade name); butyl methoxyl biphenyl formyl-methane; 2-hydroxyl-4-methoxyl group benzophenone; 2-Phenylbenzimidazole-5-sulfonic acid; octyldimethyl-para-amino benzoic acid; octocrylene; 2-ethylhexyl N; N-dimethyl para-aminobenzoate; para-amino benzoic acid; 2-Phenylbenzimidazole-5-sulfonic acid; octocrylene; hydroxyl methoxy benzophenone; high menthyl Salicylate; ethylhexyl salicylate; 4; 4 '-methoxyl group-tert-butyl group dibenzoyl methane; 4-isopropyl diphenyl formoxyl methane; the 3-benzylidene camphor; 3-(4-methyl benzal) Camphora; titanium dioxide such as MT-100 are available from Tayca; zinc oxide; silicon dioxide; ferrum oxide; Eusolex
TM6300, octocrylene, Parsol 1789 and their mixture.
Be particularly useful for of the present inventionly being as the United States Patent (USP) 4,937,370 of the Sabatelli that is published in June 26 nineteen ninety and being published in those uv-protectors in the United States Patent (USP) 4,999,186 of Sabatelli on March 12nd, 1991.Uv-protector disclosed by the invention has two distinct chromophore parts in single molecule, described different chromophories partly show different ultraviolet radiation absorption spectrums.One of them chromophore part mainly has absorption in the UVB radiation scope, and another chromophore part has strong absorption in the UVA radiation scope.For conventional ultraviolet protective agent, these ultraviolet protective agents can provide higher effect, wideer uv absorption scope, lower skin penetration and more permanent effect.
Its accurate consumption will depend on selected sunscreen and required sun protection factor (SPF).SPF is that the commonly used of anti-erythema photoprotection of sunscreen measured.Referring to FederalRegister, the 43rd volume, the 166th phase, 38206-38269 page or leaf, on August 25th, 1978.
Brightening agent
Compositions of the present invention also comprises about 0.001% to about 10%, more preferably from about 0.1% to about 5% brightening agent.This compositions that is applicable to brightening agent of the present invention and moisture form is compatible.Preferred water dissolubility brightening agent.Be applicable to brightening agent of the present invention be meant with handle before compare the active component that not only changes skin appearance but also improve hyperpigmentation disease.
Be applicable to that useful brightening agent of the present invention comprises ascorbic acid compound, Azelaic Acid, butylated hydroxyanisole (BHA), gallic acid and derivant thereof, glycyrrhizic acid, hydroquinone, kojic acid, arbutin, mulberry extract and their mixture.It is believed that it is favourable using whitener composition, brightens beneficial effect because they can provide by different mechanism.
Preferably, can be used for ascorbic acid compound of the present invention is the Ascorbate or derivatives thereof.The water soluble salt derivant of example comprises, but be not limited to L-ascorbic acid 2-glucoside, L-ascorbyl phosphate ester salt such as L-ascorbyl phosphoric acid ester sodium, L-ascorbyl phosphate kalium salt, L-ascorbyl phosphate kalium salt, L-ascorbyl phosphate ester magnesium salt, L-ascorbyl calcium phosphate, L-ascorbyl aluminium phosphate salt.Also can use L-ascorbyl sulfuric acid.Embodiment is L-ascorbyl sulfuric ester sodium salt, L-ascorbyl sulfuric ester potassium salt, L-ascorbyl sulfuric ester magnesium salt, L-ascorbyl sulfuric ester calcium salt and L-ascorbyl sulfate aluminium salt.
Annexing ingredient
The present composition also can comprise other annexing ingredient, selected according to the desirable characteristics of final products by the technical staff, and described annexing ingredient is used to make compositions more acceptant on cosmetology or aesthetics, and the beneficial effect of additional purpose perhaps is provided for it.Be applicable to that component of the present invention carries out easy classification by beneficial effect or its supposition action mode of determining, yet given classification to its purposes without limits.It should also be understood that a kind of component can provide multiple beneficial effect.
(i) antioxidant and free radical scavenger
Antioxidant and radical scavenger be for providing ultra-violet radiation resisting protection and resist other environmental agent that causes skin lesion particularly useful, and described ultraviolet radiation can cause the increase of peeling off in the horny layer or the change of skin texture.Preferred anti-oxidants/free radical scavenger comprises, for example, and tocopherol sorbic acid ester and other Renascin, more preferably tocopherol sorbic acid ester.For example, can be applicable to the tocopherol sorbic acid ester that uses of the present invention in local emulsion is described in the people's such as Bissett that announced on July 11st, 1989 the United States Patent (USP) 4,847,071.
(ii) antiinflammatory
By for example helping uniformity and the acceptable colour of skin and/or color, antiinflammatory can strengthen the beneficial effect of skin appearance.Preferably, antiinflammatory comprises steroid antiinflammatory and non-steroidal anti-inflammatory agents.The preferred steroid antiinflammatory that is suitable for is a hydrocortisone.Also can use so-called " natural " antiinflammatory.For example, can use α bisabolol, Aloe, Manjistha (, especially extracting in the Radix Rubiae) and Guggal (, especially extracting in India's Myrrha), cola extract, Chamomile and gorgonian extract from the Myrrha platymiscium from the Rubia plant.
(iii) antimicrobial
Used " antimicrobial " is meant can destroy microorganisms, prevent growth of microorganism or prevent the chemical compound of the pathogenic effects of microorganism.For example, antimicrobial can be used for controlling acne.Be applicable to that preferred antimicrobial of the present invention is benzoyl peroxide, erythromycin, tetracycline, clindamycin, Azelaic Acid, sulfur resorcinol, phenyl phenol and Irgasan
TMDP 300 (CibaGeigy Corp., the U.S.).The antimicrobial that can in emulsion of the present invention, add safe and effective amount, preferred about 0.001% to about 10%, and more preferably from about 0.01% to about 5%, and also more preferably from about 0.05% to about 2%.
(iv) chelating agen
Term used herein " chelating agen " is meant by reaction formation coordination compound removes metal ion so that metal ion is difficult for the chemical compound of participation or catalyzed chemical reaction from system.It is particularly useful with the protection of resisting other environmental agent that can cause skin lesion for the opposing ultraviolet radiation is provided to comprise chelating agen, and described ultraviolet radiation can cause excessively peeling off or texture changes.Be applicable to that the chelating agen of example of the present invention is disclosed in the people's such as Bissett that announced on January 30th, 1996 United States Patent (USP) 5,487,884; Be published in people's such as Bush the PCT publication 91/16035 and 91/16034 in October 31 nineteen ninety-five.Preferred chelating agen has furil-dioxime and derivant thereof.
(v) other component
Except that said components, the present composition can also comprise antiseptic and preservative enhancer, but antiseptic as water solublity or solubilising, methyl ester, ethyl ester, propyl diester and butyl ester, benzylalcohol, imidazolidinyl urea, ethylenediaminetetraacetic acid and the salt thereof, bromo nitryl propylene glycol (2-bromo-2-nitropropane-1,3-glycol) and the phenoxypropanol that comprise Germall 115, hydroxy benzoic acid; Defoamer; Binding agent; Bio-additive; Extender; Coloring agent; Quintessence oil and its solubilizing agent; Other natural extract; The chemical compound that stimulates collagen to produce; Culture propagation filtrate and other material.
Preparation method
Preferably, compositions of the present invention can be prepared by the preparation method that may further comprise the steps:
(a) preparation first mixture, it comprises the following steps:
(a1) first oily components is mixed to form first emulsion with the first surface activating agent system and first aqueous carrier under about 70 ℃ to 80 ℃ temperature; The amount of first aqueous carrier is first oily components and first surface activating agent system gross weight about 0.5 to about 10 times;
(a2) mixture with (a1) is cooled to about 50 ℃;
(a3) mixture with (a2) adds the 3rd aqueous carrier, and the temperature of the 3rd aqueous carrier is enough low, is not higher than 40 ℃ temperature so that the mixture that is obtained is cooled to immediately;
(b) preparation second mixture, it comprises the following steps:
(b1) second oily components is mixed to form second emulsion with the second surface activating agent system and second aqueous carrier under about 20 ℃ to 40 ℃ temperature; The amount of second aqueous carrier is second oily components and second surface activating agent system gross weight about 0.5 to about 20 times;
(c) mix first mixture and second mixture.
Typically, add polyhydric alcohol carrier, carboxylic acid/carboxylate copolymer and water-soluble wetting agent, although this is not that this method is essential.The used component of this method is identical with those above-mentioned components.
First mixture is by first surface activating agent, first oily components, first aqueous carrier and the preparation of the 3rd aqueous carrier.In step (a1), first oily components, first surface activating agent system and first aqueous carrier are mixed together under about 70 ℃ to 80 ℃ temperature in the anchor agitator to form first emulsion.Preferably, first surface activating agent system is at first mixed with first oily components, then this mixture is added first aqueous carrier.Amount first oil component and first surface activating agent system gross weight about 0.5 to about 10 times preferably that are used for first aqueous carrier of step (a1), more preferably from about 1 to about 7 times.In step (a2), the mixture of step (a1) is cooled to 50 ℃, preferably in about 20 minutes, finish this process.Have been found that this cooling procedure can make mixture become transparent.In step (a3), mix with the 3rd aqueous carrier by mixture step (a2), make its further cooling.With the temperature of blended the 3rd aqueous carrier of mixture of step (a2) for enough low be not higher than 40 ℃, preferred about 30 ℃ so that the mixture of gained is cooled to immediately.Be not bound by theory, it is believed that the second step cooling procedure provides the stable transparent mixture, described mixture has a small amount of as far as possible surfactant.
Second emulsion is independently by second surface activating agent, second oily components and the preparation of second aqueous carrier.In step (b1), second oily components, second surface activating agent system and second aqueous carrier are mixed together under about 20 ℃ to 40 ℃ temperature in the anchor agitator to form second emulsion.Preferably, second surface activating agent system is at first mixed with second oily components, then this mixture is added second aqueous carrier.Amount second oil component and second surface activating agent system gross weight about 0.5 to about 20 times preferably that are used for second aqueous carrier of step (b1), more preferably from about 1 to about 10 times.Preferably the polyhydric alcohol carrier is added second emulsion.Preferably,, earlier the polyhydric alcohol carrier is mixed with second surface activating agent system with before second oily components mixes in second surface activating agent system.
At last, mix first mixture and second mixture until even (step c).Preferably mix with low relatively rotating speed with anchor agitator in this step, rotating speed is preferably about 5rad/s (50rpm) to about 10.5rad/s (100rpm).This step can at room temperature be carried out.
In compositions of the present invention, preferably add carboxylic acid/carboxylate copolymer and water-soluble wetting agent.Preferably, carboxylic acid/carboxylate copolymer and additional water-soluble polymer (if existence) are distributed under about 70 ℃ to 80 ℃ temperature in the 4th aqueous carrier until evenly.When with these polymer dispersed, can use high speed agitator and control rotary speed to be no more than about 523rad/s (5000rpm), to avoid destroying the structure of described polymer.When having nertralizer, can subsequently it be added this dispersion.Preferably water-soluble wetting agent is added in this polymer mixture.Remaining ingredient (if existence) suppresses plant extract, ultraviolet absorber, brightening agent and antiseptic as sebum absorbent, viscosity skin treatment agents, sebum, can add in the polymer mixture.This polymer mixture (if being comprised) can be added in the mixture of step (c).
In compositions of the present invention, when comprising carboxylic acid/carboxylate copolymer, except that in first emulsion, comprising a certain amount of oiliness composition, in the present composition, also can disperse to comprise this first oily components by carboxylic acid/carboxylate copolymer, for example, silicone oil.In this case, preferably this first extra oily components is added in the above-mentioned polymer mixture.
Embodiment
The following example has further described and has illustrated the embodiment in the scope of the invention.These embodiment that given only are illustrative, and unintelligible for being limitation of the present invention, because can carry out multiple change under the condition that does not deviate from spirit and scope of the invention.Unless hereinafter explanation in addition, the composition of Shi Yonging is all discerned with chemical name or CTFA name herein.
Compositions
Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | ||
01 | Cetearyl polyoxyethylene ether-12 | 0.013 | 0.01 | 0.02 | 0.04 | 0.02 | 0.013 |
01 | Cetearyl polyoxyethylene ether-20 | 0.05 | 0.05 | 0.13 | 0.14 | 0.054 | 0.05 |
01 | Cetearyl polyoxyethylene ether-30 | 0.09 | 0.1 | 0.15 | 0.24 | 0.097 | 0.09 |
01 | Polyglyceryl-3-diisopstearate | 0.14 | 0.1 | 0.32 | 0.39 | 0.156 | 0.14 |
01 | The PEG-20 castor oil hydrogenated | 0.04 | 0.04 | 0.15 | 0.12 | 0.048 | 0.04 |
01 | The 2 ethyl hexanoic acid cetyl | 0.025 | 0.03 | 0.23 | 0.07 | 0.028 | 0.025 |
01 | Limnanthes Alba Seed Oil *1 | 0.05 | 0.05 | 0.15 | 0.15 | 0.06 | 0.05 |
01 | 2-Methylpentadecane | - | - | - | 0.1 | 0.1 | - |
01 | The different nonyl ester of different n-nonanoic acid | - | - | - | - | - | 0.1 |
01 | Benzylalcohol | 0.3 | 0.3 | 0.3 | - | 0.12 | 0.2 |
02 | Deionized water | 1.6 | 1.6 | 4.3 | 4.3 | 1.72 | 1.6 |
03 | Deionized water | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 |
03 | Sodium benzoate | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
03 | EDTA 2-Na | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 |
03 | Glycerol | 0.72 | 2.0 | - | 2.0 | - | 2.0 |
03 | Polymethyl acid glyceride and propylene glycol and PVM/MA copolymer *2 | 1.5 | - | 1.5 | 2.0 | - | - |
03 | 1,3 butylene glycol | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 |
03 | Methyl parahydroxybenzoate | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 |
04 | Menthol | 0.01 | - | 0.01 | 0.05 | 0.05 | - |
04 | Spice *3 | 0.05 | 0.05 | 0.06 | - | 0.05 | - |
04 | Tea tree oil *4 | - | - | - | - | - | 0.1 |
04 | The PEG-40 castor oil hydrogenated | 0.4 | 0.5 | - | 0.2 | 0.4 | 0.4 |
04 | The PEG-20 castor oil hydrogenated | 0.2 | - | - | - | - | 0.2 |
04 | Polysorbate-20 | - | - | - | 0.3 | 0.2 | - |
04 | Lauric acid polyglycereol-6 ester | - | - | 0.6 | - | - | - |
04 | 1,3 butylene glycol | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
05 | Deionized water | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
06 | Acrylic acid/alkyl acrylate copolymer 1 *5 | - | - | - | - | 0.23 | 0.2 |
06 | Acrylic acid/alkyl acrylate copolymer 2 *6 | 0.25 | 0.25 | 0.25 | 0.3 | - | - |
06 | Deionized water | Surplus to 100% | |||||
07 | Deionized water | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
08 | Sodium hydroxide | 0.07 | 0.1 | 0.1 | 0.85 | 0.2 | 0.06 |
08 | Deionized water | - | - | - | 0.12 | 0.15 | 0.1 |
09 | Polydimethyl siloxanes/polydimethy siloxanes alcohol *7 | 1.5 | - | 2.0 | - | 1.0 | - |
09 | Ring-type polymethyl siloxane/dimethiconol *8 | - | 1.5 | - | 1.5 | - | 1.0 |
10 | Deionized water | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
10 | Methyl parahydroxybenzoate | 0.1 | 0.05 | 0.1 | 0.05 | 0.07 | 0.07 |
10 | 1,3 butylene glycol | 4.0 | 2.0 | 4.0 | 3.0 | 3.0 | 4.0 |
10 | Xanthan gum *9 | 0.04 | 0.04 | 0.04 | 0.04 | - | - |
10 | Carbomer *10 | - | - | - | - | 0.2 | - |
10 | Hyaluronate sodium *11 | 0.05 | - | - | - | 0.02 | 0.02 |
11 | D-panthenol *12 | - | 1.0 | 1.0 | 1.0 | 2.0 | 1.0 |
11 | Nicotiamide *13 | - | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
11 | Zizyphus Fructus Jujubae berry extract *14 | 0.1 | - | 0.15 | 0.1 | - | 0.15 |
11 | The Radix Hamamelidis Mollis extract *15 | - | - | - | 0.1 | - | - |
11 | Flos Caryophylli extract *16 | - | - | 0.1 | - | - | - |
11 | Ascorbyl glucoside magnesium | - | - | - | - | 2.0 | - |
11 | Benzophenone-1 | - | - | - | - | - | 2.0 |
11 | Titanium dioxide *17 | - | - | - | - | - | 1.0 |
11 | Cellulose powder *18 | - | - | - | - | 3.0 | - |
11 | Vinyldimethicone/methylsiloxane silsesquioxane cross linked polymer *19 | - | - | - | - | - | 5.0 |
11 | Deionized water | 10 | 10 | 10 | 10 | 10 | 10 |
Compositions
Phase | Embodiment 7 | Embodiment 8 | |
01 | Cetearyl polyoxyethylene ether-12 | 0.013 | 0.01 |
01 | Cetearyl polyoxyethylene ether-20 | 0.05 | 0.05 |
01 | Cetearyl polyoxyethylene ether-30 | 0.09 | 0.1 |
01 | Polyglyceryl-3-diisopstearate | 0.14 | 0.1 |
01 | The PEG-20 castor oil hydrogenated | 0.04 | 0.04 |
01 | The 2 ethyl hexanoic acid cetyl | 0.025 | 0.03 |
01 | Limnanthes Alba Seed Oil *1 | 0.05 | 0.05 |
01 | Benzylalcohol | 0.3 | 0.3 |
02 | Deionized water | 1.6 | 1.6 |
03 | Deionized water | 30.0 | 30.0 |
03 | Sodium benzoate | 0.07 | 0.07 |
03 | EDTA 2-Na | 0.04 | 0.04 |
03 | Glycerol | 0.72 | 2.0 |
03 | Polymethyl acid glyceride and propylene glycol and PVM/MA copolymer *2 | 1.5 | - |
03 | 1,3 butylene glycol | 2.3 | 2.3 |
03 | Methyl parahydroxybenzoate | 0.07 | 0.07 |
04 | Menthol | 0.01 | - |
04 | Spice *3 | 0.05 | 0.05 |
04 | Two lauryl ether-10 phosphoric acid ester sodiums of polyoxyethylene | 0.45 | - |
04 | Glycerin polyether-25 PCA isostearate | - | 0.45 |
04 | 1,3 butylene glycol | 0.6 | 0.6 |
05 | Deionized water | 2.0 | 2.0 |
06 | Acrylic acid/alkyl acrylate copolymer 2 *6 | 0.25 | 0.25 |
06 | Deionized water | Surplus to 100% | |
07 | Deionized water | 5.0 | 5.0 |
08 | Sodium hydroxide | 0.07 | 0.1 |
09 | Polydimethyl siloxanes/polydimethy siloxanes alcohol *7 | 1.5 | - |
09 | Ring-type polymethyl siloxane/dimethiconol *8 | - | 1.5 |
10 | Deionized water | 20.0 | 20.0 |
10 | Methyl parahydroxybenzoate | 0.1 | 0.05 |
10 | 1,3 butylene glycol | 4.0 | 2.0 |
10 | Xanthan gum *9 | 0.04 | 0.04 |
10 | Hyaluronate sodium *11 | 0.05 | - |
11 | D-panthenol *12 | - | 1.0 |
11 | Nicotiamide *13 | - | 2.0 |
11 | Zizyphus Fructus Jujubae berry extract *14 | 0.1 | - |
11 | Deionized water | 10 | 10 |
The component definition
*1 Limnanthes Alba Seed Oil: commodity are called Cropure MDF, available from Croda
*2 polymethyl acid glycerides and propylene glycol and PVM/MA copolymer: commodity are called Lubrajel Oil, available from Guardian Lab
*3 spice: comprise limonene
*4 tea tree oil: comprise 4-terpineol and γ-terpinene, available from SouthernCross Botanicals.
*5 acrylic acid/alkyl acrylate copolymer 1: commodity are called PEMULENTR-1, available from B.F.Goodrich
*6 acrylic acid/alkyl acrylate copolymer 2: commodity PEMULEN TR-2 by name is available from B.F.Goodrich
*7 polydimethyl siloxanes/polydimethy siloxanes alcohol: commodity are called DCQ2-1403, available from Dow Corning
*8 ring-type polymethyl siloxane/dimethiconols: commodity are called DCQ2-1401, available from Dow Corning
*9 xanthan gum: commodity are called Keltrol T, available from Kelco
*10 carbomers: commodity are called Carbopol 981, available from B.F.Goodrich
*11 hyaluronate sodiums: available from Chisso corp.
*12 pantothenylol: available from Roche
*13 nicotiamide: available from Roche
*14 Zizyphus Fructus Jujubae berry extracts: available from Ichimaru Pharcos
*15 Radix Hamamelidis Mollis extracts: commodity are called Hamamerisu Liquid, available from Iwase
*16 Flos Caryophylli extracts: commodity are called Choji Extract BG, available from Iwase
*17 titanium dioxide: commodity are called titanium dioxide MT-100, available from Tayca
*18 cellulose powders: commodity are called Celluflow C-25, available from Chissocorp.
*19 vinyldimethicone/methylsiloxane silsesquioxane cross linked polymer: commodity are called KSP-100, available from Shinetsu Chemical
Preparation method
(a1) will 01 be heated to about 80 ℃ mutually.To 02 be heated to about 78 ℃ mutually.By phase 01 adding phase 02 and mixing are carried out emulsifying.
(a2), the mixture of (a1) is cooled to about 50 ℃ about 10 to about 20 minutes time.
(a3) mixture with (a2) adds phase 03, and 03 is room temperature mutually.
(b1) under about 25 ℃, by phase 04 adding 05 is made its emulsifying mutually.
(c) mixture of step (a3) and the product of step (b1) are mixed.
(d1) if comprised, will 06 be heated to about 80 ℃ mutually, and will phase 06 mix homogeneously with the rotating speed that is no more than 523rad/s (5000rpm) with high speed agitator.
(d2) under about 80 ℃, phase 06 is added phase 07, and this mixture is cooled to about 45 ℃.
(d3) incite somebody to action the mixture of 09 adding (d2) mutually.
(d4) incite somebody to action the mixture of 08 adding (d4) mutually.
(d5) will be mutually 10 be heated to about 80 ℃ and will phase 10 mix homogeneously with the rotating speed that is no more than 523rad/s (5000rpm) with high speed agitator.The mixture that phase 10 is added (d4).
(d6) will phase 11 mix homogeneously with high speed agitator with the rotating speed that is no more than 523rad/s (5000rpm).The mixture that phase 11 is added (d5).
At last, the mixture with step (c) mixes with the mixture of step (d6).
Previous embodiment embodiment disclosed and representative has many advantages.For example, embodiment 1 to 8 is particularly suited for providing the transparent distillate medicinal water that is applicable to skin of face.When being used for skin of face, the compositions of embodiment 1 to 8 can be skin the beneficial effect of preserving moisture, slickness and flexibility is provided, and can not stay be clamminess sense and/or greasy feeling to skin.
In embodiment 1 to 8, comprise mutually that 01,02,03,04 and 05 base composition has transparent appearance and under the wavelength of 340nm absorptance be no more than about 2.The compositions of embodiment 1 to 8 has translucent appearance.Embodiment 1 to 5,7 and 8 compositions can provide aesthstic beneficial effect because of spice and/or menthol.The compositions of embodiment 6 can provide extra conditioning beneficial effect because of tea tree oil.
Claims (10)
1. skin care compositions, described compositions comprises:
(a) mean diameter is less than first emulsion of 100nm, and described emulsion comprises the HLB value greater than 10 first surface activating agent system, first oily components and first aqueous carrier; Wherein said first surface activating agent system comprises two or more non-ionic surface active agents, and described non-ionic surface active agent is selected from an alkyl or the trialkyl glyceride of polyoxyalkylene alkyl, polyoxyalkylene castor oil hydrogenated and straight or branched with C12-18 alkyl substituent; Wherein said first oily components is selected from emollient, silicone oil and their mixture; And the weight ratio of wherein said first surface activating agent system and described first oily components is 5: 1 to 1: 1;
(b) mean diameter is less than second emulsion of 50nm, and described emulsion comprises the HLB value greater than 8 second surface activating agent system, second oily components and second aqueous carrier; Wherein said second surface activating agent system comprises one or more non-ionic surface active agents, and described non-ionic surface active agent is selected from the polyoxyalkylene castor oil hydrogenated, has the polyglycereol Arrcostab of C10-20 alkyl substituent, polysorbate, polyoxyethylene sterol, polyethylene glycol hydrogenated sterol, hydroxylated lecithin, polyoxyethylene alkyl ether phosphate ester and salt thereof and glycerin polyether-25 PCA isostearate; Wherein said second oily components is selected from spice, comprises the hydrophobicity plant extract of terpenoid, hydrophobic vitamin and their mixture; And the weight ratio of wherein said second surface activating agent system and described second oily components is 20: 1 to 3: 1; With
(c) the 3rd aqueous carrier.
2. skin care compositions as claimed in claim 1, wherein the absorptance that has under the wavelength of 340nm of the base composition of being made up of component (a) to (c) basically is less than 2.
3. skin care compositions as claimed in claim 1, wherein said first oily components comprises emollient.
4. skin care compositions as claimed in claim 1, wherein said first surface activating agent system comprise at least a HLB and are lower than 10 non-ionic surface active agent greater than 10 non-ionic surface active agent and at least a HLB.
5. skin care compositions as claimed in claim 1, wherein said second surface activating agent system is made up of greater than 8 non-ionic surface active agent HLB substantially.
6. skin care compositions as claimed in claim 1, wherein said second emulsion also comprises the polyhydric alcohol carrier, and it is selected from 1,3 butylene glycol, glycerol, pentanediol and propylene glycol.
7. skin care compositions as claimed in claim 1, described compositions also comprises the acrylic acid/esters copolymer, is represented by following general formula:
R wherein
51Be hydrogen or alkyl, wherein at least one R independently with 1 to 30 carbon atom
51Be hydrogen, R
52As R
51Define, n, n ', m and m ' are integer, wherein n+n '+m+m ' is 40 to 100, n " be 1 to 30 integer, and l is restricted to: the molecular weight of copolymer is 500,000 to 3,000,000.
8. skin care compositions as claimed in claim 1, described compositions also comprises extra water-soluble polymer.
9. skin care compositions as claimed in claim 1, described compositions also comprises extra water-soluble wetting agent.
10. method for preparing the skin care compositions of claim 1 said method comprising the steps of:
(a) preparation first mixture, it may further comprise the steps:
(a1) described first oily components is mixed to form described first emulsion with described first surface activating agent system and described first aqueous carrier under 70 ℃ to 80 ℃ temperature; The amount of described first aqueous carrier is described first oily components and described first surface activating agent system gross weight 0.5 to 10 times;
(a2) mixture with described (a1) is cooled to 50 ℃;
(a3) mixture with described (a2) adds the 3rd aqueous carrier, and the temperature of described the 3rd aqueous carrier should be enough low, is not higher than 40 ℃ temperature so that the mixture that is obtained is cooled to immediately;
(b) preparation second mixture, it may further comprise the steps:
(b1) described second oily components is mixed to form described second emulsion with described second surface activating agent system and described second aqueous carrier under 20 ℃ to 40 ℃ temperature; The amount of described second aqueous carrier is described second oily components and described second surface activating agent system gross weight 0.5 to 20 times;
(c) mix described first mixture and described second mixture.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US44427303P | 2003-01-31 | 2003-01-31 | |
US60/444,273 | 2003-01-31 | ||
PCT/US2004/002362 WO2004069222A1 (en) | 2003-01-31 | 2004-01-28 | Skin care composition comprising first and second emulsions |
Publications (2)
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CN1744877A CN1744877A (en) | 2006-03-08 |
CN1331459C true CN1331459C (en) | 2007-08-15 |
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CNB2004800030707A Expired - Fee Related CN1331459C (en) | 2003-01-31 | 2004-01-28 | Skin care composition comprising first and second emulsions |
Country Status (7)
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EP (1) | EP1587495A1 (en) |
JP (1) | JP2006515001A (en) |
KR (1) | KR100739388B1 (en) |
CN (1) | CN1331459C (en) |
BR (1) | BRPI0407169A (en) |
CA (1) | CA2513517A1 (en) |
MX (1) | MXPA05008144A (en) |
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US20080102050A1 (en) * | 2006-10-26 | 2008-05-01 | Mingxla Li | Water-based skin care composition with polyalkylsilsesquioxane powder emulsion and method for making the same |
JP2010024176A (en) * | 2008-07-18 | 2010-02-04 | Kao Corp | Wrinkle-improving agent |
US20100124540A1 (en) * | 2008-11-18 | 2010-05-20 | Gordon Gerald Guay | Skin compositions |
CN101889963B (en) * | 2010-08-05 | 2011-09-28 | 上海媚兰生物科技发展有限公司 | Microemulsion composition and preparation method thereof |
JP2013047206A (en) * | 2011-07-25 | 2013-03-07 | Nikko Chemical Co Ltd | Fine emulsion composition containing ultraviolet absorber, and cosmetic |
WO2014098264A1 (en) | 2012-12-21 | 2014-06-26 | L'oreal | Cosmetic composition |
JP2014122193A (en) * | 2012-12-21 | 2014-07-03 | L'oreal Sa | Cosmetic composition comprising oil, nonionic surfactant and vitamin b3 |
CN106074384A (en) * | 2016-08-08 | 2016-11-09 | 甘肃新天马制药股份有限公司 | A kind of pirlimycin micellar preparation and preparation method thereof |
JP7046619B2 (en) * | 2017-03-29 | 2022-04-04 | 株式会社コーセー | Oil-in-water cosmetic composition |
CN108354859A (en) * | 2018-04-28 | 2018-08-03 | 云南省药物研究所 | A kind of preparation method of the anti-acne chemical product of the extract containing trilliaceae and application |
CN112789024B (en) * | 2018-10-03 | 2023-11-17 | 高露洁-棕榄公司 | Emulsion-based personal care compositions and methods therefor |
CN113057898B (en) * | 2021-04-01 | 2022-04-19 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Raspberry type emulsion and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1348353A (en) * | 1999-04-14 | 2002-05-08 | 宝洁公司 | Transparent micro emulsion |
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2004
- 2004-01-28 BR BR0407169-7A patent/BRPI0407169A/en not_active Application Discontinuation
- 2004-01-28 CN CNB2004800030707A patent/CN1331459C/en not_active Expired - Fee Related
- 2004-01-28 MX MXPA05008144A patent/MXPA05008144A/en unknown
- 2004-01-28 EP EP04706036A patent/EP1587495A1/en not_active Withdrawn
- 2004-01-28 CA CA002513517A patent/CA2513517A1/en not_active Abandoned
- 2004-01-28 KR KR1020057013913A patent/KR100739388B1/en not_active IP Right Cessation
- 2004-01-28 JP JP2005518372A patent/JP2006515001A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1348353A (en) * | 1999-04-14 | 2002-05-08 | 宝洁公司 | Transparent micro emulsion |
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Publication number | Publication date |
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CN1744877A (en) | 2006-03-08 |
CA2513517A1 (en) | 2004-08-19 |
KR20050099980A (en) | 2005-10-17 |
KR100739388B1 (en) | 2007-07-13 |
JP2006515001A (en) | 2006-05-18 |
MXPA05008144A (en) | 2006-02-17 |
BRPI0407169A (en) | 2006-02-07 |
EP1587495A1 (en) | 2005-10-26 |
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