CN100536820C - Cosmetic and/or dermatological use of a composition containing at least one oxidation-sensitive hydrophilic active principle stabilized by at least one maleic anhydride copolymer - Google Patents
Cosmetic and/or dermatological use of a composition containing at least one oxidation-sensitive hydrophilic active principle stabilized by at least one maleic anhydride copolymer Download PDFInfo
- Publication number
- CN100536820C CN100536820C CNB031451497A CN03145149A CN100536820C CN 100536820 C CN100536820 C CN 100536820C CN B031451497 A CNB031451497 A CN B031451497A CN 03145149 A CN03145149 A CN 03145149A CN 100536820 C CN100536820 C CN 100536820C
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- copolymer
- purposes
- ascorbic acid
- skin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Cosmetics (AREA)
- Medicinal Preparation (AREA)
Abstract
In a cosmetic composition containing an aqueous phase, a combination of at least one oxidation sensitive hydrophilic active principle (a) and at least one maleic anhydride copolymer (b) are used as depigmenting agents. (a) Is ascorbic acid or its derivatives. (b) Comprises at least one maleic anhydride comonomers and at least one of e.g. vinyl acetate, vinyl alcohol or styrene. In a cosmetic composition containing an aqueous phase, a combination of at least one oxidation sensitive hydrophilic active principle (a) and at least one maleic anhydride copolymer (b) are used as depigmenting agents. (a) Is ascorbic acid or its derivatives. (b) Comprises at least one maleic anhydride comonomers and at least one of vinyl acetate, vinyl alcohol, vinyl alcohol, vinyl pyrrolidone, olefins containing 2-20C atoms or styrene.
Description
Technical field
The present invention relates to accept to contain in the medium cosmetic and/or the dermal application of the compositions of at least a oxidation sensitive hydrophilic active composition and at least a copolymer-maleic anhydride at the physiology that comprises water.
Background technology
Can introduce various active component in the known cosmetic composition to skin and/or the effect of hair generation particular procedure.Yet some in these active component are present in the water-bearing media unstable and contacts the defective of decomposing easily with water, particularly cause owing to oxidative phenomena.Therefore they lose its activity along with the time is rapid, and this unstability is conflicted mutually with the expection effectiveness.
Because its multiple beneficial characteristic, people have attempted to prepare ascorbic acid or vitamin C for a long time.Particularly, ascorbic acid promotes the synthetic of connective tissue and particularly collagen, strengthens the defence of skin histology to external action, and for example ultraviolet radiation and pollution compensates the vitamin E deficiency of skin, makes discolor element and have the effect of free radical resisting of skin.The outstanding material standed for that last two kinds of character make its cosmetics that become resisting age of skin or prevention skin aging or skin use active component.Unfortunately, because its (α-ketolide) chemical constitution, ascorbic acid is extremely sensitive to some extraneous parameter and particularly oxidative phenomena.Therefore in the presence of these parameters, particularly the ascorbic acid of preparation decomposes (Pharm.Acta.Helv., 1969,44,611-667 rapidly along with temperature or some pH condition under the existence of oxygen, light or metal ion; STPPharma, 1985,4,281-286).
So prior art had designed already that some solutions reduce and/or the decomposition of the ascorbic acid that slows down.
Therefore the ascorbic acid (ester of magnesium ascorbyl phosphate or fatty acid and ascorbic acid) of chemical derivative form is used in preparation, but the bioavailability of these derivants very low (J.Am.Acad.Dermatol., 1996,34,29-33).
Utilize particular envelope, the paired compartment under inert atmosphere for example, as disclosed among the patent US 5 935584, perhaps, can improve the unstability of ascorbic acid for oxygen by biphase Emulsion (one in this Emulsion is made up of the dry powder that contains ascorbic acid and it second is the use of liquid phase mutually).This biphase mixing must be carried out (WO 98/43598) in use.These solutions exist not enough on the complexity of cost and production operation and seriously limit its application.
Thereby the another kind of solution that prior art provides is to use the glycol of high concentration or polyhydric alcohol to reduce the dissolubility of oxygen in preparation, protects ascorbic acid (WO 96/24325, EP 0,755 674, US 5 981 578) thus.Described polyhydric alcohol randomly blending in liposome, disclosed as patent US 6 020 367.Yet these solutions exist makes the sticky shortcoming of preparation, and its beauty treatment property is difficult to improve.In addition, the existence of the above-claimed cpd of high concentration may produce the stimulation phenomenon.
Ascorbic acid also can be formulated in the anhydrous medium, and for example polysiloxane-based (US 6 194452), it can form anhydrous barrier around ascorbic acid.The major defect of this solution is to lack pure and fresh sense when coating.
So compositions that particularly need be fit to use at cosmetic field, wherein unsettled hydrophilic active composition is stabilized in oxide isolation, it is comfortable in when coating, can not produce any skin irritation and compatible with the restriction of the industrial implementation of its manufacture process after the coating.
People have understood ascorbic acid to a large amount of collagens that exist in the skin for many years, and the biosynthetic influence of protein macromolecule (Arch.Biochem.Biophys., 152,1972, p.318-328).It works on two levels.At first, as the cofactor of hydroxylase, enzyme participates in the hydroxylating of proline and lysine, and ascorbic acid promotes (Biochemistry, 78 (5), 1981, p2279-2282 of this root phase in the assembling of tropocollagen molecule; TheYale Journal of Biology and Medecine, 58,1985, p.553-559).In addition, it by the amount that increases coding I and III type procollagen mRNA promote collagen biosynthesis (The Journal of Investive Dermatology, 90 (4), 1988, p.420-424).Magnesium ascorbyl phosphate also promote collagen synthetic (Skin Pharmacol., 6,1993, p.65-71).When having these character, handle skin flbroblast with ascorbic acid and can confirm that Dan Baijutang increases (Journal of BiochemicalEngineering, 1991,113).
Summary of the invention
Recently, the application company proves that the ascorbyl magnesium phosphate that adds causes the number showed increased of fibroblast in dot matrix in the culture medium of cultivating reconstruct skin, simultaneously proteinic synthetic (FR-02/01510) of significant stimulation extracellular matrix.The place can observe this phenomenon especially at corium epidermis junction, measures the synthetic stimulation to main composition (IV and VII Collagen Type VI, and laminin) at this place.This phenomenon is the relief that strengthens this contact, promote the result of the adhesive effect of exchange between corium and the epidermis and these two kinds of tissues, and can resist aging adverse effect to these factors thus.
Not only by total content, fibroblasts proliferation ability and the synthesizing activity of raising collagen and the amount of procollagen I and III, and by strengthening the adhesive effect and the effectiveness of corium epidermis junction, ascorbic acid and derivant thereof are particularly suitable for preventing and/or treating the skin sign of endogenous aging (intrinsic ageing).
Target of the present invention provides a kind of oxidation sensitive composition of active components that is selected from ascorbic acid and derivant thereof that contains, it has good beauty treatment character, this relates to touching simultaneously feels and toleration, its preservation need not to be noted especially in time, and it keeps the activity of this active component in preventing and/or treating the aged skin sign of endogenous.
The application company chances on, and copolymer-maleic anhydride can reach above-mentioned target in the use that its aqueous phase contains in the compositions of oxidation sensitive active component (for example ascorbic acid).
In view of the understanding of the application company, this type of contain the unitary polymer of maleic anhydride always never with oxidisability is decomposed responsive hydrophilic active composition and unites and be used to improve its stable purpose.Especially in the situation of ascorbic acid, be like this.
So a theme of the present invention is beauty treatment and/or the dermatosis purposes of compositions in preventing and/or treating the aged skin sign of endogenous, said composition can accept to contain in the medium at least a oxidation sensitive hydrophilic active composition and at least a copolymer-maleic anhydride that is selected from ascorbic acid and its derivant at the physiology that comprises water.Described copolymer is to exist with the amount of enough stablizing this oxidation sensitive hydrophilic active composition.Preferably, this oxidation sensitive active component and copolymer are present in aqueous phase simultaneously.
Another theme of the present invention prevents and/or treats purposes in the cosmetic composition of the aged skin sign of endogenous by at least a oxidation sensitive hydrophilic active composition of ascorbic acid and its derivant and the cooperative programs that at least a copolymer-maleic anhydride is formed of being selected from the conduct that comprises water.
Another aspect of the present invention relates at least a oxidation sensitive hydrophilic active composition that is selected from ascorbic acid and its derivant and at least a copolymer-maleic anhydride comprise water in preparation the purposes of skin composition that is used for preventing and/or treating the aged skin sign of endogenous.
According to the present invention, term " hydrophilic active composition " is interpreted as and is meant under the ambient temperature (25 ℃) that in water dissolubility is at least 0.25% chemical compound.
According to the present invention, term " oxidation sensitive hydrophilic active composition " is interpreted as the active component that is meant any natural or synthetic source that can decompose by oxidation mechanism.This oxidative phenomena can have the existence of multiple reason, particularly oxygen, light or metal ion, high temperature or some pH condition.
In ascorbic acid derivates, can mention, for example but do not hint and be limited to: salt or ester, particularly 5,6-two-O-dimetylsilyl acid ascorbyl ester (ascorbate) (Exsymol sells under reference title PRO-AA), the potassium salt (Senju Pharmaceutical sells under reference title SEPIVITALEPC) of dl-alpha-tocopherol base dl-ascorbyl phosphoric acid, the ascorbyl magnesium phosphate, ascorbyl sodium phosphate (Roche sells for 50 times at reference title Stary-C) and ascorbyl glucosides (Hayashibara sale).
One preferred especially aspect, described oxidation sensitive hydrophilic active composition is an ascorbic acid.
According to the present invention, term " copolymer-maleic anhydride " is interpreted as and is meant and anyly is selected from vinylacetate, vinyl alcohol, vinylpyrrolidone, contains the polymer that the copolyreaction of the alkene (for example vaccenic acid, ethylene, isobutene., diisobutylene or isooctene) of 2-20 carbon atom and cinnamic comonomer obtains, the randomly part or all of hydrolysis of maleic anhydride comonomer by one or more maleic anhydride comonomers and one or more.The preferred hydrophilic polymer that uses that is to say that dissolubility is more than or equal to the polymer of 2g/l in water.
More be particularly suitable for implementing copolymer of the present invention and be the copolymer that obtains by the unitary copolyreaction of one or more maleic anhydrides and wherein this maleic anhydride unit be hydrolysed form and the preferably form of basic salt, for example form of ammonium, sodium, potassium or lithium salts.
Of the present invention one preferred aspect in, described polymer has 0.1-1, the more preferably unitary molfraction of the maleic anhydride of 0.4-0.9.
According to a preferred aspect of the present invention, the unitary mol ratio of maleic anhydride that is equivalent to described oxidation sensitive hydrophilic active composition is 0.005-10 and preferred 0.01-1.
The weight-average molar mass of copolymer-maleic anhydride is preferably 1000-500000 and preferred 1000-50000.
The preferred copolymer that uses styrene and maleic anhydride to form with 50/50 ratio.
Can use, for example, Atofina is with the reference title
The form of phenylethylene/maleic anhydride (50/50) copolymer 30% ammonium salt in water of selling, or Atofina is with the reference title
The form of phenylethylene/maleic anhydride (50/50) copolymer 40% sodium salt in water of selling.
Described copolymer exists with the amount that is enough to produce Expected Results in the present composition, that is to say, is enough to stablize the amount of oxidation sensitive hydrophilic active composition.Preferably, this copolymer is to exist in the concentration with respect to water gross weight 0.1-40 weight %, and particularly exists in the concentration with respect to the 0.1-10 weight % of water gross weight.
The compositions that the present invention uses is used for local coating at skin and/or its machining surface bulk-growth thing, therefore comprising physiology can accept medium, that is to say and the compatible medium of skin histology (for example skin, scalp, eyelashes, eyebrow, hair, fingernail and mucosa).This physiology can be accepted medium and can be more specifically can accept organic solvent by water and optional physiology and form, described physiology can be accepted organic solvent and be selected from, for example, contain the lower alcohol of a 1-8 carbon atom and particularly 1-6 carbon atom, for example ethanol, isopropyl alcohol, propanol or butanols; Polyethylene Glycol with 6-80 ethylene oxide unit; Or polyhydric alcohol, for example propylene glycol, isoamyl glycol, butanediol, glycerol or Sorbitol.
When described physiology can be accepted medium and is aqueous medium, generally has the pH with skin-compatible, preferred 3-9 and more preferably 3.5-7.5.
Compositions of the present invention can provide any pharmaceutical dosage form that is usually used in local coating, and the particularly form of water or water/alcoholic solution, oil-in-water (O/W) or Water-In-Oil (W/O) or multiple (triple: W/O/W or the O/W/O) form of Emulsion, the form of hydrogel or utilize the form of the fat of bead in the dispersion of aqueous phase, these beads can be the nanoparticles of polymer, for example nanosphere or Nano capsule, the perhaps lipid capsule of ion and/or nonionic (liposome, niosome or elaiosome).These compositionss prepare according to conventional method.
In addition, the compositions of the present invention's use can be the different fluid of degree and can have the apparent of white or coloured cream, ointment, milk, lotion, serosity, paste or foam.They can randomly be coated on the skin with aerosol form.They also can provide with solid form, for example Bang form.
When the compositions of the present invention's use contained oil phase, the latter was preferably contained at least a oil.Can contain other fatty material in addition.
As operable oil in the present composition, can mention, for example:
The hydrocarbon ils of-animal origin, for example perhydro Squalene;
The hydrocarbon ils of-plant origin, liquid glycerin three esters that for example contain the fatty acid of 4-10 carbon atom, for example enanthic acid or sad triglyceride, perhaps, for example Helianthi, corn, Semen sojae atricolor, calabash, Semen Vitis viniferae, Semen Sesami, hazelnut, Fructus Pruni, macadamia, arara, Semen Ricini or American Avocado Tree oil, the triglyceride of caprylic/capric, for example those or the Dynamit Nobel that sell of St é arineries Dubois sell with Miglyol 810,812 and 818 those, Jojoba oil, or candlenut oil (karite buttel oil).
-synthetic ester and ether, particularly fatty acid, formula R for example
1COOR
2And R
1OR
2Oil, R wherein
1Expression contains the residue and the R of the fatty acid of 8-29 carbon atom
2Expression contains the side chain or the non-side chain hydrocarbon chain of 3-30 carbon atom, for example purcellin oil, isononyl isononanoate, isopropyl myristate, Palmic acid 2-Octyl Nitrite, stearic acid 2-octyl group dodecyl ester, erucic acid 2-octyl group dodecyl ester or isostearic acid iso stearyl ester; The hydroxylating ester, lactic acid iso stearyl ester for example, heptanoate, caprylate or the decanoin of octyl hydroxystearate, hydroxy stearic acid octyl group dodecyl ester, malic acid two iso stearyl esters, citric acid three different cetyl esters or aliphatic alcohol; Polyol ester, propylene glycol dicaprylate for example, neopentyl glycol two heptanoates and diethylene glycol two different pelargonates; And pentaerythritol ester, for example pentaerythritol tetraoctyl stearate.
The straight or branched hydrocarbon in-inorganic or synthetic source, for example volatility or non-volatile liquid paraffin and derivant thereof, liquid petroleum ether, poly decene or Parleam, for example parleam oil.
-have the aliphatic alcohol of 8-26 carbon atom, for example spermol, stearyl alcohol and its mixture (cetearyl alcohol), octyldodecanol, 2-butyl capryl alcohol, 2-hexyldecanol, 2-undecyl pentadecanol, oleyl alcohol or an inferior oleyl alcohol.
-part hydrocarbonaceous and/or contain the fluorinated oil of siloxanes, for example document JP-A-2-295912 those disclosed.
-polysiloxane oil for example contains the volatility or the non-volatile polymethyl siloxane (PDMS) of linearity or cyclosiloxane chain, and it is liquid or pasty state, particularly Cyclomethicone (Cyclomethicone) at ambient temperature, for example encircles six siloxanes; Contain hang alkyl, alkoxyl or phenyl or alkyl, alkoxyl or phenyl be positioned at the polydimethylsiloxane of this siloxane chain end, described group has 2-24 carbon atom; Or phenylating type siloxane, for example poly-trimethicone class of phenyl, phenyl polydimethylsiloxane class, phenyl trimethyl first siloxy group diphenyl siloxane class, diphenyl polydimethylsiloxane class, diphenyl methyl diphenyl disiloxane class, (2-phenylethyl) trimethyl first siloxy group esters of silicon acis and PSI class;
-its mixture.
Term " hydrocarbon ils " is interpreted as and is meant, in above-mentioned oil, any mainly contain carbon and hydrogen atom and randomly contain ester, ether, fluoridize, the oil of carboxylic acid and/or alcohol radical.
Other fatty material that can exist in oil phase is for example, to contain the fatty acid of 8-30 carbon atom, for example stearic acid, lauric acid, Palmic acid and oleic acid; Wax, for example lanoline, Cera Flava, Brazil wax or candelilla wax, paraffin or montan wax or microwax, ceresin or ceresine; Or synthetic wax, for example Tissuemat E or Fischer-Tropsch wax; Silicone resin, for example trifluoromethyl C
1-4Alkyl polydimethylsiloxane and trifluoro propyl polydimethylsiloxane; And silicone elastomer, the product that product that the product sold down in title " KSG " of Shin-Etsu for example, DowCorning are sold down at title " Trefil ", " BY29 " or " EPSX " or GrantIndustries sell down in title " Gransil ".
One of ordinary skill in the art can select these fatty materials in several ways, thereby preparation has expection character, for example compositions of denseness or texture.
According to a specific embodiment of the present invention, compositions of the present invention is Water-In-Oil (W/O) or oil-in-water (W/O) Emulsion.The ratio of this oil phase in Emulsion can be the 5-80 weight % and the preferred 5-50 weight % of said composition gross weight.
Described Emulsion generally contain at least a be selected from both sexes, anion, cation or nonionic emulsifier single with or the emulsifying agent that uses with mixture, and randomly contain coemulsifier.(W/O or O/W) suitably selects emulsifying agent according to the Emulsion that will obtain.Emulsifying agent and coemulsifier generally exist in the ratio of compositions with said composition gross weight 0.3-30 weight % and preferred 0.5-20 weight %.
For W/O Emulsion, can mention as emulsifying agent, for example, dimethicone copolyol, for example Dow Corning is at the following Cyclomethicone of selling of title " DC 5225 C " and the mixture of dimethicone copolyol, with the alkyl dimethicone copolyol, for example the lauryl polymethyl siloxane copolyol of Dow Corning sale under title " Dow Corning 5200 formulation auxiliary agents " and Goldschmidt are with title Abil EM 90
RThe cetyl poly dimethyl copolyol of selling.Surfactant as W/O Emulsion, also can use the linked solid organopolysiloxane elastomer that contains at least a oxidation alkylene group, those that obtain according to the embodiment of the method for the embodiment 3,4 of document US-A-5 412 004 and 8 and document US-A-5 811487 for example, particularly the product of the embodiment 3 of patent US-A-5 412 004 (synthetic embodiment) and for example Shin Etsu sell for 21 times at reference title KSG those.
For O/W Emulsion, can mention that as emulsifying agent for example, nonionic emulsifier is as the fatty acid of oxidation alkylene (more especially polyoxyethylene alkylene) and the ester of glycerol; The ester of the oxidation alkylene of fatty acid and sorbitan; Oxidation of fatty acids alkylene (ethylene oxideization and/or propylene oxideization) ester; Oxidation alkylene (ethylene oxideization and/or the propylene oxideization) ester of aliphatic alcohol; Sugar ester, for example stearic acid sucrose ester; With their mixture, the mixture of stearic acid glyceryl ester and PEG-40 stearate for example.
In known manner, cosmetic of the present invention or skin composition also can contain adjuvant commonly used in cosmetics or the skin field, for example hydrophilic or lipotropy gellant, antiseptic, solvent, spice, filler, UV sunscreen, antibacterial, abnormal flavour absorbent, coloring material, plant extract or salt.The content of these multiple adjuvant is those that used always in the field that is considered, for example accounts for the 0.01-20% of said composition gross weight.According to its essence, these adjuvant can be incorporated in fatty phase, water and/or the lipid ball.
As operable filler in compositions of the present invention, can mention, for example, pigment, silicon dioxide powder; Talcum; Those that the microgranule of polyamide and particularly Atochem sell with title Orgasol; The polyethylene powder; Based on the microsphere of acrylic copolymer, for example by those of selling with title Polytrap by DowCorning of making of ethylene glycol dimethacrylate/lauryl methyl acrylate copolymer; Expanding powder, for example tiny balloon and particularly Kemanord Plast microsphere that sell with title Expancel or that Matsumoto sells with title Micropearl F 80 ED; The polyorganosiloxane resin microballon, for example ToshibaSilicone sell with title Tospearl those; With their mixture.These filleies can exist with the amount of said composition gross weight 0-20 weight % and 1-10 weight %.
According to one preferred embodiment, compositions of the present invention can also contain at least a organic preventing light agent and/or at least a inorganic preventing light agent, they have activity (absorbent) at UV-A and/or UV-B district, its water soluble or fat, perhaps be insoluble to cosmetics solvent commonly used, and it is selected from following reagent, represents with its INCI name below:
Para-amino benzoic acid (PABA) derivant, particularly PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA (specifically selling with title " Escalol 507 ") by ISP, glyceryl PABA or PEC-25PABA (selling with title " Uvinul P25 ") by BASF.
Salicyclic acid derivatives, homosalate (homosalate) (Rona/EMIndustries with title " Eusolex HMS " sell) particularly, ethylhexyl salicylate (Haarmann and Reimer sell with title " Neo Heliopan OS "), dipropylene glycol salicylate (Scher sells with title " Dipsal ") and TEA salicylate (Haarmann and Reimer sell with title " Neo Heliopan TS ").
Dibenzoyl methane derivant, particularly PAROSOL 1789 (selling down in trade name " Parsol 1789 " by Hoffmann-LaRoche particularly), or isopropyl diphenyl formoxyl methane.
Cinnamic acid derivative, ethylhexyl methoxy cinnamate (Hoffmann-LaRoche trade name " Parsol MCX " sell down) particularly, the methoxy cinnamic acid isopropyl ester, methoxy cinnamic acid isopentyl vinegar (Haarmann and Reimer sell down in trade name " Neo Heliopan E1000 "), cinoxate, methoxy cinnamic acid DEA ester, cinnamic acid diisopropyl methyl ester, or glyceryl ethylhexoate dimethoxy-cinnamic acid ester
β, β-diphenylacrylate, particularly octocrylene (BASF specifically sells down in trade name " Uvinul N539 ") or etocrylene (BASF specifically sells down in trade name " Uvinul N35 "),
Benzophenone; benzophenone-1 particularly; (BASF sells down in trade name " Uvinul 400 "); benzophenone-2; (BASF sells down in trade name " Uvinul D50 "); benzophenone-3 or oxybenzone; (Oxybenzone); (BASF sells down in trade name " Uvinul M40 "); benzophenone-6; (Norquay sells down in trade name " Helisorb 11 "); benzophenone-8; (American Cyanamid sells down in trade name " Spectra-Sorb UV-24 "); benzophenone-12; or 2-; the just own ester of (4-diethylamino-2-hydroxy benzoyl) benzoic acid
The benzylidene camphor derivant, 3-benzylidene camphor (Chimex with title " Mexoryl SD " make) particularly, 4 methyl benzylidene camphor (Merck sells with title " Eusolex6300 "), or polyacrylamide base methyl benzylidene camphor (Chimex makes with title " Mesoryl SW ")
Pyrrolotriazine derivatives, particularly aniso-triazine (anisotriazine) (CibaSpecialty Chemicals sells down in trade name " Tinosorb S "), ethylhexyl triazinone (BASF sells down in trade name " Uvinul T150 " particularly), diethylhexyl amide-based small triazinone (Sigma 3V sells down in trade name " Uvasorb HEB ") or 2,4,6-three (diisobutyl-4 '-amino-toluenyl malonic ester)-s-triazine
Benzotriazole derivatives, particularly drometrizole cyclotrisiloxane (RhodiaChimie trade name " Silatrizole " sell down) or Tinuvin 360 (solid form or the micronization form of Ciba Specialty Chemicals in trade name " Tinosorb M " aqueous dispersion that Fairmount Chemical sells down in trade name " Mixxim BB/100 ")
Anthranilic acid derivative, particularly ortho-aminobenzoic acid
Base ester (Haarmann and Reimer sell down in trade name " Neo Heliopan MA "),
Imdazole derivatives, particularly Octyl Nitrite dimethoxybenzylidenegroup group dioxo imidazolylpropionic acid ester.
The toluenyl malonic ester derivant particularly contains the polysiloxane (Hoffmann-Laroche trade name " Parsol SLX " sell down) of benzal malonic acid functional group,
With their mixture.
Inorganic preventing light agent is selected from by coating or the pigment or the nano dye (particle mean size of primary fine particles: generally be 5nm-100nm that form of coating metal-oxide not, preferred 10nm-50nm), titanium oxide (amorphous or crystal for example, rutile and/or anatase form), ferrum oxide, zinc oxide, zirconium oxide or Cs2O nano dye, they itself all are known UV preventing light agents; Or conventional coating materials, for example aluminium oxide and/or aluminium stearate; By coating or not the nano dye that forms of coating metal-oxide be specifically to be disclosed among patent application EP 518 772 and the EP 518 773.
More particularly preferred organic preventing light agent is selected from ethylhexyl salicylate, ethylhexyl methoxy cinnamate, octocrylene, benzophenone-3,4 methyl benzylidene camphor, 2,4,6-three-(diisobutyl 4 '-amino toluenyl malonic ester)-s-triazine, aniso-triazine, ethylhexyl triazinone, diethylhexyl butyramide triazinone, methylene dibenzo triazolyl tetramethyl butyl phenol, drometrizole cyclotrisiloxane and their mixture.
Preventing light agent in the present composition generally the ratio with the 0.1-20 weight % of said composition gross weight have and the 0.2-15 weight % of said composition gross weight preferably.
Of the present invention another preferred aspect, compositions for use can also contain at least a chafe macromole in addition or prevent other active component of its decomposition and/or the reagent of the differentiation of a kind of propagation that promotes fibroblast or horn cell and/or horn cell.
Promoting the skin macromole or preventing can mention in the active component of its decomposition:
-act on synthetic those active component of collagen, for example extract of Centella asiatica; Asiaticoside and derivant; Ascorbic acid or vitamin C and derivant thereof; Synthetic peptide, iamine for example, the palmityl oligopeptide that biological peptide CL or Sederma sell; By the peptide of plant extract, for example Coletica is in trade name
The soya hydrolysate of selling; And phytohormone, for example auxin;
-or act on synthetic those active component of elastin laminin, for example LSN is in trade name
The extract of the saccharomyces cerevisiae of following sale; Secma is in trade name
The extract of the alga Macrocystis pyrifera of following sale;
-or act on synthetic those active component of glucosaminoglycan, for example Brooks is at trade name Biomin
The ordinary Lactobacillus of selling (Lactobacillusvulgaris) acts on the product of the milk fermentation of stimulating the secretion of milk; Alban M ü ller is in trade name
The extract of the brown alga Padina pavonica that sells; Specifically by Silab in trade name
Down or LSN in trade name
The extract of the saccharomyces cerevisiae of following sale;
-or act on synthetic those active component of fibronectin, for example Seporga is in trade name
The extract of the Salina zooplankton of following sale; Specifically by AlbanM ü ller with trade name
The yeast extract that provides; With by Sederma with trade name
The Matrixyl of selling;
-or act on inhibiting those active component of metalloproteases (MMP), MMP1,2,3 or 9 more specifically for example.Can mention: biostearin (retinoids) and derivant; Oligopeptide and lipopeptid, lipoamino acid; Coletica is in trade name
The Fructus Hordei Germinatus extract of following sale; Fructus Vaccinii Bracteati or Herba Rosmarini Officinalis extract; Lycopene; Or osajin, its derivant or contain the extract of their plant extract, particularly bean (for example Ichimaru Pharcos is at trade name Flavos terone
Following sale), or the extract of Trifolium pratense, the extract of Caulis et Folium Lini, the extract of kakkon or the extract of Salvia farinacea.
-or act on the inhibitory action of serine protease, for example leukocyte elastase or cathepsin G.Can mention: LSN is with trade name
The peptide extract of pulse family (Semen Pisi sativi (the Pisumsativum)) seed of selling; Heparinoid (heparinoids); With false dipeptide.
In the active component that promotes epidermis macromole (for example filaggrin and keratin), specifically can mention: Silab is in trade name
The extract of the lupin of following sale; Gattefoss é is in trade name
The extract of the Fagus sinensis Oliv. Fagussylvatica bud of following sale; With Seporga in trade name
The extract of the Salinazooplankton of following sale.
The reagent of operable promotion fibroblast proliferation in the present composition for example, is selected from vegetable protein or polypeptide, and (for example LSN is at trade name Eleseryl SH-VEG for the extract of extract, particularly Semen sojae atricolor
The soybean extract of following sale or Silab are in trade name
The soybean extract of following sale); And phytohormone, for example gibberellins and chtokinin.
The reagent of operable promotion angle albuminous cell propagation specifically is biostearin in the present composition, and for example retinol and ester thereof comprise the retinyl cetylate; Phloroglucinol; The extract of the Semen Juglandis powder that Gattefoss é sells; The extract of the Rhizoma Solani tuber osi of selling with Sederma.
Promote the reagent of angle albuminous cell differentiation to comprise for example inorganic substances, for example calcium; Silab is in trade name
The extract of the lupin of following sale; β-paddy steroid base (sitosteryl) sodium sulfate, Seporga is in trade name
The following sale; With Solabia in trade name
The extract of the corn of following sale.
Compositions of the present invention can be coated in skin or mucosa.Therefore can in the cosmetic treatments method that to prevent and/or treat the aged skin sign of endogenous be purpose, use, comprise compositions of the present invention is coated in skin or mucosa.
The specific embodiment
The following example illustrates the present invention but does not play the qualification effect.According to situation, chemical compound is introduced according to chemical name or according to CTFA (International Cosmetic IngredientDictionary and Handbook) title.
Embodiment
Embodiment 1: the preservation test of acceleration
The purpose of this test is the decomposition of research oxidation sensitive hydrophilic active composition after preserving 2 months under 45 ℃.Prepare shown in multiple solution and its table composed as follows:
Table I
| Compositions (in the water) | Ascorbic acid | Polymer 1 | Polymer 2 |
| Solution A (contrast 1) | 15％ | - | - |
| Solution B | 15％ | 1％ | - |
| Solution C | 15％ | - | 1％ |
| Solution D (contrast 2) | 5％ | - | - |
| Solution E | 5％ | 1％ | - |
| Solution F | 5％ | - | 1％ |
Complete soln transfers to pH6 with 8.9mol/l KOH.
The percentage ratio of polymer is in active substance.
Polymer 1: phenylethylene/maleic anhydride (50/50) copolymer, be the form of 30% ammonium salt in water, by Atofina in the reference title
The following sale.
Polymer 2: phenylethylene/maleic anhydride (50/50) copolymer is the form of sodium salt, by Atofina in the reference title
The following sale.
The degree of decomposition of measuring is represented with following ratio:
(C
0-C
2 months)/C
0
And the C that the ascorbic acid when t=0 is arranged
0The C of concentration and the ascorbic acid in the time of t=2 month
2 monthsConcentration is under the described condition shown in as above showing.
The concentration of ascorbic acid is by HPLC technical measurement (LaChrom Merck system).Analysis condition is as described below:
Post: Lichrosphere100 RP18 (250mm)
Eluant: 0.1M phosphate buffer, pH2.1
Flow: 1ml/ minute
Under 257nm, detect
It is 0.05-1mg/ml that diluted sample makes the concentration of ascorbic acid.
Shown in the following Table II of gained result:
Table II:
Find by Table II, compared with the control, in the presence of polymer 1 of the present invention and polymer 2, be improved in the stability of ascorbic acid under 5 or 15% the concentration, in addition also like this in the presence of air oxygen.Because described polymer is hydrophilic, is enough to they are joined in the aqueous ascorbic acid to stablize ascorbic acid.
Embodiment 2:
The adding of cooperative programs of the present invention is closed tenascin and collagen VII's The observation of the influence that becomes
Present embodiment has been described the proteic immunohistochemistry labelling method that utilizes tenascin and collagen VII by the microscopic examination skin biopsy, and the adding of cooperative programs of the present invention (containing ascorbic acid and copolymer of the present invention) is to the influence of reconstruct skin.
1. the preparation of reconstruct skin
The reconstruct skin that uses is according to described schemes such as Asselineau (Models inDermato.Published by Loire and Maibach, 1987, Vol III, 1-7) preparation.Improvement to this scheme is as described below:
-normal adult human skin fibroblast with whenever the amount corium 10
6The ratio of individual cell is used;
The inoculation of-angle albuminous cell is to carry out with the ratio that each diameter 1.5cm encircles 50000 cells.The angle albuminous cell that uses derives from same donor and be in the 1st in the seeded process of corium equivalent and goes down to posterity;
The persistent period of-dipping phase is 7 days;
The persistent period of-emersion phase (emergence phase) is 7 days.
2. the adding of cooperative programs of the present invention
The final replacing of the medium of dipping phase is to carry out in the presence of the cooperative programs of the form ascorbic acid of 40% sodium salt in water and phenylethylene/maleic anhydride copolymer.Culture sealing subsequently (mounted) is used for the emersion phase in grid, and this time interim, all replacings of medium (per 2 days) are to carry out in the presence of above-mentioned cooperative programs.
3.a. the analysis of collagen VII
When the end of emersion phase, analyze reconstruct skin.Systematicness preparation check sample and parallel analysis.
Sampling is also freezing in liquid nitrogen.By Tissue Teck preparation section.Detect the collagen of VII type by immunohistochemistry with the frozen section of thickness 5 μ m.(USA) (the anti-mouse immuning ball protein of the bonded rabbit of FITC, DAKO Denmark) carries out conventional IiT with the link coupled conjugate of fluorescein for LH7.2, Chemicon International Inc. with antigen VII monoclonal antibody.
3.b.tenascin analysis
The scheme of using is the scheme described in the above-mentioned 3.a, just in this case, (TN2 is Chemicon) with the link coupled conjugate of fluorescein (the anti-mouse immuning ball protein of the bonded rabbit of FITC with anti-tenascin monoclonal antibody, DAKO Denmark) detects tenascin.
4. observe
When using microscopic examination, the intensity of the phosphor region corresponding with corium epidermis junction and thickness are for having added ascorbic acid and much bigger with the sample of the cooperative programs of the phenylethylene/maleic anhydride copolymer of 40% sodium-salt form in the water.All observed from the analysis of collagen VII and the analysis of tenascin.
Also observe fibroblastic increase in the dot matrix of arranged vertical more with substrate angle albuminous cell.
Embodiment 3:O/W anti-aging cream
Prepare following compositions in mode conventional concerning one of ordinary skill in the art.
Phase A
Water 18.33g
Glycerol 3g
Phase B
Sorbitan tristearate 0.68g
PEG-40 stearate 1.5g
Spermol 3g
Glyceryl stearate 2.25g
Myristic acid myristyl ester 1.5g
Ethylhexyl palmitate 1.5g
Parleam 2.5g
The sub-fat of sal (Shorea robusta seed butter) 1.5g
Butyrospermum (butyrospermum parkii) (shea fat) fruit 0.5g
D5 7.5g
Phenyl phenol 1g
Phase C
Water 43.94g
Ascorbic acid 5g
Potassium hydroxide (50% solution) 3g
Phenylethylene/maleic anhydride copolymer, 30% ammonium salt 3.3g in water
(
，Atofina)
Obtain dense and softish cream, it can be to the aging-resistant sign, and wherein ascorbic acid has good stable for the time.
Embodiment 4:O/W anti-aging cream
Prepare following compositions in mode conventional concerning one of ordinary skill in the art.
Phase A
Tetramethylolmethane tetraethyl alkyl caproate 6g
Polypropylene acyl group dimethyl taurine ammonium 0.6g
Water 14.95g
Methyl parahydroxybenzoate 0.2g
Glycerol 3g
Phenyl phenol 0.5g
Phase B
PTFE 4g
Cetearyl alcohol (with) cetearyl alcohol ether (ceteareth)-30 1.5g
Octocrylene 7g
PAROSOL 1789 2g
Ethylhexyl salicylate 5g
Glycolipid 0.5g
Propyl p-hydroxybenzoate 0.1g
Vaseline 1g
Polysorbate 60 1g
Spermol 0.5g
Phase C
Capryl alcohol 0.15g
Glyceryl starch 2g
Phase D
Water 41g
Ascorbic acid 5g
Potassium hydroxide (50% solution) 3g
Styrene maleic anhydride copolymer, 40% sodium salt 2.5g in the water
(
，Atofina)
Obtain soft and fresh cream in when coating, this cream can be crease-resistant with microgroove and wherein ascorbic acid have good stable.
Claims (13)
1. the cooperative programs of being made up of ascorbic acid and maleic anhydride and styrol copolymer are used for preventing and/or treating the purposes of the cosmetic composition that contains water of the aged skin sign of endogenous in preparation.
2. ascorbic acid and maleic anhydride and styrol copolymer contain the purposes of skin composition that is used for preventing and/or treating the aged skin sign of endogenous of water in preparation.
3. claim 1 or 2 purposes is characterized in that the maleic anhydride unit of copolymer is a hydrolysed form.
4. the purposes of claim 3, the maleic anhydride unit that it is characterized in that copolymer is the form of basic salt.
5. claim 1 or 2 purposes is characterized in that ascorbic acid and described copolymer are simultaneously at aqueous phase.
6. claim 1 or 2 purposes is characterized in that described copolymer has the unitary molfraction of maleic anhydride of 0.4-0.9.
7. claim 1 or 2 purposes is characterized in that this copolymer is styrene and the maleic anhydride copolymer with 50/50 ratio.
8. claim 1 or 2 purposes is characterized in that this copolymer is styrene and the copolymer-maleic anhydride with ammonium salt, sodium salt, potassium salt or lithium salt form.
9. claim 1 or 2 purposes, the unitary mol ratio of maleic anhydride that it is characterized in that being equivalent to ascorbic acid is 0.005-10.
10. the purposes of claim 9, the unitary mol ratio of maleic anhydride that it is characterized in that being equivalent to ascorbic acid is 0.01-1.
11. the purposes of claim 1 or 2 is characterized in that this copolymer exists with the concentration of the 0.1-40 weight % of water.
12. the purposes of claim 11 is characterized in that this copolymer exists with the concentration of the 0.1-10 weight % of water.
13. the purposes of claim 1 or 2 is characterized in that said composition contains at least a promotion skin macromole in addition or prevents the active component of its decomposition and/or promote fibroblast or the reagent of the propagation of angle albuminous cell and/or angle albuminous cell differentiation.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0207638 | 2002-06-20 | ||
| FR02/07638 | 2002-06-20 | ||
| US39425502P | 2002-07-09 | 2002-07-09 | |
| US60/394255 | 2002-07-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1500474A CN1500474A (en) | 2004-06-02 |
| CN100536820C true CN100536820C (en) | 2009-09-09 |
Family
ID=34276774
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031451497A Expired - Lifetime CN100536820C (en) | 2002-06-20 | 2003-06-19 | Cosmetic and/or dermatological use of a composition containing at least one oxidation-sensitive hydrophilic active principle stabilized by at least one maleic anhydride copolymer |
| CN 03149435 Expired - Fee Related CN1287763C (en) | 2002-06-20 | 2003-06-19 | Application of compound containing easily-oxidable hydrophilic active component and stabilized by maleic anhydride copolymer in face beautifying and/or dermological field |
| CN 03145148 Expired - Fee Related CN1240368C (en) | 2002-06-20 | 2003-06-19 | Cosmetic and/or skin applied of composition containing easy oxidation hydrophilic active component stablized by maleic anhydride copolymer |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03149435 Expired - Fee Related CN1287763C (en) | 2002-06-20 | 2003-06-19 | Application of compound containing easily-oxidable hydrophilic active component and stabilized by maleic anhydride copolymer in face beautifying and/or dermological field |
| CN 03145148 Expired - Fee Related CN1240368C (en) | 2002-06-20 | 2003-06-19 | Cosmetic and/or skin applied of composition containing easy oxidation hydrophilic active component stablized by maleic anhydride copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN100536820C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3045363B1 (en) * | 2015-12-22 | 2018-01-26 | L'oreal | PROCESS FOR TREATING KERATIN FIBERS WITH AN ETHYLENE POLYMER WITH A MALEIC ANHYDRIDE GROUP AND A POLYOL |
| FR3048610B1 (en) * | 2016-03-08 | 2020-03-27 | ISP Investments LLC. | ACTIVE FAT AND / OR ACTIVATED WAX USING THE NON-WATER-SOLUBLE FRACTION OF CARICA PAPAYA SUC |
| US20200383887A1 (en) * | 2019-06-04 | 2020-12-10 | L'oreal | Oxygenate skin treatment system |
| KR20230074062A (en) * | 2020-07-31 | 2023-05-26 | 로레알 | Composition for keratin care containing Sphingomonas fermented extract |
-
2003
- 2003-06-19 CN CNB031451497A patent/CN100536820C/en not_active Expired - Lifetime
- 2003-06-19 CN CN 03149435 patent/CN1287763C/en not_active Expired - Fee Related
- 2003-06-19 CN CN 03145148 patent/CN1240368C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1240368C (en) | 2006-02-08 |
| CN1535670A (en) | 2004-10-13 |
| CN1496733A (en) | 2004-05-19 |
| CN1500474A (en) | 2004-06-02 |
| CN1287763C (en) | 2006-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11596813B2 (en) | Skin care formulations | |
| JP3950086B2 (en) | Use of a composition comprising at least one oxidation-sensitive hydrophilic active ingredient stabilized by at least one maleic anhydride copolymer for cosmetic and / or dermatological use | |
| JP3606857B2 (en) | Cosmetic and / or dermatological use of a composition comprising at least one oxidation-sensitive hydrophilic active agent stabilized by at least one N-vinylimidazole polymer or copolymer | |
| KR102044562B1 (en) | cosmetic compositions | |
| US20050147572A1 (en) | Cosmetic composition containing a protein and an enzyme inhibitor | |
| CN111671716A (en) | Antioxidant skin color brightening composition and application thereof in cosmetics | |
| CN101766550A (en) | Combination of monosaccharides and ascorbic acid and its use in cosmetic | |
| JP3878624B2 (en) | Cosmetic and / or dermatological composition comprising an ascorbic acid derivative stabilized by at least one amphiphilic polymer derived from polyisobutylene | |
| CN100536820C (en) | Cosmetic and/or dermatological use of a composition containing at least one oxidation-sensitive hydrophilic active principle stabilized by at least one maleic anhydride copolymer | |
| WO2007108438A1 (en) | External composition for promoting of glutathione production and relevant method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20090909 |
|
| CX01 | Expiry of patent term |