Patent Application
20100172858
The present invention relates to a cosmetic composition for treating keratinous fibres, in particular human keratinous fibres such as the hair, comprising at least one polymer obtained from dielectrophilic monomers, to use of this composition for treating hair and also to a treatment method that uses it.
The hair is generally damaged and weakened by the action of external atmospheric agents such as the light and bad weather, and by mechanical or chemical treatments such as brushing, combing, bleaching, permanent waves and/or colouring. As a result the hair is often difficult to control, in particular it is difficult to untangle or style, and the hair, even thick hair, holds an attractive style with difficulty due to the fact that the hair lacks vitality, volume and liveliness.
Thus, to overcome this, it is now normal to use styling products which make it possible to condition the hair by giving it, in particular, body, bulk or volume.
These styling products are generally cosmetic hair compositions comprising one or more polymers which have a high affinity for the hair and which usually have the role of forming a film at its surface with a view to modifying its surface properties, especially for conditioning it.
One drawback linked to the use of these hair compositions lies in the fact that the cosmetic effects conferred by such compositions have a tendency to disappear, especially after the first shampooing.
Furthermore, it is known from document FR 2 833 489 to use electrophilic monomers that polymerize by an anionic route directly at the surface of the hair in the presence of a nucleophilic agent such as hydroxide ions (OH−) contained in water having a neutral pH. Thus, once deposited on the hair, these monomers form a polymer that results in a satisfactory sheathing.
However, the sheathing obtained from these compositions does not have a sufficient resistance relative to the various external attacks which the hair may undergo. Furthermore, the use of monomers to be polymerized on the hair for the purposes of polymerization is not always practical to implement and is not easily reproducible in terms of final properties of the polymer formed.
There is therefore a real need to find cosmetic compositions, especially for conditioning hair, which withstand shampooing and external attacks while keeping good cosmetic properties, that is to say giving the hair body, bulk or volume and this in a long-lasting manner.
Thus, one subject of the present invention is a cosmetic composition for treating keratinous fibres, in particular human keratinous fibres such as the hair, which comprises at least one polymer soluble in the composition and obtained from dielectrophilic monomers.
The composition of the invention makes it possible to give the hair body, bulk or volume in a long-lasting fashion.
Such a composition makes it possible, in particular, to obtain conditioning of the hair that has good resistance with respect to the various external attacks, especially with respect to fatty substances, such as sebum, and with respect to successive shampooing.
Another subject of the invention is a method for the cosmetic treatment of keratinous fibres that uses the cosmetic composition according to the invention.
Another subject of the present invention consists of use of the cosmetic composition for treating keratinous fibres, especially conditioning and/or dyeing keratinous fibres.
The polymer used in the present invention may be obtained from dielectrophilic monomers known in the art and according to polymerization processes that are themselves known from the prior art.
By way of dielectrophilic monomers, mention may especially be made of the electrophilic monomers of formula (I) below:
in which:
The expression “electrophilic (or electron-withdrawing or inductive-withdrawing (—I)) group” is understood to mean any group that is more electronegative than carbon. Reference may be made to the work P R Wells Prog. Phys. Org. Chem., Vol. 6, 111 (1968).
The expression “group that is not very or not at all electrophilic” is understood to mean any group having an electronegativity that is less than or equal to that of carbon.
The alkenyl or alkynyl groups preferably have 2 to 20 carbon atoms, better still 2 to 10 carbon atoms.
As a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group preferably having from 1 to 20 carbon atoms, mention may especially be made of linear or branched alkyl, alkenyl or alkynyl groups, such as methyl, ethyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, octyl, butenyl or butynyl; cycloalkyl or aromatic groups.
As a substituted hydrocarbon-based group, mention may be made, for example, of hydroxyalkyl or polyhaloalkyl groups.
As examples of unmodified polyorganosiloxanes, mention may especially be made of polyalkylsiloxanes such as polydimethylsiloxanes, polyarylsiloxanes such as polyphenylsiloxanes, polyarylalkylsiloxanes such as polymethylphenylsiloxanes.
Among the modified polyorganosiloxanes, mention may especially be made of polydimethylsiloxanes having polyoxyalkylene and/or siloxy and/or silanol and/or amine and/or imine and/or fluoroalkyl groups.
Among the polyoxyalkylene groups, mention may especially be made of polyoxyethylene groups and polyoxypropylene groups preferably having 1 to 200 oxyalkylene units.
Among the monofluoroalkyl or polyfluoroalkyl groups, mention may especially be made of groups such as —(CH2)n(CF2)m—CF3 or —(CH2)n—(CF2)m—CHF2 with n=1 to 20 and m=1 to 20.
The substituents R1 to R4 may optionally be substituted by a group having a cosmetic activity. The cosmetic activities particularly used are obtained from groups having dyeing, antioxidant, UV screening and conditioning functions.
By way of examples of groups having a dyeing function, mention may especially be made of azo, quinone, methine, cyanomethine and triarylmethane groups.
By way of examples of groups having an antioxidant function, mention may especially be made of groups of butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) or vitamin E type.
By way of examples of groups having a UV screening function, mention may especially be made of groups of benzophenone, cinnamate, benzoate, benzylidene camphor and dibenzoylmethane type.
Among the electrophilic monomers corresponding to the formula (I), mention may be made, for example, of:
described in Sayyah, J. Polymer Research, 2000, p. 97;
R=Bu (F), 4-tolyl (G), 2-ethylphenyl (H), 2,6-diethylphenyl (I)
According to one variant of the invention, the polymer obtained from dielectrophilic monomers is obtained from cyanoacrylate monomers. Among these monomers, mention may especially be made of the monomers from the family of cyanoacrylates and their derivatives of formula (II):
X denoting NH, S or O;
R1 and R2 having the same meanings as previously, preferably R1 and R2 representing a hydrogen atom;
R′3 representing a hydrogen atom or R such as defined in the formula (I).
Preferably, X denotes O.
By way of compounds of formula (II), mention may be made of the monomers:
a) belonging to the family of polyfluoroalkyl 2-cyanoacrylates such as:
the 2,2,3,3-tetrafluoropropyl ester of 2-cyano-2-propenoic acid of formula:
or else the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula:
b) alkyl or alkoxyalkyl 2-cyanoacrylates:
in which R′3 represents a C1-C10 alkyl or (C1-C4)alkoxy(C1-C10)alkyl or C2-C10 alkenyl radical.
Mention may more particularly be made of ethyl 2-cyanoacrylate, methyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, isobutyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate and iso-amyl cyanoacrylate, allyl 2-cyanoacrylate, methoxypropyl 2-cyanoacrylate.
Within the context of the invention, it is preferred to use the monomers b). According to one preferred embodiment, the cyanoacrylate monomer or monomers are chosen from C6-C10 alkyl cyanoacrylates.
The particularly preferred monomers are octyl cyanoacrylate monomers of formula (V) and mixtures thereof:
The amount of polymer obtained from electrophilic monomers contained in the composition of the invention may vary over a wide range. Conventionally, the amount of this polymer is between 0.1% and 100% (pure polymer); preferably between 1% and 80%, and especially between 2% and 70%.
The polymer used in the composition of the invention comprises at least three repeat units; it may be in the form of a homopolymer or a copolymer which may be linear or branched, crosslinked or non-crosslinked; it may be random, alternating, block or gradient, or even starburst.
The composition of the invention may contain one or more polymers obtained from dielectrophilic monomers. It may also contain other units obtained from monomers other than the dielectrophilic monomers described previously, such as (meth)acrylic, (meth)acrylate or vinyl monomers.
By way of example, mention may be made of:
H2C═CR1(Z)x(R2)mX (I)
in which:
In the radical R2, the heteroatom or heteroatoms, when they are present, may be inserted into the chain of said radical R2, or else said radical R2 may be substituted by one or more groups such as hydroxyl, —CF3, CN, epoxy or amino (NH2, NHR′ or NR′R″ with R′ and R″, which are identical or different, representing a linear or branched C1-C22, especially methyl or ethyl, alkyl). In particular, R2 may be or may comprise:
Alternatively, X may represent (c) a ring:
in which R′4 and R′5 form, with the nitrogen atom, a saturated or unsaturated, optionally aromatic, ring comprising in total 5, 6, 7 or 8 atoms, and especially 4, 5 or 6 carbon atoms and/or 2 to 4 heteroatoms chosen from O, S and N; said ring possibly being fused with one or more other saturated or unsaturated, optionally aromatic, rings each comprising 5, 6 or 7 atoms, and especially 4, 5, 6, 7 or 8 carbon atoms and/or 2 to 4 heteroatoms chosen from O, S and N; and R′6 is chosen from H, —CH3 and —C2H5.
For example, X may form a ring that may or may not be aromatic, comprising a tertiary amine group or may represent a heterocycle that may or may not be aromatic, containing a secondary or tertiary nitrogen.
Among these preferred X radicals, mention may be made of the radicals of indolyl, isoindolinyl, imidazolyl, imidazolinyl, piperidinyl, pyrazolynyl, pyrazolyl, quinoline, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl, quinidinyl, thiazolinyl, morpholine, guanidino, amidino radicals, and mixtures thereof.
Among the preferred monomers of formula (I), mention may be made, alone or as mixtures, of dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, morpholinoethyl (meth)acrylate, vinylimidazole, vinylpyridine, vinylamine, allylamine, and the above monomers in which R═H or methyl.
The ester monomers of (meth)acrylic acid of formula CH2═CHCOOR′1 (II) or CH2═C(CH3)COOR′1 (II′) with R′1 representing a saturated or unsaturated, optionally aromatic (aryl, arylkyl or alkylaryl), linear, branched or cyclic carbon-based, especially hydrocarbon-based (alkyl) chain having 1 to 30 carbon atoms, optionally comprising 1 to 2 ether functional groups (—O—) and optionally 1 to 12, especially 1 to 8, functional groups chosen from —OH (hydroxy), —OR′ with R′═C1-C6 alkyl (alkoxy), —CN, halogen, especially Cl, F, Br or I; —CO—, SO3H, —COOH, —OCOO—, —COO—, —OCONR—, —OCONH—, —NH—CONH—, —NR—CONR—, —CF3, —CN, epoxy, —NHCO—, —N(R)CO— with R=linear or branched C1-C22 alkyl optionally comprising 1-12 heteroatoms.
Thus, mention may be made of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-isobutyl, hexyl, cyclohexyl 2-ethylhexyl, octyl, isooctyl, isodecyl, decyl, dodecyl, lauryl, myristyl, cetyl, palmityl, stearyl, behenyl, oleyl, tridecyl, hexadecyl, isobornyl; hydroxyethyl, hydroxypropyl; phenyl, benzyl, furfuryl; tetrahydrofurfuryl, ethoxyethyl, methoxyethyl; glycerol, 2,2,2-trifluoroethyl, and poly(ethylene-isobutylene) (meth)acrylates; and (meth) acrylonitriles.
The amide monomers of (meth)acrylic acid of formula CH2═CHCONR′2R″2 (III) or CH2═C(CH3)CONR′2R″2 (III′) with R′2, R″2, which are identical or different, representing hydrogen or a saturated or unsaturated, optionally aromatic, linear, branched or cyclic carbon-based, especially hydrocarbon-based (alkyl) chain having 1 to 30 carbon atoms, optionally comprising 1 to 2 ether functional groups (—O—) and optionally 1 to 12, especially 1 to 8, functional groups chosen from —OH (hydroxy), —OR′ with R′═C1-C6 alkyl (alkoxy), —CN, halogen, especially Cl, F, Br or I; —CO—, SO3H, —COOH, —OCOO—, —COO—, —OCONR—, —OCONH—, —NH—CONH—, —NR—CONR—, —CF3, —CN, epoxy, —NHCO—, —N(R)CO— with R=linear or branched C1-C22 alkyl optionally comprising 1-12 heteroatoms. Thus, mention may be made of (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-octyl(meth)acrylamide, N-undecyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide.
The vinyl ester monomers of formula CH2═CH—OCO—R′3 or CH2═C(CH3)—OCO—R′3 with R′3 representing a saturated or unsaturated, optionally aromatic, linear, branched or cyclic carbon-based, especially hydrocarbon-based chain having 1 to 30 carbon atoms, optionally comprising 1 to 2 ether functional groups (—O—) and optionally 1 to 12, especially 1 to 8, functional groups chosen from —OH (hydroxy), —OR′ with R′═C1-C6 alkyl (alkoxy), —CN, halogen, especially Cl, F, Br or I; —CO—, SO3H, —COOH, —OCOO—, —COO—, —OCONR—, —OCONH—, —NH—CONH—, —NR—CONR—, —CF3, —CN, epoxy, —NHCO—, —N(R)CO— with R=linear or branched C1-C22 alkyl optionally comprising 1-12 heteroatoms.
Mention may especially be made of vinyl acetate, vinyl propionate, vinyl butyrate (or butanoate), vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate, vinyl neodecanoate, vinyl pivalate, vinyl cyclohexanoate, vinyl benzoate, vinyl 4-tert-butylbenzoate and vinyl trifluoroacetate.
The vinyl ether monomers of formula CH2═CHOR′4 or CH2═C(CH3)OR′4 with R′4 representing a saturated or unsaturated, optionally aromatic, linear, branched or cyclic carbon-based, especially hydrocarbon-based chain having 1 to 30 carbon atoms, optionally comprising 1 to 2 ether functional groups (—O—) and optionally 1 to 12, especially 1 to 8, functional groups chosen from —OH (hydroxy), —OR′ with R′═C1-C6 alkyl (alkoxy), —CN, halogen, especially Cl, F, Br or I; —CO—, SO3H, —COOH, —OCOO—, —COO—, —OCONR—, —OCONH—, —NH—CONH—, —NR—CONR—, —CF3, —CN, epoxy, —NHCO—, —N(R)CO— with R=linear or branched C1-C22 alkyl optionally comprising 1-12 heteroatoms.
Mention may be made of methyl vinyl ether, ethyl vinyl ether, ethylhexyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and isobutyl vinyl ether.
The vinyl monomers of formula CHR″5=CR5R′5 (VI) in which:
R″5 is H or COOH, and R5 is H, CN or COOH, and R′5 is chosen from:
Examples of such vinyl monomers are vinyl alcohol, vinylcyclohexane; vinylpyrrolidone, vinylcaprolactam, N-vinyl acetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide; N-methyl-N-vinylacetamide; styrene, methylstyrene, 4-tert-butylstyrene, 4-acetoxystyrene, styrenesulphonic acid, 4-methoxystyrene, 3-methylstyrene; 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, dimethylstyrene, 2,6-dichlorostyrene, 2,4-dimethylstyrene; 2,5-dimethylstyrene, 3,5-ethoxystyrene, 2,4-ethoxystyrene, 4-fluorostyrene; vinyl butyral; vinyl carbazol; vinyl chloride; vinyl formal; vinylidene chloride, vinylidene fluoride, 2-vinylnaphthalene; N-methylmaleimide; 1-octene, 1-butene, cis-chlorobutadiene, trans-chlorobutadiene, chlorotrifluoroethylene; cis-isoprene, trans-isoprene, 1-octadecene, butadiene, hexadecene and eicosene.
The following anionic monomers, and salts thereof: maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate (CH2═CH—C(O)—O—(CH2)2—COOH); styrenesulphonic acid, 2-acrylamido-2-methylpropanesulphonic acid, vinylbenzoic acid, vinylphosphonic acid, sulfopropyl (meth)acrylate, and from among the salts: sodium or potassium (meth)acrylate.
The following amphoteric monomers: N,N-dimethyl-N-(2-methacryloyloxyethyl)-N-(3-sulphopropyl)ammonium betaine (especially SPE from Raschig); N,N-dimethyl-N-(3-methacrylamidopropyl)-N-(3-sulphopropyl)ammonium betaine (SPP from Raschig), and 1-(3-sulphopropyl)-2-vinylpyridinium betaine (SPV from Raschig), and also 2-methacryloyloxyethylphosphoryl-choline.
The multivalent compounds comprising at least two polymerizable functional groups of vinyl, (meth)acrylic, allyl or (meth)acrylamide type, and especially the difunctional monomers such as 1,3-butanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate, and N,N-dimethyldiallylammonium chloride.
Among the preferred non-dielectrophilic additional monomers, mention may be made of those chosen from vinyl neodecanoate, vinyl tert-butylbenzoate; vinylpyrrolidone; vinylcaprolactam, ethyl, methyl, tert-butyl or isobornyl (meth)acrylate; vinyl acetate, crotonic acid; (meth)acrylic acid, methacryoyl ethyl betaine, octylacrylamide; N-methyl-N-vinylimidazolinium chloride, 1-eicosene, tert-butylacrylamide, acrylamide, hexadecane, and mixtures thereof.
According to one embodiment of the invention, the polymer used in the present invention is obtained from at least 10% of dielectrophilic monomers, preferably at least 50% and more preferably 100% of dielectrophilic monomers.
The polymer obtained from dielectrophilic monomers may be obtained according to conventional radical or anionic polymerization methods described, for example, in “Chimie et physicochimie des polymères” (Chemistry and Physical Chemistry of Polymers) published by Dunod; Y. Gnanou, M. Fontanille, 10, 1998. The expression “radical polymerization” is understood to mean any polymerization initiated by a radical generator. The expression “anionic polymerization” is understood to mean any polymerization initiated by a nucleophile or anion, provided by a specific compound or by water.
These methods are described in detail in Patent Application WO 2003/053380 for synthesis via a nucleophilic route. The synthesis may also be carried out by a radical route by means of a radical initiator. By way of a radical initiator, mention may be made of initiators of the peroxide, azo, persulphate or redox type, or mixtures thereof. Among the peroxides, mention may be made of hydroperoxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide or decanoyl peroxide. Mention may especially be made of the commercial peroxides especially sold by Arkema under the following names TRIGONOX 21S and TRIGONOX 141 sold by Akzo, the initiator being activated either via a photochemical route, or via a thermal route.
Mention may also be made of the derivatives such as: potassium persulphate, ammonium persulphate and sodium persulphate.
Azo derivatives such as 2,2′-azobis(amidinopropane) dihydrochloride (V50) and 4,4′-azobis(4-cyanovaleric acid) (ACVA).
When the polymer used in the composition of the invention is obtained from cyanoacrylate monomers, the synthesis of these polymers is especially described in U.S. Pat. No. 3,527,224, U.S. Pat. No. 3,591,767, U.S. Pat. No. 3,667,472, U.S. Pat. No. 3,995,641, U.S. Pat. No. 4,035,334 and U.S. Pat. No. 4,650,826.
According to one particular embodiment, the polymer used in the composition of the invention is obtained from dielectrophilic cyanoacrylate monomers of formula (I) which polymerize via an anionic route in the presence of a nucleophilic agent capable of generating a carbanion in contact with a nucleophilic agent, such as the hydroxide ions contained in water at a neutral pH. The term “carbanion” is understood to mean the chemical species defined in “Advanced Organic Chemistry, Third Edition”, by Jerry March, page 141.
The nucleophilic agent is a molecular compound, an oligomer, a dendrimer or a polymer having nucleophilic functional groups. Non-limitingly, mention may be made, as nucleophilic functional groups, of the functional groups: R2N−, NH2−, Ph3C−, R3C−, PhNH−, pyridine, ArS−, R—C≡C−, RS−, SH−, RO−, R2NH, ArO−, N3−, OH−, ArNH2, NH3, I−, Br−, Cl−, RCOO−, SCN−, ROH, RSH, NCO−, CN−, NO3−, ClO4−, H2O, Ph representing a phenyl group; Ar representing an aryl group and R representing a C1-C10 alkyl group or a modified or unmodified polyorganosiloxane residue or a polyoxyalkylene group.
The composition of the invention may be in the form of a solution, dispersion or emulsion or gels.
The composition generally contains a cosmetically acceptable medium. Such a medium may comprise water, organic compounds, solvents or non-solvents such as alcohols, linear, branched or cyclic esters, ethers, ketones or a mixture thereof.
The organic solvent is, for example, chosen from: aromatic alcohols such as benzyl alcohol; liquid fatty alcohols, especially C10-C30 liquid fatty alcohols; modified or unmodified polyols such as glycerol, glycol, propylene glycol, dipropylene glycol, butylene glycol, butyl diglycol; volatile silicones such as cyclopentasiloxane, cyclohexasiloxane, polydimethylsiloxanes that may or may not be modified by alkyl and/or amine and/or imine and/or fluoroalkyl and/or carboxylic and/or betaine and/or quaternary ammonium functional groups, liquid modified polydimethylsiloxanes, mineral, organic or vegetable oils, alkanes and more particularly C5 to C10 alkanes; liquid fatty acids, liquid fatty esters and more particularly liquid fatty alcohol benzoates or salicylates.
The organic solvent is preferably chosen from organic oils; silicones such as volatile silicones, silicone gums or oils that may or may not be aminated and mixtures thereof; mineral oils; vegetable oils such as olive oil, castor oil, rapeseed oil, coconut oil, wheatgerm oil, sweet almond oil, avocado oil, macadamia oil, apricot oil, safflower oil, candlenut oil, camelina oil, tamanu oil, lemon oil or else organic compounds such as C5-C10 alkanes, acetone, methyl ethyl ketone, liquid esters of C1-C20 acids and of C1-C8 alcohols such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, liquid C10-C30 fatty alcohols such as oleyl alcohol, liquid C10-C30 fatty alcohol esters such as C10-C30 fatty alcohol benzoates and mixtures thereof; polybutene oil, isononyl isononanoate, isostearyl malate, pentaerythritol tetraisostearate, tridecyl trimelate, the cyclopentasiloxane (14.7 wt %)/polydimethylsiloxane, dihydroxylated in alpha and omega positions (85.3 wt %) mixture, or mixtures thereof.
According to one preferred embodiment, the organic solvent is composed of a silicone or a mixture of silicones such as liquid polydimethylsiloxanes and liquid modified polydimethylsiloxanes, their viscosity at 25° C. is between 0.1 cst and 1 000 000 cst and more preferably between 1 cst and 30 000 cst.
Mention will preferably be made of the following oils:
The composition may also contain hydrocarbons and especially paraffin oil, liquid petroleum, or hydrogenated polyisobutylene, isododecane, or else ISOPARs, volatile isoparaffins. Mention may also be made of the vegetable oils formed from fatty acid and polyol esters, in particular triglycerides, such as sunflower oil, sesame oil or rapeseed oil, or the esters derived from acids or alcohols such as palmitates, adipates and benzoates, especially diisopropyl adipate.
According to one particular embodiment, the composition of the invention comprises at least one polymerizable dielectrophilic monomer and at least one polymer obtained from dielectrophilic monomers. The polymerizable monomer or monomers present in the composition may be chosen from the monomers described above used for obtaining the polymer. According to one particular embodiment, the polymerizable monomer present in the composition and the monomers used in the synthesis of the polymer used in the composition of the invention are of the same nature, or even identical. By way of example of this embodiment, mention may be made of a composition comprising a polymerizable cyanoacrylate monomer and a polymer obtained from cyanoacrylate monomers.
The polymerizable dielectrophilic monomer or monomers present in the composition may be present in an amount ranging from 0.1 to 80% by weight, preferably in an amount ranging from 0.2 to 60% by weight, and especially in an amount ranging from 0.5 to 50% by weight, relative to the total weight of the cosmetic composition.
When the composition of the invention contains, in addition to the polymer used in the invention, polymerizable dielectrophilic monomers then the composition may contain a nucleophilic agent. The nucleophilic agent may also be added to the composition of the invention at the time of use.
According to this particular embodiment, the composition may in addition contain a polymerization inhibitor, in particular chosen from mineral or organic acids such as phosphoric acid, hydrochloric acid, nitric acid, benzenesulphonic or toluenesulphonic acid, sulphuric acid, carbonic acid, acetic acid, formic acid, propionic acid, benzoic acid, mono-, di- or tri-chloroacetic acid, salicylic acid, trifluoroacetic acid, octanoic acid, heptanoic acid and hexanoic acid. When it is present, the amount of polymerization inhibitor may vary from a few ppm to 30% by weight of the total weight of the composition, especially between 10 ppm and 15%.
The cosmetic composition according to the invention may comprise other conventional additives in the field of cosmetic compositions for hair treatment. As such, mention may be made of reducing agents, fatty substances, plasticizers, softeners, anti-foaming agents, moisturizers, pigments, clays, mineral fillers, UV screening agents, mineral colloids, peptizers, solubilizers, fragrances, preservatives, anionic, cationic, non-ionic or amphoteric surfactants, fixture or non-fixture polymers, polyols, proteins, vitamins, direct or oxidation dyes, pearling agents, propellants, and mineral or organic thickeners such as benzylidene sorbitol and N-acylamino acids, oxyethylenated or non-oxyethylenated waxes, paraffins, C10-C30 fatty acids such as stearic acid, lauric acid, C10-C30 fatty amides such as lauric diethanolamide, C10-C30 fatty alcohol esters such as C10-C30 fatty alcohol benzoates and mixtures thereof, and thickeners.
According to one particular embodiment, the composition of the invention is a composition for dyeing keratinous fibres which comprises the polymer obtained from dielectrophilic monomers, and at least one pigment.
Such a composition makes it possible to obtain lasting and visible colourings especially on dark hair since the surface pigment masks the natural colour of the fibre.
Furthermore, such a composition makes it possible to result in visible and highly chromatic colourings especially on a dark keratinous fibre without it being necessary to lighten or bleach the keratinous fibres and, consequently, without physical damage to the keratinous fibres.
Within the meaning of the present invention, the term “pigment” is understood to mean any organic and/or mineral entity having a solubility in water that is less than 0.01% at 20° C., preferably less than 0.0001% and that has an absorption between 350 and 700 nm, preferably an absorption with a maximum.
The pigments used in the composition according to the invention may especially be chosen from the organic and/or mineral pigments known from the art, especially those which are described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.
These pigments may be in the form of a powder or of a pigment paste. They may be coated or uncoated.
The pigments according to the invention may, for example, be chosen from white or coloured pigments, lakes, special effect pigments, such as pearlescent agents or glitter, and mixtures thereof.
As examples of white or coloured mineral pigments, mention may be made of titanium dioxide which may or may not be surface-treated, zirconium or cerium oxides, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. For example, the following mineral pigments may be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 as a mixture with TiO2, ZrO2, Nb2O5, CeO2, ZnS.
As examples of white or coloured organic pigments, mention may be made of nitroso, nitro, azo, xanthene, quinoline, anthraquinone or phthalocyanine compounds, compounds of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.
In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments coded in the Colour Index under the references CI-42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments coded in the Colour Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Colour Index under the references CI-61565, 61570, 74260, the orange pigments coded in the Colour Index under the references CI 11725, 15510, 45370, 71105, the red pigments coded in the Colour Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidizing polymerization of indolic or phenolic derivatives such as are described in Patent FR 2 679 771.
It is also possible to use pigment pastes made of organic pigments such as the products sold by Hoechst under the name:
The pigments according to the invention may also be in the form of composite pigments such as are described in Patent EP 1 184 426. These composite pigments may be composed, in particular, of particles having an inorganic core, at least one binder ensuring the attachment of the organic pigments to the core, and at least one organic pigment at least partially covering the core.
The term “lake” is understood to mean dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium. Among the organic dyes, mention may be made of cochenille carmine.
As examples of lakes, mention may be made of the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 10 (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090).
The expression “special effect pigments” is understood to mean pigments which generally create a coloured appearance (characterized by a certain hue, a certain vividness and a certain lightness) which is not uniform and changes as a function of the conditions of observation (light, temperature, observation angles, etc.). They thereby contrast with white or coloured pigments which provide a conventional opaque, semi-transparent or transparent uniform colour.
As examples of special effect pigments, mention may be made of white pearlescent pigments such as mica covered with titanium dioxide, or with bismuth oxychloride, coloured pearlescent pigments such as mica covered with titanium dioxide and iron oxides, mica covered with titanium oxide and especially with ferric blue or chromium oxide, mica covered with titanium dioxide and with an organic pigment such as defined previously and also pearlescent pigments based on bismuth oxychloride. By way of pearlescent pigments, mention may be made of the following pearlescent agents: Cellini sold by Engelhard (Mica-TiO2-lake), Prestige sold by Eckhart (Mica-TiO2), Prestige Bronze sold by Eckhart (Mica-Fe2O3), Colorona sold by Merck (Mica-TiO2—Fe2O3).
Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC by Wacker), interference holographic glitter (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also comprise fluorescent pigments, whether these are substances which are fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by Quantum Dots Corporation.
Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation having a wavelength between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they may be manufactured according to the processes described, for example, in U.S. Pat. No. 6,225,198 or U.S. Pat. No. 5,990,479, in the publications which are cited therein and in the following publications: Dabboussi B. O. et al. “(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocristallites” Journal of Physical Chemistry B, Vol. 101, 1997, pp 9463-9475, and Peng, Xiaogang et al., “Epitaxial Growth of highly Luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility” Journal of the American Chemical Society, Vol. 119, No. 30, pp 7019-7029.
The variety of pigments which can be used in the present invention makes it possible to obtain a rich palette of colours, and also particular optical effects such as interference, metallic effects.
According to one particular embodiment, the pigments are coloured pigments. The expression “coloured pigment” is understood to mean pigments other than white pigments.
The average size of the pigment used within the scope of the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferably between 30 nm and 50 μm.
The pigments used in the cosmetic composition according to the invention may be surface-treated by an organic agent.
Thus, the pigments that have previously been surface-treated used within the scope of the invention are pigments which have completely or partially undergone a surface treatment of chemical, electronic, electrochemical, mechano-chemical or mechanical nature, with an organic agent such as those which are described, in particular, in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64, before being dispersed in the composition according to the invention. These organic agents may be, for example, chosen from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and derivatives thereof; anionic surfactants, lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and its derivatives; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; proteins; alkanolamines; silicone-based compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes, siloxysilicates; organic fluoro compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
The surface-treated pigments used within the scope of the invention may also have been treated by a mixture of these compounds and/or have undergone several surface treatments.
The surface-treated pigments used within the scope of the present invention may be prepared according to the surface-treatment techniques well known to a person skilled in the art or found as such commercially.
Preferably, the surface-treated pigments are covered by an organic layer.
The organic agent with which the pigments are treated may be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
The surface treatment may thus be carried out, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments. This method is especially described in U.S. Pat. No. 4,578,266.
Preferably, an organic agent covalently bonded to the pigments will be used.
The agent for the surface treatment may represent from 0.1 to 50% by weight of the total weight of the surface-treated pigments or fillers, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 10% by weight.
Preferably, the surface treatments of the pigments are chosen from the following treatments:
The pigment or pigments are generally present in the composition in total amounts that are generally between 0.05 and 50% by weight of the total weight of the composition, preferably between 0.1 and 35% by weight, even more preferably between 0.5 and 20% by weight.
The composition according to the present invention may additionally comprise one or more nonsurface-treated fillers.
The composition according to the present invention may additionally comprise one or more nonsurface-treated pigments.
According to one preferred embodiment, the composition of the invention is an anhydrous composition, that is to say containing less than 1% by weight of water relative to the total weight of the composition.
According to another embodiment, it contains water and one or more liquid organic solvents.
The organic solvent or solvents of the composition generally represent from 0.01 to 99%, preferably from 50 to 99% by weight relative to the total weight of the composition.
The compositions may be in various dosage forms such as a lotion, an aerosol mousse, a conditioner or a shampoo, a gel or a wax. The compositions may be contained in a pump dispenser or an aerosol spray. After application to the hair, the compositions of the invention may be rinsed out or left on.
When the composition is contained in an aerosol, it may contain a propellant. The propellant consists of compressed or liquefied gases normally used for preparing aerosol compositions. Preferably air, carbon dioxide, compressed nitrogen or else a soluble gas such as dimethyl ether, halogenated hydrocarbons (fluorocarbons in particular) or non-halogenated hydrocarbons (butane, propane, isobutane) and mixtures thereof will be used.
Another subject of the invention is a method for treating keratinous fibres which consists in applying the composition of the invention to the fibres. When the composition also contains a polymerizable dielectrophilic monomer then it is necessary, in order to initiate the polymerization of the latter, to use a nucleophilic agent either simultaneously or during a post-treatment.
According to one variant, the method for treating keratinous fibres is a hair dyeing method which consists in applying the composition of the invention containing a pigment.
The method of the invention may comprise additional intermediate or final steps such as the application of a cosmetic product, a rinsing step, a drying step. The drying may be carried out under a hood dryer, using a hairdryer and/or using a straightening iron. In particular, the application of the compositions according to the invention may be followed by rinsing.
Another subject of the invention is a multi-compartment device or kit comprising a first compartment, comprising a composition containing at least one polymerizable dielectrophilic monomer such as defined previously and optionally at least one anionic and/or radical polymerization inhibitor, and a second compartment, comprising a second composition containing one or more polymers obtained from a dielectrophilic monomer, one of the two or both compositions possibly containing one or more cosmetic additives such as defined previously.
The examples which follow are intended to illustrate the invention without however being limiting.
In the examples which follow, the reactants used were:
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 1 g of octyl cyanoacrylate followed by 9 g of cyclomethicone (D5). The mixture was stirred for around 1 minute. 7.25 g of water (HPLC quality) were then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of 2-octyl cyanoacrylate, followed by 0.5 g of THF. The mixture was stirred for around 1 minute. 0.1 g of water (HPLC quality) was then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT.
The polymer was obtained in solution in THF at a concentration of 50%.
Added to 1 g of the solution from Example 2 were 4.5 g of cyclomethicone, the THF was evaporated under vacuum on a rotary evaporator. The polymer P2 was obtained as a 10% dispersion in cyclomethicone.
Added to 2 g of polymer from Example 2 was a mixture of 1.3 g of α,ω-dihydroxylated polydimethylsiloxane and 7.7 g of cyclopentadimethylsiloxane. The THF was then evaporated. Thus, a 10% solution of the polymer P2 in the α,ω-dihydroxylated polydimethylsiloxane/cyclopentadimethylsiloxane mixture (14.7/85.3) was obtained.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of methylheptyl cyanoacrylate, followed by 0.5 g of cyclomethicone. The mixture was stirred for around 1 minute. 25 mg of TRIGONOX 21S were added. The mixture was then brought to 75° C. for 3 hours with stirring, then cooled to RT.
The formula was then diluted by cyclomethicone to obtain a 10% solution of polymer in cyclomethicone.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of 2-octyl cyanoacrylate, followed by 0.5 g of THF. The mixture was stirred for around 1 minute. 25 mg of TRIGONOX 21S were added. The mixture was then brought to 75° C. for 3 hours with stirring, then cooled to RT. 4.5 g of D5 were then introduced to the mixture with vigorous stirring and the THF was distilled.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.2 g of methylheptyl cyanoacrylate, followed by 1.8 g of cyclomethicone. The mixture was stirred for around 1 minute. 20 mg of potassium persulphate (KPS), then 7.5 g of water were added. The mixture was then brought to 60° C. for 1 hour with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 1 g of butyl cyanoacrylate followed by 9 g of cyclomethicone (D5). The mixture was stirred for around 1 minute. 7.25 g of water (HPLC quality) were then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of butyl cyanoacrylate, followed by 0.5 g of THF. The mixture was stirred for around 1 minute. 0.1 g of water (HPLC quality) was then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT. The THF was evaporated under vacuum using a rotary evaporator. The product was dispersed in 4.5 g of cyclomethicone.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of butyl cyanoacrylate, followed by 0.5 g of cyclomethicone. The mixture was stirred for around 1 minute. 25 mg of TRIGONOX 21S were added. The mixture was then brought to 75° C. for 3 hours with stirring, then cooled to RT.
The formula was then diluted by cyclomethicone to obtain a 10% solution of polymer in cyclomethicone.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of butyl cyanoacrylate, followed by 0.5 g of THF. The mixture was stirred for around 1 minute. 25 mg of TRIGONOX 21S were added. The mixture was then brought to 75° C. for 3 hours with stirring, then cooled to RT. 4.5 g of cyclomethicone were then introduced to the mixture with vigorous stirring and the THF was distilled.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.2 g of butyl cyanoacrylate, followed by 1.8 g of cyclomethicone. The mixture was stirred for around 1 minute. 20 mg of potassium persulphate (KPS), then 7.5 g of water were added. The mixture was then brought to 60° C. for 1 hour with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 1 g of methoxypropyl cyanoacrylate followed by 9 g of cyclomethicone (D5). The mixture was stirred for around 1 minute. 7.25 g of water (HPLC quality) were then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.5 g of methoxypropyl cyanoacrylate and 0.5 g of methylheptyl cyanoacrylate, followed by 9 g of cyclomethicone (D5). The mixture was stirred for around 1 minute. 7.25 g of water (HPLC quality) were then introduced with stirring. The mixture was then brought to 60° C. for 30 minutes with stirring, then cooled to RT.
Introduced into a round-bottomed flask equipped with a magnetic stirrer bar were 0.25 g of methoxypropyl cyanoacrylate and 0.25 g of 2-octyl cyanoacrylate, followed by 0.5 g of cyclomethicone. The mixture was stirred for around 1 minute. 25 mg of Trigonox 21S were added. The mixture was then brought to 75° C. for 3 hours with stirring, then cooled to RT.
The formula was then diluted with cyclomethicone to obtain a 10% solution of polymer in cyclomethicone.
Applications to Hair of the Polymers from the Examples Above:
PROCEDURE 1: Deposit of polymer onto wet hair: 0.4 g of a composition comprising the polymer P1 to P14 having 10% of active material (AM) and cyclomethicone were applied to 2.7 g of wet natural hair and to 2.7 g of wet sensitized hair. The hair was mixed with the fingers for 1 to 2 minutes, then combed. The hair was then dried for 30 minutes under a hood dryer at 40° C.
Procedure 2: Deposit of Polymer onto Dry Hair
0.4 g of a composition comprising the polymer P1 to P14 having 10% of active material and cyclomethicone were applied to 2.7 g of natural and dry hair and to 2.7 g of sensitized and dry hair. The hair was mixed with the fingers for 1 to 2 minutes, then combed. The hair was then treated for 30 min under a hood dryer at 40° C.
A control composition comprising 10 g of 2-octyl cyanoacrylate and 90 g of Dow Corning 245 Fluid was used for treating hair according to the same mode of application as that described for procedure 1 or 2. This composition did not contain polymerized octyl cyanoacrylate.
As a result of this treatment, the hair treated according to procedure 1 and 2 was coated, the locks were smoother, glossier and this coating lasted for at least 5 shampooings in comparison with the results obtained with procedure 3. In addition, a lasting volume and gloss of the hair was observed.
By scanning electron microscopy, before shampooing, a deposit having a “tubular” and even appearance was observed on natural hair and on sensitized hair. After 5 shampooings, the deposit was still present.
0.4 g of a composition comprising the polymer P1 at a concentration of 5% AM in cyclomethicone and 5% AM of 2-octyl cyanoacrylate monomer in cyclomethicone was applied to 2.7 g of wet natural hair and 2.7 g of wet sensitized hair. After application according to procedure 1 described above, the hair was treated for 30 minutes under a hood dryer at 40° C.
RESULTS: The composition from Example 15 had a good affinity for the fibre and was evenly deposited. It remained in place on natural hair (5 shampooings).
A composition comprising P1 having 5% AM and P12 having 5% AM in cyclomethicone was applied according to the procedure from Example 15. After application according to procedure 1 described above, the hair was treated for 30 minutes under a hood dryer at 40° C.
RESULTS: The composition from Example 16 had a good affinity for the fibre and was evenly deposited. It remained in place on natural hair (5 shampooings).
| Number | Date | Country | Kind |
|---|---|---|---|
| 0655749 | Dec 2006 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP07/64359 | 12/20/2007 | WO | 00 | 3/3/2010 |
| Number | Date | Country | |
|---|---|---|---|
| 60881149 | Jan 2007 | US |
