Patent Application
20060263315
The present invention relates to a composition comprising, in a cosmetically acceptable medium, at least one electrophilic monomer and at least one amino acid other than cysteine, to its use for the cosmetic treatment of keratin fibres and to a cosmetic treatment process using such a composition.
In the field of cosmetics, it is sought to modify the surface properties of keratin fibres such as the hair, for example to give the hair a conditioning effect such as softness or sheen. To do this, cosmetic compositions based on conditioning agents such as silicones or polymers that have high affinity for keratin fibres, in particular for the hair, are generally used.
However, these conditioning agents have a tendency to be removed in the course of washing with shampoo, making it necessary to renew applications of the compositions on the hair.
To increase the remanence of a polymer deposit, it may be envisaged to perform a radical polymerization of certain monomers directly on the hair. However, substantial degradation of the hair fibres is observed, probably associated with the polymerization initiators, and the hair thus treated is difficult to disentangle.
The Applicant has found, surprisingly, that by combining at least one amino acid other than cysteine with at least one electrophilic monomer as described below, in a cosmetically acceptable medium, it is possible to obtain improved, long-lasting conditioning and sheen of the hair.
Specifically, the application of a composition comprising such a combination leads to the formation of a shiny coating or covering that is remanent, especially with respect to shampooing, even after washing the head of hair several times. The covering obtained can give, in addition to the sheen and conditioning properties, pronounced remanent styling properties.
In addition, surprisingly, the hair remains perfectly individualized and can be styled without problem.
One subject of the invention is thus a fluid composition comprising, in a cosmetically acceptable medium, at least one electrophilic monomer as described below and at least one amino acid other than cysteine.
Another subject of the present invention consists of the use of the said composition for the cosmetic treatment of keratin fibres, and more particularly the hair.
A subject of the invention is also a cosmetic process for treating keratin fibres, and more particularly the hair, using the said composition.
Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the example that follows.
According to the invention, the fluid composition comprises, in a cosmetically acceptable medium, at least one electrophilic monomer and at least one amino acid other than cysteine, the said electrophilic monomer corresponding to the general formula (A):
in which:
R1 and R2 denote, independently of each other, a sparingly- or non-electro-attractive group (sparingly or non-inductive-attractive) such as:
R3 and R4 denote, independently of each other, an electro-attractive (or inductive-attractive) group preferably chosen from —N(R)3+, —S(R)2+, —SH2+, —NH3+, —NO2, —SO2R, —C≡N, —COOH, —COOR, —COSR, —CONH2, —CONHR, —F, —Cl, —Br, —I, —OR, —COR, —SH, —SR and —OH groups, linear or branched alkenyl groups, linear or branched alkynyl groups, C1-C4 mono- or polyfluoroalkyl groups, aryl groups such as phenyl, and aryloxy groups such as phenoxyloxy,
R denotes a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based group preferably containing from 1 to 20 and better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted with one or more groups chosen from —OR′, —COOR′, —COR′, —SH, —SR′ and —OH, halogen atoms, and a polymer residue that may be obtained by radical polymerization, by polycondensation or by ring opening, R′ denoting a C1-C10 alkyl group.
For the purposes of the present invention, the term “fluid composition” means a composition having a viscosity of less than 5 Pa·s (50 poises), measured at 25° C. and at a shear rate of 1 s−1, with a Rheomat 180 viscometer from the company Mettler or with an RS600 viscometer from the company Thermo.
The viscosity is preferably in the range from 0.01 to 5 Pa·s (10 centipoises to 50 poises), better still from 0.1 to 4 Pa·s (100 centipoises to 40 poises) and even more preferentially from 0.2 to 2 Pa·s (2 to 20 poises).
The term “cosmetically acceptable medium” means a medium that is compatible with keratin fibres such as the hair.
The cosmetically acceptable medium is preferably anhydrous.
The term “anhydrous medium” means a medium containing less than 1% by weight of water relative to the total weight of the composition.
The cosmetically acceptable medium is preferably chosen from organic oils; silicones such as volatile silicones, amino or non-amino silicone gums or oils and mixtures thereof; mineral oils; plant 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 and lemon oil; waxes; or alternatively organic compounds such as C5-C10 alkanes, acetone, methyl ethyl ketone, esters of C1-C20 acids and of C1-C8 alcohols such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, C10-C30 fatty alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol; C10-C30 fatty acids such as lauric acid and stearic acid; C10-C30 fatty amides such as lauric diethanolamide, and C10-C30 fatty alkyl esters such as C10-C30 fatty alkyl benzoates, and mixtures thereof.
Preferably, the organic compounds constituting the medium are chosen from compounds that are liquid at a temperature of 25° C. and at 105 Pa (760 mmHg).
The cosmetically acceptable anhydrous medium preferably used is chosen from 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; polybutene oil, isononyl isononanoate, isostearyl malate, pentaerythrityl tetraisostearate, tridecyl trimellitate, and a mixture of cyclopentasiloxane (14.7% by weight)/polydimethylsiloxane dihydroxylated in the α and ω positions (85.3% by weight), or mixtures thereof.
The term “amino acids” means a compound which is not obtained by polycondensation of identical or different amino acids.
The amino acids that may be used according to the invention comprise at least one amine function and at least one acid function. The acid function(s) may be carboxylic, sulfonic, phosphonic or phosphoric, and are preferably carboxylic. 27
Preferably, the amino acids used in the present invention are α-amino acids, i.e. they comprise an amine function and a group R in the a position relative to the acid function. They may be represented by the following formula:
in which:
when p=2, R represents a hydrogen atom, an aliphatic group optionally containing a heterocyclic portion, or an aromatic group,
or
when p=1, R can form a heterocycle with the nitrogen atom of —N(H)p. This heterocycle is preferably a saturated 5-membered ring, optionally substituted with one or more C1-4 alkyl or hydroxyl groups.
Preferably, the aliphatic group is a linear or branched C1-4 alkyl group; a linear or branched C1-4 hydroxyalkyl group; a linear or branched C1-4 aminoalkyl group; a linear or branched (C1-4 alkyl)thio(C1-4)alkyl group; a linear or branched C2-4 carboxyalkyl group; a linear or branched ureidoalkyl group, a linear or branched guanidinoalkyl group, a linear or branched imidazoloalkyl group or a linear or branched indolylalkyl group, the alkyl portions of these last four groups comprising from one to four carbon atoms.
Preferably, the aromatic group is a C6 aryl or C7-10 aralkyl group, the aromatic nucleus optionally being substituted with one or more C1-4 alkyl or hydroxyl groups.
As amino acids that may be used in the present invention, mention may be made especially of aspartic acid, glutamic acid, alanine, arginine, asparagine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, N-phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and hydroxyproline.
Preferentially, the amino acids comprise only one amine function, which may or may not be engaged in a ring, and only one acid function. The amino acids that are particularly preferred in the present invention are alanine, asparagine, glutamine, glycine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, threonine, tyrosine and valine.
The compositions used in accordance with the invention generally have an amino acid concentration of between 0.1% and 20% by weight, preferably between 0.5% at 15% by weight and more particularly between 1% and 10% by weight relative to the total weight of the composition.
The term “electrophilic monomer” means a monomer capable of polymerizing via anionic polymerization in the presence of a nucleophilic agent, for instance the hydroxide ions (OH−) contained in water at neutral pH.
The term “anionic polymerization” means the mechanism defined in the book “Advanced Organic Chemistry”, Third Edition, by Jerry March, pages 151 to 161.
The electrophilic monomers used in accordance with the invention are the monomers of structure:
in which:
R1 and R2 denote, independently of each other, a sparingly- or non-electro-attractive group (sparingly or non-inductive-attractive) such as:
R3 and R4 denote, independently of each other, an electro-attractive (or inductive-attractive) group preferably chosen from —N(R)3+, —S(R)2+, —SH2+, —NH3+, —NO2, —SO2R, —C≡N, —COOH, —COOR, —COSR, —CONH2, —CONHR, —F, —Cl, —Br, —I, —OR, —COR, —SH, —SR and —OH groups, linear or branched alkenyl groups, linear or branched alkynyl groups, C1-C4 mono- or polyfluoroalkyl groups, aryl groups such as phenyl, and aryloxy groups such as phenoxyloxy,
R denotes a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based group preferably containing from 1 to 20 and better still from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted with one or more groups chosen from —OR′, —COOR′, —COR′, —SH, —SR′ and —OH, halogen atoms, and a polymer residue that may be obtained by radical polymerization, by polycondensation or by ring opening, R′ denoting a C1-C10 alkyl group.
The term “electro-attractive or inductive-attractive group (—I)” means any group that is more electronegative than carbon. Reference may be made to the publication P. R. Wells, Prog. Phys. Org. Chem., Vol 6, 111 (1968).
The term “sparingly or non-electro-attractive group” means any group whose electronegativity is less than or equal to that of carbon.
The alkenyl or alkynyl groups preferably contain from 2 to 20 carbon atoms and better still from 2 to 10 carbon atoms.
As saturated or unsaturated, linear, branched or cyclic hydrocarbon-based groups preferably containing from 1 to 20 carbon atoms and better still from 1 to 10 carbon atoms, mention may be made especially 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.
Examples of substituted hydrocarbon-based groups that may be mentioned include hydroxyalkyl and polyhaloalkyl groups.
Examples of unmodified polyorganosiloxanes that may especially be mentioned include polyalkylsiloxanes such as polydimethylsiloxanes, polyarylsiloxanes such as polyphenylsiloxanes, and polyarylalkylsiloxanes such as polymethylphenylsiloxanes.
Among the modified polyorganosiloxanes that may especially be mentioned are polydimethylsiloxanes containing polyoxyalkylene and/or siloxy and/or silanol and/or amine and/or imine and/or fluoroalkyl groups.
Among the polyoxyalkylene groups that may especially be mentioned are polyoxyethylene groups and polyoxypropylene groups preferably containing 1 to 200 oxyalkylene units.
Among the mono- or polyfluoroalkyl groups that may especially be mentioned are 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 with a group having cosmetic activity. The cosmetic activities that are particularly used are obtained from groups having colouring, antioxidant, UV-screening and conditioning functions.
As examples of groups having a colouring function, mention may be made especially of azo, quinone, methine, cyanomethine and triarylmethane groups.
As examples of groups having an antioxidant function, mention may be made especially of groups of butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) or vitamin E type.
As examples of groups having a UV-screening function, mention may be made especially of groups of the benzophenone, cinnamate, benzoate, benzylidenecamphor and dibenzoylmethane type.
As examples of groups having a conditioning function, mention may be made especially of cationic groups and groups of fatty ester type.
Among the monomers mentioned above, the ones that are preferred are the monomers of the cyanoacrylate family and the derivatives thereof of formula (B):
X denoting NH, S or O,
R1 and R2 having the same meanings as above,
R′3 possibly denoting a hydrogen atom or a group R as defined for formula (A).
Preferably, X denotes O.
Compounds of formula (B) that may be mentioned include the monomers:
or the ester 2,2,2-trifluoroethyl 2-cyano-2-propenoate of formula:
b) the C1-C10 alkyl or (C1-C4 alkoxy)(C1-C10 alkyl) cyanoacrylates.
Mention may be made more particularly 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 isoamyl cyanoacrylate.
In the context of the invention, it is preferred to use the monomers b).
The monomers that are the most particularly preferred are those of formula F and mixtures thereof:
in which: Z=-(CH2)7—CH3,
The monomers used in accordance with the invention may be covalently bonded to supports such as polymers, oligomers or dendrimers. The polymer or the oligomer may be linear, branched, in comb form or in block form. The distribution of the monomers of the invention over the polymeric, oligomeric or dendritic structure may be random, in an end position or in the form of blocks.
The compositions used in accordance with the invention generally have a concentration of electrophilic monomer according to the invention of between 0.001% and 80% by weight, preferably between 0.002% and 75% by weight, more particularly between 0.1% and 40% by weight and even more preferentially between 1% and 20% by weight relative to the total weight of the composition.
Polymerization inhibitors and more particularly anionic and/or radical polymerization inhibitors may also be introduced into the compositions, in order to enhance the stability of the composition over time. In a non-limiting manner, the following polymerization inhibitors may be mentioned: sulfur dioxide, nitric oxide, lactone, boron trifluoride, hydroquinone and derivatives thereof such as hydroquinone monoethyl ether, tert-butylhydroquinone (TBHQ), benzoquinone and derivatives thereof such as duroquinone, catechol and derivatives thereof such as t-butylcatechol and methoxycatechol, anisole and derivatives thereof such as methoxyanisole, hydroxyanisole or butylhydroxyanisole, pyrogallol, 2,4-dinitrophenol, 2,4,6-trihydroxybenzene, p-methoxyphenol, hydroxybutyltoluene, alkyl sulfates, alkyl sulfites, alkyl sulfones, alkyl sulfoxides, alkyl sulfides, mercaptans and 3-sulfonene, and mixtures thereof. The alkyl groups preferably denote groups containing 1 to 6 carbon atoms.
It is also possible to use mineral or organic acids, the latter containing one or more carboxylic or sulfonic groups, with a pKa of between 0 and 6, such as phosphoric acid, hydrochloric acid, nitric acid, benzenesulfonic acid, toluenesulfonic acid, sulfuric acid, carbonic acid, hydrofluoric acid, acetic acid, formic acid, propionic acid, benzoic acid, mono-, di- or trichloroacetic acid, salicylic acid and trifluoroacetic acid.
The amount of inhibitor may range from 10 ppm to 20%, more preferentially from 10 ppm to 5% and even more preferentially from 10 ppm to 1% by weight relative to the total weight of the composition.
The compositions in accordance with the invention may also contain at least one agent usually used in cosmetics, chosen, for example, from reducing agents, fatty substances, plasticizers, softeners, antifoams, moisturizers, pigments, clays, mineral fillers, UV-screening agents, mineral colloids, peptizers, solubilizers, fragrances, preserving agents, anionic, cationic, nonionic or amphoteric surfactants, fixing or non-fixing polymers, polyols, proteins, vitamins, direct or oxidation dyes, nacreous agents, propellants, and mineral or organic thickeners such as benzylidenesorbitol and N-acylamino acids.
These agents or the amino acid(s) may optionally be encapsulated. The capsule may be of polycyanoacrylate type.
The composition is preferably used on the keratin fibres, such as the hair, preferably in the presence of a nucleophilic agent, for cosmetic treatment thereof.
It is especially used to give a conditioning effect such as softness; disentangling; sheen; volume, and/or a styling effect such as hair hold.
A cosmetic treatment process according to the invention comprises the application of a composition as defined above to keratin fibres such as the hair, preferably in the presence of a nucleophilic agent as defined below.
The nucleophilic agents capable of initiating anionic polymerization are systems that are known per se, which are capable of generating a carbanion on contact with a nucleophilic agent, such as the hydroxide ions contained in water at neutral pH. The term “carbanion” means the chemical species defined in “Advanced Organic Chemistry”, third edition, by Jerry March, page 141.
The nucleophilic agents may consist of a molecular compound, an oligomer, a dendrimer or a polymer containing nucleophilic functions. In a non-limiting manner, nucleophilic functions that may be mentioned include the following functions: 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− and H2O, Ph representing a phenyl group; Ar representing an aryl group and R representing a C1-C10 alkyl group.
Preferably, the nucleophilic agent is water. This water may be provided by wetting beforehand.
It is also possible, in order to modify the reaction kinetics, to moisten the keratin fibres such as the hair beforehand using an aqueous solution whose pH has been adjusted using a base, an acid or an acid/base mixture. The acid and/or the base may be mineral or organic.
It is also possible to modify the anionic polymerization kinetics by preimpregnating the keratin fibres such as the hair with a nucleophilic agent other than water. The nucleophilic agent may be used pure, as a solution or in the form of an emulsion, or may be encapsulated.
To modify the anionic polymerization kinetics, it is also possible to increase the nucelophilicity of the keratin fibres such as the hair via chemical conversion of the keratin material.
Examples of chemical conversions that may be mentioned include the reduction of the disulfide bridges of which keratin is partly composed, into thiols, before applying the composition of the invention. In a non-exhaustive manner, as reducing agents for the disulfide bridges of which keratin is partly composed, mention may be made of the following compounds:
anhydrous sodium thiosulfate,
powdered sodium metabisulfite,
thiourea,
ammonium sulfite,
thioglycolic acid,
thiolactic acid,
ammonium thiolactate,
glyceryl monothioglycolate,
ammonium thioglycolate,
thioglycerol,
2,5-dihydroxybenzoic acid,
diammonium dithioglycolate,
strontium thioglycolate,
calcium thioglycolate,
zinc formosulfoxylate,
isooctyl thioglycolate,
di-cysteine,
monoethanolamine thioglycolate.
To modify the anionic polymerization kinetics, and more specifically to reduce the rate of polymerization of the monomers of the invention, it is possible to increase the viscosity of the composition. To do this, one or more polymers that have no reactivity towards the monomers in accordance with the invention may be added to the composition of the invention. In this context, mention may be made, in a non-exhaustive manner, of poly(methyl methacrylate) (PMMA) or alternatively cyanoacrylate-based copolymers as described in U.S. Pat. No. 6,224,622.
In order to improve, inter alia, the adhesion of the poly(cyanoacrylate) formed in situ, the fibre may be pretreated with polymers of any type, or a haircare treatment may be performed before applying the composition of the invention, for instance a direct dyeing or oxidation dyeing, permanent-waving or hair relaxing operation.
The application of the compositions as described above may or may not be followed by rinsing.
The compositions may be in the form of a lotion, a spray or a mousse, and may be applied as a shampoo or a hair conditioner.
Another subject of the invention consists of a cosmetic process for treating keratin fibres, comprising at least two steps, one step comprising the application of at least one amino acid other than cysteine as defined above, and, with or without intermediate rinsing, another step comprising the application of at least one electrophilic monomer as defined above, the order of the steps being unimportant.
One particular embodiment of the invention consists of the application of at least one amino acid other than cysteine before the application of at least one electrophilic monomer.
Another particular embodiment of the invention consists of the application of at least one electrophilic monomer as defined above before the application of at least one amino acid other than cysteine.
One preferred embodiment of the invention consists of a process comprising the steps consisting in:
The order of the two steps (1) and (2) may be inverted.
The application of a cosmetic product may also precede the first step or follow the second step. Each step may also be interrupted by rinsing and optionally by drying, the drying possibly being performed using a hood, a hairdryer and/or a smoothing iron.
The steps of the processes described above may be repeated so as to obtain several layers depending on the type of deposit desired in terms of chemical nature, mechanical strength, thickness, appearance and/or feel.
A subject of the invention is also a kit comprising a first composition containing at least one electrophilic monomer as defined above and optionally at least one anionic and/or radical polymerization inhibitor as defined above, and also a second composition comprising, in a cosmetically acceptable medium, at least one amino acid other than cysteine, as defined above.
The example that follows is given as an illustration of the present invention.
In the example that follows, all the amounts are indicated as weight percentages of active material relative to the total weight of the composition, unless otherwise indicated.
A composition A comprising the following ingredients was prepared, the proportions being indicated as weight percentages.
A 1 -g lock of natural chestnut-brown hair was moistened with 0.5 g of an aqueous solution containing 0.2 mol/l of glycine.
0.16 g of composition A was then applied to the lock.
After a leave-on time of 15 minutes, the lock was dried for two minutes with a hairdryer. The lock obtained is shinier than a lock that has been moistened with 0.5 g of water instead of the glycine solution.
| Number | Date | Country | Kind |
|---|---|---|---|
| 05 03152 | Mar 2005 | FR | national |
This application claims benefit of U.S. Provisional Application No. 60/669,891, filed Apr. 11, 2005, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. §119 to French Patent Application No. FR 05 03152, filed Mar. 31, 2005, the contents of which are also incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60669891 | Apr 2005 | US |
