PROCESS FOR TREATING KERATINIC MATERIALS USING A COMPOSITION COMPRISING A MODIFIED PHOTODIMERIZABLE

专利摘要:
The present invention relates generally to a process for treating keratin materials, preferably keratinous fibers, comprising the following steps: c) applying to the keratin materials a composition comprising at least one photocrosslinkable polymer comprising at least one group during photodimerizable and at least one hydrophobic pendant group, and d) irradiation of said composition on the keratin materials to crosslink the polymer.
公开号:FR3046072A1
申请号:FR1563288
申请日:2015-12-23
公开日:2017-06-30
发明作者:Gabin Vic；Eric Parris；Frederic Woodland
申请人:LOreal SA；
IPC主号:

专利说明:

PROCESS FOR TREATING KERATINIC MATERIALS BY MEANS OF A COMPOSITION COMPRISING A PHOTODIMERIZABLE POLYMER
AMENDED
The present invention relates to a process for treating keratin materials, such as keratinous fibers and in particular the hair, with a composition comprising at least one modified photocrosslinkable polymer. Such a composition makes it possible to obtain a jacket that is resistant to washing.
It is known to those skilled in the art to use photocurable materials such as materials derived from vinyl monomers, and especially monomers (meth) acrylates.
Thus, the document US Pat. No. 5,300,285 describes a method for waving the hair and a composition for carrying out this method, and in particular a neutralizing composition based on silicone, comprising a vinyl-functional silicone, a free radical photoinitiator and a solvent. This composition acts as a substitute for neutralizing solutions based on hydrogen peroxide when it is applied to the hair after a process of permanent deformation of the hair and photocrosslinking of the composition. This composition has the advantage of functioning simultaneously as a keratin crosslinking agent, while giving the hair benefits such as conditioning and a soft touch. The photocrosslinking of the composition is triggered by the photoinitiator (generally an acetophenone derivative), which releases a radical under irradiation in the UVA range (350-385 nm).
Unfortunately, the photopolymerization of the vinyl-functional silicone in the presence of a photoinitiator leads to irreversible photocrosslinking of the vinyl-functional silicone. In other words, once photocrosslinked, the deposit can not be easily removed at any time from the hair.
Japanese Patent JP 09249812 discloses interpenetrating networks containing chelate-forming molecules and their uses, and more particularly compositions containing partially saponified polyvinyl acetate polymers with stilbazolium groups, crosslinked and containing chelating agents. This previously crosslinked material can then be used as it is in medical or cosmetic applications. However, there is no mention in this doucment of an application on the hair before irradiation.
The document EP1572139 describes a photodimerizable composition making it possible to deposit on keratin materials, in particular the hair. This document teaches that such deposits make it possible to obtain a residual deposit that provides durable cosmetic properties over time and is easily removable. The deposits obtained from the crosslinkable compounds described in this document, however, have a limited remanence. Moreover, the deposition of these compounds on the hair is not uniform and very largely depends on the level of damage to the hair. Thus, the result is not uniform between the tip and the hairline.
The present invention therefore aims to provide a method for treating keratin materials from a composition comprising a photocurable polymer which does not have the disadvantages of the compositions of the state of the art. In particular, the objective of the invention is to develop photodimerizable compositions resistant to washes, allowing a uniform deposition on the whole of the hair, on natural hair and damaged hair.
Thus, the subject of the present invention is a process for treating keratin materials, comprising the application of a composition comprising at least one photocrosslinkable polymer comprising at least one photodimerizable pendant group and at least one hydrophobic pendant group and an irradiation step of the composition on keratin materials for crosslinking the composition.
For the purposes of the present invention, and unless a different indication is given: an "alkylene chain" represents a divalent C1-C20 acyclic hydrocarbon chain; especially C1-C6, more particularly Cr C2 when the chain is linear; optionally substituted with one or more groups, identical or different, selected from i) hydroxy, ii) (CrC2) alkoxy, iii) (poly) hydroxy (C2-C4) alkoxy (di) (CrC2) (alkyl) amino, iv) Ra-Za-C (Zb) -Zc-, and v) Ra-Za-S (O) t ~ Zc- with Za, Zb, which may be identical or different, representing an oxygen atom, sulfur atom or an NRa group Zc, representing a bond, an oxygen atom, sulfur atom, or an NRa group; Ra, representing an alkali metal, a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and Ra 'represents a hydrogen atom or an alkyl group; more particularly the group iv) are chosen from carboxylate -C (O) 0 'or -C (O) 0Metal (Metal = alkali metal), carboxyl -C (O) -OH, guanidino H2H-C (NH2) -NH- , amidino H2H-C (NH2) -, (thio) ureo H2N-C (O) -NH- and H2N-C (S) -NH-, aminocarbonyl -C (O) -NRa'2 or aminothiocarbonyl -C (S) ) -NRa'2; carbamoyl Ra'-C (O) -NRa'- or thiocarbamoyl Ra'-C (S) -NRa'- with Ra ', which may be identical or different, representing a hydrogen atom or a (CrC4) alkyl group; the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent borne by a carbon atom, chosen from: a C1-C16 alkyl radical, preferably a C1-C18 alkyl radical, optionally substituted with one or more radicals selected from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) poly (C 2 -C 4) alkoxyalkyl, acylamino, amino substituted by two identical or different C 1 -C 4 alkyl radicals, optionally carrying at least one hydroxyl group or, the two radicals may form, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another identical heteroatom or different from nitrogen; a halogen atom; a hydroxyl group; a C 1 -C 2 alkoxy radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (CrC4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group, ii) an amino group optionally substituted by one or two optionally substituted C 1 -C 3 alkyl radicals, said radicals alkyl which can form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered saturated or unsaturated heterocycle optionally comprising at least one other heteroatom which is different from or different from nitrogen, iii) a quaternary ammonium group -N + R'R "R" ', M' for which R ', R ", R'", which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M 'represents the counter-ion of the organic acid, mineral or of the corresponding halide, iv) or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) radical; alkyl, preferably methyl; an acylamino radical (-NR-C (O) -R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is an alkyl radical; C1-C2; a carbamoyl radical ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical or a phenyl radical; an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); a cyano group; a nitro or nitroso group; a polyhaloalkyl group, preferentially trifluoromethyl; the cyclic, cycloalkyl or heterocyclic part of a nonaromatic radical may be substituted by at least one substituent chosen from hydroxyl groups; C 1 -C 4 alkoxy, (poly) C 2 -C 4 hydroxyalkoxy; C1-C4 alkyl; alkylcarbonylamino (RC (O) -N (R ') -) in which the radical R' is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is an alkyl radical; CrC2, amino optionally substituted with one or two identical or different C 1 -C 4 alkyl groups, themselves optionally carrying at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising 5- to 7-membered, optionally substituted saturated or unsaturated compound optionally comprising at least one other non-nitrogen heteroatom; alkylcarbonyloxy (RC (O) -O-) in which the radical R is a C 1 -C 4 alkyl radical, an amino group optionally substituted by one or two identical or different C 1 -C 4 alkyl groups, themselves optionally bearing at least one hydroxyl group, said alkyl radicals being capable of forming, with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle optionally comprising at least one other heteroatom which is different from or different from nitrogen; alkoxycarbonyl (RGC (O) -) in which the radical R is a C 1 -C 4 alkoxy radical, G is an oxygen atom, or an amino group optionally substituted with a C 1 -C 4 alkyl group, which may itself carry at least one hydroxyl group, said alkyl radical being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle optionally comprising at least one other heteroatom which is different from or different from nitrogen; a cyclic, cycloalkyl or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted by one or more oxo groups; a cycloalkyl radical is a mono or bicyclic hydrocarbon radical comprising from 3 to 10 carbon atoms, preferably from 4 to 7 carbon atoms such as cyclopentyl or cyclohexyl; a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; an "aryl" radical represents a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; a "heteroaryl radical" represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and wherein at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt; a "heterocyclic radical" is a radical which may contain one or two unsaturated but non-aromatic, mono or polycyclic, condensed or non-fused, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from the nitrogen atom, from oxygen, sulfur and selenium; a "heterocycloalkyl radical" is a heterocyclic radical comprising at least one saturated ring; a "cationic heteroaryl radical" is a heteroaryl group as defined previously which comprises an endocyclic or exocyclic quaternized cationic group, o when the cationic charge is endocyclic, it is taken in the mesomeric effect of electronic delocalization, for example it is pyridinium, imidazolium or indolinium group:
with R and R 'being a heterorayl substituent as defined above and particularly a (hydroxy) (CrC8) alkyl group such as methyl; when the charge is exocyclic, for example it is a substituent R + ammonium, phosphonium such as trimethylammonium, being outside the heteroaryl such as pyridinyl, indolyl, imidazolyl, or naphthalimidyl in question:
with R a heteroaryl substituent as defined above and R + an ammonium group RaRbRcN + -, phosphonium RaRbRcP + - or ammonium RaRbRcN + - (CrC6) alkylamino with Ra, Rb and Rc identical or different represent a hydrogen atom or a group (CrC8 ) alkyl such as methyl; a "cationic aryl with an exocyclic charge" is understood to mean an aryl ring whose quaternized cationic group is outside said ring, in particular R + ammonium or phosphonium substituent such as trimethylammonium, located outside the ring. aryl such as phenyl, or naphthyl:
an "alkyl radical" is a linear or branched C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 8 hydrocarbon radical; an "alkenylene radical" is a divalent unsaturated hydrocarbon radical as defined above which may contain from 1 to 4 double bonds -C = C-, conjugated or otherwise; particularly the alkenylene group contains 1 or 2 unsaturation (s); the expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxyl, ii) alkoxy C1-C4, iii) acylamino, iv) amino optionally substituted by one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a heterocylle comprising from 5 to 7 ring members, optionally comprising another heteroatom different from or not nitrogen; v) or a quaternary ammonium group -N + R'R "R '", M' for which R ', R ", R'", which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group; or -N + R'R "R '" forms a heteroaryl such as imidazolium optionally substituted with a C1-C4 alkyl group, and Me represents the counter-ion of the corresponding organic, inorganic acid or halide ; an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C 1 -C 16 preferably C 1 -C 8; when the alkoxy group is optionally substituted, it implies that the alkyl group is optionally substituted as defined above; the term "organic or inorganic acid salt" is intended to mean, more particularly, the salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4, iv) acids alkylsulfonic: Alk-S (O) 20H such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C (O) OH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4; the term "anionic counterion" means an anion or an anionic group derived from organic or inorganic acid salt counterbalancing the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S (O) 20 'such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 20 'such as benzenesulphonate and toluenesulphonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkyl sulphates: Alk-O-S (O) O 'such as methysulphate and ethylsulphate; x) arylsulfates: Ar-O-S (O) O 'such as benzenesulphate and toluenesulphate; xi) Alkoxysulfates: Alk-O-S (O) 20 'such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-O-S (O) 20 ', xiii) phosphates O = P (OH) 2 O-, O = P (O-) 2-OH = P (O') 3, H0- [P (0) (0 -)] wP (0) (0 ') 2 with w being an integer; (xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate disulfate (O =) 2S (O ') 2 or SO42' and monosulfate HS04 '; the anionic counterion, derived from organic or inorganic acid salt, ensures the electroneutrality of the molecule so it is understood that when the anion comprises several anionic charges then the same anion can be used for the electroneutrality of several cationic groups in the same molecule or else can be used for the electroneutrality of several molecules; for example, polymers which comprise two cationic entities may contain either two "monocharged" anionic ions or contain an anionic counterion "bicharged" such that (0 =) 2S (O ') 2 or 0 = P (O') 2 -0H; furthermore, the addition salts that can be used in the context of the invention are especially chosen from addition salts with a cosmetically acceptable base, such as alkalinizing agents as defined below, such as alkali metal hydroxides such as sodium hydroxide potash, ammonia, amines or alkanolamines; the expression "at least one" is equivalent to "one or more"; and the term "inclusive" for a range of concentrations means that the range terminals fall within the defined range.
By "photodimerizable" group is meant, in the sense of the present invention, a chemical group leading to photodimerization reactions under irradiation. In the context of the invention, photodimerization is a chemical reaction between two double bonds (type 2 + 2) or two pairs of double bonds (type 4 + 4), and more particularly between two double bonds (type 2 2).
The case of a reaction between two double bonds can be schematized as follows:
These photodimerization reactions are defined in the document "Advanced Organic Chemistry, Marck J, 4th Edition, Wiley Interscience, NY 1992, p 855".
Thus, the double bond, when it is photo-stimulated, generally when it is subjected to UV radiation, is able to react with another double bond by cyclization.
According to the present invention, the double bond is said to be activated, that is to say that it is photodimerizable spontaneously without requiring the presence of a photoinitiator or a chemical initiator. The activation of this double bond is generally induced by the presence of an electron-withdrawing substituent in the alpha position of this photodimerizable double bond. As an electroattractive substitute, mention may be made of aromatic nuclei, such as phenyl optionally substituted by one or more halogen atoms, or electron-withdrawing groups such as NO 2, CN, R'-YC (Y ') -, R'- C (Y ') - Y-, R'-YC (Y') -Y-, R'-YS (O) 2-, -S (O) 2 -Y-R ', with R' representing an atom of hydrogen or a (CrC4) alkyl group optionally substituted with one or more halogen atoms, Y, and Y ', which may be identical or different, representing an oxygen, sulfur or NR "atom with R" representing a hydrogen atom; or a (CrC6) alkyl group.
The method according to the invention comprises a step a) of applying a composition comprising a polymer comprising at least one photodimerizable pendant group and at least one hydrophobic pendant group.
Preferably, the pendant photodimerizable groups that can be used according to the invention are chosen from the following monovalent radicals of formulas (I) and (II):
as well as their geometric isomers, formula (I) and (II) in which: Y and Z denote independently of each other a nitrogen atom or a group C (R) with R representing a hydrogen atom or a (CrC4) alkyl group such as methyl; - A represents a bond or a divalent group selected from radicals (CrC8) alkylenes, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio) carbonyls, (C2-C8) alkenylenes and combinations thereof; B represents a monovalent group selected from alkyl radicals (Cr C8), aryl radicals, optionally cationic heteroaryl, cycloalkyl, optionally cationic heterocycloalkyl, (thio) carbonyl, (C2-C8) alkenyls and combinations thereof; X represents a divalent group chosen from (C2-C8) alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio) carbonyl, (C2-C8) alkenylene radicals and combinations thereof; p represents an integer inclusive of between 1 and 5, in particular between 1 and 3, preferably p is 1;
represents the bond that connects the part of the monovalent radical to the rest of the molecule; and each of the groups mentioned may optionally be substituted by one or more halogen atoms or groups chosen from (C 1 -C 6) alkyl, hydroxy, amino, (C 1 -C 6) alkylamino, phenyl, and carboxy groups ( CrC6) alkoxy, (C1-C6) alkoxy (thio) carbonyl, hydrogen (thio) carbonyl, sulfonate R-O-S (O) 2- or RS (O) 2-O-, amide RR'NC (O) or RC (O) -N (R ') - or acyl RC (O) -, ammonium RR'R "N + - with R, R', and R", identical or different, representing a hydrogen atom or a (CrC4) alkyl group.
The dimerisable pendant groups according to the invention are especially those mentioned in patents US-2,811,510, EP 0 313 220, EP 0 313 221, EP 092 901, GB 2 030 575 and GB 2 076 826, as well as in the articles "Chemical Vol 83, 1983, p 507, "Polym, Paint color Journal 1988, 178, p 209" and "Current Trends in Polymer Photochemistry, Ellis Morwood Edition, NY, 1995". By way of example, mention may be made more particularly of the photodimerizable pendant groups chosen from the monovalent radicals of the following compounds: stilbene, - styrylpyridinium (stilbazolium) of formula and their geometric isomers
where • R1 and R3, which may be identical or different, represent a halogen atom or a (CrC6) alkyl group; or two contiguous R1 or R3 groups together with the carbon atoms which carry it a benzo group; R2 represents the hydrogen atom, a (CrC6) alkyl group optionally substituted by one or more halogen atoms such as chlorine or hydroxy, preferably R2 represents a (Cr C6) alkyl group such as methyl, ethyl, propyl; • q and r, represent an integer inclusive between 0 and 4; and • Q ", represents an anionic counterion preferably chosen from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulphates, methanesulphonates, p-toluenesulphonate;
represents the bond which connects the part of the monovalent radical to the remainder of the molecule, it being understood that the pendant group A2 may be connected to the remainder of the molecule via R2; preferably the link
is on the phenyl in the para position of the styryl group on Al or connected to the rest of the molecule via R2 on A2; preferentially the styryl group of and A2 is in para of the pyridinium group; styrylazolium of formula and their geometric isomers:
where: A represents a sulfur atom, an oxygen atom, or a group N R2 or C (R2) 2; and •
, Q ', r, q, R1, R2, and R3 being as defined above, preferably the bond
is on the para-phenyl group of the stryryl group, styrylpyrazine, chalcone, (thio) cinnamate and (thio) cinnamamide, maleimide, (thio) coumarin, - thymine, uracil, butadiene anthracene, pyridone, pyrrolizinone, acridizinium salts, furanone, phenylbenzoxazole, and their derivatives.
According to a particular embodiment, the photodimerizable pendant group or groups are chosen from: a) the photodimerizable group (s) carrying a stylbazolium function of formula (Ia) or (Ib) and their geometric isomers:
wherein: R represents a hydrogen atom, a C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl group; R 'represents a hydrogen atom or a C4-C4 alkyl group, and X- denotes an anionic counterion, preferably chosen from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulphates and methanesulphonates; p-toluenesulfonate; preferably the styryl group is in para of the pyridinium group and / or para of the bond;
X '(Ib) in which R "denotes a divalent alkylene radical having from 2 to 8 carbon atoms, R' represents a hydrogen atom or a C4-C4 alkyl group, and X 'having the same meaning as that described for the previous formula (la);
having the same meaning as before; preferably the styryl group is in para of the pyridinium group; or b) photodimerizable groups bearing a styrylazolium function of formula (IIa):
(Ha) wherein:
R 1 denotes hydrogen atom, a C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl group; A denotes a sulfur atom, an oxygen atom, or a group N R 'or C (R') 2, R '; with R 'representing the hydrogen atom or a C 1 -C 4 alkyl group, R' preferably representing the hydrogen atom; and X 'having the same meaning as that described for the preceding formula (la);
having the same meaning as before; preferably the styryl group is on phenyl in para
Such photodimerizable pendant groups have activated double bonds, so that the photodimerization of these double bonds is triggered spontaneously in the UVA domain, without requiring a photoinitiator.
By photoinitiator is meant, in the sense of the present invention, a compound which initiates the photodimerization reaction and releases a radical under irradiation, especially in the UV field.
According to a particular embodiment, the composition of the invention is free of photoinitiator.
According to the present invention, the polymer comprises one or more hydrophobic pendant groups. As hydrophobic pendant group, there may be mentioned: - saturated or unsaturated (C 1 -C 30) alkyl groups, optionally substituted and / or interrupted by one or more heteroatoms, - alkenyl groups, - aryl groups such as phenyl, pyridyl, furyl, indoyl, benzofuryl, thiophenyl, imizadoyl, oxazoyl, thiazoyl, pyrazinyl, pyrimidinyl; fluorinated groups such as fluoro-carbon groups, such as -CF3, -CHF2, -OCF3, -SCF3, CF3C (O) -, silicone groups such as -SiRaRbRc such that -Si (CH3) 3, polydimethylsiloxane- PDMS, -Si (OR) 3, PDMS α, α-diaminopropyl, PDMS α, α-dihydroxyalkyl, PDMS α, ω-dicarboxyalkyl, with Ra, Rb and Rc, identical or different, representing an optionally interrupted (CsC) alkyl group and / or terminated by one or more non-contiguous heteroatoms such as O, or S; and R representing a (CrC6) alkyl group.
Preferably the group (s) during (s) hydrophobic (s) are selected from a group (C2-C22) alkyl, more preferably from a group (C3-C16) alkyl.
The skeleton of the polymer may be of a varied nature. This polymer backbone can be natural or synthetic. As skeletons of natural polymers, mention may be made of polysaccharides. As a polysaccharide, mention may be made of xanthan, carrageenan, chitosan, cellulose and its derivatives, alginate, starch, dextran, pullulan, galactomannan and their biologically acceptable salts, as well as their derivatives. As synthetic skeleton, mention may be made of polyvinyl polymers and polydiorganosiloxanes.
Among the polyvinyl polymers, mention may be made of poly (vinyl acetate), partially or totally hydrolysed, and polyvinyl alcohol (PVA).
As regards the polymers having photodimerizable pendant groups bearing a stylbazolium function, they are obtained by reacting the polymer in question with a chemical entity comprising a group of formula (Ia) or (Ib).
Preferably, the chemical entity comprising a group (Ia) has a reactive group W of aldehyde or acetal type.
As chemical entities that can be used for grafting styrylpyridinium type groups, there may be mentioned the quaternary salts of 2- (4-formylstyryl) -pyridinium, 4- (4-formyl-styryl) -pyridinium, 2- (3-formylstyryl) ) -pyridinium, N-methyl-2- (4-formylstyryl) pyridinium, N-methyl-3- (4-formylstyryl) -pyridinium, N-methyl-2- (3-formylstyryl) -pyridinium, N-methyl-2 - (2-formylstyryl) pyridinium, N-ethyl-2- (4-formyl-styryl) -pyridinium, N- (2-hydroxyethyl) -2- (4-formylstyryl) -pyridinium, N- (2-hydroxyethyl) - 4- (4-Formylstyryl) -pyridinium, N-methyl-4- (4-formylstyryl) -pyridinium, N-methyl-4- (3-formylstyryl) -pyridinium.
The quaternary salts of pyridinium may be chloride, bromide, iodide, perchlorate, tetrafluoroborate, methosulphate, phosphate, sulphate, methanesulphonate or p-toluenesulfonate salts. Such chemical entities are described in GB-A-2030575.
Examples of entities that may be mentioned include 4- (4-formylphenylethenyl) 1-methylpyridiunium methosulfate, 1- (3-ethoxycarbonylmethyl) -4- [2- (4-formylphenyl) ethenyl] pyridinium bromide, methoxycarbonylpropyl) -4- [2- (4-formylphenyl) ethenyl] pyridinium bromide. Such entities are described in US 2007/0112094.
Preferably, n-methyl-4- (4-formylstyryl) pyridinium methylsulphate (RN = 74401-04-0) is used, in particular marketed by WAKO.
The synthesis, described hereinafter, of these polymers functionalized with photodimerizable groups such as those comprising a styryl group and hydrophobic groups is feasible by drawing on the protocol of T. Uhlich et al. (Reactive & Functional Polymers, 28, 55-40 (1995)).
Compound of formula (III) to (VIII) · in which, R, identical or different, represents a hydrogen atom, or a (CrCio) alkyl group, optionally substituted and / or interrupted by one or more heteroatoms, preferably R represents a hydrogen atom or a group (Cr C4) alkyl such as methyl, ethyl, or propyl, more preferably R represents a hydrogen atom; R1 represents a hydrogen atom, or a (CrCio) alkyl group, optionally substituted and / or interrupted by one or more heteroatoms, preferably R1 represents a hydrogen atom or a (CrC4) alkyl group; R2 represents a saturated or unsaturated (CrC3o) alkyl group, optionally substituted and / or interrupted by one or more heteroatoms, an alkenyl group, an aryl group such as phenyl, pyridyl, furyl, indoyl, benzofuryl, thiophenyl, imizadoyl, oxazoyl, thiazoyl, pyrazinyl, pyrimidinyl; a fluorinated group such as a fluoro-carbon group such as -CF3, -CHF2, -OCF3, -SCF3, CF3C (O) -a silicone group such as -SiRaRbRc such as -Si (CH3) 3, polydimethylsiloxane-PDMS, If (OR) 3, PDMS α, ω diaminopropyl, PDMS α, α-dihydroxyalkyl, PDMS α, ω-dicarboxyalkyl, with Ra, Rb and Rc, identical or different, representing a (Ci-Cs) alkyl group optionally interrupted and / or terminated by one or more non-contiguous heteroatoms such as O, or S; and R representing a (CrC6) alkyl group; preferably R2 represents a (C2-C22) alkyl group, more preferably (C3-C16) alkyl; A represents a group derived from a photodimerizable compound, preferably styrylpyridinium such as (I), (II), (Ai), (A2), (Ia), (Ib) or (IIa) as defined above, more particularly chosen from ( Ai) or (la) as defined previously; X represents an oxygen atom or a sulfur, preferably oxygen; X ', and X ", represent an oxygen atom, sulfur atom or a group N (R3) with R3 represents a hydrogen atom or a group (CrC4) alkyl, preferably X' and X" represent a d oxygen;
Mostly the products obtained are of formula (VI).
Advantageously, these chemical entities react with a polymer of the polyvinyl alcohol or polyvinyl acetal type as described in the documents cited above and also such as the polymer (III) described in the above scheme for which X, X and X "represent an atom of oxygen, R and R1 being as previously described.
For example, a polyvinyl alcohol graft polymer having units of the following structure is thus obtained, A representing a group (I), (A) or (la):
Polyvinyl alcohol polymers grafted with a stryrylpyridinium group are described in particular in the publication Ichimura K. et al., Preparation and Characteristics of photocrosslinkable polyvinyl alcohol, Journal of Polymer Science, Polymer Chemistry Edition, Vol 20, 1419-1432 (1982). .
The polymers can be obtained by reacting partially hydrolysed polyvinyl alcohol or polyvinylacetate with formyl or acetal-form styrylpyridinium salts as described in GB-A-2030575, WO 96/29312, US 5061603, GB-A-2076826, EP -A-092,901.
Cellulose polymers grafted with styrylpyrydinium groups are described in US 2007/0112094.
Preferably, the chemical entity having a group (A ·)) or (la) has a reactive group which is a halogen atom such as chlorine.
In this variant, the chemical entity responds, for example, to the formula:
Advantageously, the photocrosslinkable polymer comprising groups (Ib) is for example obtained by reaction of the above entity with the polysaccharide chosen from those defined above.
For their part, polymers having photodimerizable groups carrying a styrylazolium function are obtained by reaction of the polymer with a chemical entity comprising a group of formula (IIa).
Preferably, the chemical entity comprising a group (IIa) carries a reactive group W of aldehyde or acetal type.
As chemical entities that can be used to graft groups of the styrylazolium type, mention may be made of those described in EP-A-313220.
Advantageously, these chemical entities react with a polyvinyl alcohol or polyvinyl acetal type polymer as described in the documents cited above.
A polyvinyl alcohol graft polymer having units of the following structure is thus obtained with B corresponding to the group
or (IIa) as previously defined:
Polyvinyl alcohol polymers grafted with a styrylazolium group are especially described in EP-A-313220. In this document, these polymers can be obtained by reacting polyvinyl alcohol or polyvinylacetate partially hydrolysed with styrylazolium salts with an aldehyde or acetal group.
According to one embodiment, the polymer carrying photodimerizable group (s) and hydrophobic group (s) is in the form of particles, in particular dispersed particles. Thus, in the latter case, the polymer particles are more particularly polyvinyl alcohol particles.
According to a preferred embodiment, the polymer bearing photodimerizable group (s) and hydrophobic group (s) of the invention is soluble in the cosmetic medium.
Thus, according to one variant embodiment, the polymer is a polyvinyl acetate (PVA) polymer functionalized in part by one or more hydroxyl function (s) and one or more function (s) of formula (IX):
The degree of polymerization of the PVA can be between 100 and 5000 and the degree of substitution, in% of functions of formula (I) as defined above, can be between 0.1 and 25.
The following scheme represents a variant where the polymer is the polymer (III) as defined above bearing functions grafted by stylbazolium entities such as those of formula (A1) as defined above, which is capable of crosslinking under the effect of light, as illustrated below.
These materials react to radiation that can have both a component of UV light and visible light, in particular a low dose of UV.
Preferably, the following scheme represents the polymer which is PVA-SbQ (PVAcetate type polymer carrying some hydrolysed functions and some functions grafted by stylbazolium entities), which is capable of crosslinking under the effect of light, as illustrated below. after.
These materials are particularly preferred because they do not require a photoinitiator and react to radiation which may include both a component of UV light and visible light, in particular a low dose of UV.
Pendant groups having a reactivity in both UV light and visible light are preferred.
According to another variant embodiment, the photocrosslinkable polymer is represented by a natural polymer which is functionalized by photodimerizable groups and hydrophobic groups.
It may in particular be a polysaccharide that can be chosen from chondroitin sulfate, keratan, keratan sulfate, heparin, heparin sulfate, xanthan, carrageenan, hyaluronic acid, chitosan, cellulose and its derivatives, alginate, starch, dextran, pullulan, galactomannan and their biologically acceptable salts.
The degree of functionalization is of course adjusted to be able to confer the degree of crosslinking required during activation.
According to the invention, the degree of functionalization in a photodimerizable unit is at least 0.1%, or even at least 0.5%, or even at least 2%.
Preferably, in a composition according to the invention, the photodimerizable groups are carried by a polymer of the polyvinyl acetate or polysaccharide type.
The crosslinkable polymer may be conveyed in an aqueous medium.
The composition may contain a single polymer bearing photodimerizable pendant groups of different or different nature.
It is also possible to use a mixture of polymers having different functions.
Consequently, the reactions can take place between two photodimerizable groups of the same chemical nature or not.
The activated double bonds can react on another double bond of the same chemical nature or react with another double bond of different chemical nature. By way of example of a polymer useful in the invention, mention may be made of the PVA polymer comprising pendant groups below called PVA-SbQ-propional in which the amount of SbQ unit is between, inclusive limits, 0.5 and 5 mol%, preferably between 2 and 4 mol%, for example of the order of 2 mol%, the amount of propional group is between, inclusive limits, 2 and 20 mol%, preferably between 5 and 15 mol% , for example of the order of 10 mol%, the amount of hydroxyl group is between, inclusive limits, 50 and 97.5 mol%, preferably between 60 and 97.5 mol%, for example about 86 mol%:
with Q 'as previously defined preferably mesylate CH3OSO3 ·;
According to a particular embodiment, the molecular weight Mw of the PVA is between 10,000 and 100,000 g / mol, preferably between 25,000 and 80000 g / mol.
According to a particular embodiment, the molecular weight Mw is of the order of 27000 g / mol.
The polymer (s) comprising at least one photodimerizable group and a hydrophobic group represent (s) preferably from 0.01 to 25%, better still from 0.1 to 20%, and better still from 1 to 15% of the total weight. of the composition.
The composition according to the invention may further comprise an effective amount of at least one photosensitizer.
By photosensitizer is meant in the sense of the present invention, an ingredient that changes the wavelength of irradiation, thereby triggering the photodimerization reaction.
For example, the photodimerization of dimethylmaleimide groups is triggered by irradiation centered on the wavelength range of 270 to 300 nm. In the presence of a photosensitizer such as thioxanthone, the photodimerization becomes effective with an irradiation centered on the wavelength range of 360 to 430 nm.
Among the photosensitizers that may be used according to the invention, there may be mentioned thioxanthone, bengal rose, phloxine, eosin, erythrosine, fluorescein, acriflavine, thionine, riboflavin, proflavine, chlorophylls , hematoporphyrin, methylene blue and mixtures thereof.
In practice, the photosensitizer used according to the invention represents 0.00001% to 5% by total weight of the composition.
The composition may further comprise one or more fatty substances.
By "fatty substance" is meant an organic compound insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa), that is to say, of solubility less than 5% and preferably less than 1%, more preferably less than 0.1%.
The fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as, for example, chloroform, ethanol, benzene, liquid petrolatum or decamethylcyclopentasiloxane.
The fatty substances may be solid or liquid, preferably liquid.
The liquid fatty substances that can be used in the invention are liquid at ambient temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa). They preferably have a viscosity less than or equal to 2 Pa.s, better still less than or equal to 1 Pa.s and better still less than or equal to 0.1 Pa.s at the temperature of 25 ° C. and at a shear rate. of 1 s'1.
The liquid fatty substances that may be used in the composition according to the invention are generally not oxyalkylenated and preferably do not contain a carboxylic acid function COOH.
Preferably, the liquid fatty substances are chosen from hydrocarbons, fatty alcohols, fatty esters, fatty ethers, silicones and their mixtures.
Even more preferentially, they are chosen from hydrocarbons, fatty alcohols, fatty esters and silicones, preferably volatile silicones, and mixtures thereof.
By liquid hydrocarbon is meant a hydrocarbon composed solely of carbon atoms and hydrogen, liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa), of mineral or vegetable origin. or synthetic.
More particularly, the liquid hydrocarbons are chosen from: linear or branched C6-C16 alkanes, which may be cyclic. By way of examples, mention may be made of hexane, undecane, dodecane, tridecane and isoparaffins such as isohexadecane, isododecane and isodecane, and mixtures thereof. linear or branched hydrocarbons of animal or synthetic mineral origin, of more than 16 carbon atoms, such as paraffin or petroleum jelly oils, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as that sold under the Parléam® brand by NOF Corporation, the squalane.
In a preferred variant, the liquid hydrocarbon or hydrocarbons are chosen from linear or branched, optionally cyclic C6-C16 alkanes.
By liquid fatty alcohol is meant a non-glycerolated and non-oxyalkylenated fatty alcohol, liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).
Preferably, the liquid fatty alcohols of the invention comprise from 8 to 30 carbon atoms, more preferably from 8 to 20 carbon atoms.
The liquid fatty alcohols of the invention can be saturated or unsaturated.
Saturated liquid fatty alcohols are preferably branched. They may optionally comprise in their structure at least one aromatic cycle or not. Preferably, they are acyclic.
More particularly, the liquid saturated fatty alcohols of the invention are chosen from octyldodecanol, isostearyl alcohol and 2-hexyldecanol. Octyldodecanol is particularly preferred.
The unsaturated liquid fatty alcohols have in their structure at least one double or triple bond, and preferably one or more double bonds. When more than one double bond is present, it is preferably 2 or 3 and may or may not be conjugated.
These unsaturated fatty alcohols can be linear or branched.
They may optionally comprise in their structure at least one aromatic cycle or not. Preferably, they are acyclic.
More particularly, the liquid unsaturated fatty alcohols of the invention are chosen from oleic (or oleyl) alcohol, linoleic (or linoleyl) alcohol, linolenic (or linolenyl) alcohol, and undecylenic alcohol. Oleyl alcohol is particularly preferred.
By liquid fatty ester is meant an ester derived from a fatty acid and / or a fatty alcohol, liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa).
The esters are preferably the liquid esters of linear or branched C 1 -C 26 saturated or unsaturated aliphatic mono- or polyacids and linear or branched C 1 -C 26 saturated or unsaturated aliphatic mono- or polyalcohols, the total number of the carbon atoms of the esters being greater than or equal to 10.
Preferably, for the monoalcohol esters, at least one of the alcohol or the acid from which the esters of the invention are derived is branched.
Among monoesters of monoacids and monoalcohols, mention may be made of ethyl and isopropyl palmitates, alkyl myristates such as isopropyl or ethyl myristate, isocetyl stearate, isononanoate of 2 ethylhexyl, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.
It is also possible to use esters of C 4 -C 22 di- or tricarboxylic acids and of C 1 -C 22 alcohols and esters of mono-, di- or tricarboxylic acids and of non-sugar alcohols di-, tri- , tetra- or pentahydroxylated C4-C26.
Mention may especially be made of diethyl sebacate, diisopropyl sebacate, di (2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, di-di-adipate and the like. (2-ethylhexyl), diisostearyl adipate, di (2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, trisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, citrate of trioctyldodecyl, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononate.
The composition may also comprise, as liquid fatty ester, esters and diesters of sugars and of C6-C30 fatty acids, preferably of C12-C22 fatty acids. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms.
These sugars can be monosaccharides, oligosaccharides or polysaccharides.
Suitable sugars include, for example, sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their alkylated derivatives, such as than methylated derivatives such as methylglucose.
The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30, preferably C 12 -C 22 fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise.
The esters according to this variant can also be chosen from mono-, di-, tri- and tetraesters, polyesters and their mixtures.
These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates, and mixtures thereof, such as, in particular, the oleo-palmitate, oleostearate and palmito-stearate mixed esters.
More particularly, mono- and di-esters, and especially mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, oleostearates, sucrose, glucose or methylglucose are used.
By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Finally, it is also possible to use natural or synthetic esters of mono-, di- or triacids with glycerol.
Among these, we can mention vegetable oils.
As vegetable oils or synthetic triglycerides, used in the composition of the invention as liquid fatty esters, there may be mentioned for example: triglyceride oils of plant or synthetic origin, such as liquid triglycerides of fatty acids having from 6 to 30 carbon atoms, such as the triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soya, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, olive, rapeseed, copra, wheat germ, sweet almond, apricot, safflower, bancoulan nut , camellina, tamanu, babassu and pracaxi triglycerides of caprylic / capric acids such as those sold by the company STEARINERIES DUBOIS or those sold under the names Miglyol® 810, 812 and 818 by the company DYNAMIT NOBEL, the oil of jojoba, the oil of shea butter.
Preferably, as esters according to the invention, liquid fatty esters derived from monoalcohols will be used.
Myristate or isopropyl palmitate are particularly preferred.
The liquid fatty ethers are chosen from liquid dialkyl ethers such as dicaprylyl ether.
The liquid fatty substance (s) that may be used in the composition according to the invention may be chosen from silicones.
Preferably, the liquid silicone or silicones are chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from amino groups, aryl groups and alkoxy groups.
Organopolysiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or nonvolatile.
The nonvolatile liquid silicones that may be used in the composition according to the invention may preferably be liquid nonvolatile polydialkylsiloxanes, polyorganosiloxanes modified with organofunctional groups chosen from amine groups, aryl groups and alkoxy groups, as well as mixtures thereof.
These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C.
Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or MIRASIL® oils marketed by RHODIA;
the oils of the MIRASIL® series marketed by RHODIA) the oils of the 200 series of the company Dow Corning; - VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC.
Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA.
The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
The organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.
The polyalkylarylsiloxanes are particularly chosen from polydimethyl / methylphenylsiloxanes, linear and / or branched polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C.
Among these polyalkylarylsiloxanes, mention may be made by way of example of the products sold under the following names: SILBIONE® oils of the 70 641 series from RHODIA; - the RHODORSIL® 70 633 and 763 RHODIA series of oils; - DOW CORNING 556 COSMETIC GRAD FLUID oil from Dow Corning; the silicones of the PK series of BAYER, such as the product PK20; the silicones of the PN, PH series of BAYER, such as the PN1000 and PH 1000 products; - some oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.
Among the organomodified silicones, mention may also be made of polyorganosiloxanes comprising: substituted or unsubstituted amino groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; alkoxylated groups, such as the product marketed under the name "Silicone Copolymer F-755" by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT.
The volatile silicones are more particularly chosen from those having a boiling point between 60 ° C. and 260 ° C., and more particularly still from: (i) cyclic silicones containing from 3 to 7 silicon atoms and preferably from 4 to 6 .
It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name "VOLATILE SILICONE 7207" by the company UNION CARBIDE or "SILBIONE 70045 V 2" by Rhodia, the decamethylcyclopentasiloxane marketed under the name "VOLATILE SILICONE 7158 "by the company UNION CARBIDE," SILBIONE 70045 V 5 "by RHODIA, and mixtures thereof.
Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "VOLATILE SILICONE FZ 3109" marketed by UNION CARBIDE, of chemical structure:
Mention may also be made of cyclic silicone mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '(hexamethylcyclotetrasiloxane). 2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane.
Linear volatile silicones having 2 to 9 silicon atoms and having a viscosity less than or equal to 5 × 10 -6 m 2 / s at 25 ° C. They are, for example, hexamethyldisiloxane, octamethyltrisioloxane and decamethyltetrasiloxane marketed especially under the name "SH 200" by the company TORAY SILICONE. Silicones included in this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". Preferably, linear volatile silicones contain from 2 to 7 silicon atoms, more preferably from 3 to 6 silicon atoms.
Preferably, the volatile silicones are chosen from cyclic silicones containing from 4 to 6 silicon atoms and linear silicones containing from 4 to 6 silicon atoms.
Preferably, the silicones are chosen from volatile silicones.
Preferably, the liquid fatty substance (s) is or are chosen from linear or branched C6-C16 alkanes such as undecane, tridecane and isododecane, and mixtures thereof; triglyceride oils of plant origin such as coconut oil or avocado oil; fatty esters such as isopropyl myristate; branched fatty alcohols; linear or cyclic volatile silicones comprising less than 7 silicon atoms, preferably 4 to 6 silicon atoms; and their mixtures.
Even more preferentially, the liquid fatty substances are chosen from linear or branched C6-C16 alkanes, in particular such as isododecane, undecane, tridecane and their mixtures, and linear or cyclic volatile silicones comprising less than 7 carbon atoms. silicon atoms, preferably from 4 to 6 silicon atoms.
By non-liquid fatty substance is meant a solid compound or a compound having a viscosity greater than 2 Pa.s at a temperature of 25 ° C. and at a shear rate of 1 s -1.
In a first variant of the invention, the non-liquid fatty substances are chosen from non-silicone non-liquid fatty substances. Preferably, the non-silicone non-liquid fatty substances are chosen from fatty alcohols, fatty acid esters and / or fatty alcohol esters, non-silicone waxes, amines and fatty, non-liquid and preferably solid ethers.
More particularly, the non-liquid fatty alcohols according to the invention are chosen from saturated or unsaturated alcohols, linear or branched, containing from 8 to 30 carbon atoms.
For example, cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol) may be mentioned. More particularly, cetylstearyl alcohol is used.
The fatty acid esters and / or non-liquid fatty alcohol esters that can be used in the composition according to the invention are generally chosen from solid esters derived from C 9 -C 26 fatty acids and from C 9 -C 26 fatty alcohols. .
By way of example, octyldodecyl behenate, isoketyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate and oleate may be mentioned as examples. decyl alcohol, myristyl stearate, octyl palmitate, octyl pelargonate, octyl stearate, alkyl myristates such as cetyl, myristyl or stearyl myristate, and hexyl stearate .
The non-silicone wax or waxes are chosen in particular from carnauba wax, candelila wax, alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of blackcurrant sold by the company BERTIN (France), animal waxes such as beeswax, or modified beeswaxes (cerabellina) and ceramides.
The solid amides that can be used in the composition according to the invention are chosen from ceramides or ceramide analogues, such as natural or synthetic glycoceramides, which correspond to the following formula (IV):
(IV) in which: R 'denotes a linear or branched, saturated or unsaturated, alkyl radical derived from C14-C30 fatty acids, this radical possibly being substituted by a hydroxyl group in the alpha position, or a hydroxyl group in omega position esterified with a saturated or unsaturated C16-C30 fatty acid; - R "denotes a hydrogen atom or a (glycosyl) n, (galactosyl) m or sulfogalactosyl radical, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8; - R '"denotes a hydrocarbon radical C15-C26, saturated or unsaturated in the alpha position, this radical may be substituted by one or more C1-C14 alkyl radicals; It being understood that in the case of natural ceramides or glycoceramides, R '' may also denote a C15-C26 alpha-hydroxyalkyl radical, the hydroxyl group optionally being esterified with a C16-C30 alpha-hydroxy acid.
Preferred ceramides in the context of the present invention are those described by DOWNING in Arch. Dermatol, Vol. 123, 1381-1384, 1987, or those described in French patent FR 2 673 179.
The most preferred ceramide or ceramides that can be used in the composition according to the invention are the compounds for which R 'denotes a saturated or unsaturated alkyl derived from C 16 -C 22 fatty acids, R "denotes a hydrogen atom and R'" denotes a C15 saturated linear radical.
Preferably, the following compounds may be chosen: N-linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N-palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, N-behenoyldihydrosphingosine and a mixture of these compounds.
Even more preferably, the ceramides for which R 'denotes a saturated or unsaturated alkyl radical derived from fatty acids, R "denotes a galactosyl or sulphogalactosyl radical and R'" denotes a group -CH = CH- (CH 2) 12- CH3. Other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes, such as those sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general.
The non-liquid fatty ethers that can be used in the composition according to the invention are chosen from dialkyl ethers, in particular dicetyl ether and distearyl ether, alone or as a mixture.
In a second variant of the invention, the non-liquid fatty substance (s) may be chosen from non-liquid silicone fatty substances, such as silicone gums or resins.
The silicone gums that can be used in accordance with the invention are, in particular, polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights ranging from 200,000 to 1,000,000 used alone or as a mixture in a solvent.
Said solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures.
More particularly useful products according to the invention are mixtures such as: - mixtures formed from an end-hydroxylated polydimethylsiloxane, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such that the product Q2 1401 marketed by the company Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500,000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMSs of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5 × 10 -6 m 2 / s. This product preferably comprises 15% of SE 30 gum and 85% of an SF 96 oil.
The organopolysiloxane resins used in accordance with the invention are crosslinked siloxane systems containing the units: (R 7) 2 SiO 2/2, (R 7) 3 SiO 1/2, R 7 SiO 3/2 and SiO 4/2 in which R 7 represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R 7 denotes a lower C 1 -C 4 alkyl group, more particularly methyl.
Among these resins may be mentioned the product marketed under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure.
Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.
When it comprises, the (s) fat (s), preferably liquid (s), is or are present in the composition in an amount ranging from 1 to 30%, better still from 3 to 20% by weight, and more preferably from 5 to 15% by weight, relative to the total weight of the composition.
The composition may further comprise one or more surfactants. As examples of surfactants, mention may be made of anionic, amphoteric, zwitterionic, cationic or nonionic surfactants.
The term "anionic surfactant" is understood to mean a surfactant comprising as ionic or ionizable groups only anionic groups. These anionic groups are preferably chosen from the groups -C (O) OH, -C (O) O-, -SO 3 H, -S (O) 20 -, - O (O) 20H, -SO (O) 20 ' , -P (O) OH2, -P (O) 20-, -P (O) O2-, -P (OH) 2, = P (O) OH, -P (OH) O ', = P (0) 0 ', = POH, = PO-, the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline earth metal, or an ammonium. As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates, alkyl amide sulphonates and alkyl aryl sulphonates. , alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, D-galactoside-uronic acid salts, alkyl ether-carboxylic acid salts, alkyl aryl ether-carboxylic acid salts, salts of of alkyl amidoether carboxylic acids, and the corresponding non-salified forms of all these compounds, alkyl and acyl of all these compounds having from 6 to 40 carbon atoms and the aryl group denoting a phenyl group.
These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
The salts of C 6 -C 24 alkyl monoesters and of polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside-citrates, C 6 -C 24 alkyl polyglycoside-tartrates and polyglycoside-sulphosuccinates. C6-C24 alkyl.
When the agent or the anionic surfactants are in the salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular aminoalcohols or alkaline earth metal salts such as magnesium salts. By way of example of aminoalcohol salts, mention may be made in particular of the salts of mono-, di- and triethanolamine, the salts of mono-, di- or triisopropanolamine and the salts of 2-amino-2-methyl-1-one. propanol, 2-amino-2-methyl-1,3-propanediol and tris (hydroxy-methyl) amino methane.
The alkali metal or alkaline earth metal salts and in particular the sodium or magnesium salts are preferably used.
Of the abovementioned anionic surfactants, it is preferred to use C 8 -C 24 alkyl sulphates, C 6 -C 24 alkyl ether sulphates comprising from 2 to 50 ethylene oxide units, especially in the form of alkali metal or ammonium salts. , aminoalcohols, and alkaline earth metals, or a mixture of these compounds.
In particular, it is preferred to use the (C 12 -C 20) alkylsulphates, the (C 12 -C 20) alkyl ethersulphates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium or aminoalcohol salts. , and alkaline earth metals, or a mixture of these compounds. More preferably, it is preferred to use sodium lauryl ether sulfate with 2.2 moles of ethylene oxide.
The amphoteric or zwitterionic surfactant (s) that can be used in the present invention are preferably non-silicone. They may be in particular derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may in particular be made of (C 8 -C 20) alkyl betaines, sulfobetaines, (C 8 -C 20) alkylamido (C 3 -C 8) alkyl betaines and (C 8 -C 20) alkylamidalkyl (C 6 -C 8) sulfobetaines.
Among the derivatives of secondary or tertiary aliphatic amines, optionally quaternized, which may be used, as defined above, there may also be mentioned the compounds of the respective structures (A10) and (A20) as follows: Ra-C (O) -NH-CH2 -CH 2 -N + (Rb) (Rc) -CH 2 C (O) Cr, M +, X '(A 10)
Formula (A10) in which:
Ra represents a C 10 -C 30 alkyl or alkenyl group derived from an acid RaCOOH, preferably present in hydrolysed coconut oil, a heptyl, nonyl or undecyl group;
Rb represents a beta-hydroxyethyl group; and
Rc represents a carboxymethyl group; M + represents a cationic counterion derived from an alkali metal, alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and X 'represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl (CrC4) sulphates, alkyl (CrC4) - or alkyl (CrC4) aryl sulphonates, in particular methyl sulphate and ethyl sulphate; or else M + and X 'are absent;
Ra'-C (O) -NH-CH 2 -CH 2 -N (B) (B ') (A 20)
Formula (A20) wherein: B is -CH2-CH2-0-X '; B 'represents the group - (CH2) ZY', with z = 1 or 2; X 'represents the group -CH2-C (O) OH, -CH2-C (O) OZ', -CH2-CH2-C (O) OH, -CH2-CH2-C (O) OZ ', or an atom hydrogen; Y 'represents the group -C (O) OH, -C (O) OZ', -CH2-CH (OH) -SO3H or the group -CH2-CH (OH) -SO3-Z '; Z 'represents a cationic counterion derived from an alkaline or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
Ra 'represents a C10-C30 alkyl or alkenyl group of a Ra'-C (O) OH acid preferably present in coconut oil or in hydrolyzed linseed oil, an alkyl group, especially in Cm and its iso form, an unsaturated Cm group.
These compounds of formula (A10) and (A20) are classified in the CTFA dictionary, 5th edition, 1993, under the names cocoamphodiacétate disodium, lauroamphodiacétate disodium, caprylamphodiacétate disodium, capryloamphodiacétate disodium, cocoamphodipropionate disodium, lauroamphodipropionate disodium, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid, cocoamphodipropionic acid. By way of example, mention may be made of cocoamphodiacetate marketed by Rhodia under the trade name MIRANOL® C2M concentrate.
It is also possible to use compounds of formula (A'20);
Ra "-NH-CH (Y") - (CH2) n-C (O) -NH- (CH2) n -N (Rd) (Re) (B'20)
Wherein Y "is -C (O) OH, -C (O) OZ", -CH2-CH (OH) -SO3H or -CH2-CH (OH) -SO3-Z ";
Rd and Re, independently of one another, represent a C 1 -C 4 alkyl or hydroxyalkyl radical; Z "represents a cationic counterion derived from an alkaline or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
Ra "represents a C10-C30 alkyl or alkenyl group of an acid Ra'-C (O) OH which is preferably present in coconut oil or in hydrolysed linseed oil. n and n ', independently of one another, denotes an integer ranging from 1 to 3.
Among the compounds of formula (A'20), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and marketed by Chimex under the name Chimexane HB.
Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of alkyl (C 8 -C 20) betaines such as cocobetaine, (C 8 -C 20) alkylamido (C 3 -C 8) alkylbetaines, such as cocamidopropylbetaine, the compounds of formula (B'20) such as the sodium salt of diethylaminopropyl lauryl amino succinamate (INCI name) sodium diethylaminopropyl cocoaspartamide) and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactant (s) is (are) chosen from cocamidopropylbetaine and cocobetaine.
The cationic surfactant (s) that may be used in the composition according to the invention comprise, for example, primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated, quaternary ammonium salts, and mixtures thereof. As quaternary ammonium salts, there may be mentioned, for example: - those of the following general formula (A30):
(A30)
Formula (A30) in which: R8 to R11, which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one R8 to R11 groups have from 8 to 30 carbon atoms, and preferably from 12 to 24 carbon atoms; and X 'represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl (Cr C4) sulphates, alkyl (CrC4) - or alkyl (CrC4) aryl sulphonates, in particular methyl sulphate and ethylsulfate.
The aliphatic groups of R8 to R11 may further comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens.
The aliphatic groups of R8 to R11 are, for example, chosen from C1-C30alkyl, C1-C30alkoxy, (C2-C6) polyoxyalkylene, C1-C30alkylamide, (C2-C22) alkylamido (C2-C6) alkyl, (C2-C6) alkyl, C22) acetate, and hydroxyalkyl to CrC30, X- is an anionic counterion selected from halides, phosphates, acetates, lactates, alkyl (CrC4) sulfates, alkyl (CrC4) - or alkyl (CrC4) aryl sulfonates. Among the quaternary ammonium salts of formula (A3), tetraalkylammonium chlorides, for example dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group comprises from about 12 to 22 carbon atoms, are preferred. carbon, in particular behenyltrimethylammonium, distearyl dimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides, or distearoylethylhydroxyethylmethylammonium methosulphate, dipalmitoylethylhydroxyethylammonium methosulphate or distearoylethylhydroxyethylammonium methosulphate, or, finally, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl (myristyl acetate) ammonium chloride sold under the name CERAPHYL® 70 by VAN DYK; the quaternary ammonium salts of imidazoline, for example those of the following formula (A40):
(A40)
Formula (A40) wherein: R12 represents an alkenyl or alkyl group having 8 to 30 carbon atoms, for example derived from tallow fatty acids; R13 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group having from 8 to 30 carbon atoms; R14 represents a C1-C4 alkyl group; R15 represents a hydrogen atom, a C1-C4 alkyl group; X 'represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, alkyl (Cr C4) sulphates, alkyl (CrC4) - or alkyl (CrC4) aryl sulphonates.
Preferably, R12 and R13 denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R14 denotes a methyl group, R15 denotes a hydrogen atom. Such a product is for example marketed under the name REWOQUAT® W 75 by the company REWO; the quaternary di- or triammonium salts, in particular of the following formula (A5): (A50)
Formula (A50) in which: R16 denotes an alkyl group having from about 16 to 30 carbon atoms, optionally hydroxylated and / or interrupted by one or more oxygen atoms; R17 is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms or a group - (CH2) 3-N + (R16a) (R17a) (R18a), X-; R16a, R17a, R18a, R18, R19, R20 and R21, which are identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and X-, which may be identical or different, represent an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C 1 -C 4) alkyl sulphates, (C 1 -C 4) alkyl or (C 1 -C 4) alkyl. -C4) aryl-sulfonates, in particular methylsulfate and ethylsulfate.
Such compounds are, for example, the Finquat CT-P proposed by Finetex (Quaternium 89), the Finquat CT proposed by Finetex (Quaternium 75); quaternary ammonium salts containing one or more ester functions, such as those of formula (A6) below:
(A60)
Formula (A60) in which: R22 is selected from C1-C6 alkyl groups and hydroxyalkyl or C1-C6 dihydroxyalkyl groups, R23 is selected from: - the group
the linear or branched, saturated or unsaturated C 1 -C 22 hydrocarbon-based R 27 groups, the hydrogen atom, R 25 is chosen from:
the saturated or unsaturated linear or branched C1-C6 hydrocarbon groups R29, the hydrogen atom, R24, R26 and R28, which are identical or different, are chosen from linear or branched C7-C21 hydrocarbon groups; saturated or unsaturated; r, s and t, identical or different, are integers of 2 to 6, r1 and t1 identical or different, being 0 or 1 with r2 + r1 = 2r and t1 + t2 = 2t y is an integer ranging from 1 to 10, x and z, which may be identical or different, are integers ranging from 0 to 10, X 'represents an anionic counterion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0 then R23 is R27 and when z is 0 then R25 is R29.
The alkyl groups R22 may be linear or branched, and more particularly linear.
Preferably, R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group. Advantageously, the sum x + y + z is from 1 to 10.
When R 23 is a hydrocarbon R 27 group, it may be long and have 12 to 22 carbon atoms, or short and have 1 to 3 carbon atoms.
When R 25 is a hydrocarbon R 29 group, it preferably has 1 to 3 carbon atoms.
Advantageously, R24, R26 and R28, which are identical or different, are chosen from linear or branched, saturated or unsaturated C 1 -C 12 hydrocarbon-based groups, and more particularly from saturated or linear C 1 -C 12 alkyl and alkenyl groups. or unsaturated.
Preferably, x and z, identical or different, are 0 or 1.
Advantageously, y is 1.
Preferably, r, s and t, which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
The anionic counterion X 'is preferably a halide, such as chloride, bromide or iodide; an alkyl (CrC4) sulfate; alkyl (CrC4) or alkyl (CrC4) aryl sulfonate. However, it is possible to use methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.
The anionic counterion X 'is even more particularly chloride, methylsulfate or ethylsulfate.
In the composition according to the invention, the ammonium salts of formula (A60) are used more particularly in which: R22 denotes a methyl or ethyl group, x and y are equal to 1, z is equal to 0 or 1, - r, s and t are equal to 2, - R23 is chosen from: • the group
• methyl, ethyl or C4-C22 hydrocarbon groups, • the hydrogen atom,
- R25 is chosen from: • the group • the hydrogen atom, - R24, R26 and R28, identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
Advantageously, the hydrocarbon radicals are linear.
Examples of the compounds of formula (A60) include salts, especially diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium, monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof, especially diacyloxyethyldimethylammonium chloride or methylsulfate. The acyl groups preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl group, the latter groups may be identical or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldisopropanolamine, optionally oxyalkylenated, with fatty acids or with mixtures of fatty acids of plant or animal origin, or with transesterification of their methyl esters. This esterification is followed by quaternization using an alkylating agent such as an alkyl halide, preferably methyl or ethyl, a dialkyl sulphate, preferably methyl or ethyl sulphate. methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin.
Such compounds are, for example, sold under the names DEHYQUART® by the company HENKEL, STEPANQUAT® by the company STEPAN, NOXAMIUM® by the company CECA, REWOQUAT® WE 18 by the company REWO-WITCO.
The composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts.
It is also possible to use the ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180.
The behenoylhydroxypropyltrimethylammonium chloride proposed by KAO can be used under the name Quatarmin BTC 131.
Preferably the ammonium salts containing at least one ester function contain two ester functions.
Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose the salts of cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethyl-hydroxyethylmethylammonium, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride. dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
Examples of nonionic surfactants that can be used in the composition used according to the invention are described, for example, in "Handbook of Surfactants" by M. R. PORTER, Blackie & Son (Glasgow and London), 1991, pp 116-178. They are chosen in particular from alcohols, alpha-diols, alkyl (CrCo) phenols, these compounds being polyethoxylated, polypropoxylated and / or polyglycerolated, and having at least one fatty chain comprising, for example, from 8 to 40 carbon atoms. , the number of ethylene oxide groups and / or propylene oxide may range in particular from 1 to 200 and the number of glycerol groups ranging in particular from 1 to 30.
Mention may also be made of copolymers of ethylene oxide and of propylene oxide, esters of fatty acids and of sorbitan, optionally oxyethylenated, esters of fatty and sucrose acids, esters of polyoxyalkylenated fatty acids, alkylpolyglycosides, optionally oxyalkylenated. alkylglucoside esters, N-alkylglucamine and N-acyl-methylglucamine derivatives, aldobionamides, oxyethylenated and / or oxypropylenated silicones and amine oxides, and mixtures thereof.
The composition according to the invention may thus comprise a surfactant chosen from fatty acid esters and polyols.
By fatty acid esters and polyols' according to the invention is meant fatty acid esters (or fatty acid polymers) and polyol in which the fatty acid comprises a C6-C22 alkyl chain, preferably C16-C20, and the polyol is selected from glycerol, polyglycerol, sorbitan, and mixtures thereof. The fatty acid can also be in a polymeric form, as is the case of polyhydroxystearic acid (polymer 12-hydroxystearic acid).
In a particular embodiment, the fatty acid and polyol ester is a C 16 -C 20 fatty acid ester and glycerol and / or sorbitan, and mixtures thereof.
Examples of linear or branched C16-C20 fatty acids include stearic acid, isostearic acid, lauric acid, myristic acid, palmitic acid. As an example of a C 16 -C 20 fatty acid polymer, mention may be made of poly-12-hydroxystearic acid.
Preferably, stearic acid, isostearic acid, poly12-hydroxystearic acid and mixtures thereof are used.
By polyglycerols is meant compounds of formula
in which the degree of condensation n ranges from 1 to 11, preferably from 2 to 6 and even more preferably from 3 to 6.
According to one particular embodiment, the fatty acid and polyol ester contains 2 to 10 moles (units) of polyols, preferably 2 to 4 moles of polyols, in particular 2 to 4 units of glycerol or a mixture of polyglycerols (glycerol). , di-, tri-, tetra-, penta-, oligoglycerols).
Even more preferably, the fatty acid and polyol ester contains 4 moles or units) of polyol, in particular 4 moles (or units) of glycerol.
According to a preferred embodiment, said fatty acid and polyol ester is, in addition, a fatty acid ester of a dicarboxylic acid having 2 to 16 carbon atoms, preferably 8 to 14 carbon atoms, such as azelaic acid, sebacic acid, dodecanedioic acid, and preferably sebacic acid (C10), and polyol. As examples of fatty acid and polyol esters that may be used in the composition of the invention, mention may be made of isostearic acid and polyol esters and their mixtures, in particular esters of isostearic acid and of glycerol and / or sorbitan, such as for example the polyglycerolated isostearate (4 moles) (INCI name: Polyglyceryl-4 Isostearate) sold under the name Isolan GI34® by the company Goldschmidt, the polyglycerolated diisostearate (3 moles) sold under the name Lameform TGI® denomination by Cognis; the polyglycerolated distearate (2 moles) sold under the name Emalex PGSA® by the company Nihon emulsion; polyglycerol monoisostearate (10 moles) sold under the name Nikkol decaglyn 1-IS by the company Nihon Surfactant (INCI name: Polyglyceryl-10 isostearate); the polyglyceryl-4 diisostearate polyhydroxystearate sebacate sold under the name ISOLAN GPS by Goldschmidt; the mixture of sorbitan isostearate and glycerol isostearate, such as the product sold under the name Arlacel 986 by the company ICI, the mixture of isostearate of sorbitan and polyglyceryl isostearate (3 moles) marketed under the name Arlacel 1690 by the company Uniqema, the mixture of sorbitan isostearate and polyglycerol isostearate (3 moles) sold under the name Arlacel 1690® by Uniqema, PEG-30 dipolyhydrostearate sold under the name Arlacel P135 by the company Uniqema, and their mixtures.
The composition according to the invention may thus comprise at least one surfactant chosen from fatty acid esters, preferably C 16 -C 20 fatty acid esters, in particular stearic acid or isostearic acid, and polyol chosen from glycerol and / or or sorbitan.
The nonionic surfactants may also be chosen from mono or polyoxyalkylenated, mono- or polyglycerolated nonionic surfactants. The oxyalkylenated units are more particularly oxyethylenated units, oxypropylene, or their combination, preferably oxyethylenated. As examples of oxyalkylenated nonionic surfactants, mention may be made of: oxyalkylenated (C 8 -C 24) alkyl phenols; • C8-C30 alcohols, saturated or not, linear or branched, oxyalkylenated; • C8-C30 amides, saturated or not, linear or branched, oxyalkylenated; Saturated or unsaturated, linear or branched, C 8 -C 30 acid esters of polyethylene glycols; Saturated or unsaturated, linear or branched C8-C30 acid esters of polyoxyethylenated sorbitol; • oxyethylenated vegetable oils, saturated or not; • condensates of ethylene oxide and / or propylene oxide, among others, alone or in mixtures; Oxyethylenated and / or oxypropylenated silicones; • and their mixtures.
Surfactants having a number of moles of ethylene oxide and / or propylene of between 1 and 100, preferably between 2 and 50, preferably between 2 and 30. Advantageously, the nonionic surfactants do not comprise oxypropylene units.
According to a preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 moles of ethylene oxide; linear or branched, saturated or unsaturated C8-C30 acid esters, and polyoxyethylenated sorbitol esters comprising from 1 to 100 moles of ethylene oxide. By way of example of mono- or poly-glycerolated nonionic surfactants, the C 8 -C 40 mono- or polyglycerolated alcohols are preferably used.
In particular, mono- or poly-glycerolated C 8 -C 40 alcohols correspond to the following formula (A70): R290- [CH2-CH (CH20H) -O] m -H (A70)
Formula (A70) in which: R29 represents a linear or branched, C8-C40, preferably C8-C30, alkyl or alkenyl radical; and m represents a number ranging from 1 to 30 and preferably from 1 to 10. By way of example of compounds of formula (A70) suitable in the context of the invention, mention may be made of 4 mole lauric alcohol. glycerol (INCI name: POLYGLYCERYL-4AURYL ETHER), lauryl alcohol with 1.5 moles of glycerol, oleic alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 OLEYL ETHER), oleic alcohol with 2 moles of glycerol (INCI name: POLYGLYCERYL-2 OLEYL ETHER), cetearyl alcohol with 2 moles of glycerol, cetearyl alcohol with 6 moles of glycerol, oleocetyl alcohol with 6 moles of glycerol, and octadecanol with 6 moles of glycerol. The alcohol of formula (A70) can represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that in a commercial product several species of polyglycerolated fatty alcohols can coexist in the form of a mixed.
Among the mono- or poly-glycerolated alcohols, it is more particularly preferred to use the C8 / C10 alcohol with one mole of glycerol, the C10 / C12 alcohol with 1 mole of glycerol and the C12 alcohol with 1.5 mole of glycerol.
According to another embodiment of the invention, the nonionic surfactants are chosen from polyoxyalkylenated silicones and more particularly polyoxyalkylenated polydimethylsiloxanes in which the polyoxyalkylene group represents an alternating sequence of oxygen atoms and linear or branched alkylene groups, in particular C2 to C10, preferably C2 to C6 and more preferably C2 and or C3 (respectively ethylene and propylene), the number of alkylene groups being between 1 and 100, preferably between 5 and 50 and more preferably between 10 and 10; and 40. By way of example, mention may be made of the PEG / PPG 18/18 dimethicone type silicones proposed under the designation 5225C by Dow Corning.
Mention may also be made of mixed alkyl / polyoxyalkylene polydimethylsiloxanes in which the alkyl group is a linear or branched C8 to C30, preferably C12 to C22, chain, and the polyoxyalkylene group is an alternating sequence of oxygen atoms and alkylene groups. linear or branched, C2 to C10, preferably C2 to C6 and more preferably C2 and or C3 (respectively ethylene and propylene), the number of alkylene groups being between 1 and 100, preferably between 2 and 30 and more preferentially between 5 and 15, the distribution of the groups being such that the ethylene groups are the most numerous. By way of example, mention may be made of the silicones of Cetyl PEG / PPG-10/1 dimethicone type as proposed under the name ABIL EM 90 by Evonik,
Preferably, the surfactant used in the composition of the invention is a nonionic surfactant chosen from mono- or polyoxyalkylenated surfactants, especially mono- or polyoxyethylenated surfactants, mono or polyoxypropylenated, or a combination thereof, more particularly from polyoxyalkylenated silicones.
When it comprises, surfactants are present in the composition in proportions ranging from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight, more preferably from 0.5 to 20% by weight. , relative to the total weight of the composition.
The composition may comprise a cosmetically acceptable medium.
The cosmetically acceptable medium that can be used in the compositions of the invention may comprise a solvent chosen from water, organic solvents and a mixture thereof.
The organic solvents may be chosen from alcohols, polyols, polyol ethers and their mixtures, the alcohols being preferably chosen from lower C 1 -C 6 alkanols, and preferably chosen from ethanol, propanol and isopropanol, and polyols being preferentially chosen from propylene glycol, hexylene glycol, glycerin and pentanediol.
Preferably, the solvent (s) represent (s) 0.1% to 99% of the total weight of the composition.
Preferably, the composition is aqueous.
According to this variant, the amount of water may vary from 5 to 98% by weight, better still from 15% by weight to 95% by weight, better still from 25 to 90% by weight and even more preferably from 30 to 90% by weight. weight relative to the total weight of the composition. The composition according to the invention may also contain additives normally used in cosmetics, such as thickening agents, preserving agents, perfumes and dyes, as well as most of the usual cosmetic agents.
These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition. Those skilled in the art will take care to choose these optional additives and their amounts so that they do not adversely affect the properties of the compositions of the present invention.
The method of the invention comprises, after step a) of applying the composition, a step b) irradiating the composition on the keratin materials to crosslink the polymer.
This irradiation may consist of illumination with ambient light or with an artificial light source, of the composition applied to the keratin materials
Ambient or artificial light may emit radiation in the visible and / or in the UV. Preferably, it emits at least a proportion of radiation in the UV, for example a UV proportion of at least 2% of the total irradiance of the ambient light.
According to a particular embodiment, the exposure comprises, or even consists of, the illumination in ambient light of the surface of said layer, in particular for a duration of at least 1 minute.
The duration of exposure to ambient light may range more particularly from 10 seconds to 30 minutes, in particular from 2 to 15 minutes.
According to another particular embodiment, the exposure comprises, or even consists of, illumination with an artificial light source of the surface of said layer.
The duration of exposure to said artificial light can range from 1 second to 20 minutes, in particular from 1 second to 1 minute.
The crosslinking can be done with natural or artificial light, for example by means of lighting with a lamp, a flash, a laser, LEDs, for example in the form of a matrix of LEDs.
The artificial light source may emit radiation in the visible range and / or UV radiation.
The emitted light may or may not be monochromatic. The wavelength of the light emitted is preferably centered on 365 nm, in particular between 100 nm and 500 nm, and better still between 200 nm and 420 nm.
Advantageously, the crosslinking is initiated by simple illumination without requiring a photoinitiator.
Preferably, it will be an artificial light source emitting an energy of between 0.5 and 5 W / cm 2, the exposure times being adapted accordingly.
The crosslinking can occur with reduced light intensity, the lighting system can produce this light intensity for example between 500 mJ / cm2 and 10J / cm2.
The dual characteristic of the absence of photoinitiator and relatively low light intensity is particularly advantageous because it makes it possible to limit the harmful effects of aggressive initiators or prolonged exposure to intense light, in particular in UV wavelengths. . Those skilled in the art will be able to adapt the characteristics of the illumination, in particular in terms of exposure time and wavelengths of the radiation, with regard to the nature of the photocurable polymer (s) (s). ) (A) implemented.
According to a preferred embodiment, the composition is applied to keratin fibers such as the hair.
According to this embodiment, the composition can be applied to the keratin fibers wet or dry, clean or not. The keratinous fibers are preferably dried after application of the composition and before irradiation.
It is also possible to include in the process, before or after irradiation step b), a pause at ambient temperature, or under heat, or under red light.
According to another aspect, the subject of the invention is a composition in the form of a water-in-oil emulsion comprising an aqueous phase dispersed in a fatty phase, the composition comprising one or more surfactant (s) and one or more polymers (s). ) photocrosslinkable (s) comprising at least one photodimerizable pendant group and at least one pendant hydrophobic group. The following example illustrates the invention without limiting its scope. Quantities are given, unless otherwise indicated, in percentages by mass.
Examples
Example 1
The PVA-SbQ-Propional polymer was obtained according to the method described above.
4 g of PVA-SbQ solution propional to 5% MA polymer was dried in a Teflon mold to form a PVA-SbQ propional film. The film obtained is irradiated in UVA at 365 nm for an energy of 8 J / cm 2. The film is then placed in a beaker of water with stirring for 48 hours. The resulting film is insoluble and remains intact after 1H. After 48H, the film is a bit fragmented, in rather large pieces.
4 g of PVA-SbQ 5% MA polymer solution was dried in a Teflon mold to form a PVA-SbQ film. The film obtained is irradiated in UVA at 365 nm for an energy of 8 J / cm 2. The film is then placed in a beaker of water with stirring for 48 hours. The film breaks up after 1 hour. After 48H, the film remains insoluble but fragments into more pieces.
Example 2
The following compositions were produced as inverse emulsion (amount in% by weight of active ingredient)
* Partially saponified polyvinyl acetate polymer bearing stilbazolium groups, adsorbed on polyvinyl acetate particles. This dispersion has a solids content of 40%.
Composition A according to the invention was applied to fine, short hair at the rate of 2 to 4 g of composition per 1/4 head. The treated hair was irradiated with UVA at 365 nm for an energy of 8 J / cm 2.
Hair and cosmetics were added after application and after 1 and 5 shampoos. In particular, a net intake of styling, volume, density and body is observed up to 5 shampoos.
Compositions A and C were also applied to locks of natural hair with 90% white, moist hair, which were dried and then irradiated in UVA at 365 nm for an energy of 8 J / cm 2. The locks were then treated with a coloring composition obtained from a solution which comprises: 0.4668 g of RED 80 dye (SI RI US ROT F3B-BAYER), 0.125 ml of pure acetic acid, and -qsp 100ml of water.
This solution is diluted 5 times to obtain the dye composition.
The locks thus treated are subjected to 10 washes with shampoos.
Using a SPECTRA FLASH SF600X spectrophotometer from DATACOLOR, the color variation of the locks is evaluated.
The "red 80" dye which has an affinity with the polymer makes it possible to evaluate the amount of polymer remaining after several shampoos.
The color of the locks was evaluated before and after washing in the L * a * b * system. In this system L * a * b *, the three parameters denote respectively the intensity (L *), a * indicates the green / red color axis and b * the blue / yellow color axis.
The variation of the color of the locks before and after washing is measured by (ΔΕ) according to the following equation:
In this equation, L *, a * and b * represent the values measured after washing and LO *, aO * and bO * represent the values measured before washing.
The higher the value of ΔΕ, the greater the color difference of the wick before and after washing is important, and in this case, the film remanence is important.
The results are shown in the table below
These results show an improvement in the post-shampoo sheathing remanence with the composition of the invention compared with the comparative composition which contains a PVA-SbQ polymer without a hydrophobic group.

权利要求:
Claims (15)
[1" id="c-fr-0001]
1. Process for the treatment of keratinous substances, preferably keratinous fibers, comprising the following steps: a) application to the keratin materials of a composition comprising at least one photocrosslinkable polymer comprising at least one photodimerizable pendant group and at least one pendant group hydrophobic, and b) irradiation of said composition on the keratin materials to crosslink the polymer.
[2" id="c-fr-0002]
2. Method according to claim 1, characterized in that the (or) group (s) photodimerizable (s) is (are) chosen (s) from the following monovalent radicals of formulas (I) and (II):

as well as their geometric isomers, formula (I) and (II) in which: Y and Z denote independently of each other a nitrogen atom or a group C (R) with R representing a hydrogen atom or a (C 1 -C 4) alkyl group such as methyl; A represents a bond or a divalent group selected from (CVC) alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio) carbonyl, (C 2 -C 8) alkenylene radicals; and their combinations; B represents a monovalent group selected from alkyl radicals (Cr C8), aryl radicals, optionally cationic heteroaryl, cycloalkyl, optionally cationic heterocycloalkyl, (thio) carbonyl, (C2-C8) alkenyls and combinations thereof; X represents a divalent group selected from (C2-C8) alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio) carbonyl, (C2-C8) alkenylene radicals and combinations thereof - p represents an inclusive integer preferably between 1 and 5, in particular between 1 and 3, preferably p is 1;

represents the bond that connects the part of the monovalent radical to the rest of the molecule; and each of the groups mentioned may optionally be substituted with one or more halogen atoms or groups selected from (C 1 -C 8) alkyl, hydroxy, amino, (di) (C 1 -C 6) alkylamino, phenyl, carboxy, ( CrCe) alkoxy, (CrCo) alkoxyflhio] carbonyl, hydrogen (thio) carbonyl, sulfonato R-O-S (O) 2- or RS (O) 2-O-, amide RR'NC (O) - or RC (O) -N (R ') - or acyl RC (O) -, ammonium RR'R''N + - with R, R', and R ", identical or different, representing a hydrogen atom or a group (CrC ^ alkyl.
[3" id="c-fr-0003]
3. Method according to claim 2, characterized in that the (or) group (s) photodimerizable (s) is (are) chosen (s) from the monovalent radicals of the following compounds: - stilbene, • styrylpyridinium (stilbazolium) of formula and their geometric isomers

where R1 and R3, which may be identical or different, represent a halogen atom or a (CrC6) alkyl group; or two contiguous R1 or R3 groups together with the carbon atoms which carry it a benzo group; R 2 represents a hydrogen atom, a (C 1 -C 6) alkyl group optionally substituted by one or more halogen atoms such as chlorine or hydroxyl, preferably R 2 represents a (C 1 -C 6) alkyl group such as methyl, ethyl, propyl; * q and r, represent an integer inclusive between 0 and 4; and * Q ', represents an anionic counter ion preferably selected from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; *

represents the bond which connects the part of the monovalent radical to the remainder of the molecule, it being understood that the pendant group A2 may be connected to the remainder of the molecule via R2; preferably the link

is on the phenyl in the para position of the styryl group on Al or connected to the rest of the molecule via R2 on A2; preferentially, the styryl group of Al and A2 is in para of the pyridinium group; "Styrylazolium of formula and their geometric isomers;

where * A represents a sulfur atom, an oxygen atom, or a group N R2 or C (R2) 2; and

, Q ', r, q, R1, R2, and R3 being as defined above, preferably the bond

is on the para phenyl of the stryryl group, - styrylpyrazine, - chalcone, - (thio) cinnamate and (thio) cinnamamide, - maleimide, - (thio) coumarin, - thymine, - uracil, - butadiene anthracene, - pyridone , - pyrrolizinone, - acridizinium salts, - furanone, phenylbenzoxazole, and - their derivatives.
[4" id="c-fr-0004]
4. Method according to any one of the preceding claims, characterized in that the photocrosslinkable polymer has a natural or synthetic skeleton chosen from polysaccharides, polyvinyl polymers and polydiorganosiloxanes, preferably from polyvinyl acetate. ), preferably partially saponified.
[5" id="c-fr-0005]
5. Method according to any one of the preceding claims, characterized in that the (or) polymer (s) comprising at least one photodimerizable group is a polymer soluble or dispersed in the composition.
[6" id="c-fr-0006]
6. Method according to any one of the preceding claims, characterized in that the polymer comprising at least one photodimerizable group is in the form of particles, preferably dispersed particles.
[7" id="c-fr-0007]
7. Process according to claim 6, characterized in that the particles are particles of polyvinyl alcohol.
[8" id="c-fr-0008]
8. Method according to any one of the preceding claims, characterized in that the hydrophobic group is selected from - a group (CrCsoJalkyl, saturated or unsaturated, optionally substituted and / or interrupted by one or more heteroatoms, - an alkenyl group, - an aryl group such as phenyl, pyridyl, furyl, indoyl, benzofuryl, thiophenyl, imizadoyl, oxazoyl, thiazoyl, pyrazinyl, pyrimidinyl; a fluorinated group such as a fluoro-carbon group such as -CF3, -CHF2, -OCF3, - SCF3, CF3C (O) -, a silicone group such as -SiRaRbRc such that -Si (CH3) 3, polydimethylsiloxane-PDMS, -Si (OR) 3, PDMS α, ω diaminopropyl, PDMS α, ω dihydroxyalkyl, α-PDMS , ωdicarboxyalkyl, with Ra, Rb and Rc, identical or different, representing a (CrC8) alkyl group optionally interrupted and / or terminated by one or more non-contiguous heteroatoms such as O, or S; and R representing a group (C 1 -C 5); C6) alkyl, preferably from a group (C2-C22) alk yl, more preferably from (C3-C16) alkyl.
[9" id="c-fr-0009]
9. Process according to any one of the preceding claims, characterized in that the polymer comprising at least one photodimerizable group and at least one hydrophobic group represents 0.01 to 25%, preferably 0.1 to 20%, and better still. at 15% of the total weight of the composition.
[10" id="c-fr-0010]
10. Method according to any one of the preceding claims, characterized in that the composition further comprises a solvent, preferably selected from water, alcohols, polyols, polyol ethers and mixtures thereof, the alcohols being preferentially chosen from lower C1-C6 alkanols, and preferably chosen from ethanol, propanol and isopropanol, the polyols preferably being chosen from propylene glycol, hexylene glycol, glycerine and pentanediol.
[11" id="c-fr-0011]
11. Method according to the preceding claim, characterized in that the (or) solvent (s) represents (s) 0.1% to 99% of the total weight of the composition.
[12" id="c-fr-0012]
12. Method according to any one of the preceding claims, characterized in that the composition comprises one or more fatty substances.
[13" id="c-fr-0013]
13. Method according to any one of the preceding claims characterized in that it comprises, prior to the irradiation step and subsequent to the application step, a drying of keratin materials.
[14" id="c-fr-0014]
14. Method according to any one of the preceding claims, characterized in that it comprises before or after the irradiation step (b) a pause at room temperature, or under heat, or under red light.
[15" id="c-fr-0015]
15. Method according to one of the preceding claims, characterized in that the irradiation is irradiation with radiation in the UVA or in the visible range, and preferably radiation in the UVA.

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法律状态:
2016-11-11| PLFP| Fee payment|Year of fee payment: 2 |

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2017-06-30| PLSC| Publication of the preliminary search report|Effective date: 20170630 |

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2017-11-13| PLFP| Fee payment|Year of fee payment: 3 |

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2019-11-15| PLFP| Fee payment|Year of fee payment: 5 |

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2020-11-12| PLFP| Fee payment|Year of fee payment: 6 |

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2021-11-15| PLFP| Fee payment|Year of fee payment: 7 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1563288A|FR3046072B1|2015-12-23|2015-12-23|PROCESS FOR TREATING KERATINIC MATERIALS USING A COMPOSITION COMPRISING A MODIFIED PHOTODIMERIZABLE POLYMER|

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FR1563288|2015-12-23|FR1563288A| FR3046072B1|2015-12-23|2015-12-23|PROCESS FOR TREATING KERATINIC MATERIALS USING A COMPOSITION COMPRISING A MODIFIED PHOTODIMERIZABLE POLYMER|

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US16/064,485| US20190000743A1|2015-12-23|2016-12-20|A process for treating keratin substances using a composition comprising a modified photo-dimerizable polymer|

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ES16825378T| ES2884901T3|2015-12-23|2016-12-20|A method of treating keratin substances using a composition comprising a modified photodimerizable polymer|

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EP16825378.9A| EP3393592B1|2015-12-23|2016-12-20|A process for treating keratin substances using a composition comprising a modified photo-dimerizable polymer|

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CN201680074416.5A| CN108367167B|2015-12-23|2016-12-20|Method for treating keratin materials using a composition comprising a modified photodimerisable polymer|

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PCT/EP2016/081892| WO2017108767A1|2015-12-23|2016-12-20|A process for treating keratin substances using a composition comprising a modified photo-dimerizable polymer|

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JP2018532643A| JP6991976B2|2015-12-23|2016-12-20|The process of treating keratinous materials with a composition containing a modified photodimerizable polymer|