WO2017102650A1 - Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer - Google Patents

Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer Download PDF

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Publication number
WO2017102650A1
WO2017102650A1 PCT/EP2016/080642 EP2016080642W WO2017102650A1 WO 2017102650 A1 WO2017102650 A1 WO 2017102650A1 EP 2016080642 W EP2016080642 W EP 2016080642W WO 2017102650 A1 WO2017102650 A1 WO 2017102650A1
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Prior art keywords
alkyl
composition
group
chosen
optionally substituted
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PCT/EP2016/080642
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French (fr)
Inventor
Grégory MIALLET
Delphine Charrier
Mladen MILIC
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L'oreal
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Publication of WO2017102650A1 publication Critical patent/WO2017102650A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/548—Associative polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/87—Application Devices; Containers; Packaging

Definitions

  • Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer
  • a subject of the present invention is a device for dispensing a product for dyeing and/or lightening keratin fibres comprising compositions A and B, and also a dyeing process using said device.
  • the present invention also relates to a kit comprising said device and a composition comprising a conditioning agent.
  • oxidation dyeing or permanent dyeing. More particularly, this dyeing method uses one or more oxidation dyes, usually one or more oxidation bases optionally combined with one or more couplers.
  • oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or ara-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured entities.
  • the shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen in particular from aromatic meia-diamines, meia-aminophenols, meia-diphenols and certain heterocyclic compounds, such as indole compounds.
  • Permanent dyeing processes thus consist in using, with the dye composition containing the oxidation dyes, an aqueous composition comprising at least one oxidizing agent, such as hydrogen peroxide, under alkaline pH conditions in the vast majority of cases.
  • the alkaline agent conventionally used is aqueous ammonia or can be chosen from other alkaline agents, such as alkanolamines.
  • compositions in particular the compositions comprising oxidation dyes, are obviously sensitive to oxidation and as a result contain reducing agents or antioxidants. This action of protection against oxidation is also reinforced by virtue of the inert atmosphere that is sometimes used during the packaging of these compositions.
  • compositions of this type indeed results from their sensitivity to oxidation. This is because, during their use, they are brought into contact with atmospheric oxygen and this then requires that they be used rapidly. If they are not used rapidly, the compositions become unusable after storage and are lost.
  • alkaline compositions in particular dyeing compositions, and oxidizing compositions, which are packaged separately in one and the same pressurized container and which make it possible to avoid the composition being brought into contact with air when they are used.
  • These compositions can be in the form of a foam or cream.
  • the strength of the dyeing and also the coverage of the hair, in particular of white hair still requires further improvement, as do the rheological properties of the product(s) stemming from the pressurized container, in particular in terms of ease of mixing of the dyeing or lightening and oxidizing compositions, of the uniformity of the mixture and of the quality of application to keratin fibres (in particular in terms of the wetting nature, of the adhesion to the roots and of the ease with which the mixture can be spread along the locks of hair).
  • the objective of the present invention is thus to provide dyeing compositions which are in particular in cream or gel form, having good use qualities, in particular mixing and application qualities, while at the same time having high dyeing and/or lightening performance levels.
  • a subject of which is thus a device for dispensing a product for dyeing and/or lightening keratin fibres, constituted of a container comprising:
  • the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent,
  • the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent, one and/or the other of the compositions of the two compartments comprising at least one associative thickening polymer;
  • a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B.
  • the invention also relates to a process for lightening and/or dyeing human keratin fibres using this device.
  • a subject of the invention is a process for lightening and/or dyeing human keratin fibres, in which the following are applied to said fibres:
  • composition A comprising at least one alkaline agent and optionally at least one dyeing agent
  • composition B comprising at least one chemical oxidizing agent
  • compositions A and B being packaged in a device constituted of a container, which is preferably pressurized, comprising at least two compartments a and b separate from one another, the compartment a comprising the composition A and the compartment b comprising the composition B, the device comprising a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to deliver the compositions A and B simultaneously.
  • the device and the process of the invention make it possible to obtain good lightening and/or dyeing properties on keratin fibres, and in the case of dyeing, in particular dyeing which is strong, intense and/or chromatic, resistant to external agents (shampoos, perspiration, light), uniform and not very selective.
  • the device comprising the compositions also produces good use qualities, in particular the application of the compositions A and B is easy and the distribution is uniform along the keratin fibres.
  • the device and the process of the invention also produce good cosmetic properties, in particular in terms of disentangling, suppleness and softness of the hair.
  • the mixture of the compositions A and B rinses off easily after the leave-on time.
  • compositions A and B used in the dyeing and/or lightening process according to the invention mix easily, prior to the application to the keratin fibres or directly on the keratin fibres during simultaneous application of the compositions A and B to the hair.
  • the human keratin fibres treated via the process according to the invention are preferably the hair.
  • composition A of the device according to the invention comprises at least one alkaline agent.
  • This agent can be chosen from mineral or organic or hybrid alkaline agents or mixtures thereof.
  • the mineral alkaline agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.
  • the organic alkaline agent(s) are preferably chosen from organic amines with a pKb at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pKb corresponding to the highest basicity function.
  • Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.
  • organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds having the formula below:
  • W is a Ci-C 6 alkylene residue optionally substituted with a hydroxyl group or a Ci-C 6 alkyl radical
  • Rx, Ry, Rz and Rt which may be identical or different, represent a hydrogen atom or a Ci-C 6 alkyl, CrC 6 hydroxyalkyl or CrC 6 aminoalkyl radical. Mention may be made, as examples of such amines, of 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine or spermidine.
  • alkanolamine is intended to mean an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C C 8 alkyl groups bearing one or more hydroxyl radicals.
  • Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different CrC 4 hydroxyalkyi radicals are in particular suitable for performing the invention.
  • amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid function chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functions.
  • the amino acids may be in neutral or ionic form.
  • amino acids that may be used in the present invention, mention may be made in particular of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.
  • the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.
  • Such basic amino acids are preferably chosen from those corresponding to the formula below:
  • R denotes a roup chosen from:
  • the compounds corresponding to the formula above are histidine, lysine, arginine, ornithine and citrulline.
  • the organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.
  • the organic amine may also be chosen from amino acid dipeptides.
  • amino acid dipeptides that may be used in the present invention, mention may be made in particular of carnosine, anserine and balenine.
  • the organic amine may also be chosen from compounds comprising a guanidine function.
  • amines of this type that may be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made in particular of creatine, creatinine, 1 ,1 -dimethylguanidine, 1 ,1 -diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3- guanidinopropionic acid, 4-guanidinobutyric acid and 2- ([amino(imino)methyl]amino)ethane-1 -sulfonic acid.
  • the composition according to the invention contains, as alkaline agent, aqueous ammonia and/or at least one alkanolamine and/or at least one basic amino acid, more advantageously aqueous ammonia and/or at least one alkanolamine.
  • the alkaline agent is chosen from aqueous ammonia, alkanolamines, preferably monoethanolamine, and mixtures thereof.
  • the composition A has a content of alkaline agent(s) ranging from 0.01 % to 30% by weight, preferably from 0.1 % to 20% by weight and better still from 1 % to 10% by weight, relative to the weight of said composition. It should be noted that this content is expressed as NH 3 when the alkaline agent is aqueous ammonia.
  • composition A according to the invention may comprise at least one dyeing agent.
  • the dyeing agents may be chosen from oxidation dye precursors, direct dyes, and mixtures thereof.
  • the composition A comprises at least one dyeing agent chosen from oxidation dye precursors, direct dyes, and mixtures thereof, it preferably comprises at least one oxidation dye precursor.
  • oxidation dye precursors use may be made of oxidation bases and couplers.
  • the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and addition salts thereof.
  • para-phenylenediamines examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, ⁇ , ⁇ -diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(p-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis(p-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis(p-hydroxyethyl)a
  • para-phenylenediamine para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2-p-acetylaminoethyloxy-para-phenylenediamine, and addition salts thereof with an acid, are particularly preferred.
  • bis(phenyl)alkylenediamines examples that may be mentioned include N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, ⁇ , ⁇ '- bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine, 1 ,8-bis(2,5-diaminophenoxy)-3
  • para-aminophenols examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, 4-methylaminophenol and addition salts thereof with an acid.
  • ortho-aminophenols examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and addition salts thereof.
  • heterocyclic bases examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and addition salts thereof.
  • pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308.
  • Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2- carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5- a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)ethanol, 2-(
  • pyrimidine derivatives mention may be made of the compounds described, for example, in patents DE 2359399, JP 88-169571 , JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.
  • 2,4,5,6-tetraaminopyrimidine 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof, and the tautomeric forms thereof, when
  • Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole. Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt or solvate thereof.
  • Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and addition salts thereof: 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 4,5-diamino-1
  • Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one and/or a salt or solvate thereof.
  • Heterocyclic bases that will preferentially be used include 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol- 1 -one and/or 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol and/or a salt or solvate thereof.
  • composition A comprises at least one heterocyclic oxidation base chosen from:
  • R-i represents an amino group, a Ci to C 4 alkyl group optionally substituted with one or more hydroxyl or amino groups, or a Ci to C 4 alkoxy group optionally substituted with one or more hydroxyl or amino groups,
  • R 2 represents an amino group, a Ci to C 4 alkyl group, optionally substituted with one or more hydroxyl or amino groups, a Ci to C 4 alkoxy group, optionally substituted with one or more hydroxyl or amino groups; and Z-i represents a covalent bond, and -NR' 6 (CH2)q- radical or an -0(CH 2 ) p - radical in which R' 6 represents a hydrogen atom or a Ci-C 6 alkyl radical optionally substituted with one or more hydroxyl groups, p denoting an integer ranging from 0 to 6, q denoting an integer ranging from 0 to 6, and R'i is a cationic radical; and
  • R' 3 , R' 4 and R' 5 may be a hydrogen atom or an optionally substituted Ci-C 4 alkyl radical.
  • R' 3 , R' 4 and R' 5 independently represent a hydrogen atom or a C1-C4 alkyl radical.
  • R' 4 and R' 5 can together form a partially saturated or unsaturated 5- or 8- membered ring, in particular a cyclopentene or cyclohexene, which is optionally substituted.
  • R1 represents a C1-C4 alkyl group which is substituted with one or more hydroxyl or amino groups
  • R4 represents an amino group, a C1-C4 alkyl group which is optionally substituted with one or more hydroxyl or amino groups, or a C1-C4 alkoxy group which is optionally substituted with one or more hydroxyl or amino groups.
  • R1 represents a C1-C4 alkyl group which is substituted with at least one hydroxyl group, more particularly a hydroxyethyl group, and R4 represents an amino group.
  • R 2 represents a Ci to C 4 alkoxy group, optionally substituted with one or more hydroxyl groups, and preferentially represents a hydroxyethoxy group.
  • the 3-aminopyrazolo[1 ,5-a]pyridines of formulae (II) and (I I I) are compounds that are known and are described in particular in patent US 5 457 200. These compounds may be prepared according to synthetic methods that are well known in the literature and as described, for example, in patent US 5 457 200.
  • cationic group for formula (III) mention may be made, for R'- ⁇ , of a cationic heterocycle or a heterocycle substituted with a cationic radical.
  • R'i May also be chosen from the cationic radicals trialkylammonium, tri(hydroxyalkyl)ammonium, hydroxyalkyldialkylammonium or di(hydroxyalkyl)alkylammonium.
  • cationic oxidation bases of formula (III) the following bases are most particularly preferred:
  • heterocyclic bases that are of use for the invention, use will preferentially be made of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or 2, 3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one and/or 2-[(3-aminopyrazolo[1 ,5- a]pyridin-2-yl)oxy]ethanol and/or a salt or solvate thereof.
  • couplers that may be used in the composition according to the invention, mention may be made in particular of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines, and addition salts of these compounds with an acid.
  • meta-phenylenediamines meta- aminophenols, meta-diphenols, naphthalene-based couplers
  • heterocyclic couplers for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolone
  • couplers are more particularly chosen from 2,4-diamino-1 -(p- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(p-hydroxyethyl)amino-2- methylphenol, 3-aminophenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2-amino-4-(p-hydroxyethylamino)- 1 -methoxybenzene, 5-amino-6-chloro-2-methylphenol, 1 ,3-diaminobenzene, 1 ,3- bis(2,4-diaminophenoxy)propane, sesamol, 1 -amino-2-methoxy-4,5- methylenedioxybenzene, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy- N-methylindole,
  • the addition salts of the oxidation bases and of the couplers are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • the oxidation base(s) are each generally present in an amount of from 0.0001 % to 10% by weight relative to the total weight of the composition of the invention, and preferably from 0.005% to 5% by weight relative to the total weight of the composition A.
  • the coupler(s) each generally represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition A of the invention.
  • the composition A comprises at least one oxidation dye precursor chosen from the compounds of formula ( ⁇ ) previously described, preferably 2-(4,5-diamino-1 H-pyrazol-1 -yl)ethanol or an addition salt thereof and at least one halogenated aminophenol coupler, preferably 5-amino 6- chloro 2-methyl phenol
  • the dyeing agent may be chosen from direct dyes which may be synthetic or natural.
  • the direct dyes may be in particular cationic or non-ionic.
  • nitrobenzene dyes By way of examples of particularly suitable direct dyes, mention may be made of nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanines, for instance tetraazacarbocyanines (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes and natural direct dyes, alone or as mixtures.
  • nitrobenzene dyes By way of examples of particularly suitable direct dyes, mention may be made of nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanines, for instance
  • direct dyes from among: azo; methine; carbonyl; azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanine and natural direct dyes, alone or as mixtures.
  • the composition A comprises at least one dyeing agent chosen from direct dyes, preferably from cationic direct dyes.
  • Suitable cationic direct dyes include azo direct dyes; (poly)methine dyes such as cyanins, hemicyanins and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
  • cationic direct dyes mention may be made in particular of the hydrazono cationic dyes of formulae (Ilia) and (lll'a), the azo cationic dyes (IVa) and (IV'a) and the diazo cationic dyes (Va) below:
  • Het + represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferably with one or more (CrC 8 )alkyl groups such as methyl;
  • Ar + represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferably ammonium, particularly tri(Ci- C 8 )alkylammonium such as trimethylammonium;
  • Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably with one or more electron-donating groups such as i) optionally substituted (CrC 8 )alkyl, ii) optionally substituted (CrC 8 )alkoxy, iii) (di)(Ci-C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl
  • Ar' represents an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferably with one or more groups (Ci-C 8 )alkyl, hydroxyl or (d- C 8 )alkoxy;
  • Ar represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably with one or more (C C 8 )alkyl, hydroxyl, (di)(Ci-C 8 )(alkyl)amino, (Ci-C 8 )alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (Ci-C 8 )alkyl group, which is optionally substituted, preferably with a hydroxyl group;
  • the substituent R a with a substituent of Het + and/or R b with a substituent of Ar and/or R a with R b form, together with the atoms that bear them, a (hetero)cycloalkyl;
  • R a and R b represent a hydrogen atom or a (CrC 4 )alkyl group, which is optionally substituted with a hydroxyl group;
  • An " represents an anionic counterion, such as mesylate or halide.
  • the direct dyes correspond to the following formulae:
  • - R 1 representing a (Ci-C 4 )alkyl group such as methyl
  • - R 2 and R 3 which may be identical or different, representing a hydrogen atom or a (C C 4 )alkyl group, such as methyl
  • R 4 representing a hydrogen atom or an electron-donating group such as optionally substituted (CrC 8 )alkyl, optionally substituted (CrC 8 )alkoxy, or (di)(Ci- C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; in particular, R 4 represents a hydrogen atom;
  • - Z represents a CH group or a nitrogen atom, preferably CH
  • An " represents an anionic counterion, such as mesylate or halide.
  • the dye of formulae (llla-1 ) and (IVa-1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:
  • the direct dye(s) more particularly represent from 0.0001 % to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of composition A.
  • composition B according to the invention comprises at least one chemical oxidizing agent.
  • chemical oxidizing agent is intended to mean an oxidizing agent other than atmospheric oxygen.
  • the oxidizing agent(s) suitable for the present invention is (are) chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, such as for example persulfates or perborates, peracids and precursors thereof and alkali metal or alkaline-earth metal percarbonates.
  • the chemical oxidizing agent is hydrogen peroxide.
  • the chemical oxidizing agent(s) generally represent(s) from 0.1 % to 50% and preferably from 1 % to 20% by weight relative to the total weight of the composition B.
  • composition A of the device according to the invention is devoid of chemical oxidizing agent as described above.
  • compositions A and B of the device of the invention comprises at least one associative thickening polymer, well known to those skilled in the art and in particular of non-ionic, anionic, cationic or amphoteric nature.
  • thickening polymer is intended, for the purposes of the present invention, to mean a polymer having, in solution or in dispersion containing 1 % by weight of active material in water or in ethanol at 25°C, a viscosity greater than 0.2 poise at a shear rate of 1 s '
  • the viscosity is measured with a Haake RS600 viscometer from Thermo Electron. This viscometer is a controlled-stress viscometer with cone-plate geometry (for example having a diameter of 60 mm).
  • hydrophilic polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
  • Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.
  • hydrophobic group is intended to mean a radical or polymer bearing a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 6 carbon atoms, preferably 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 14 to 30 carbon atoms.
  • the hydrocarbon-based group is derived from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, cetyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, such as, for example, polybutadiene. These associative polymers involve in their structure at least one repeating unit other than an alkylene oxide unit or glycidol unit and, in this sense, are different from surfactants.
  • the composition according to the invention comprises at least one associative thickening polymer chosen from associative polyurethanes, which are more particularly cationic or non-ionic, associative cellulose derivatives, which are more particularly cationic or non-ionic, associative vinyllactams, associative unsaturated polyacids, associative aminoplast ethers, and associative polymers or copolymers comprising at least one ethylenically unsaturated monomer comprising a sulfonate group, alone or as mixtures.
  • associative thickening polymer chosen from associative polyurethanes, which are more particularly cationic or non-ionic, associative cellulose derivatives, which are more particularly cationic or non-ionic, associative vinyllactams, associative unsaturated polyacids, associative aminoplast ethers, and associative polymers or copolymers comprising at least one ethylenically unsaturated monomer comprising a
  • associative thickening polymers mention may be made of associative polyurethane derivatives, such as those obtained by polymerization of:
  • a non-ionic monourethane which is the reaction product of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.
  • this polymer is a terpolymer of methacrylic acid / methyl acrylate / dimethyl meta-isopropenyl benzyl isocyanate of behenyl alcohol which is ethoxylated (40 EO) in aqueous dispersion at 25%.
  • This product is provided under the reference Viscophobe DB1000 by the company Amerchol.
  • R and R' which may be identical or different, represent a hydrophobic group or a hydrogen atom
  • X and X' which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L"; L, L' and L", which may be identical or different, represent a group derived from a diisocyanate;
  • P and P' which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group
  • Y represents a hydrophilic group
  • r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25;
  • n, m and p each range, independently of each other, between 0 and 1000; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
  • the only hydrophobic groups of these polyurethanes are the groups R and R' located at the chain ends.
  • the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group; X and X' each represent a group L"; n and p are between 1 and 1000 and L, L', L", P, P', Y and m have the meaning indicated as in formula (A).
  • the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group, X and X' each represent a group L", n and p are 0 and L, L', L", P, P', Y and m have the meaning as in formula (A) indicated previously.
  • n and p are 0 is intended to mean that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation.
  • the protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group, X and X' both independently represent a group comprising a quaternary amine, n and p are zero, and L, L', Y and m have the meaning indicated in formula (A).
  • the number-average molecular weight of the cationic associative polyurethanes is usually between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000 g/mol.
  • X and/or X' denote(s) a group comprising a tertiary or quaternary amine
  • X and ' may represent one of the following formulae: for X
  • R 2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
  • Ri and R 3 which may be identical or different, denote a linear or branched Ci- C 30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
  • a " is a physiologically acceptable counterion.
  • Z represents -0-, -S- or -NH-
  • R 4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
  • the groups P and P' comprising an amine function may represent at least one of the following formulae: R «
  • R 5 and R 7 have the same meanings as R 2 defined above;
  • R 6 , Rs and R 9 have the same meanings as Ri and R 3 defined above;
  • R-io represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P;
  • a " is a cosmetically acceptable counterion.
  • hydrophilic group is intended to mean a polymeric or non-polymeric water-soluble group.
  • hydrophilic polymer in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
  • the associative polyurethanes of formula (A) are formed from diisocyanates and from various compounds bearing functions containing a labile hydrogen.
  • the functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively.
  • polyurethanes in the present invention encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
  • a first type of compound involved in the preparation of the polyurethane of formula (A) is a compound comprising at least one unit bearing an amine function.
  • This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function.
  • a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
  • this compound may comprise more than one unit containing an amine function.
  • it is a polymer bearing a repetition of the unit containing an amine function.
  • Examples of compounds containing an amine function include N-methyldiethanolamine, N-tert-butyldiethanolamine and N- sulfoethyldiethanolamine.
  • a third compound involved in the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).
  • This compound is formed from a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
  • this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol.
  • this compound may be, for example, ohydroxylated hydrogenated polybutadiene.
  • the hydrophobic group of the polyurethane of formula (A) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit.
  • the hydrophobic group is introduced via the quaternizing agent.
  • This quaternizing agent is a compound of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • the cationic associative polyurethane may also comprise a hydrophilic block.
  • This block is provided by a fourth type of compound involved in the preparation of the polymer.
  • This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
  • the functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
  • hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
  • the hydrophilic group termed Y in formula (A) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
  • hydrophilic group Y cationic associative polyurethanes comprising such a group are, however, preferred.
  • the associative polyurethane derivatives of the invention may also be non-ionic polyether polyurethanes. More particularly, said polymers comprise, in their chain, both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks which can be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.
  • these polyether polyurethanes comprise at least two lipophilic
  • hydrophobic hydrocarbon chains containing more particularly from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains possibly being pendent chains or chains at the end of the hydrophilic block.
  • pendent chains it is possible for one or more pendent chains to be envisioned.
  • the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
  • the polyether polyurethanes can be multiblock, in particular in triblock form.
  • the hydrophobic blocks can be at each end of the chain (for example: triblock copolymer having a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer).
  • These same polymers can also be graft polymers or star polymers.
  • the non-ionic hydrophobic-chain polyether polyurethanes can be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups.
  • the non-ionic polyether polyurethanes comprise a urethane linkage between the hydrophilic blocks, whence arises the name.
  • non-ionic polyether polyurethanes comprising a hydrophobic chain
  • hydrophilic blocks are linked to the hydrophobic blocks via other chemical bonds.
  • non-ionic polyether polyurethanes comprising a hydrophobic chain
  • Rheolate 205® containing a urea group sold by the company Rheox, or Rheolate® 208, 204 or 212, Rheolate FX1 100 and also Acrysol RM 184®.
  • the product DW 1206B® from Rohm & Haas containing a C 20 alkyl chain and a urethane linkage, sold at a solids content of 20% in water, may also be used.
  • Use may also be made of solutions or dispersions of these polymers, in particular in water or in aqueous/alcoholic medium.
  • the products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.
  • polyether polyurethanes that can be used according to the invention may also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271 , 380.389 (1993).
  • a polyether polyurethane that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
  • Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %);
  • Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
  • composition may likewise comprise polymers derived from associative celluloses such as:
  • - quaternized cationic celluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof,
  • - quaternized cationic hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
  • the alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • Examples of quaternized alkylhydroxyethylcelluloses containing C 8 -C 30 hydrophobic chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C i2 alkyl) and Quatrisoft LM- X 529-8® (Ci8 alkyl), Softcat SL100 sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (C i2 alkyl) and Crodacel QS® (C i8 alkyl) sold by the company Croda;
  • non-ionic cellulose derivatives such as hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C 8 -C 2 2, for instance the product Natrosol Plus Grade 330 CS® (Ci 6 alkyls) sold by the company Ashland, the product Polysurf 67 CS ® sold by the company Ashland or the product Bermocoll EHM 100® sold by the company Berol Nobel; - cellulose derivatives modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® sold by the company Amerchol.
  • groups comprising at least one hydrophobic chain such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof
  • the alkyl groups are preferably C 8 -C 2 2, for instance the product Natrosol Plus Grade 330
  • polymers in particular described in FR 0 101 106 are more particularly cationic polymers and comprise:
  • X denotes an oxygen atom or a radical NR 6 ,
  • R 5 and R 6 denote, independently of each other, a hydrogen atom or a linear or branched Ci-C 5 alkyl radical
  • R 2 denotes a linear or branched Ci-C 4 alkyl radical
  • R 3 , R 4 and R 5 denote, independently of each other, a hydrogen atom, a linear or branched Ci-C 30 alkyl radical or a radical of formula (IV):
  • Y, Yi and Y 2 denote, independently of each other, a linear or branched C 2 -Ci 6 alkylene radical
  • R 7 denotes a hydrogen atom or a linear or branched Ci-C 4 alkyl radical or a linear or branched CrC 4 hydroxyalkyl radical
  • R 8 denotes a hydrogen atom or a linear or branched Ci-C 30 alkyl radical, p, q and r denote, independently of each other, either the value zero or the value 1 ,
  • n and n denote, independently of each other, an integer ranging from 0 to 100, x denotes an integer ranging from 1 to 100,
  • Z denotes an organic or mineral acid anion, with the proviso that:
  • R 3 , R 4 , R 5 or R 8 denotes a linear or branched C9-C30 alkyl radical
  • the poly(vinyllactam) polymers may be crosslinked or noncrosslinked and may also be block polymers.
  • the counterion Z " of the monomers of formula (b) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
  • R 3 , R 4 and R 5 denote, independently of each other, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
  • the monomer b) is a monomer of formula (b) for which, even more preferentially, m and n are equal to 0.
  • the vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (d):
  • s denotes an integer ranging from 3 to 6
  • R denotes a hydrogen atom or a C1-C5 alkyl radical
  • R10 denotes a hydrogen atom or a C1-C5 alkyl radical
  • radicals R 9 and R10 denotes a hydrogen atom.
  • the monomer (d) is vinylpyrrolidone.
  • the poly(vinyllactam) polymers may also contain one or more additional monomers, preferably cationic or non-ionic monomers.
  • vinylpyrrolidone/ dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers vinylpyrrolidone/dimethylaminopropylmethacrylamide/ cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropy lammonium tosylate or chloride terpolymers are in particular used.
  • the vinylpyrrolidone / dimethylaminopropylmethacrylamide / lauryl dimethylmethacrylamidopropylammonium chloride terpolymer is provided in water at 20% by the company ISP under the name Styleze W20.
  • the associative polyvinyllactam derivatives of the invention may also be non- ionic copolymers of vinylpyrrolidine and of hydrophobic-chain hydrophobic monomers, of which mention may be made, by way of example, of:
  • associative unsaturated polyacid derivatives mention may be made of those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of unsaturated carboxylic acid non-ethoxylated (Ci 0 -C 3 o)alkyl ester type.
  • R-i denotes H, CH 3 , or C 2 H 5 , i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of (Cio-C 30 )alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (f) below: CH ⁇ C— C— OR, (f)
  • R 2 denotes H or CH 3 or C 2 H 5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH 3 (methacrylate units), R 3 denoting a Ci 0 - C 3 o and preferably C12-C22 alkyl radical.
  • (Ci 0 -C 3 o)-Alkyl esters of unsaturated carboxylic acids comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
  • anionic associative polymers of this type use is more particularly made of polymers formed from a mixture of monomers comprising:
  • R 2 denotes H or CH 3
  • R 3 denoting an alkyl radical containing from 12 to 22 carbon atoms
  • crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
  • anionic associative polymers of this type preference is given to those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci 0 -C 30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those constituted of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of Ci 0 -C 30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.
  • Pemulen TR1 ® the products sold by the company Goodrich under the trade names Pemulen TR1 ®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1 ®, and the product sold by the company SEPPIC under the name Coatex SX®.
  • the anionic associative polymers may also be copolymers comprising among their monomers an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid and an ester of an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
  • these compounds also comprise as monomer an ester of an ⁇ , ⁇ - monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.
  • Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.
  • thickening polymers of aminoplast ether type they are any product resulting from the condensation of an aldehyde with an amine or an amide, and also any structural unit formed from an aminoplast residue and a divalent hydrocarbon-based residue linked to the aminoplast residue by an ether bond.
  • polymers with an aminoplast ether backbone are preferably chosen from those containing at least one unit of structure (g) below: in which:
  • -AMP is an aminoplast residue with alkylene (or divalent alkyl) units
  • - R denotes a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 acyl radical, -RO1 is a divalent alkyleneoxy residue,
  • the polymers with an aminoplast ether backbone are chosen from those containing at least one unit of structure (h) below: in which:
  • R0 2 is a group other than RO, bonded to AMP by means of a heteroatom and comprising at least two carbon atoms, and
  • R 2 or R 3 which may be identical or different, represent an end group that may denote a hydrogen atom, an RO 1 H group, an R0 2 H group, an AMP(OR)p group or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl, aryloxyalkyl or cycloalkoxyalkyl,
  • -a being a number greater than 1 and preferably greater than 2.
  • aminoplast residues bearing their OR groups integrated into the polymers may be chosen, in a non-limiting manner, from structures (1 ) to (12) below:
  • - Ri denotes C1-C4 alkyl
  • - y is a number at least equal to 2
  • - x denotes 0 or 1 .
  • aminoplast residue(s) bearing their OR groups is (are) chosen from those of structure (13) below:
  • the divalent alkyleneoxy residues are preferably those corresponding to the diols of general formula (14) below:
  • -Z, Z', Z2 and Z3 are C 2 -C 4 alkylene radicals and preferably -CH 2 -CH(Z4)- and - CH 2 -CH(Z4)-CH 2 - radicals, -Z1 being a linear or cyclic, branched or unbranched, aromatic or non-aromatic radical optionally comprising one or more heteroatoms and having from 1 to 40 carbon atoms,
  • -Z4 denoting a hydrogen atom or a CrC 4 alkyl radical or a CrC 3 acyl radical, it being understood that at least one of the Z4 radicals of the Z, Z', Z2 and Z3 radicals is other than an acyl radical.
  • Z4 denotes a hydrogen atom or a methyl radical.
  • t 0 and Z, Z' and Z3 denote -CH 2 CH 2 -, and at least one of y or y' is other than 0.
  • the compounds of formula (14) are then polyethylene glycols.
  • aminoplast ether polymers of formula (g) contain at least one saturated or unsaturated, linear or cyclic chain comprising at least 8 carbon atoms, and are in particular described in patent US 5 914 373 to which reference may be made for further details.
  • polymers comprising an aminoplast ether backbone As polymers comprising an aminoplast ether backbone (g), mention may in particular be made of the products Pure-Thix® L [PEG-180/Octoxynol-40/TMMG Copolymer (INCI name)], Pure-Thix M® [PEG-180/Laureth-50/TMMG Copolymer (INCI name)], Pure-Thix® HH [Polyether-1 (INCI name)], and Pure Thix TX-1442® [PEG-18 / dodoxynol-5 / PEG-25 tristyrylphenol / tetramethoxy methyl glycoluril copolymer] proposed by the company Sud-Chemie.
  • the associative thickening polymers which are part of the ingredients in the composition according to the invention can also be chosen from associative polymers comprising at least one ethylenically unsaturated monomer comprising a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic portion.
  • said polymers are neutralized partially or totally with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as monoethanolamine, diethanolamine or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
  • a mineral base sodium hydroxide, potassium hydroxide or aqueous ammonia
  • organic base such as monoethanolamine, diethanolamine or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
  • these associative polymers may or may not be crosslinked, and are preferably crosslinked polymers.
  • the crosslinking agents originate from at least one monomer having at least two ethylenic unsaturations (carbon-carbon double bond).
  • the crosslinking monomers containing at least two ethylenic unsaturations are chosen, for example, from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, tetra- or diethylene glycol di(meth)acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis(meth)acrylamide or divinylbenzene, allylic ethers of alcohol
  • Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate is more particularly used.
  • the degree of crosslinking generally varies from 0.01 mol% to 10 mol% relative to the polymer.
  • the ethylenically unsaturated monomers comprising a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C 2 2)alkylsulfonic acids and N-(Ci-C 2 2)alkyl(meth)acrylamido(Ci- C 2 2)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
  • (Meth)acrylamido(C1 -C22)alkylsulfonic acids such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, can more particularly be used.
  • acrylamidomethanesulfonic acid acrylamidoethanesulfonic acid
  • acrylamidopropanesulfonic acid 2-acrylamido-2-methylpropanesulfonic
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • amphiphilic polymers present in the composition according to the invention may also be chosen from random amphiphilic AMPS polymers modified by reaction with a C 6 -C 2 2 n-monoalkylamine or di-n-alkylamine such as those described in application WO 00/31 154.
  • R-i and R 3 which may be identical or different, denote a hydrogen atom or a linear or branched Ci-C 6 alkyl radical (preferably methyl); Y denotes O or NH; R 2 denotes a hydrophobic hydrocarbon-based radical as defined previously; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.
  • the radical R 2 is advantageously chosen from linear C 6 -Ci 8 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl and n-dodecyl) and branched or cyclic C 6 -Ci8 alkyl radicals (for example cyclododecane (Ci 2 ) or adamantane (Ci 0 )); C 6 -Ci 8 perfluoroalkyl radicals (for example the group of formula -(CH 2 )2-(CF 2 )9-CF 3 ); the cholesteryl radical (C 27 ) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups, for instance naphthalene or pyrene. Preference is more particularly given, among these radicals, to linear alkyl radicals and more particularly to the n-dodecyl radical
  • the monomer of formula (k) comprises at least one alkylene oxide unit (x > 1 ) and preferably a polyoxyalkylene chain.
  • the polyoxyalkylene chain preferentially is constituted of ethylene oxide units and/or propylene oxide units and even more particularly is constituted of ethylene oxide units.
  • the number of oxyalkylene units generally varies from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
  • the copolymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid and maleic acid, or mixtures of these compounds.
  • hydrophilic monomers chosen, for example, from (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid and maleic acid, or mixtures of these compounds.
  • the distribution of the monomers in the copolymer may be random or block.
  • - terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C 6 - Ci 8 )alkylacrylamide units, such as those described in patent US-5 089 578;
  • Ri has the same meaning as that indicated above in formula (j) and R 4 denotes a linear or branched C 6 -C 2 2, in particular C 8 -C 2 2 and more preferentially C10-C22 alkyl.
  • the polymers for which X + denotes sodium or ammonium are more particularly preferred.
  • the associative thickening polymers of the invention are preferably non-ionic or cationic.
  • these associative thickening polymers are celluloses or cellulose derivatives, preferably chosen from non-ionic or cationic celluloses or cellulose derivatives.
  • the associative thickening polymers are chosen from cellulose derivatives, which are preferably non-ionic, in particular hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyi or alkylaryl groups, or mixtures thereof, and in which the alkyl groups preferably C 8 -C 22 alkyl groups.
  • the content of associative thickening polymer(s) represents from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, better still from 0.1 % to 2% by weight relative to the weight of the composition comprising same.
  • composition A and/or the composition B may also comprise one or more surfactants.
  • the surfactant(s) are chosen from anionic, amphoteric, zwitterionic, cationic and non-ionic surfactants, and preferentially non-ionic surfactants.
  • anionic surfactants that may be used in the dye composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglycoside polycarboxylic acid and alkyl monoester
  • 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 of polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside-citrates, C 6 -C 24 alkyl polyglycoside- tartrates and C 6 -C 24 alkyl polyglycoside-sulfosuccinates.
  • anionic surfactant(s) When the anionic surfactant(s) is (are) in salt form, it (they) may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline- earth metal salts such as the magnesium salts.
  • alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline- earth metal salts such as the magnesium salts.
  • amino alcohol salts examples include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-1 -propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
  • Use is preferably made of alkali metal or alkaline-earth metal salts and in particular of sodium or magnesium salts.
  • anionic surfactants use is preferably made of (C 6 - C 24 )alkyl sulfates, (C 6 -C 24 )alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline- earth metal salts, or a mixture of these compounds.
  • (Ci 2 -C 2 o)alkyl sulfates In particular, it is preferred to use (Ci 2 -C 2 o)alkyl sulfates, (Ci 2 -C 2 o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
  • amphoteric or zwitterionic surfactant(s), which are preferably non-silicone, which may be used in the present invention may in particular be derivatives of optionally quaternized aliphatic secondary or tertiary amines, in which derivatives 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, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
  • R a represents a Ci 0 -C 3 o alkyl or alkenyl group derived from an acid
  • RaCOOH preferably present in hydrolysed copra oil, or a heptyl, nonyl or undecyl group;
  • ⁇ R b represents a beta-hydroxyethyl group
  • ⁇ R c represents a carboxymethyl group
  • ⁇ M + represents a cationic counterion derived from an alkali metal or 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, (C1 -C4)alkyl sulfates,
  • (C1 -C4)alkyl- or (C1 -C4)alkylaryl sulfonates in particular methyl sulfate and ethyl sulfate; or alternatively M+ and X- are absent;
  • ⁇ X' represents the group -CH 2 -C(0)OH, -CH 2 -C(0)OZ ⁇ -CH 2 -CH 2 -C(0)OH, -CH 2 -CH 2 -C(0)OZ ⁇ or a hydrogen atom;
  • ⁇ Y' represents the group -C(0)OH, -C(0)OZ', -CH 2 -CH(OH)-S0 3 H or the group -CH 2 -CH(OH)-S0 3 -Z';
  • ⁇ Z' represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
  • ⁇ R a' represents a Ci 0 -C 3 o alkyl or alkenyl group of an acid R a -C(0)OH, which is preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, in particular a Ci 7 group and its iso form, or an unsaturated Ci 7 group.
  • cocoamphodiacetate sold by the company Rhodia under the trade name Miranol ® C2M Concentrate.
  • ⁇ Y" represents the group -C(0)OH, -C(0)OZ", -CH 2 -CH(OH)-S0 3 H or the group -CH 2 -CH(OH)-S0 3 -Z";
  • ⁇ Rd and Re independently of one another, represent a Ci-C 4 alkyl or hydroxyalkyl radical
  • ⁇ Z" represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
  • Ra- represents a Ci 0 -C 30 alkyl or alkenyl group of an acid R a "-C(0)OH, which is preferably present in coconut oil or in hydrolysed linseed oil;
  • ⁇ n and n' independently of one another, denote an integer ranging from 1 to 3.
  • Use is preferably made, among the abovementioned amphoteric or zwitterionic surface-active agents, of (C 8 -C 2 o)alkyl betaines, such as cocoyl betaine, (C 8 - C 2 o)alkylamido (C 3 -C 8 )alkyl betaines, such as cocamidopropyl betaine, and of the compounds of formula (B'2), such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide), and mixtures thereof.
  • C 8 -C 2 o)alkyl betaines such as cocoyl betaine
  • C 8 - C 2 o)alkylamido (C 3 -C 8 )alkyl betaines such as cocamidopropyl betaine
  • B'2 such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (
  • amphoteric or zwitterionic surfactant(s) is (are) chosen from cocamidopropylbetaine, cocobetaine and the sodium salt of diethylaminopropyl laurylaminosuccinte, and mixtures thereof.
  • the cationic surfactant(s) that may be used in the dye composition according to the invention comprise, for example, optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
  • quaternary ammonium salts examples include:
  • R 8 to Rii which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R 8 to Rii comprises 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, (CrC 4 )alkyl sulfates, (C C 4 )alkyl or (Ci-C 4 )alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate.
  • the aliphatic groups of R 8 to Rn may also comprise heteroatoms in particular such as oxygen, nitrogen, sulfur and halogens.
  • the aliphatic groups of R 8 to Rn are chosen, for example, from C 1 -C30 alkyl, d- C 3 o alkoxy, polyoxy(C 2 -C 6 )alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C 2 - C 6 )alkyl, (Ci 2 -C 2 2)alkyl acetate, and C 1 -C30 hydroxyalkyl groups;
  • X " is an anionic counterion chosen from halides, phosphates, acetates, lactates, (CrC 4 )alkyl sulfates, and (Ci-C 4 )alkylsulfonates or (Ci-C 4 )alkylarylsulfonates.
  • quaternary ammonium salts of formula (B3) preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chlor
  • alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow;
  • ⁇ R-13 represents a hydrogen atom, a C C 4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;
  • ⁇ Ri 4 represents a C C 4 alkyl group
  • ⁇ Ri 5 represents a hydrogen atom or a C C 4 alkyl group
  • ⁇ X " represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (CrC 4 )alkyl sulfates, (CrC 4 )alkyl or (d- C 4 )alkylaryl sulfonates.
  • R12 and Ri 3 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, Ri 4 denotes a methyl group and Ri 5 denotes a hydrogen atom.
  • a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;
  • ⁇ R-16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;
  • R-I7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH 2 ) 3 -N + (R 16a )(R 17a )(R 18a ), X " ;
  • R 16a , Ri7a, Risa, Ri8, Ri9, R20 and R21 which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms;
  • ⁇ X- which may be identical or different, represents an organic-or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl(CrC 4 ) sulfates, alkyl(CrC 4 )- or alkyl(Ci-C 4 )aryl-sulfonates, more particularly methyl sulfate and ethyl sulfate.
  • organic-or inorganic anionic counterion such as that chosen from halides, acetates, phosphates, nitrates, alkyl(CrC 4 ) sulfates, alkyl(CrC 4 )- or alkyl(Ci-C 4 )aryl-sulfonates, more particularly methyl sulfate and ethyl sulfate.
  • Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75); -quaternary ammonium salts containing one or more ester functions, such as those of formula (B6) below:
  • ⁇ R22 is chosen from CrC 6 alkyl groups and CrC 6 hydroxyalkyl or CrC 6 dihydroxyalkyl groups;
  • ⁇ R23 is chosen from:
  • ⁇ R25 is chosen from:
  • Ci-C 6 hydrocarbon-based groups R 29 are - saturated or unsaturated, linear or branched Ci-C 6 hydrocarbon-based groups R 29 ,
  • R 2 4, R26 and R 2 8, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;
  • ⁇ r, s and t which may be identical or different, are integers ranging from 2 to 6,
  • ⁇ 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 organic or inorganic anionic counterion
  • the alkyl groups R22 may be linear or branched, and more particularly linear.
  • R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
  • the sum x + y + z is from 1 to 10.
  • R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
  • R 25 is a hydrocarbon-based group R 2 g, it preferably contains 1 to 3 carbon atoms.
  • R 24 , R26 and R 2 s which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C 2 i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn- C 21 alkyl and alkenyl groups.
  • x and z which may be identical or different, are 0 or 1 .
  • y is equal to 1.
  • r, s and t which may be identical or different, have the value 2 or 3 and more particularly still are equal to 2.
  • the anionic counterion X " is preferably a halide, such as chloride, bromide or iodide; a (CrC 4 )alkyl sulfate or a (CrC 4 )alkyl- or (Ci-C 4 )alkylarylsulfonate.
  • a halide such as chloride, bromide or iodide
  • a (CrC 4 )alkyl sulfate or a (CrC 4 )alkyl- or (Ci-C 4 )alkylarylsulfonate e.g., a halide, such as chloride, bromide or iodide
  • a (CrC 4 )alkyl sulfate or a (CrC 4 )alkyl- or (Ci-C 4 )alkylarylsulfonate e.g., a halide, such as chloride, bromide or
  • the anionic counterion X " is even more particularly chloride, methyl sulfate or ethyl sulfate.
  • R22 denotes a methyl or ethyl group
  • - R2 3 is chosen from:
  • - R2 5 is chosen from:
  • R24, R26 and R 2 e which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
  • the hydrocarbon-based radicals are linear.
  • examples that may be mentioned include salts, in particular the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof.
  • the acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
  • This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably methyl or ethyl sulfate, methyl methanesulfonate, methyl para- toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably methyl or ethyl sulfate, methyl methanesulfonate, methyl para- toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • Such compounds are sold, for example, under the names Dehyquart ® by the company Henkel, Stepanquat ® by the company Stepan, Noxamium ® by the company CECA or Rewoquat ® WE 18 by the company Rewo-Witco.
  • composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
  • ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
  • Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.
  • the ammonium salts comprising at least one ester function comprise two ester functions.
  • cationic surfactants that may be present in the dye composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethyl- hydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
  • non-ionic surfactants that may be used in the dye composition used according to the invention are described, for example, in the Handbook of Surfactants by M.R.
  • the non-ionic surfactants are more particularly chosen from oxyalkylenated, glycerolated non-ionic surfactants.
  • the oxyalkylene units are more particularly oxyethylene or oxypropylene units, or their combination, preferably oxyethylene units.
  • oxyalkylenated or glycerolated non-ionic surfactants of:
  • esters of saturated or unsaturated, linear or branched, C 8 -C 3 o acids and of polyethylene glycols • esters of saturated or unsaturated, linear or branched, C 8 -C 3 o acids and of polyethylene glycols;
  • the oxyalkylenated non-ionic surfactants preferably have a number of moles of ethylene oxide and/or of propylene oxide ranging from 1 to 100, preferably from 2 to 50 and preferably between 2 and 30.
  • the non-ionic surfactants do not comprise any oxypropylene units.
  • the oxyalkylenated non-ionic surfactants are chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 35 mol of ethylene oxide; and oxyethylenated esters of saturated or unsaturated, linear or branched C 8 -C 30 acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.
  • glycerolated non-ionic surfactants glycerolated C 8 -C 40 alcohols are preferably used.
  • lauryl alcohol containing 4 mol of glycerol (I NCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol comprising 1.5 mol of glycerol, oleyl alcohol comprising 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol comprising 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleyl/cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
  • glycerolated alcohols it is more particularly preferred to use the C 8 /Cio alcohol containing 1 mol of glycerol, the C10/C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.
  • the surfactant(s) is (are) chosen from non-ionic, anionic or amphoteric surfactants. More particularly, the surfactant(s) that may be present in the composition(s) of the device is (are) chosen from non-ionic and anionic surfactants, and mixtures thereof.
  • the amount of the surfactant(s), when it (they) is (are) present varies preferably from 0.1 % to 35% by weight, even better still from 0.5% to 30% by weight, better still from 1 % to 25% by weight relative to the weight of the composition A and/or B.
  • the composition A and/or the composition B comprise(s) at least one surfactant, preferably chosen from non-ionic surfactants, preferablyoxyalkylenated non-ionic surfactants, more preferably chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, or particular from 2 to 35 mol of ethylene oxide.
  • at least one surfactant preferably chosen from non-ionic surfactants, preferablyoxyalkylenated non-ionic surfactants, more preferably chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, or particular from 2 to 35 mol of ethylene oxide.
  • the composition A and/or the composition B comprise(s) at least one oxyalkylenated non-ionic surfactant, preferably chosen from oxyethylenated C 8 -C 30 alcohols, comprising from 1 to 10 mol of ethylene oxide, preferably from 2 to 5 mol of ethylene oxide and at least one oxyalkylenated non-ionic surfactants, preferably chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 1 to 100 mol of ethylene oxide, preferably from 15 to 35 mol of ethylene oxide.
  • the total content of surfactants in the mixture of the compositions A and B is at least 7% by weight, preferably at least 10% by weight, relative to the total weight of the mixture of the compositions A and B.
  • the composition A comprises at least one anionic surfactant, preferably chosen from those mentioned above, in particular (C 6 - C 2 4)alkyl sulfates, and at least one non-ionic surfactant chosen from those mentioned above.
  • the composition A comprised at least one surfactant, the total content of surfactants in the composition A being at least 10%, preferably at least 15%, but still at least 20% by weight, relative to the total weight of the composition.
  • composition A and/or the composition B may comprise one or more fatty substances.
  • fatty substance is intended to mean an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They bear in their structure at least one hydrocarbon- based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups.
  • the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
  • organic solvents for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
  • the fatty substances of the invention do not contain any salified carboxylic acid groups.
  • the fatty substances of the invention are not (poly)oxyalkylenated or (poly)glycerolated ethers.
  • oil is intended to mean a fatty substance that is liquid at ambient temperature (25°C) and at atmospheric pressure (760 mmHg).
  • non-silicone oil is intended to mean an oil not containing any silicon atoms (Si) and the term “silicone oil” is intended to mean an oil containing at least one silicon atom.
  • the fatty substances are chosen from C 6 -Ci 6 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides, and plant waxes, non-silicone waxes and silicones, and mixtures thereof.
  • the fatty alcohols, esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group, comprising 6 to 30 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular, with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • C 6 -Ci 6 hydrocarbons they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
  • a hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.
  • the triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides comprising from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
  • liquid fatty acid triglycerides comprising from 6 to 30 carbon atoms
  • heptanoic or octanoic acid triglycerides or alternatively, for example, sunflower oil, corn oil, soybean oil, m
  • the linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms are preferably chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®.
  • C 6 -Ci 6 alkanes they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
  • oils of animal, vegetable, mineral or synthetic origin that may be used in the composition of the invention, examples that may be mentioned include:
  • fluoro oils that may be chosen from perfluoromethylcyclopentane and perfluoro-1 ,3- dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or alternatively bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.
  • the fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and a mixture thereof (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.
  • esters of a fatty acid and/or of fatty alcohols which are advantageously different from the triglycerides mentioned previously, mention may be made in particular of esters of saturated or unsaturated, linear or branched Ci-C 2 6 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C 2 6 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.
  • dihydroabietyl behenate octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristyl stearate;
  • esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C 2 -C 2 6 di-, tri-, tetra- or pentahydroxy alcohols may also be used.
  • esters mentioned above it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.
  • alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stea
  • composition may also comprise, as fatty ester, sugar esters and diesters of C 6 -C 3 o and preferably C12-C22 fatty acids.
  • sugar esters and diesters of C 6 -C 3 o and preferably C12-C22 fatty acids.
  • sugar esters are intended to mean oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms.
  • sugars may be monosaccharides, oligosaccharides or polysaccharides.
  • sucrose or saccharose
  • glucose or galactose
  • ribose or fucose
  • maltose fructose
  • mannose mannose
  • arabinose xylose
  • lactose and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C 6 -C 3 o and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
  • esters may be chosen, for example, from oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, oleopalmitate, oleostearate and palmitostearate mixed esters.
  • monoesters and diesters and in particular sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate.
  • esters or mixtures of esters of sugar and of fatty acid examples include:
  • Ryoto Sugar Esters for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-tri ester-polyester;
  • sucrose mono-dipalmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE.
  • the fatty substances are chosen from compounds that are liquid or pasty at ambient temperature (25°C) and at atmospheric pressure.
  • the fatty substance is a compound that is liquid at a temperature of 25°C and at atmospheric pressure.
  • the fatty substance is a compound that is non-liquid at a temperature of 25°C and at atmospheric pressure, and is preferably solid.
  • the fatty substances are advantageously chosen from C 6 -Ci 6 alkanes, non- silicone oils of vegetable, mineral or synthetic origin, fatty alcohols, esters of a fatty acid and/or of a fatty alcohol, and silicone or non-silicone waxes, or mixtures thereof.
  • the fatty substances chosen from liquid petroleum jelly, C 6 -Ci 6 alkanes, and fatty alcohols, or mixtures thereof.
  • composition A or B according to the invention may comprise from 0.1 % to 40% by weight of fatty substance relative to its total weight, preferably from 0.5% to 30%, better still from 1 % to 20%, even better still from 1 % to 10%.
  • the composition A comprises less than 10% by weight, preferably less than 7%, advantageously less than 5% by weight of fatty substance, better still less than 1 % by weight, relative to its total weight.
  • the composition B comprises at least one fatty substance preferably chosen from C 6 -Ci 6 alkanes, non-silicone oils of vegetable, mineral or synthetic origin, fatty alcohols, esters of fatty acid and/or of fatty alcohol or mixtures thereof, preferably chosen from non-silicone oils of mineral or synthetic origin and fatty alcohols, and mixtures thereof.
  • the composition B comprises at least one mineral oil and at least one fatty alcohol.
  • composition A and/or the composition B comprise(s) at least one cationic polymer distinct from the associative thickening polymer.
  • cationic polymer denotes any polymer containing cationic groups and/or groups that can be ionized into cationic groups.
  • the cationic polymer present in the composition according to the invention is a linear, random, graft or block homopolymer or copolymer and comprises at least one cationic group and/or group that can be ionized into a cationic group chosen from primary, secondary, tertiary and/or quaternary amine groups that form part of the main polymer chain or that are borne by a side substituent directly connected thereto.
  • the cationic charge density of the cationic polymers according to the invention is greater than 1 meq/g, even more particularly greater than or equal to 4 meq/g.
  • This charge density is determined by the Kjeldahl method. It may also be calculated from the chemical nature of the polymer.
  • the cationic polymers used generally have a number-average molecular weight of between 500 and 5 ⁇ 10 6 approximately, and preferably between 10 3 and 3 ⁇ 10 6 .
  • cationic polymers mention may more particularly be made of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type.
  • cationic polymers that can be used in the context of the invention, mention may be made of the following polymers, alone or as a blend:
  • R 3 which may be identical or different, denote a hydrogen atom or a CH 3 radical
  • A which may be identical or different, represent a linear or branched Ci-C 6 and preferably C 2 -C 3 alkyl group or a Ci-C 4 hydroxyalkyl group;
  • R 4 , R 5 and R 6 which may be identical or different, represent a Ci-Ci 8 alkyl group or a benzyl radical, and preferably a Ci-C 6 alkyl group;
  • Ri and R 2 which may be identical or different, represent hydrogen or a Ci-C 6 alkyl group, and preferably methyl or ethyl;
  • X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • the polymers of family (1 ) may also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • the crosslinked polymers of methacryloyloxy(Ci-C 4 )alkyl tri(Ci-C 4 )alkylammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide.
  • Use may more particularly be made of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil.
  • This dispersion is sold under the name Salcare® SC 92 by the company Ciba.
  • Use may also be made of a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names of Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
  • Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and disclosed in particular in US 4 131 576, such as hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • the commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
  • Cationic guar gums described more particularly in US 3 589 578 and US 4 031 307 such as guar gums containing trialkylammonium cationic groups.
  • Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, chloride).
  • Such products are sold in particular under the trade names Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar C162 by the company Meyhall.
  • Polymers constituted of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers.
  • Such polymers are described, in particular, in FR 2 162 025 and FR 2 280 361 .
  • Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis- unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis- unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may
  • polymers are described, in particular, in FR 2 252 840 and FR 2 368 508.
  • alkyl radical is C1-C4 and preferably denotes methyl, ethyl or propyl.
  • Such polymers are described in particular in FR 1 583 363.
  • the mole ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8:1 and 1 .4:1 ; the resulting polyaminoamide is reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5:1 and 1 .8:1.
  • Such polymers are described in particular in US 3 227 615 and US 2 961 347.
  • Polymers of this type are sold in particular under the name Hercosett 57, PD 170 or Delsette 101 by the company Hercules.
  • Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (V) or (VI):
  • R 9 denotes a hydrogen atom or a methyl radical
  • R 7 and R 8 independently of each other, denote a Ci-C 8 alkyl group, a hydroxyalkyl group in which the alkyl group is C1-C5, an amidoalkyl group in which the alkyl is Ci-C 4
  • R 7 and R 8 can also denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl
  • R 7 and R 8 independently of each other, preferably denote a C1-C4 alkyl group
  • Y " is an organic or mineral anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • the cyclopolymers preferably comprise at least one unit of formula (V).
  • copolymers they also comprise an acrylamide monomer.
  • R 10 , Rii , Ri2 and Ri 3 which may be identical or different, represent Ci-C 2 o aliphatic, alicyclic or arylaliphatic radicals or hydroxyalkylaliphatic radicals in which the alkyl radical is Ci-C 4 , or alternatively Rio, Rn , R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively R1 0 , Rn , R12 and R-I3 represent a linear or branched Ci-C 6 alkyl radical substituted with a nitrile, ester, acyl or amide group or a group -CO-0-Ri 4 -D or -CO-NH-R 14 -D where Ri 4 is an alkylene and D is a quaternary ammonium group;
  • A-i and B-i represent C 2 -C 2 o polymethylene groups which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  • X denotes an anion derived from a mineral or organic acid
  • A-i , R-io and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;
  • A-i denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical
  • D denotes: a) a glycol residue of formula: -0-Z-0-, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CH 2 -CH 2 -0)x-CH 2 -CH 2 - and -[CH 2 -CH(CH 3 )-0]y-CH 2 -CH(CH 3 )- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
  • a bis-secondary diamine residue such as a piperazine derivative
  • Y denotes a linear or branched hydrocarbon-based radical, or alternatively the radical -CH 2 -CH 2 -S- S-CH 2 -CH 2 -;
  • X " is an anion, such as chloride or bromide.
  • These polymers have a number-average molecular weight generally between 1000 and 100 000.
  • Polymers of this type are described in particular in FR 2 320 330, FR 2 270 846, FR 2 316 271 , FR 2 336 434, FR 2 413 907, US 2 273 780, US 2 375 853, US
  • R 10 , Rn, Ri 2 and Ri 3 which may be identical or different, denote a Ci-C 4 alkyl or hydroxyalkyi radical, n and p are integers ranging from 2 to 20 approximately, and X " is an anion derived from a mineral or organic acid.
  • Such polymers may be prepared according to the processes described in US 4 157 388, US 4 702 906 and US 4 719 282. They are in particular described in patent application EP 122 324.
  • examples that may be mentioned include the products Mirapol A 15, Mirapol AD1 , Mirapol AZ1 and Mirapol 175 sold by the company Miranol.
  • cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, polyquaternary ureylenes and chitin derivatives.
  • cationic polymers that may be used in the context of the present invention, it is preferred to use, alone or as mixtures, polymers of families (1 ), (7), (8) and (9). In accordance with one more particular embodiment of the invention, it is preferred to use polymers of families (7), (8) and (9).
  • the content of cationic polymer(s), when it (they) is (are) present represents from 0.01 % to 10% by weight, more particularly from 0.05% to 6% by weight, and even more preferentially between 0.1 % and 5% by weight relative to the weight of the composition comprising same.
  • the composition A and/or the composition B preferably the composition A, comprises at least one cationic polymer, preferably chosen from the polymers of families (7) and (8) as described above, alone or as mixtures, and even more preferentially the polymers having repeating units of formulae (W) and (U) as described above.
  • the composition A comprises at least one cationic polymer of family (7) and at least one cationic polymer of family (8).
  • composition A and/or the composition B may also contain various adjuvants conventionally used in hair lightening compositions, such as anionic, amphoteric or non-ionic polymers, distinct from the associative thickening polymers mentioned above, or mixtures thereof; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers.
  • adjuvants conventionally used in hair lightening compositions such as anionic, amphoteric or non-ionic polymers, distinct from the associative thickening polymers mentioned above, or mixtures thereof; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers.
  • the above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of each composition.
  • composition A and/or B according to the invention may comprise water and/or one or more organic solvents.
  • organic solvents examples include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1 ,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol or phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl or monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, in particular Ci-C 4 alkyl ethers, for instance diethylene glycol monoethyl
  • the organic solvents when they are present, generally represent between 1 % and 40% by weight relative to the total weight of the dye composition, and preferably between 5% and 30% by weight relative to the total weight of the dye composition.
  • the composition A and the composition B are aqueous.
  • compositions A if it is aqueous, are generally between 3 and 12, preferably between 5 and 1 1 . It is preferentially between 7 and 1 1 , limits included.
  • the oxidizing composition B also preferably comprises one or more acidifying agents.
  • acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
  • the pH of the oxidizing composition when it is aqueous, is less than 7.
  • compositions A and B may each have a viscosity, measured at 25°C and atmospheric pressure, ranging from 1000 to 60 000 mPa.s, preferably from 5000 to 40 000 mPa.s.
  • composition A may have a viscosity ranging from 10 000 to 40 000 mPa.s.
  • composition B may have a viscosity ranging from 5000 to 15 000 mPa.s.
  • the viscosity of the compositions may be measured at 25°C using a Brookfield LVT viscometer equipped with an M4 spindle rotating at a speed of 12 rpm. The measurement is taken after 1 minute.
  • compositions A and B may be in the form of a gel or cream. According to one particular embodiment, the compositions A and B of the device according to the invention are such that:
  • composition A comprises:
  • At least one alkaline agent preferably chosen from aqueous ammonia, alkanolamines, preferably monoethanolamine, and mixtures thereof,
  • At least one dyeing agent preferably chosen from oxidation dye precursors, at least one associative thickening polymer, as described above, preferably chosen from associative cellulose derivatives, which are preferably non-ionic, in particular hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C 8 -C 2 2 alkyl groups, at least one anionic surfactant, preferably chosen from (Ci 2 -C 2 o)alkyl sulfates as described above,
  • At least one cationic polymer as described above preferably chosen from polymers of families (7) and (8) alone or as mixtures, and even more preferentially of polymers having repeating units of formulae (W) and (U),
  • composition B comprises:
  • At least one oxidizing agent preferably hydrogen peroxide
  • At least one fatty substance as described above preferably chosen from non-silicone oils of mineral or synthetic origin, fatty alcohols and mixtures thereof,
  • composition A and/or the composition B comprise(s) at least one non-ionic surfactant as described above, preferably chosen from oxyethylenated C 8 -C 3 o alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 35 mol of ethylene oxide.
  • the total content of surfactants in the mixture of the compositions A and B is at least 7% by weight, preferably at least 10% by weight, relative to the total weight of the mixture of the compositions A and B.
  • the dispensing device according to the invention is constituted of a container comprising:
  • the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent,
  • the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent
  • compositions A and B of the two compartments comprising at least one associative thickening polymer
  • the container of the device is pressurized (aerosol device).
  • it comprises one or more propellant gases.
  • propellant gas suitable for implementing the invention, mention may be made of the gases normally used in the cosmetics field, in particular optionally halogenated volatile hydrocarbons, for example n-butane, propane, isobutane, pentane, and halogenated derivatives thereof; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen and oxygen, alone or as mixtures.
  • gases normally used in the cosmetics field in particular optionally halogenated volatile hydrocarbons, for example n-butane, propane, isobutane, pentane, and halogenated derivatives thereof; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen and oxygen, alone or as mixtures.
  • the walls of the container containing the compartments a and b are preferably rigid, the container possibly being in this case a can, for example made of metal or plastic.
  • the compartments a and b are flexible pouches. They may be made of metal, such as aluminium, or plastic.
  • the propellant gas is in the volume defined between the walls of the container and the flexible pouches.
  • the device comprises a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B, in separate form (side by side for example) or in mixture form, preferably in separate form, by means of at least one dispensing orifice.
  • the means for delivering the compositions comprise at least one dispensing valve.
  • each compartment is surmounted by a valve.
  • the compartments are surmounted by a single valve connecting them.
  • the valve(s) is (are) in selective fluidic communication with the inside of the compartment(s) via a valve inlet orifice, the communication being established in response to the activating of an activating means, such as a push-button.
  • the dispensing means of the device may comprise a diffuser which caps the valve(s).
  • the device comprises a single diffuser which caps the two valves.
  • the push-button may be part of the diffuser.
  • the diffuser may be equipped with one or more dispensing pipes provided to convey the composition(s) up to one or more dispensing orifices.
  • the device When the device comprises a single diffuser, it may be equipped with two composition conveying pipes, each pipe communicating with the outlet orifice of a valve.
  • the two pipes each open into a dispensing orifice (not communicating with one another before the dispensing orifice). According to this configuration, the mixing of the compositions is carried out only after dispensing of the latter (thus after the dispensing orifices).
  • the two pipes open into a mixing chamber equipped with a static mixer, from which a single pipe is directed to a single dispensing orifice.
  • the mixing of the compositions is carried out just before discharge thereof from the device.
  • the compositions A and B can be delivered in mixture form prior to the application to the keratin fibres, or can be delivered simultaneously in separate form, the mixing taking place after application to the keratin fibres (when the compositions leave simultaneously side by side).
  • the compartments a and b are flexible pouches, a dispensing valve surmounting each of the compartments, a single diffuser capping the two valves.
  • the dispensing valve(s), like the content of propellant gas(es), are adjusted so as to enable the dispensing of the compositions in appropriate respective proportions.
  • the dispensed composition A/composition B weight ratio ranges from 0.25 to 4 and preferably from 0.5 to 2.
  • this ratio is 1.
  • a subject of the invention is also a kit comprising:
  • composition C comprising at least one conditioning agent chosen from silicones, cationic polymers and amphoteric polymers, and mixtures thereof.
  • the cationic polymers may be chosen from the cationic polymers described above, in particular the polymers of families (7) and (8) as described above, alone or as mixtures, and even more preferentially the polymers having repeating units of formulae (W) and (U) as described above.
  • the silicones that may be used in the compositions of the present invention are in particular polyorganosiloxanes, which may be oils, waxes, resins or gums.
  • the silicones that may be used in the compositions of the present invention may be in the form of aqueous solutions, i.e. dissolved, or optionally in the form of dispersions or microdispersions, or of aqueous emulsions.
  • Silicones are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.
  • the silicones may be volatile or non-volatile.
  • the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and more particularly still from:
  • cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
  • cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
  • These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone 7207 by the company Union Carbide or Silbione 70045 V 2 by the company Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone 7158 by the company Union Carbide, and Silbione 70045 V 5 by the company Rhodia, and mixtures thereof.
  • silicones are non-volatile, use is preferably made of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and polyorganosiloxanes modified with organofunctional groups, and mixtures thereof.
  • silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups (Dimethicone according to the CTFA name) for example having a viscosity of from 5x10 "6 to 2.5 m 2 /s at 25°C and preferably 1 x10 "5 to 1 m 2 /s. The viscosity of the silicones is measured, for example, at 25°C according to standard ASTM 445 Appendix C.
  • polyalkylsiloxanes mention may be made, in a non-limiting manner, of the following commercial products:
  • oils of the 200 series from the company Dow Corning such as, more particularly, DC200 with a viscosity of 60 000 cSt,
  • polydialkylsiloxanes and in particular polydimethylsiloxanes containing dimethylsilanol end groups such as the oils of the 48 series from the company Rhodia.
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethylmethylphenylsiloxanes and polydimethyldiphenylsiloxanes with a viscosity of from 1 x10 "5 to 5x10 2 m 2 /s at 25°C.
  • the silicone gums that may be present in the composition according to the invention are in particular polydiorganosiloxanes having high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent.
  • This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.
  • a polydimethylsiloxane gum with a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product being an SF 30 gum corresponding to a dimethicone, having a number- average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane,
  • the product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m 2 /s and of an oil SF 96 with a viscosity of 5x10 "6 m 2 /s.
  • This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.
  • the organopolysiloxane resins that may be present in the composition according to the invention are crosslinked siloxane systems containing the following units: R2S1O2/2, 3S1O1/2, RS1O3/2 and S1O4/2 in which R represents a hydrocarbon group containing 1 to 16 carbon atoms or a phenyl group.
  • R represents a hydrocarbon group containing 1 to 16 carbon atoms or a phenyl group.
  • R denotes a C1-C4 alkyl group, more particularly methyl, or a phenyl group.
  • organomodified silicones that may be present in the composition according to the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
  • organomodified silicones mention may be made of polyorganosiloxanes comprising:
  • C 6 -C 2 4 alkyl groups such as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils Silwet L 722, L 7500, L 77 and L 71 1 by the company Union Carbide, and the (Ci 2 )alkylmethicone copolyol sold by the company Dow Corning under the name Q2 5200,
  • organomodified silicones mention may also be made of amino silicones.
  • amino silicone is intended to mean any silicone comprising at least one primary, secondary or tertiary amine function or a quaternary ammonium group.
  • amino silicones that may be used in the cosmetic composition according to the present invention are chosen from:
  • T is a hydrogen atom or a phenyl or hydroxyl (-OH), or CrC 8 alkyl, and preferably methyl, or
  • Ci-C 8 alkoxy preferably methoxy group
  • a denotes the number 0 or an integer from 1 to 3, and preferably 0,
  • b denotes 0 or 1 , and in particular 1 ,
  • n and n are numbers such that the sum (n + m) can range in particular from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10,
  • R 1 is a monovalent group of formula -C q H 2q L in which q is a number from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups:
  • R 2 may denote a hydrogen atom, a phenyl, benzyl or saturated monovalent hydrocarbon-based group, for example a Ci-C 20 alkyl group
  • Q " represents a halide ion, for example fluoride, chloride, bromide or iodide.
  • amino silicones corresponding to the definition of formula (V) are chosen from the compounds corresponding to formula (VI) below:
  • R, R' and R which may be identical or different, denote a C1-C4 alkyl group, preferably CH 3 ; a C1-C4 alkoxy group, preferably methoxy; or OH;
  • A represents a linear or branched, C 3 -C 8 and preferably C 3 -C 6 alkylene group;
  • m and n are integers dependent on the molecular weight and the sum of which is between 1 and 2000.
  • R, R' and R which may be identical or different, each represent a C1-C4 alkyl group or hydroxyl
  • A represents a C 3 alkylene group
  • m and n are such that the weight-average molecular weight of the compound is between approximately 5000 and 500 000.
  • the compounds of this type are named "amodimethicone" in the CTFA dictionary.
  • R, R' and R" which may be identical or different, each represent a C1-C4 alkoxy group or hydroxyl, at least one of the groups R and R" is an alkoxy group and A represents a C 3 alkylene group.
  • the hydroxyl/alkoxy mole ratio is preferably between 0.2/1 and 0.4/1 and advantageously equal to 0.3/1.
  • m and n are such that the weight-average molecular weight of the compound is between 2000 and 10 6 . More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.
  • R and R which are different, each represent a
  • n is such that the weight-average molecular weight of the compound is between 2000 and 200 000. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.
  • the molecular weight of these silicones is determined by gel permeation chromatography (ambient temperature, polystyrene standard, ⁇ styragem columns, eluent THF, flow rate of 1 mm/minute, 200 ⁇ of a solution containing 0.5% by weight of silicone in THF are injected, and detection is performed by refractometry and UV-metry).
  • a product corresponding to the definition of formula (V) is in particular the polymer known in the CTFA dictionary as Trimethylsilyl Amodimethicone, corresponding to formula (VII) below:
  • a compound of formula (VII) is sold, for example, under the name Q2-8220 by the company OSI.
  • R 3 represents a monovalent C Ci 8 hydrocarbon-based group, and in particular a C1-C18 alkyl or C 2 -Ci 8 alkenyl group, for example methyl,
  • R 4 represents a divalent hydrocarbon-based group, in particular a Ci-Ci 8 alkylene group or a divalent Ci-Ci 8 , for example Ci-C 8 , alkyleneoxy group,
  • Q " is a halide ion, in particular chloride
  • r represents a mean statistical value from 2 to 20 and in particular from 2 to 8
  • s represents a mean statistical value from 20 to 200 and in particular from 20 to
  • a compound falling within this class is the product sold by the company Union Carbide under the name Ucar Silicone ALE 56.
  • R 6 which may be identical or different, represent a monovalent hydrocarbon- based group having from 1 to 18 carbon atoms, and in particular a C Ci 8 alkyl group, a C 2 -Cis alkenyl group or a ring comprising 5 or 6 carbon atoms, for example methyl,
  • R 5 represents a divalent hydrocarbon-based group, in particular a Ci-Ci 8 alkylene group or a divalent Ci-Ci 8 , for example Ci-C 8 alkyleneoxy group linked to the Si by an Si-C bond,
  • R 7 which may be identical or different, each represent a hydrogen atom, a monovalent hydrocarbon-based group containing from 1 to 18 carbon atoms, and in particular a Ci-Ci 8 alkyl group, a C 2 -Ci 8 alkenyl group or an -R 5 -N HCOR 6 group;
  • X " is an anion, such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.),
  • r represents a mean statistical value from 2 to 200 and in particular from 5 to
  • R 8 , R 9 , R 10 and R 11 which may be identical or different, each denote a Ci-C 4 alkyl group or a phenyl group,
  • R 12 denotes a C C 4 alkyl group or a hydroxyl group
  • - n is an integer ranging from 1 to 5
  • - m is an integer ranging from 1 to 5
  • - x is chosen such that the amine number is between 0.01 and 1 meq/g.
  • one particularly advantageous embodiment involves their joint use with cationic and/or non-ionic surfactants.
  • Cationic Emulsion DC939 by Dow Corning, which comprises, aside from amodimethicone, a cationic surfactant, namely trimethylcetylammonium chloride and a non-ionic surfactant of formula Ci 3 H 27 -(OC 2 H 4 ) 12 -OH, known under the CTFA name Trideceth-12.
  • Another commercial product that may be used according to the invention is the product sold under the name Dow Corning Q2 7224 by the company Dow Corning, comprising, in combination, trimethylsilyl amodimethicone of formula (X) described above, non-ionic surfactant of formula C 8 H 17 -C 6 H 4 -(OCH 2 CH 2 ) 4 o-OH, known under the CTFA name Octoxynol-40, a second non-ionic surfactant of formula Ci 2 H 2 5-(OCH 2 - CH 2 )6-OH, known under the CTFA name lsolaureth-6, and propylene glycol.
  • the silicones of the invention may also be silicones grafted with anionic groups, such as the compounds VS 80 or VS 70 sold by the company 3M.
  • silicones can also be used in the form of emulsions, nanoemulsions or microemulsions.
  • the particularly preferred silicones in accordance with the invention are:
  • non-volatile silicones chosen from the family of polydialkylsiloxanes with trimethylsilyl end groups, such as oils having a viscosity of between 0.2 and 2.5 m 2 /s at 25°C, for instance the oils of the DC200 series from Dow Corning, in particular the one with a viscosity of 60 000 cSt, or of the Silbione 70047 and 47 series, and more particularly the oil 70 047 V 500 000 sold by the company Rhodia Chimie, and polydialkylsiloxanes with dimethylsilanol end groups, such as dimethiconols, or polyalkylarylsiloxanes, for instance the oil Silbione 70641 V 200 sold by the company Rhodia Chimie;
  • polysiloxanes bearing amine groups such as amodimethicones, trimethylsilyl amodimethicones and polysiloxanes bearing quaternary ammonium groups.
  • the silicones that are even more particularly preferred in accordance with the invention are polysiloxanes bearing amine groups.
  • the viscosities of the silicones may in particular be determined by the standard
  • the conditioning agent(s) may represent from 0.01 % to 10% by weight, preferably from 0.1 % to 5% by weight, more particularly from 0.3% to 5% by weight, and more particularly from 0.3% to 3% by weight, relative to the total weight of the composition C.
  • the invention also relates to a process for lightening and/or dyeing human keratin fibres, in which the following are applied to said fibres:
  • composition A comprising at least one alkaline agent and optionally at least one dyeing agent
  • composition B comprising at least one chemical oxidizing agent
  • compositions A and B comprising at least one associative thickening polymer
  • compositions A and B being packaged in a device constituted of a container, which is preferably pressurized, comprising at least two compartments a and b separate from one another, the compartment a comprising the composition A and the compartment b comprising the composition B, the device comprising a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to deliver the compositions A and B simultaneously.
  • the mixing of the compositions A and B can be carried out just before the application to the keratin fibres or directly on the keratin fibres, for example during a simultaneous application of the compositions A and B to the hair.
  • a composition obtained by extemporaneous mixing, at the time of use, of the composition A and of composition B is applied to the keratin fibres.
  • compositions A and B are applied simultaneously to the keratin fibres (without prior mixing), and then mixed directly on the keratin fibres, for example by massaging.
  • compositions A and B are applied simultaneously to the keratin fibres, the mixing of the compositions being carried out just before discharge thereof from the device.
  • compositions may be applied to wet or dry keratin fibres.
  • composition resulting from the mixing is usually left in place on the fibres for a period generally from 1 minute to 1 hour, preferably from 5 minutes to 30 minutes.
  • the temperature during the treatment process is conventionally between ambient temperature (between 15 and 25°C) and 80°C and preferably between ambient temperature and 60°C.
  • the human keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.
  • a composition C as defined above comprising at least one conditioning agent chosen from silicones, cationic polymers and amphoteric polymers, and mixtures thereof, is applied to the keratin fibres after removal of the mixture of the compositions A and B, preferably by rinsing, and optional shampooing followed by rinsing that may occur before the application of the composition C.
  • the application of the composition C may optionally be followed by rinsing, the keratin fibres then being dried or left to dry.
  • compositions are prepared (the amounts are expressed in g% of active material):
  • Composition A A:
  • Trideceth-2 carboxamide MEA (Amidet A15/LAO 55 from 4
  • Polyquaternium-6 (Merquat 100 from Nalco) 0.8
  • compositions A and B are packaged in an aerosol container comprising two flexible pouches and equipped with a diffuser comprising a push-button, and are dispensed simultaneously side by side in 1/1 proportions.
  • compositions mix rapidly on the hair and the mixture readily uniformly distributes on the hair.
  • the use qualities are good: good wetting/glidance nature, ease of application, good root adhesion, good consistency on the head, good ease of spreading along the locks of hair.
  • the hair is then easily rinsed, then washed with a standard shampoo and dried. A strong chestnut brown colouration is obtained.

Abstract

Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer The present invention relates to a device for dispensing a product for dyeing and/or lightening keratin fibres constituted of a container comprising: i) at least two compartments a and b separate from one another, the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent, the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent, one and/or the other of the compositions of the two compartments comprising at least one associative thickening polymer; ii)a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B. It also relates to a process for dyeing human keratin fibres using said device, and also to a kit comprising said device and a composition comprising a conditioning agent.

Description

Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer
A subject of the present invention is a device for dispensing a product for dyeing and/or lightening keratin fibres comprising compositions A and B, and also a dyeing process using said device. The present invention also relates to a kit comprising said device and a composition comprising a conditioning agent.
Among the methods for dyeing human keratin fibres, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. More particularly, this dyeing method uses one or more oxidation dyes, usually one or more oxidation bases optionally combined with one or more couplers.
In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or ara-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, can give access to coloured entities.
The shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen in particular from aromatic meia-diamines, meia-aminophenols, meia-diphenols and certain heterocyclic compounds, such as indole compounds.
The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
Permanent dyeing processes thus consist in using, with the dye composition containing the oxidation dyes, an aqueous composition comprising at least one oxidizing agent, such as hydrogen peroxide, under alkaline pH conditions in the vast majority of cases. The alkaline agent conventionally used is aqueous ammonia or can be chosen from other alkaline agents, such as alkanolamines.
These compositions, in particular the compositions comprising oxidation dyes, are obviously sensitive to oxidation and as a result contain reducing agents or antioxidants. This action of protection against oxidation is also reinforced by virtue of the inert atmosphere that is sometimes used during the packaging of these compositions.
The difficulty encountered with compositions of this type indeed results from their sensitivity to oxidation. This is because, during their use, they are brought into contact with atmospheric oxygen and this then requires that they be used rapidly. If they are not used rapidly, the compositions become unusable after storage and are lost.
In the hair dyeing field, there are alkaline compositions, in particular dyeing compositions, and oxidizing compositions, which are packaged separately in one and the same pressurized container and which make it possible to avoid the composition being brought into contact with air when they are used. These compositions can be in the form of a foam or cream.
However, the strength of the dyeing and also the coverage of the hair, in particular of white hair, still requires further improvement, as do the rheological properties of the product(s) stemming from the pressurized container, in particular in terms of ease of mixing of the dyeing or lightening and oxidizing compositions, of the uniformity of the mixture and of the quality of application to keratin fibres (in particular in terms of the wetting nature, of the adhesion to the roots and of the ease with which the mixture can be spread along the locks of hair).
There is a constant need to develop devices which make it possible to deliver dyeing and/or lightening compositions which have good use qualities such as ease of application and rinsability, and which remain sufficiently stable over time, while retaining effective dyeing properties, in particular in terms of coverage of the hair, more particularly white hair, but also of intensity, uniformity, chromaticity and selectivity of the dyeing obtained, with moreover good cosmetic properties.
The objective of the present invention is thus to provide dyeing compositions which are in particular in cream or gel form, having good use qualities, in particular mixing and application qualities, while at the same time having high dyeing and/or lightening performance levels.
This aim and others are achieved by means of the present invention, a subject of which is thus a device for dispensing a product for dyeing and/or lightening keratin fibres, constituted of a container comprising:
i) at least two compartments a and b separate from one another,
the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent,
the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent, one and/or the other of the compositions of the two compartments comprising at least one associative thickening polymer;
ii) a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B.
The invention also relates to a process for lightening and/or dyeing human keratin fibres using this device.
More specifically, a subject of the invention is a process for lightening and/or dyeing human keratin fibres, in which the following are applied to said fibres:
a composition A comprising at least one alkaline agent and optionally at least one dyeing agent; and
a composition B comprising at least one chemical oxidizing agent;
one and/or the other of the two compositions comprising at least one associative thickening polymer,
the compositions A and B being packaged in a device constituted of a container, which is preferably pressurized, comprising at least two compartments a and b separate from one another, the compartment a comprising the composition A and the compartment b comprising the composition B, the device comprising a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to deliver the compositions A and B simultaneously.
The device and the process of the invention make it possible to obtain good lightening and/or dyeing properties on keratin fibres, and in the case of dyeing, in particular dyeing which is strong, intense and/or chromatic, resistant to external agents (shampoos, perspiration, light), uniform and not very selective.
The device comprising the compositions also produces good use qualities, in particular the application of the compositions A and B is easy and the distribution is uniform along the keratin fibres.
The device and the process of the invention also produce good cosmetic properties, in particular in terms of disentangling, suppleness and softness of the hair.
The mixture of the compositions A and B rinses off easily after the leave-on time.
In addition, the compositions A and B used in the dyeing and/or lightening process according to the invention mix easily, prior to the application to the keratin fibres or directly on the keratin fibres during simultaneous application of the compositions A and B to the hair.
Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.
In that which follows and unless otherwise indicated, the limits of a range of values are included in this range.
The term "at least one" associated with an ingredient of the composition signifies "one or more".
The human keratin fibres treated via the process according to the invention are preferably the hair.
Alkaline agent:
The composition A of the device according to the invention comprises at least one alkaline agent.
This agent can be chosen from mineral or organic or hybrid alkaline agents or mixtures thereof.
The mineral alkaline agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.
The organic alkaline agent(s) are preferably chosen from organic amines with a pKb at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pKb corresponding to the highest basicity function.
Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.
The organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds having the formula below:
Rx Rz
W N
Ry " Rt
in which W is a Ci-C6 alkylene residue optionally substituted with a hydroxyl group or a Ci-C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a Ci-C6 alkyl, CrC6 hydroxyalkyl or CrC6 aminoalkyl radical. Mention may be made, as examples of such amines, of 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine or spermidine.
The term "alkanolamine" is intended to mean an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C C8 alkyl groups bearing one or more hydroxyl radicals.
Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different CrC4 hydroxyalkyi radicals are in particular suitable for performing the invention.
Among the compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1 -propanol, triisopropanolamine, 2-amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3- dimethylamino-1 ,2-propanediol and tris(hydroxymethylamino)methane.
More particularly, the amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form, and comprise at least one acid function chosen more particularly from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functions. The amino acids may be in neutral or ionic form.
As amino acids that may be used in the present invention, mention may be made in particular of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.
Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.
Such basic amino acids are preferably chosen from those corresponding to the formula below:
Figure imgf000006_0001
in which R denotes a roup chosen from:
Figure imgf000006_0002
(CH2)2NHCONH2 -(CH2)2NH C— NH2
NH
The compounds corresponding to the formula above are histidine, lysine, arginine, ornithine and citrulline.
The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.
The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made in particular of carnosine, anserine and balenine.
The organic amine may also be chosen from compounds comprising a guanidine function. As amines of this type that may be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made in particular of creatine, creatinine, 1 ,1 -dimethylguanidine, 1 ,1 -diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3- guanidinopropionic acid, 4-guanidinobutyric acid and 2- ([amino(imino)methyl]amino)ethane-1 -sulfonic acid.
Mention may be made in particular of guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds.
According to one embodiment of the invention, the composition according to the invention contains, as alkaline agent, aqueous ammonia and/or at least one alkanolamine and/or at least one basic amino acid, more advantageously aqueous ammonia and/or at least one alkanolamine.
Preferably, the alkaline agent is chosen from aqueous ammonia, alkanolamines, preferably monoethanolamine, and mixtures thereof.
Advantageously, the composition A has a content of alkaline agent(s) ranging from 0.01 % to 30% by weight, preferably from 0.1 % to 20% by weight and better still from 1 % to 10% by weight, relative to the weight of said composition. It should be noted that this content is expressed as NH3 when the alkaline agent is aqueous ammonia.
Dyeing agents As indicated previously, the composition A according to the invention may comprise at least one dyeing agent.
The dyeing agents may be chosen from oxidation dye precursors, direct dyes, and mixtures thereof.
According to one advantageous embodiment, the composition A comprises at least one dyeing agent chosen from oxidation dye precursors, direct dyes, and mixtures thereof, it preferably comprises at least one oxidation dye precursor. As oxidation dye precursors, use may be made of oxidation bases and couplers.
By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and addition salts thereof.
Among the para-phenylenediamines, examples that may be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(p-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis(p-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis(p-hydroxyethyl)amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-Y-hydroxypropyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2- isopropyl-para-phenylenediamine, N-(p-hydroxypropyl)-para-phenylenediamine, 2- hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para- phenylenediamine, N-ethyl-N-(p-hydroxyethyl)-para-phenylenediamine, Ν-(β,γ- dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para- phenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para- phenylenediamine, 2-p-acetylaminoethyloxy-para-phenylenediamine, Ν-(β- methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para- phenylenediamine, 2-p-hydroxyethylamino-5-aminotoluene, 3-hydroxy-1 -(4 - aminophenyl)pyrrolidine, and addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para- phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para- phenylenediamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2-p-acetylaminoethyloxy-para-phenylenediamine, and addition salts thereof with an acid, are particularly preferred.
Among the bis(phenyl)alkylenediamines, examples that may be mentioned include N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, Ν,Ν'- bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(p-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine, 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and addition salts thereof.
Among the para-aminophenols, examples that may be mentioned include para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, 4-methylaminophenol and addition salts thereof with an acid.
Among the ortho-aminophenols, examples that may be mentioned include 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and addition salts thereof.
Among the heterocyclic bases, examples that may be mentioned include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and addition salts thereof.
Other pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2- carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5- a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)ethanol, 2-(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1 ,5-a]pyridine, 3,4-diaminopyrazolo[1 ,5-a]pyridine, pyrazolo[1 ,5- a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1 ,5- a]pyridin-5-ol, 3-aminopyrazolo[1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[1 ,5-a]pyridin-6-ol and 3-aminopyrazolo[1 ,5-a]pyridin-7-ol, 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2- yl)oxy]ethanol, and addition salts thereof.
Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399, JP 88-169571 , JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives mention may be made of the compounds described in patents DE 3843892 and DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5- diamino-1 -methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3- dimethylpyrazole, 4,5-diamino-3-methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3- phenylpyrazole, 4-amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1 -benzyl-4,5-diamino-3- methylpyrazole, 4, 5-diamino-3-tert-butyl-1 -methylpyrazole, 4,5-diamino-1 -tert-butyl-3- methylpyrazole, 4,5-diamino-1 -(p-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1 - ethyl-3-methylpyrazole, 4,5-diamino-1 -ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5- diamino-1 -ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 - methylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -isopropylpyrazole, 4,5-diamino-3- methyl-1 -isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5-triaminopyrazole, 3,5-diamino-1 -methyl-4- methylaminopyrazole and 3,5-diamino-4-(p-hydroxyethyl)amino-1 -methylpyrazole, and addition salts thereof. Use may also be made of 4,5-diamino-1 -(p- methoxyethyl)pyrazole. Use will preferably be made of a 4,5-diaminopyrazole and even more preferentially of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or a salt or solvate thereof.
Pyrazole derivatives that may also be mentioned include diamino-N,N- dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and addition salts thereof: 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-bis(2- hydroxyethyl)-1 ,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-dimethylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3-diamino-5,6,7,8-tetrahydro-1 H,6H- pyridazino[1 ,2-a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5-(pyrrolidin-1 -yl)-1 ,2- dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1 -yl)-1 ,2-diethyl-1 ,2- dihydropyrazol-3-one or 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one.
Use will preferably be made of 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1 -one and/or a salt or solvate thereof.
Heterocyclic bases that will preferentially be used include 4,5-diamino-1 -(p- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol- 1 -one and/or 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol and/or a salt or solvate thereof.
According to one embodiment, the composition A comprises at least one heterocyclic oxidation base chosen from:
i) the heterocyclic oxidation bases of formula (I), addition salts thereof and solvates thereof:
Figure imgf000011_0001
in which R-i represents an amino group, a Ci to C4 alkyl group optionally substituted with one or more hydroxyl or amino groups, or a Ci to C4 alkoxy group optionally substituted with one or more hydroxyl or amino groups,
ii) the compounds of formula (II) or (III), addition salts thereof and solvates thereof:
Figure imgf000012_0001
in which R2 represents an amino group, a Ci to C4 alkyl group, optionally substituted with one or more hydroxyl or amino groups, a Ci to C4 alkoxy group, optionally substituted with one or more hydroxyl or amino groups; and Z-i represents a covalent bond, and -NR'6(CH2)q- radical or an -0(CH2)p- radical in which R'6 represents a hydrogen atom or a Ci-C6 alkyl radical optionally substituted with one or more hydroxyl groups, p denoting an integer ranging from 0 to 6, q denoting an integer ranging from 0 to 6, and R'i is a cationic radical; and
the radicals R'3, R'4 and R'5, independently, may be a hydrogen atom or an optionally substituted Ci-C4 alkyl radical. By way of example, mention may be made of methyl, ethyl, hydroxyethyl, aminoethyl, propyl and butyl radicals. According to one particular embodiment, R'3, R'4 and R'5 independently represent a hydrogen atom or a C1-C4 alkyl radical.
R'4 and R'5 can together form a partially saturated or unsaturated 5- or 8- membered ring, in particular a cyclopentene or cyclohexene, which is optionally substituted.
iii) the diaminopyrazole derivatives of formula (Γ), addition salts thereof and solvates thereof:
Figure imgf000013_0001
R1 represents a C1-C4 alkyl group which is substituted with one or more hydroxyl or amino groups,
R4 represents an amino group, a C1-C4 alkyl group which is optionally substituted with one or more hydroxyl or amino groups, or a C1-C4 alkoxy group which is optionally substituted with one or more hydroxyl or amino groups.
Preferably, in the compounds of formula (Γ), R1 represents a C1-C4 alkyl group which is substituted with at least one hydroxyl group, more particularly a hydroxyethyl group, and R4 represents an amino group.
Among the preferred compounds of formula (Γ), mention will be made of 2-(4,5-diamino-1 H-pyrazolol-1-yl)ethanol or an addition salt thereof. Preferably, in the compounds of formula (I), Ri represents an amino group.
Preferably, in the compounds of formula (II), R2 represents a Ci to C4 alkoxy group, optionally substituted with one or more hydroxyl groups, and preferentially represents a hydroxyethoxy group.
Among the compounds of formula (I), use will preferably be made of 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one, an addition salt thereof or a solvate thereof.
Among the compounds of formula (II), use will preferably be made of 2-[(3- amino-pyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol, an addition salt thereof or a solvate thereof.
For the vast majority, the 3-aminopyrazolo[1 ,5-a]pyridines of formulae (II) and (I I I) are compounds that are known and are described in particular in patent US 5 457 200. These compounds may be prepared according to synthetic methods that are well known in the literature and as described, for example, in patent US 5 457 200. By way of cationic group for formula (III), mention may be made, for R'-ι, of a cationic heterocycle or a heterocycle substituted with a cationic radical. By way of example, mention may be made of imidazoles substituted with a quaternary ammonium radical or imidazoliums, piperazines substituted with a quaternary ammonium radical or piperaziniums, pyrrolidines substituted with a quaternary ammonium radical or pyrrolidiniums, and diazepanes substituted with a quaternary ammonium radical or diazepaniums. R'i May also be chosen from the cationic radicals trialkylammonium, tri(hydroxyalkyl)ammonium, hydroxyalkyldialkylammonium or di(hydroxyalkyl)alkylammonium.
As cationic oxidation bases of formula (III), the following bases are most particularly preferred:
Figure imgf000014_0001
salt of 4-(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)-1 ,1-dimethylpiperazin-1 -ium
Figure imgf000014_0002
salt of 3-[2-(3-aminopyrazo!o[1 ,5-a]pyridin-2-ylamino)ethyl]-1-methyl-3H-imidazol-1-ium
By way of heterocyclic bases that are of use for the invention, use will preferentially be made of 4,5-diamino-1 -(p-hydroxyethyl)pyrazole and/or 2, 3-diamino- 6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one and/or 2-[(3-aminopyrazolo[1 ,5- a]pyridin-2-yl)oxy]ethanol and/or a salt or solvate thereof.
Among the couplers that may be used in the composition according to the invention, mention may be made in particular of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines, and addition salts of these compounds with an acid.
These couplers are more particularly chosen from 2,4-diamino-1 -(p- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(p-hydroxyethyl)amino-2- methylphenol, 3-aminophenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2-amino-4-(p-hydroxyethylamino)- 1 -methoxybenzene, 5-amino-6-chloro-2-methylphenol, 1 ,3-diaminobenzene, 1 ,3- bis(2,4-diaminophenoxy)propane, sesamol, 1 -amino-2-methoxy-4,5- methylenedioxybenzene, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy- N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1 -H-3- methylpyrazol-5-one, 1 -phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole and 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-hydroxybenzomorpholine, addition salts thereof with an acid, and mixtures thereof.
The addition salts of the oxidation bases and of the couplers are in particular chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
The oxidation base(s) are each generally present in an amount of from 0.0001 % to 10% by weight relative to the total weight of the composition of the invention, and preferably from 0.005% to 5% by weight relative to the total weight of the composition A.
The coupler(s) each generally represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition A of the invention.
According to one particular embodiment, the composition A comprises at least one oxidation dye precursor chosen from the compounds of formula (Γ) previously described, preferably 2-(4,5-diamino-1 H-pyrazol-1 -yl)ethanol or an addition salt thereof and at least one halogenated aminophenol coupler, preferably 5-amino 6- chloro 2-methyl phenol The dyeing agent may be chosen from direct dyes which may be synthetic or natural. The direct dyes may be in particular cationic or non-ionic. By way of examples of particularly suitable direct dyes, mention may be made of nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanines, for instance tetraazacarbocyanines (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes and natural direct dyes, alone or as mixtures. In particular, mention may be made of direct dyes from among: azo; methine; carbonyl; azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanine and natural direct dyes, alone or as mixtures.
According to one embodiment, the composition A comprises at least one dyeing agent chosen from direct dyes, preferably from cationic direct dyes.
Examples of suitable cationic direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanins, hemicyanins and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
Among the cationic direct dyes, mention may be made in particular of the hydrazono cationic dyes of formulae (Ilia) and (lll'a), the azo cationic dyes (IVa) and (IV'a) and the diazo cationic dyes (Va) below:
Het+-C(Ra)=N-N(Rb)-Ar, Het+-N(Ra)-N=C(Rb)-Ar, An" Het+-N=N-Ar, An"
An" (lll'a) (IVa)
(Ilia)
Ar+-N=N-Ar", An" and Het+-N=N-Ar'-N=N-Ar, An"
(IV'a) (Va)
in which formulae (Ilia), (lll'a), (IVa), (IV'a) and (Va):
Het+ represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferably with one or more (CrC8)alkyl groups such as methyl; Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferably ammonium, particularly tri(Ci- C8)alkylammonium such as trimethylammonium; • Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably with one or more electron-donating groups such as i) optionally substituted (CrC8)alkyl, ii) optionally substituted (CrC8)alkoxy, iii) (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci- C8)alkyl-N-aryl(Ci-C8)alkylamino or, as a variant, Ar represents a julolidine group;
• Ar' represents an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferably with one or more groups (Ci-C8)alkyl, hydroxyl or (d- C8)alkoxy;
• Ar" represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably with one or more (C C8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-C8)alkoxy or phenyl groups;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group, which is optionally substituted, preferably with a hydroxyl group;
or, as a variant, the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar and/or Ra with Rb form, together with the atoms that bear them, a (hetero)cycloalkyl;
particularly, Ra and Rb represent a hydrogen atom or a (CrC4)alkyl group, which is optionally substituted with a hydroxyl group;
• An" represents an anionic counterion, such as mesylate or halide.
Mention may be made in particular of azo and hydrazono cationic dyes bearing an endocyclic cationic charge of formulae (Ilia), (IM'a) and (IVa) as defined previously. More particularly those of formulae (Ilia), (IM'a) and (IVa) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.
Preferably, the direct dyes correspond to the following formulae:
Figure imgf000017_0002
Figure imgf000017_0001
- R1 representing a (Ci-C4)alkyl group such as methyl; - R2 and R3, which may be identical or different, representing a hydrogen atom or a (C C4)alkyl group, such as methyl; and
- R4 representing a hydrogen atom or an electron-donating group such as optionally substituted (CrC8)alkyl, optionally substituted (CrC8)alkoxy, or (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; in particular, R4 represents a hydrogen atom;
- Z represents a CH group or a nitrogen atom, preferably CH,
- An" represents an anionic counterion, such as mesylate or halide.
In particular, the dye of formulae (llla-1 ) and (IVa-1 ) is chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:
Figure imgf000018_0001
When they are present, the direct dye(s) more particularly represent from 0.0001 % to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of composition A.
Oxidizing agent
The composition B according to the invention comprises at least one chemical oxidizing agent.
The expression "chemical oxidizing agent" is intended to mean an oxidizing agent other than atmospheric oxygen.
In particular, the oxidizing agent(s) suitable for the present invention is (are) chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, such as for example persulfates or perborates, peracids and precursors thereof and alkali metal or alkaline-earth metal percarbonates. Advantageously, the chemical oxidizing agent is hydrogen peroxide.
The chemical oxidizing agent(s) generally represent(s) from 0.1 % to 50% and preferably from 1 % to 20% by weight relative to the total weight of the composition B.
Preferably, the composition A of the device according to the invention is devoid of chemical oxidizing agent as described above.
Associative thickening polymer
As indicated previously, at least one of the compositions A and B of the device of the invention comprises at least one associative thickening polymer, well known to those skilled in the art and in particular of non-ionic, anionic, cationic or amphoteric nature.
The term "thickening polymer" is intended, for the purposes of the present invention, to mean a polymer having, in solution or in dispersion containing 1 % by weight of active material in water or in ethanol at 25°C, a viscosity greater than 0.2 poise at a shear rate of 1 s' The viscosity is measured with a Haake RS600 viscometer from Thermo Electron. This viscometer is a controlled-stress viscometer with cone-plate geometry (for example having a diameter of 60 mm).
It is recalled that associative polymers are hydrophilic polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region. The term "hydrophobic group" is intended to mean a radical or polymer bearing a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 6 carbon atoms, preferably 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 14 to 30 carbon atoms. Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, cetyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, such as, for example, polybutadiene. These associative polymers involve in their structure at least one repeating unit other than an alkylene oxide unit or glycidol unit and, in this sense, are different from surfactants. Preferably, the composition according to the invention comprises at least one associative thickening polymer chosen from associative polyurethanes, which are more particularly cationic or non-ionic, associative cellulose derivatives, which are more particularly cationic or non-ionic, associative vinyllactams, associative unsaturated polyacids, associative aminoplast ethers, and associative polymers or copolymers comprising at least one ethylenically unsaturated monomer comprising a sulfonate group, alone or as mixtures.
Among the associative thickening polymers, mention may be made of associative polyurethane derivatives, such as those obtained by polymerization of:
- approximately 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid,
- approximately 20 to 80% by weight of a non-surfactant α,β-monoethylenically unsaturated monomer other than the preceding one,
- approximately 0.5% to 60% by weight of a non-ionic monourethane which is the reaction product of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.
Such compounds are in particular described in EP173109 and more particularly in Example 3. More specifically, this polymer is a terpolymer of methacrylic acid / methyl acrylate / dimethyl meta-isopropenyl benzyl isocyanate of behenyl alcohol which is ethoxylated (40 EO) in aqueous dispersion at 25%. This product is provided under the reference Viscophobe DB1000 by the company Amerchol.
Also suitable are the cationic associative polyurethanes of which the family has been described in application FR 0 009 609. It can be represented more particularly by general formula (A) below:
R-X-(P)n-[L-(Y)m]r-L'-(P')p-X'-R' (A)
in which:
R and R', which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X', which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L"; L, L' and L", which may be identical or different, represent a group derived from a diisocyanate;
P and P', which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
Y represents a hydrophilic group;
r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25;
n, m and p each range, independently of each other, between 0 and 1000; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
In one very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R' located at the chain ends.
According to a first preferred embodiment, the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group; X and X' each represent a group L"; n and p are between 1 and 1000 and L, L', L", P, P', Y and m have the meaning indicated as in formula (A).
According to another preferred embodiment of the invention, the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group, X and X' each represent a group L", n and p are 0 and L, L', L", P, P', Y and m have the meaning as in formula (A) indicated previously.
The fact that n and p are 0 is intended to mean that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
In accordance with another preferred embodiment of the invention, the associative polyurethane corresponds to formula (A) in which R and R' both independently represent a hydrophobic group, X and X' both independently represent a group comprising a quaternary amine, n and p are zero, and L, L', Y and m have the meaning indicated in formula (A). The number-average molecular weight of the cationic associative polyurethanes is usually between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000 g/mol.
When X and/or X' denote(s) a group comprising a tertiary or quaternary amine, X and ' may represent one of the following formulae: for X
Figure imgf000022_0001
in which:
R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
Ri and R3, which may be identical or different, denote a linear or branched Ci- C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
A" is a physiologically acceptable counterion.
The groups L, L' and L" represent a group of formula:
— Z-C -NH- R4-NH-C-Z—
I I I I
o o
in which:
Z represents -0-, -S- or -NH-; and
R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
The groups P and P' comprising an amine function may represent at least one of the following formulae: R«
N-R7 - or — R.-N- R-—
I +
R6 R, A
¾ ,R8
N
R5-CH-R7— or — R.-CH-
I
R6- NrR9
I
Rs
Rfi ,R»
N
I — R5-C.H-R7-
^io I
or R,
or — RS-CH-R7— †jo
Re - -N -Rg A
I
R ^8
in which:
R5 and R7 have the same meanings as R2 defined above;
R6, Rs and R9 have the same meanings as Ri and R3 defined above;
R-io represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P;
A" is a cosmetically acceptable counterion.
As regards the meaning of Y, the term "hydrophilic group" is intended to mean a polymeric or non-polymeric water-soluble group. By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
The associative polyurethanes of formula (A) are formed from diisocyanates and from various compounds bearing functions containing a labile hydrogen. The functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. The term "polyurethanes" in the present invention encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof. A first type of compound involved in the preparation of the polyurethane of formula (A) is a compound comprising at least one unit bearing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
As mentioned above, this compound may comprise more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.
Compounds of this type may be represented by one of the following formulae: HZ-(P)n-ZH, or HZ-(P')p-ZH
in which Z, P, Ρ', n and p are as defined above.
Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N- sulfoethyldiethanolamine.
The second compound involved in the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula 0=C=N-R4-N=C=0, in which R4 is defined above.
Mention may particularly be made of methylene diphenyl diisocyanate, methylene cyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).
This compound is formed from a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
By way of example, this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymer chain, it may be, for example, ohydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (A) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
The functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
By way of examples, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
The hydrophilic group termed Y in formula (A) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred. The associative polyurethane derivatives of the invention may also be non-ionic polyether polyurethanes. More particularly, said polymers comprise, in their chain, both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks which can be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.
Preferably, these polyether polyurethanes comprise at least two lipophilic
(hydrophobic) hydrocarbon chains containing more particularly from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be envisioned. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
The polyether polyurethanes can be multiblock, in particular in triblock form. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer having a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer). These same polymers can also be graft polymers or star polymers.
The non-ionic hydrophobic-chain polyether polyurethanes can be triblock copolymers, the hydrophilic block of which is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups.
The non-ionic polyether polyurethanes comprise a urethane linkage between the hydrophilic blocks, whence arises the name.
By extension, also included among the non-ionic polyether polyurethanes comprising a hydrophobic chain are those in which the hydrophilic blocks are linked to the hydrophobic blocks via other chemical bonds.
As examples of non-ionic polyether polyurethanes comprising a hydrophobic chain that may be used in the invention, it is also possible to use Rheolate 205® containing a urea group, sold by the company Rheox, or Rheolate® 208, 204 or 212, Rheolate FX1 100 and also Acrysol RM 184®.
Mention may also be made of the product Elfacos T210® containing a C12-C14 alkyl chain, and the product Elfacos T212® containing a Ci8 alkyl chain, from Akzo.
The product DW 1206B® from Rohm & Haas containing a C20 alkyl chain and a urethane linkage, sold at a solids content of 20% in water, may also be used.
Use may also be made of solutions or dispersions of these polymers, in particular in water or in aqueous/alcoholic medium. As examples of such polymers, mention may be made of Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Rheox. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.
The previously described polyether polyurethanes that can be used according to the invention may also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271 , 380.389 (1993).
Even more particularly, according to the invention, it is preferred to use a polyether polyurethane that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
Such polyether polyurethanes are sold in particular by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
The composition may likewise comprise polymers derived from associative celluloses such as:
- quaternized cationic celluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof,
- quaternized cationic hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 hydrophobic chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (Ci2 alkyl) and Quatrisoft LM- X 529-8® (Ci8 alkyl), Softcat SL100 sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (Ci2 alkyl) and Crodacel QS® (Ci8 alkyl) sold by the company Croda;
- non-ionic cellulose derivatives such as hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product Natrosol Plus Grade 330 CS® (Ci6 alkyls) sold by the company Ashland, the product Polysurf 67 CS® sold by the company Ashland or the product Bermocoll EHM 100® sold by the company Berol Nobel; - cellulose derivatives modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® sold by the company Amerchol.
As regards the associative polyvinyllactams, mention may for example be made of the polymers in particular described in FR 0 101 106. Said polymers are more particularly cationic polymers and comprise:
-a) at least one monomer of vinyllactam or alkylvinyllactam type;
-b) at least one monomer of structure (a) or (b) below:
Figure imgf000028_0001
in which:
X denotes an oxygen atom or a radical NR6,
R5 and R6 denote, independently of each other, a hydrogen atom or a linear or branched Ci-C5 alkyl radical,
R2 denotes a linear or branched Ci-C4 alkyl radical,
R3, R4 and R5 denote, independently of each other, a hydrogen atom, a linear or branched Ci-C30 alkyl radical or a radical of formula (IV):
— (Y2)— (CH2-CH(R7)-0)x R8 (c)
Y, Yi and Y2 denote, independently of each other, a linear or branched C2-Ci6 alkylene radical,
R7 denotes a hydrogen atom or a linear or branched Ci-C4 alkyl radical or a linear or branched CrC4 hydroxyalkyl radical,
R8 denotes a hydrogen atom or a linear or branched Ci-C30 alkyl radical, p, q and r denote, independently of each other, either the value zero or the value 1 ,
m and n denote, independently of each other, an integer ranging from 0 to 100, x denotes an integer ranging from 1 to 100,
Z denotes an organic or mineral acid anion, with the proviso that:
- at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-C30 alkyl radical,
- if m or n is other than zero, then q is equal to 1 ,
- if m or n is equal to zero, then p or q is equal to 0.
The poly(vinyllactam) polymers may be crosslinked or noncrosslinked and may also be block polymers.
Preferably, the counterion Z" of the monomers of formula (b) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
Preferably, R3, R4 and R5 denote, independently of each other, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
More preferentially, the monomer b) is a monomer of formula (b) for which, even more preferentially, m and n are equal to 0.
The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (d):
CH(R9)=C(R10)-N^^O (d)
(CH2)S
in which:
s denotes an integer ranging from 3 to 6,
R denotes a hydrogen atom or a C1-C5 alkyl radical,
R10 denotes a hydrogen atom or a C1-C5 alkyl radical,
with the proviso that at least one of the radicals R9 and R10 denotes a hydrogen atom.
Even more preferentially, the monomer (d) is vinylpyrrolidone.
The poly(vinyllactam) polymers may also contain one or more additional monomers, preferably cationic or non-ionic monomers.
As compounds that are more particularly preferred according to the invention, mention may be made of the following terpolymers comprising at least:
a) one monomer of formula (d),
b) one monomer of formula (a) in which p=1 , q=0, R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a C9-C24 alkyl radical, and
c) one monomer of formula (b) in which R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical. Even more preferentially, terpolymers comprising, by weight, 40% to 95% of monomer (d), 0.1 % to 55% of monomer (b) and 0.25% to 50% of monomer (b) are used.
Such polymers are in particular described in patent application WO 00/68282, the content of which forms an integral part of the invention.
As poly(vinyllactam) polymers, vinylpyrrolidone/ dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/ cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopropy lammonium tosylate or chloride terpolymers are in particular used. The vinylpyrrolidone / dimethylaminopropylmethacrylamide / lauryl dimethylmethacrylamidopropylammonium chloride terpolymer is provided in water at 20% by the company ISP under the name Styleze W20.
The associative polyvinyllactam derivatives of the invention may also be non- ionic copolymers of vinylpyrrolidine and of hydrophobic-chain hydrophobic monomers, of which mention may be made, by way of example, of:
- the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P.
- the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.
Among the associative unsaturated polyacid derivatives, mention may be made of those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of unsaturated carboxylic acid non-ethoxylated (Ci0-C3o)alkyl ester type.
These polymers are in particular chosen from those for which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (e) below:
CH ~ C— C— OH
i
Ri O (e)
in which R-i denotes H, CH3, or C2H5, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of (Cio-C30)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (f) below: CH ~ C— C— OR, (f)
I I I
R2 O
in which R2 denotes H or CH3 or C2H5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denoting a Ci0- C3o and preferably C12-C22 alkyl radical.
(Ci0-C3o)-Alkyl esters of unsaturated carboxylic acids comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949.
In anionic associative polymers of this type, use is more particularly made of polymers formed from a mixture of monomers comprising:
essentially acrylic acid,
an ester of formula (f) described above in which R2 denotes H or CH3, R3 denoting an alkyl radical containing from 12 to 22 carbon atoms,
and a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
Among anionic associative polymers of this type, preference is given to those constituted of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci0-C30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those constituted of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of Ci0-C30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.
Among said above polymers, those most particularly preferred are the products sold by the company Goodrich under the trade names Pemulen TR1 ®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1 ®, and the product sold by the company SEPPIC under the name Coatex SX®.
The anionic associative polymers may also be copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
Preferentially, these compounds also comprise as monomer an ester of an α,β- monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.
An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.
As regards the thickening polymers of aminoplast ether type, they are any product resulting from the condensation of an aldehyde with an amine or an amide, and also any structural unit formed from an aminoplast residue and a divalent hydrocarbon-based residue linked to the aminoplast residue by an ether bond.
The polymers with an aminoplast ether backbone are preferably chosen from those containing at least one unit of structure (g) below:
Figure imgf000032_0001
in which:
-AMP is an aminoplast residue with alkylene (or divalent alkyl) units,
- R denotes a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 acyl radical, -RO1 is a divalent alkyleneoxy residue,
-p denotes a positive integer,
-the OR group(s) being bonded to the alkylene units of the AMP residue.
Preferably, the polymers with an aminoplast ether backbone are chosen from those containing at least one unit of structure (h) below:
Figure imgf000032_0002
in which:
-AMP, R, RO1 and p have the same meaning as above,
- R02 is a group other than RO, bonded to AMP by means of a heteroatom and comprising at least two carbon atoms, and
-q is a positive integer. Even more preferentially, the polymers correspond to formulae (III) and (lll)bis below:
Figure imgf000033_0001
in which:
-AMP, R, ROi, R02, p and q have the same meaning as above,
-R2 or R3, which may be identical or different, represent an end group that may denote a hydrogen atom, an RO1H group, an R02H group, an AMP(OR)p group or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl, aryloxyalkyl or cycloalkoxyalkyl,
-a being a number greater than 1 and preferably greater than 2.
The aminoplast residues bearing their OR groups integrated into the polymers may be chosen, in a non-limiting manner, from structures (1 ) to (12) below:
Figure imgf000033_0002
Figure imgf000034_0001
in which:
- R has the same meaning as previously,
- Ri denotes C1-C4 alkyl,
- y is a number at least equal to 2,
- x denotes 0 or 1 .
Preferably, the aminoplast residue(s) bearing their OR groups is (are) chosen from those of structure (13) below:
Figure imgf000034_0002
In which R, p and x have the same meanings as previously.
The divalent alkyleneoxy residues are preferably those corresponding to the diols of general formula (14) below:
HO-(ZO)y-(Z1 (Z20)w)t-(ZO)y'-Z30H (14),
-y and y' being numbers ranging from 0 to 1000,
-t and w being numbers ranging from 0 to 10,
-Z, Z', Z2 and Z3 are C2-C4 alkylene radicals and preferably -CH2-CH(Z4)- and - CH2-CH(Z4)-CH2- radicals, -Z1 being a linear or cyclic, branched or unbranched, aromatic or non-aromatic radical optionally comprising one or more heteroatoms and having from 1 to 40 carbon atoms,
-Z4 denoting a hydrogen atom or a CrC4 alkyl radical or a CrC3 acyl radical, it being understood that at least one of the Z4 radicals of the Z, Z', Z2 and Z3 radicals is other than an acyl radical.
Preferably, Z4 denotes a hydrogen atom or a methyl radical.
Even more preferentially, t=0 and Z, Z' and Z3 denote -CH2CH2-, and at least one of y or y' is other than 0. The compounds of formula (14) are then polyethylene glycols.
The aminoplast ether polymers of formula (g) contain at least one saturated or unsaturated, linear or cyclic chain comprising at least 8 carbon atoms, and are in particular described in patent US 5 914 373 to which reference may be made for further details.
As polymers comprising an aminoplast ether backbone (g), mention may in particular be made of the products Pure-Thix® L [PEG-180/Octoxynol-40/TMMG Copolymer (INCI name)], Pure-Thix M® [PEG-180/Laureth-50/TMMG Copolymer (INCI name)], Pure-Thix® HH [Polyether-1 (INCI name)], and Pure Thix TX-1442® [PEG-18 / dodoxynol-5 / PEG-25 tristyrylphenol / tetramethoxy methyl glycoluril copolymer] proposed by the company Sud-Chemie.
The associative thickening polymers which are part of the ingredients in the composition according to the invention can also be chosen from associative polymers comprising at least one ethylenically unsaturated monomer comprising a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic portion.
Preferentially, said polymers are neutralized partially or totally with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as monoethanolamine, diethanolamine or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
These associative polymers may or may not be crosslinked, and are preferably crosslinked polymers. In this case, the crosslinking agents originate from at least one monomer having at least two ethylenic unsaturations (carbon-carbon double bond). The crosslinking monomers containing at least two ethylenic unsaturations are chosen, for example, from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, tetra- or diethylene glycol di(meth)acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis(meth)acrylamide or divinylbenzene, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate is more particularly used. The degree of crosslinking generally varies from 0.01 mol% to 10 mol% relative to the polymer.
The ethylenically unsaturated monomers comprising a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(Ci-C22)alkylsulfonic acids and N-(Ci-C22)alkyl(meth)acrylamido(Ci- C22)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
(Meth)acrylamido(C1 -C22)alkylsulfonic acids such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, can more particularly be used.
Use is preferably made of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof.
The amphiphilic polymers present in the composition according to the invention may also be chosen from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine such as those described in application WO 00/31 154.
The hydrophobic monomers which constitute the hydrophobic portion of the polymer are preferably chosen from the acrylates or acrylamides of formula (k) below: — CH2 c o=c
Y ^CH2-CH(R3)-0^-R2 in which R-i and R3, which may be identical or different, denote a hydrogen atom or a linear or branched Ci-C6 alkyl radical (preferably methyl); Y denotes O or NH; R2 denotes a hydrophobic hydrocarbon-based radical as defined previously; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.
The radical R2 is advantageously chosen from linear C6-Ci8 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl and n-dodecyl) and branched or cyclic C6-Ci8 alkyl radicals (for example cyclododecane (Ci2) or adamantane (Ci0)); C6-Ci8 perfluoroalkyl radicals (for example the group of formula -(CH2)2-(CF2)9-CF3); the cholesteryl radical (C27) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups, for instance naphthalene or pyrene. Preference is more particularly given, among these radicals, to linear alkyl radicals and more particularly to the n-dodecyl radical.
According to one particular form of the invention, the monomer of formula (k) comprises at least one alkylene oxide unit (x > 1 ) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferentially is constituted of ethylene oxide units and/or propylene oxide units and even more particularly is constituted of ethylene oxide units. The number of oxyalkylene units generally varies from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
The copolymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid and maleic acid, or mixtures of these compounds.
These copolymers are described in particular in documents EP 750 899 and US
5 089 578 and the following publications by Yotaro Morishima: «Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, N°40, (2000), 323-336.»; «Miscelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules 2000, Vol. 33, N° 10 - 3694-3704»; «Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: salt effects on rheological behaviour- Langmuir, 2000, Vol.16, N°12, 5324-5332»; «Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2- methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221 ».
The distribution of the monomers in the copolymer may be random or block.
Among these polymers of this type, mention may be made more especially of:
- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-Ci6)alkyl(meth)acrylamide units or of (C8-Ci6)alkyl (meth)acrylate units relative to the polymer, such as those described in application EP-A-750 899;
- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6- Ci8)alkylacrylamide units, such as those described in patent US-5 089 578;
- copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n- dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
Mention will be made more particularly of the copolymers constituted of AMPS units of formula XXX) below:
Figure imgf000038_0001
in which X+ has the same definition as previously,
and of units of formula (XXXI) below:
Figure imgf000038_0002
in which x denotes an integer varying from 3 to 100, preferably from 5 to 80, and more preferably from 7 to 25; Ri has the same meaning as that indicated above in formula (j) and R4 denotes a linear or branched C6-C22, in particular C8-C22 and more preferentially C10-C22 alkyl.
The polymers that are particularly preferred are those for which x = 25, Ri denotes methyl and R4 represents n-dodecyl; they are described in the Morishima articles mentioned above.
The polymers for which X+ denotes sodium or ammonium are more particularly preferred.
By way of such associative polymers comprising a sulfonic group, mention may thus be made of the product proposed under the name Aristoflex HMS by the company Clariant.
The associative thickening polymers of the invention are preferably non-ionic or cationic.
In one preferred variant, these associative thickening polymers are celluloses or cellulose derivatives, preferably chosen from non-ionic or cationic celluloses or cellulose derivatives.
Even more preferably, the associative thickening polymers are chosen from cellulose derivatives, which are preferably non-ionic, in particular hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyi or alkylaryl groups, or mixtures thereof, and in which the alkyl groups preferably C8-C22 alkyl groups.
According to one preferred embodiment of the invention, the content of associative thickening polymer(s) represents from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, better still from 0.1 % to 2% by weight relative to the weight of the composition comprising same.
Surfactants
The composition A and/or the composition B may also comprise one or more surfactants.
In particular, the surfactant(s) are chosen from anionic, amphoteric, zwitterionic, cationic and non-ionic surfactants, and preferentially non-ionic surfactants.
The term "anionic surfactant" is intended to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups: -C(0)-OH, -C(0)-0", -S03H, -S(0)20", -OS(0)2OH, -OS(0)20", -P(0)OH2, -P(0)20", -P(0)02 ", -P(OH)2, =P(0)OH, -P(OH)0", =P(0)0", =POH, =PO"; the anionic parts comprising a cationic counterion such as those of an alkali metal, an alkaline- earth metal or an ammonium.
As examples of anionic surfactants that may be used in the dye composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkyl sulfosuccinamates, acylisethionates and N-acyltaurates, polyglycoside polycarboxylic acid and alkyl monoester salts, acyl lactylates, salts of D-galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkylaryl ether carboxylic acids, salts of alkylamido ether carboxylic acids; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising 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 C6-C24 alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglycoside- tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates.
When the anionic surfactant(s) is (are) in salt form, it (they) may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline- earth metal salts such as the magnesium salts.
Examples of amino alcohol salts that may in particular be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2- methyl-1 -propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
Use is preferably made of alkali metal or alkaline-earth metal salts and in particular of sodium or magnesium salts.
Among the anionic surfactants mentioned, use is preferably made of (C6- C24)alkyl sulfates, (C6-C24)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline- earth metal salts, or a mixture of these compounds.
In particular, it is preferred to use (Ci2-C2o)alkyl sulfates, (Ci2-C2o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
The amphoteric or zwitterionic surfactant(s), which are preferably non-silicone, which may be used in the present invention may in particular be derivatives of optionally quaternized aliphatic secondary or tertiary amines, in which derivatives 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, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C8-C20)alkyl betaines, sulfobetaines, (C8-C2o)alkylamido(C3- C8)alkyl betaines and (C8-C2o)alkylamido(C6-C8)alkyl sulfobetaines.
Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, as defined above, mention may also be made of the compounds of respective structures (B1) and (B2) below:
Ra-C(0)-NH-CH2-CH2-N+(Rb)(Rc)-CH2C(0)0-, M+ , X" (B1)
in which formula:
■ Ra represents a Ci0-C3o alkyl or alkenyl group derived from an acid
RaCOOH, preferably present in hydrolysed copra oil, or 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 or 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, (C1 -C4)alkyl sulfates,
(C1 -C4)alkyl- or (C1 -C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M+ and X- are absent;
Ra -CiOJ-NH-CHz-CHz-NiBKB') (B2)
in which formula:
■ B represents the group -CH2-CH2-0-X'; ■ Β' represents the group -(CH2)ZY\ with z = 1 or 2;
■ X' represents the group -CH2-C(0)OH, -CH2-C(0)OZ\ -CH2-CH2-C(0)OH, -CH2-CH2-C(0)OZ\ or a hydrogen atom;
■ Y' represents the group -C(0)OH, -C(0)OZ', -CH2-CH(OH)-S03H or the group -CH2-CH(OH)-S03-Z';
■ Z' represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
■ Ra' represents a Ci0-C3o alkyl or alkenyl group of an acid Ra-C(0)OH, which is preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, in particular a Ci7 group and its iso form, or an unsaturated Ci7 group.
These compounds of formulae (B1 ) and (B2) are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.
By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate.
Use may also be made of the compounds of formula (B'2):
Ra"-NH-CH(Y")-(CH2)n-C(0)-NH-(CH2)n'-N(Rd)(Re) (B'2)
in which formula:
■ Y" represents the group -C(0)OH, -C(0)OZ", -CH2-CH(OH)-S03H or the group -CH2-CH(OH)-S03-Z";
■ Rd and Re, independently of one another, represent a Ci-C4 alkyl or hydroxyalkyl radical;
■ Z" represents a cationic counterion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
■ Ra- represents a Ci0-C30 alkyl or alkenyl group of an acid Ra"-C(0)OH, which is preferably present in coconut oil or in hydrolysed linseed oil;
■ n and n', independently of one another, denote an integer ranging from 1 to 3. Among the compounds of formula (B'2), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.
Use is preferably made, among the abovementioned amphoteric or zwitterionic surface-active agents, of (C8-C2o)alkyl betaines, such as cocoyl betaine, (C8- C2o)alkylamido (C3-C8)alkyl betaines, such as cocamidopropyl betaine, and of the compounds of formula (B'2), such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide), and mixtures thereof.
More preferentially, the amphoteric or zwitterionic surfactant(s) is (are) chosen from cocamidopropylbetaine, cocobetaine and the sodium salt of diethylaminopropyl laurylaminosuccinte, and mixtures thereof.
The cationic surfactant(s) that may be used in the dye composition according to the invention comprise, for example, optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.
Examples of quaternary ammonium salts that may in particular be mentioned include:
- those corresponding to general formula B3) below:
Figure imgf000043_0001
(B3)
in which formula:
R8 to Rii, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R8 to Rii comprises 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, (CrC4)alkyl sulfates, (C C4)alkyl or (Ci-C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate. The aliphatic groups of R8 to Rn may also comprise heteroatoms in particular such as oxygen, nitrogen, sulfur and halogens.
The aliphatic groups of R8 to Rn are chosen, for example, from C1-C30 alkyl, d- C3o alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (Ci2-C22)alkylamido(C2- C6)alkyl, (Ci2-C22)alkyl acetate, and C1-C30 hydroxyalkyl groups; X" is an anionic counterion chosen from halides, phosphates, acetates, lactates, (CrC4)alkyl sulfates, and (Ci-C4)alkylsulfonates or (Ci-C4)alkylarylsulfonates.
Among the quaternary ammonium salts of formula (B3), preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;
- quaternary ammonium salts of imidazoline, such as, for example, those of formula (B4) below:
Figure imgf000044_0001
(B4)
in which formula:
represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow;
■ R-13 represents a hydrogen atom, a C C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;
■ Ri4 represents a C C4 alkyl group;
■ Ri5 represents a hydrogen atom or a C C4 alkyl group; ■ X" represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (CrC4)alkyl sulfates, (CrC4)alkyl or (d- C4)alkylaryl sulfonates.
Preferably, R12 and Ri3 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, Ri4 denotes a methyl group and Ri5 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;
- di- or triquaternary ammonium salts, in particular of formula (B5) below:
R.
(CH2)3— N 2X~
R.
(B5)
in which formula:
■ R-16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;
■ R-I7 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH2)3-N+(R16a)(R17a)(R18a), X";
■ R16a, Ri7a, Risa, Ri8, Ri9, R20 and R21 , which may be 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, represents an organic-or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl(CrC4) sulfates, alkyl(CrC4)- or alkyl(Ci-C4)aryl-sulfonates, more particularly methyl sulfate and ethyl sulfate.
Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75); -quaternary ammonium salts containing one or more ester functions, such as those of formula (B6) below:
Figure imgf000045_0001
in which formula: ■ R22 is chosen from CrC6 alkyl groups and CrC6 hydroxyalkyl or CrC6 dihydroxyalkyl groups;
■ R23 is chosen from:
O
- the group R26 c ,
- saturated or unsaturated, linear or branched C1-C22 hydrocarbon-based groups R27,
- a hydrogen atom,
■ R25 is chosen from:
O
- the group R28 ^
- saturated or unsaturated, linear or branched Ci-C6 hydrocarbon-based groups R29,
- a hydrogen atom,
■ R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;
■ r, s and t, which may be identical or different, are integers ranging from 2 to 6,
■ r1 and t1 , which may be identical or different, are equal to 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 organic or inorganic anionic counterion,
with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R23 denotes R27, and that when z is 0 then R25 denotes R2g.
The alkyl groups R22 may be linear or branched, and more particularly linear.
Preferably, R22 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 R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
When R25 is a hydrocarbon-based group R2g, it preferably contains 1 to 3 carbon atoms.
Advantageously, R24, R26 and R2s, which may be identical or different, are chosen from linear or branched, saturated or unsaturated Cn-C2i hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated Cn- C21 alkyl and alkenyl groups.
Preferably, x and z, which may be identical or different, are 0 or 1 .
Advantageously, y is equal to 1.
Preferably, r, s and t, which may be identical or different, have the value 2 or 3 and more particularly still are equal to 2.
The anionic counterion X" is preferably a halide, such as chloride, bromide or iodide; a (CrC4)alkyl sulfate or a (CrC4)alkyl- or (Ci-C4)alkylarylsulfonate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion which is compatible with the ammonium having an ester function.
The anionic counterion X" is even more particularly chloride, methyl sulfate or ethyl sulfate.
Use is made more particularly in the dye composition according to the invention of the ammonium salts of formula (B6) 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:
O
• the group R26 c
• methyl, ethyl or C14-C22 hydrocarbon-based groups,
• a hydrogen atom,
- R25 is chosen from:
O · the group R28 ^
• a hydrogen atom,
- R24, R26 and R2e, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
Advantageously, the hydrocarbon-based radicals are linear. Among the compounds of formula (B6), examples that may be mentioned include salts, in particular the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably methyl or ethyl sulfate, methyl methanesulfonate, methyl para- toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.
Preferably, the ammonium salts comprising at least one ester function comprise two ester functions.
Among the cationic surfactants that may be present in the dye composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethyl- hydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof. Examples of non-ionic surfactants that may be used in the dye composition used according to the invention are described, for example, in the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178. They are chosen in particular from alcohols, a-diols or (d- C2o)alkylphenols, these compounds being etherified by groups that are ethoxylated and/or propoxylated, glycerolated, and having at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to range in particular from 1 to 100, more particularly from 2 to 50, even more particularly from 2 to 30, and it being possible for the number of glycerol groups to range in particular from 1 to 30.
Mention may also be made of copolymers of ethylene oxide and propylene oxide, optionally oxyethylenated sorbitan fatty acid esters, sucrose fatty acid esters, oxyalkylenated fatty acid esters, optionally oxyalkylenated alkyl polyglycosides, alkyl glucoside esters, derivatives of N-alkylglucamine and of N-acylmethylglucamine, and aldobionamides,
and amine oxides.
The non-ionic surfactants are more particularly chosen from oxyalkylenated, glycerolated non-ionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or their combination, preferably oxyethylene units.
Mention may be made, as examples of oxyalkylenated or glycerolated non-ionic surfactants, of:
• oxyalkylenated (C8-C24)alkylphenols;
• saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C8-C3o alcohols;
· saturated or unsaturated, linear or branched, oxyalkylenated C8-C3o amides;
• esters of saturated or unsaturated, linear or branched, C8-C3o acids and of polyethylene glycols;
• oxyethylenated esters of saturated or unsaturated, linear or branched, C8-C3o acids and of sorbitol;
· saturated or unsaturated oxyethylenated plant oils;
• condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures;
• oxyethylenated and/or oxypropylenated silicones.
The oxyalkylenated non-ionic surfactants preferably have a number of moles of ethylene oxide and/or of propylene oxide ranging from 1 to 100, preferably from 2 to 50 and preferably between 2 and 30. Advantageously, the non-ionic surfactants do not comprise any oxypropylene units.
In accordance with a preferred embodiment of the invention, the oxyalkylenated non-ionic surfactants are chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 35 mol of ethylene oxide; and oxyethylenated esters of saturated or unsaturated, linear or branched C8-C30 acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.
As an example of glycerolated non-ionic surfactants, glycerolated C8-C40 alcohols are preferably used.
As examples of compounds of this type, mention may be made of lauryl alcohol containing 4 mol of glycerol (I NCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol comprising 1.5 mol of glycerol, oleyl alcohol comprising 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol comprising 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleyl/cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
Among the glycerolated alcohols, it is more particularly preferred to use the C8/Cio alcohol containing 1 mol of glycerol, the C10/C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.
Preferably, the surfactant(s) is (are) chosen from non-ionic, anionic or amphoteric surfactants. More particularly, the surfactant(s) that may be present in the composition(s) of the device is (are) chosen from non-ionic and anionic surfactants, and mixtures thereof.
The amount of the surfactant(s), when it (they) is (are) present, varies preferably from 0.1 % to 35% by weight, even better still from 0.5% to 30% by weight, better still from 1 % to 25% by weight relative to the weight of the composition A and/or B.
According to one embodiment, the composition A and/or the composition B comprise(s) at least one surfactant, preferably chosen from non-ionic surfactants, preferablyoxyalkylenated non-ionic surfactants, more preferably chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, or particular from 2 to 35 mol of ethylene oxide.
According to one particular embodiment, the composition A and/or the composition B comprise(s) at least one oxyalkylenated non-ionic surfactant, preferably chosen from oxyethylenated C8-C30 alcohols, comprising from 1 to 10 mol of ethylene oxide, preferably from 2 to 5 mol of ethylene oxide and at least one oxyalkylenated non-ionic surfactants, preferably chosen from oxyethylenated C8-C30 alcohols comprising from 1 1 to 100 mol of ethylene oxide, preferably from 15 to 35 mol of ethylene oxide.
Preferably, the total content of surfactants in the mixture of the compositions A and B is at least 7% by weight, preferably at least 10% by weight, relative to the total weight of the mixture of the compositions A and B.
According to one embodiment, the composition A comprises at least one anionic surfactant, preferably chosen from those mentioned above, in particular (C6- C24)alkyl sulfates, and at least one non-ionic surfactant chosen from those mentioned above.
Preferably, the composition A comprised at least one surfactant, the total content of surfactants in the composition A being at least 10%, preferably at least 15%, but still at least 20% by weight, relative to the total weight of the composition.
Fatty substance:
The composition A and/or the composition B may comprise one or more fatty substances.
The term "fatty substance" is intended to mean an organic compound that is insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1 % and even more preferentially less than 0.1 %). They bear in their structure at least one hydrocarbon- based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
The fatty substances of the invention do not contain any salified carboxylic acid groups. In addition, the fatty substances of the invention are not (poly)oxyalkylenated or (poly)glycerolated ethers.
The term "oil" is intended to mean a fatty substance that is liquid at ambient temperature (25°C) and at atmospheric pressure (760 mmHg).
The term "non-silicone oil" is intended to mean an oil not containing any silicon atoms (Si) and the term "silicone oil" is intended to mean an oil containing at least one silicon atom.
More particularly, the fatty substances are chosen from C6-Ci6 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides, and plant waxes, non-silicone waxes and silicones, and mixtures thereof.
It is recalled that the fatty alcohols, esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group, comprising 6 to 30 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular, with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
As regards the C6-Ci6 hydrocarbons, they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.
The triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides comprising from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
The linear or branched hydrocarbons of mineral or synthetic origin containing more than 16 carbon atoms are preferably chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®. As regards the C6-Ci6 alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
As oils of animal, vegetable, mineral or synthetic origin that may be used in the composition of the invention, examples that may be mentioned include:
fluoro oils that may be chosen from perfluoromethylcyclopentane and perfluoro-1 ,3- dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1 ,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or alternatively bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.
The fatty alcohols that are suitable for use in the invention are more particularly chosen from linear or branched, saturated or unsaturated alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and a mixture thereof (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.
As regards the esters of a fatty acid and/or of fatty alcohols, which are advantageously different from the triglycerides mentioned previously, mention may be made in particular of esters of saturated or unsaturated, linear or branched Ci-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched Ci-C26 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.
Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononanoate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2- ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.
Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C2-C26 di-, tri-, tetra- or pentahydroxy alcohols may also be used.
Mention may in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di(n-propyl) adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.
Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.
The composition may also comprise, as fatty ester, sugar esters and diesters of C6-C3o and preferably C12-C22 fatty acids. It is recalled that the term "sugar" is intended to mean oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.
Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C3o and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
These esters may be chosen, for example, from oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, in particular, oleopalmitate, oleostearate and palmitostearate mixed esters.
More particularly, use is made of monoesters and diesters and in particular sucrose, glucose or methylglucose monooleate or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate or oleostearate.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:
- the products sold under the names F160, F140, F1 10, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitate/stearates formed from 73% monoester and 27% diester and triester, from 61 % monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61 % diester, triester and tetraester, and sucrose monolaurate;
- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-tri ester-polyester;
- the sucrose mono-dipalmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE.
More particularly, the fatty substances are chosen from compounds that are liquid or pasty at ambient temperature (25°C) and at atmospheric pressure.
In one variant of the invention, the fatty substance is a compound that is liquid at a temperature of 25°C and at atmospheric pressure.
In another variant of the invention, the fatty substance is a compound that is non-liquid at a temperature of 25°C and at atmospheric pressure, and is preferably solid. The fatty substances are advantageously chosen from C6-Ci6 alkanes, non- silicone oils of vegetable, mineral or synthetic origin, fatty alcohols, esters of a fatty acid and/or of a fatty alcohol, and silicone or non-silicone waxes, or mixtures thereof.
Preferably, the fatty substances chosen from liquid petroleum jelly, C6-Ci6 alkanes, and fatty alcohols, or mixtures thereof.
The composition A or B according to the invention may comprise from 0.1 % to 40% by weight of fatty substance relative to its total weight, preferably from 0.5% to 30%, better still from 1 % to 20%, even better still from 1 % to 10%.
According to one embodiment, the composition A comprises less than 10% by weight, preferably less than 7%, advantageously less than 5% by weight of fatty substance, better still less than 1 % by weight, relative to its total weight.
According to one embodiment, the composition B comprises at least one fatty substance preferably chosen from C6-Ci6 alkanes, non-silicone oils of vegetable, mineral or synthetic origin, fatty alcohols, esters of fatty acid and/or of fatty alcohol or mixtures thereof, preferably chosen from non-silicone oils of mineral or synthetic origin and fatty alcohols, and mixtures thereof.
According to one embodiment, the composition B comprises at least one mineral oil and at least one fatty alcohol.
Cationic polymer
According to one embodiment, the composition A and/or the composition B comprise(s) at least one cationic polymer distinct from the associative thickening polymer.
It is recalled that, for the purposes of the present invention, the term "cationic polymer" denotes any polymer containing cationic groups and/or groups that can be ionized into cationic groups.
Preferably, the cationic polymer present in the composition according to the invention is a linear, random, graft or block homopolymer or copolymer and comprises at least one cationic group and/or group that can be ionized into a cationic group chosen from primary, secondary, tertiary and/or quaternary amine groups that form part of the main polymer chain or that are borne by a side substituent directly connected thereto. Preferably, the cationic charge density of the cationic polymers according to the invention is greater than 1 meq/g, even more particularly greater than or equal to 4 meq/g.
This charge density is determined by the Kjeldahl method. It may also be calculated from the chemical nature of the polymer.
The cationic polymers used generally have a number-average molecular weight of between 500 and 5 χ 106 approximately, and preferably between 103 and 3 χ 106 .
Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type.
These are known products and are in particular described in patents FR 2505348 or FR 2542997.
Among the cationic polymers that can be used in the context of the invention, mention may be made of the following polymers, alone or as a blend:
(1 ) Homopolymers or copolymers derived from acrylic or methacrylic esters or
V) below:
Figure imgf000057_0001
in which:
R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
A, which may be identical or different, represent a linear or branched Ci-C6 and preferably C2-C3 alkyl group or a Ci-C4 hydroxyalkyl group;
R4, R5 and R6, which may be identical or different, represent a Ci-Ci8 alkyl group or a benzyl radical, and preferably a Ci-C6 alkyl group;
Ri and R2, which may be identical or different, represent hydrogen or a Ci-C6 alkyl group, and preferably methyl or ethyl;
X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
The polymers of family (1 ) may also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Thus, among these polymers of family (1 ), mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name
Hercofloc by the company Hercules,
- the copolymers of acrylamide and of methacryloyloxyethyl-trimethylammonium chloride described, for example, in EP 80 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy,
- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937. These polymers are described in
FR 2 077 143 and FR 2 393 573,
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold in particular under the name Styleze CC 10 by ISP,
- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP, and
- the crosslinked polymers of methacryloyloxy(Ci-C4)alkyl tri(Ci-C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide. Use may more particularly be made of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names of Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
(2) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and disclosed in particular in US 4 131 576, such as hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
The commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
(3) Cationic guar gums described more particularly in US 3 589 578 and US 4 031 307, such as guar gums containing trialkylammonium cationic groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, chloride).
Such products are sold in particular under the trade names Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar C162 by the company Meyhall.
(4) Polymers constituted of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers. Such polymers are described, in particular, in FR 2 162 025 and FR 2 280 361 .
(5) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis- unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis- unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may be alkylated or, if they contain one or more tertiary amine functions, they may be quaternized. Such polymers are described, in particular, in FR 2 252 840 and FR 2 368 508. Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids, followed by an alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylene-triamine polymers in which the alkyl radical is C1-C4 and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in FR 1 583 363.
Among these derivatives, mention may be made more particularly of the adipic acid/dimethylamino-hydroxy-propyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.
(6) Polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated C3-C8 aliphatic dicarboxylic acids. The mole ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8:1 and 1 .4:1 ; the resulting polyaminoamide is reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5:1 and 1 .8:1. Such polymers are described in particular in US 3 227 615 and US 2 961 347.
Polymers of this type are sold in particular under the name Hercosett 57, PD 170 or Delsette 101 by the company Hercules.
(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (V) or (VI):
Figure imgf000060_0001
in which formulae k and t are equal to 0 or 1 , the sum k + 1 being equal to 1 ; R9 denotes a hydrogen atom or a methyl radical; R7 and R8, independently of each other, denote a Ci-C8 alkyl group, a hydroxyalkyl group in which the alkyl group is C1-C5, an amidoalkyl group in which the alkyl is Ci-C4; R7 and R8 can also denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R7 and R8, independently of each other, preferably denote a C1-C4 alkyl group; Y" is an organic or mineral anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described in particular in FR 2 080 759 and FR 2 190 406.
The cyclopolymers preferably comprise at least one unit of formula (V).
As regards the copolymers, they also comprise an acrylamide monomer.
Among the polymers defined above, mention may be made more particularly of the dimethyldiallyl-ammonium chloride homopolymer sold under the name "Merquat 100" by the company Nalco (and its homologues of low weight-average molecular weight) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name Merquat 550.
(8) The quaternary diammonium polymer containing repeating units corresponding to the formula:
R10 R12
— N+ -A. - N+- B, (VII)
I _ I
R11 X R13 X
in which formula:
R10, Rii , Ri2 and Ri3, which may be identical or different, represent Ci-C2o aliphatic, alicyclic or arylaliphatic radicals or hydroxyalkylaliphatic radicals in which the alkyl radical is Ci-C4, or alternatively Rio, Rn , R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively R10, Rn , R12 and R-I3 represent a linear or branched Ci-C6 alkyl radical substituted with a nitrile, ester, acyl or amide group or a group -CO-0-Ri4-D or -CO-NH-R14-D where Ri4 is an alkylene and D is a quaternary ammonium group;
A-i and B-i represent C2-C2o polymethylene groups which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
X" denotes an anion derived from a mineral or organic acid;
A-i , R-io and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;
in addition, if A-i denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical,
Figure imgf000061_0001
may also denote a group -(CH2)n-CO-D-OC-(CH2)n in which n is between 1 and 100 and preferably between 1 and 50, and D denotes: a) a glycol residue of formula: -0-Z-0-, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CH2-CH2-0)x-CH2-CH2- and -[CH2-CH(CH3)-0]y-CH2-CH(CH3)- where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the radical -CH2-CH2-S- S-CH2-CH2-;
d) a ureylene group of formula: -NH-CO-NH-.
Preferably, X" is an anion, such as chloride or bromide.
These polymers have a number-average molecular weight generally between 1000 and 100 000.
Polymers of this type are described in particular in FR 2 320 330, FR 2 270 846, FR 2 316 271 , FR 2 336 434, FR 2 413 907, US 2 273 780, US 2 375 853, US
2 388 614, US 2 454 547, US 3 206 462, US 2 261 002, US 2 271 378, US
3 874 870, US 4 001 432, US 3 929 990, US 3 966 904, US 4 005 193, US
4 025 617, US 4 025 627, US 4 025 653, US 4 026 945 and US 4 027 020.
It is more particularly possible to use polymers that are constituted of repeating units corresponding to the following formula (VIII):
- (CH2)p — (VIII)
Figure imgf000062_0001
^
in which R10, Rn, Ri2 and Ri3, which may be identical or different, denote a Ci-C4 alkyl or hydroxyalkyi radical, n and p are integers ranging from 2 to 20 approximately, and X" is an anion derived from a mineral or organic acid.
(9) The polyquaternary ammonium polymers constituted of repeating units of formula (IX):
ChL CH3
N— (CH2) -NH-CO-D-NH- (CH2)p - N - (CH2)2 - O— (CH2)2 (IX)
ChL CH in which p denotes an integer ranging from 1 to 6 approximately, D may be zero or may represent a group -(CH2)r-CO- in which r denotes a number equal to 4 or 7, and X" is an anion.
Such polymers may be prepared according to the processes described in US 4 157 388, US 4 702 906 and US 4 719 282. They are in particular described in patent application EP 122 324.
Among these polymers, examples that may be mentioned include the products Mirapol A 15, Mirapol AD1 , Mirapol AZ1 and Mirapol 175 sold by the company Miranol.
(10) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF.
(1 1 ) Polyamines such as Polyquart H sold by Cognis, referred to under the name polyethylene glycol (15) tallow polyamine in the CTFA dictionary.
Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, polyquaternary ureylenes and chitin derivatives.
Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use, alone or as mixtures, polymers of families (1 ), (7), (8) and (9). In accordance with one more particular embodiment of the invention, it is preferred to use polymers of families (7), (8) and (9).
According to one even more advantageous embodiment of the invention, use is made of polymers of families (7) and (8) alone or as mixtures, and even more preferentially of polymers having repeating units of formulae (W) and (U) below:
CH3 CH3
— ^ (CH2)3 -N+— (CH2)6 ^ (W)
I ci- I ci-
CH3 CH3
and in particular those of which the molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; CH3 C2H5
— ^ I N±- (CH2)3 -N+— (CH2)3 ^ (U)
Br I Br
CH3 C2H5
and in particular those in which the molecular weight, determined by gel permeation chromatography, is about 1200.
Generally, the content of cationic polymer(s), when it (they) is (are) present, represents from 0.01 % to 10% by weight, more particularly from 0.05% to 6% by weight, and even more preferentially between 0.1 % and 5% by weight relative to the weight of the composition comprising same.
According to one embodiment, the composition A and/or the composition B, preferably the composition A, comprises at least one cationic polymer, preferably chosen from the polymers of families (7) and (8) as described above, alone or as mixtures, and even more preferentially the polymers having repeating units of formulae (W) and (U) as described above.
According to one embodiment, the composition A comprises at least one cationic polymer of family (7) and at least one cationic polymer of family (8).
ADDITIVES
The composition A and/or the composition B may also contain various adjuvants conventionally used in hair lightening compositions, such as anionic, amphoteric or non-ionic polymers, distinct from the associative thickening polymers mentioned above, or mixtures thereof; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers.
The above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of each composition.
The composition A and/or B according to the invention may comprise water and/or one or more organic solvents.
Examples of organic solvents that may be mentioned include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1 ,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol or phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl or monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, in particular Ci-C4 alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
The organic solvents, when they are present, generally represent between 1 % and 40% by weight relative to the total weight of the dye composition, and preferably between 5% and 30% by weight relative to the total weight of the dye composition.
Preferably, the composition A and the composition B are aqueous.
In this case, they each preferentially comprise from 30% to 95% of water by weight, better still from 40% to 90% of water by weight, even better still from 50% to 85% of water by weight relative to the total weight of the composition. The pH of the composition A, if it is aqueous, is generally between 3 and 12, preferably between 5 and 1 1 . It is preferentially between 7 and 1 1 , limits included.
It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, and in particular the alkaline agents of the invention mentioned above.
The oxidizing composition B also preferably comprises one or more acidifying agents. Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Usually, the pH of the oxidizing composition, when it is aqueous, is less than 7.
The compositions A and B may each have a viscosity, measured at 25°C and atmospheric pressure, ranging from 1000 to 60 000 mPa.s, preferably from 5000 to 40 000 mPa.s.
More particularly, the composition A may have a viscosity ranging from 10 000 to 40 000 mPa.s.
More particularly, the composition B may have a viscosity ranging from 5000 to 15 000 mPa.s.
The viscosity of the compositions may be measured at 25°C using a Brookfield LVT viscometer equipped with an M4 spindle rotating at a speed of 12 rpm. The measurement is taken after 1 minute.
The compositions A and B may be in the form of a gel or cream. According to one particular embodiment, the compositions A and B of the device according to the invention are such that:
the composition A comprises:
at least one alkaline agent, preferably chosen from aqueous ammonia, alkanolamines, preferably monoethanolamine, and mixtures thereof,
at least one dyeing agent, preferably chosen from oxidation dye precursors, at least one associative thickening polymer, as described above, preferably chosen from associative cellulose derivatives, which are preferably non-ionic, in particular hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22 alkyl groups, at least one anionic surfactant, preferably chosen from (Ci2-C2o)alkyl sulfates as described above,
at least one cationic polymer as described above, preferably chosen from polymers of families (7) and (8) alone or as mixtures, and even more preferentially of polymers having repeating units of formulae (W) and (U),
and
the composition B comprises:
at least one oxidizing agent, preferably hydrogen peroxide,
at least one fatty substance as described above, preferably chosen from non-silicone oils of mineral or synthetic origin, fatty alcohols and mixtures thereof,
the composition A and/or the composition B comprise(s) at least one non-ionic surfactant as described above, preferably chosen from oxyethylenated C8-C3o alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 35 mol of ethylene oxide.
Preferably, the total content of surfactants in the mixture of the compositions A and B is at least 7% by weight, preferably at least 10% by weight, relative to the total weight of the mixture of the compositions A and B.
Device The dispensing device according to the invention is constituted of a container comprising:
i) at least two compartments a and b separate from one another,
the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent,
the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent,
one and/or the other of the compositions A and B of the two compartments comprising at least one associative thickening polymer;
ii) a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B. Preferably, the container of the device is pressurized (aerosol device). In other words, it comprises one or more propellant gases.
By way of propellant gas suitable for implementing the invention, mention may be made of the gases normally used in the cosmetics field, in particular optionally halogenated volatile hydrocarbons, for example n-butane, propane, isobutane, pentane, and halogenated derivatives thereof; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen and oxygen, alone or as mixtures.
The walls of the container containing the compartments a and b are preferably rigid, the container possibly being in this case a can, for example made of metal or plastic.
According to one preferred embodiment, the compartments a and b are flexible pouches. They may be made of metal, such as aluminium, or plastic.
According to this configuration, the propellant gas is in the volume defined between the walls of the container and the flexible pouches.
The device comprises a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B, in separate form (side by side for example) or in mixture form, preferably in separate form, by means of at least one dispensing orifice.
Preferably, the means for delivering the compositions comprise at least one dispensing valve. According to one embodiment, each compartment is surmounted by a valve.
According to one embodiment, the compartments are surmounted by a single valve connecting them.
The valve(s) is (are) in selective fluidic communication with the inside of the compartment(s) via a valve inlet orifice, the communication being established in response to the activating of an activating means, such as a push-button.
The dispensing means of the device may comprise a diffuser which caps the valve(s).
According to one variant, the device comprises a single diffuser which caps the two valves. The push-button may be part of the diffuser.
The diffuser may be equipped with one or more dispensing pipes provided to convey the composition(s) up to one or more dispensing orifices.
When the device comprises a single diffuser, it may be equipped with two composition conveying pipes, each pipe communicating with the outlet orifice of a valve.
According to a first embodiment, the two pipes each open into a dispensing orifice (not communicating with one another before the dispensing orifice). According to this configuration, the mixing of the compositions is carried out only after dispensing of the latter (thus after the dispensing orifices).
According to a second embodiment, the two pipes open into a mixing chamber equipped with a static mixer, from which a single pipe is directed to a single dispensing orifice. According to this configuration, the mixing of the compositions is carried out just before discharge thereof from the device. Thus, the compositions A and B can be delivered in mixture form prior to the application to the keratin fibres, or can be delivered simultaneously in separate form, the mixing taking place after application to the keratin fibres (when the compositions leave simultaneously side by side). Preferably, according to this embodiment, the compartments a and b are flexible pouches, a dispensing valve surmounting each of the compartments, a single diffuser capping the two valves.
It should be noted that the dispensing valve(s), like the content of propellant gas(es), are adjusted so as to enable the dispensing of the compositions in appropriate respective proportions. In practice, the dispensed composition A/composition B weight ratio ranges from 0.25 to 4 and preferably from 0.5 to 2.
Even more preferentially, this ratio is 1.
A subject of the invention is also a kit comprising:
- the device for dispensing a dyeing and/or lightening product as described above,
- a composition C comprising at least one conditioning agent chosen from silicones, cationic polymers and amphoteric polymers, and mixtures thereof.
The cationic polymers may be chosen from the cationic polymers described above, in particular the polymers of families (7) and (8) as described above, alone or as mixtures, and even more preferentially the polymers having repeating units of formulae (W) and (U) as described above.
The silicones that may be used in the compositions of the present invention are in particular polyorganosiloxanes, which may be oils, waxes, resins or gums.
The silicones that may be used in the compositions of the present invention may be in the form of aqueous solutions, i.e. dissolved, or optionally in the form of dispersions or microdispersions, or of aqueous emulsions.
Silicones are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.
The silicones may be volatile or non-volatile.
When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and more particularly still from:
(i) cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone 7207 by the company Union Carbide or Silbione 70045 V 2 by the company Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone 7158 by the company Union Carbide, and Silbione 70045 V 5 by the company Rhodia, and mixtures thereof.
Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone FZ 3109 sold by the company Union Carbide, of chemical structure:
D' D" - D'■
CH, CH, with D" : — Si - O— with D' : - Si - O
CH3 CBH17
Mention may also be made of mixtures of cyclic silicones with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetrakis(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 ,1 '-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane;
(ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10"6 m2/s at 25°C. This is for example the decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers Volatile Silicone Fluids for Cosmetics.
When the silicones are non-volatile, use is preferably made of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and polyorganosiloxanes modified with organofunctional groups, and mixtures thereof.
These silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups (Dimethicone according to the CTFA name) for example having a viscosity of from 5x10"6 to 2.5 m2/s at 25°C and preferably 1 x10"5 to 1 m2/s. The viscosity of the silicones is measured, for example, at 25°C according to standard ASTM 445 Appendix C. Among these polyalkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:
- the Silbione oils of the 70 047 series or the Mirasil oils sold by the company Rhodia, for instance the oil 70 047 V 500 000,
- the oils of the 200 series from the company Dow Corning, such as, more particularly, DC200 with a viscosity of 60 000 cSt,
- the Viscasil oils from the company General Electric and certain oils of the SF series (SF 96, SF 18) from the company General Electric.
Mention may also be made of polydialkylsiloxanes and in particular polydimethylsiloxanes containing dimethylsilanol end groups (Dimethiconol according to the CTFA name) such as the oils of the 48 series from the company Rhodia.
Mention may also be made of polydimethylsiloxanes containing aminoethyl, aminopropyl and α,ω-silanol groups.
In this category of polyalkylsiloxanes, mention may also be made of the products sold under the names Abil Wax 9800 and 9801 by the company Goldschmidt, which are poly(CrC2o)alkylsiloxanes.
The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethylmethylphenylsiloxanes and polydimethyldiphenylsiloxanes with a viscosity of from 1 x10"5 to 5x102 m2/s at 25°C.
Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:
- Silbione oils of the 70 641 series from the company Rhodia,
- the oils of the Rhodorsil 70 633 and 763 series from the company Rhodia,
- the oil Dow Corning 556 Cosmetic Grade Fluid from the company Dow Corning,
- the silicones of the PK series from the company Bayer, such as the product PK20,
- the silicones of the PN and PH series from the company Bayer, such as the products PN1000 and PH1000,
- certain oils of the SF series from the company General Electric, such as SF
1023, SF 1 154, SF 1250 and SF 1265.
The silicone gums that may be present in the composition according to the invention are in particular polydiorganosiloxanes having high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.
Mention may be made more particularly of the following products:
- polydimethylsiloxane gums,
- polydimethylsiloxane/methylvinylsiloxane gums,
- polydimethylsiloxane/diphenylsiloxane gums,
- polydimethylsiloxane/phenylmethylsiloxane gums,
- polydimethylsiloxane/diphenylsiloxane/methylvinylsiloxane gums.
Products that may be used more particularly are the following mixtures:
- mixtures formed from a polydimethylsiloxane hydroxylated at the end of the chain (known as dimethiconol according to the nomenclature of the CTFA dictionary) and from a cyclic polydimethylsiloxane (known as cyclomethicone according to the nomenclature of the CTFA dictionary), such as the product Q2 1401 sold by the company Dow Corning,
- mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric, this product being an SF 30 gum corresponding to a dimethicone, having a number- average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane,
- mixtures of two PDMSs with different viscosities, and more particularly of a
PDMS gum and of a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m2/s and of an oil SF 96 with a viscosity of 5x10"6 m2/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.
The organopolysiloxane resins that may be present in the composition according to the invention are crosslinked siloxane systems containing the following units: R2S1O2/2, 3S1O1/2, RS1O3/2 and S1O4/2 in which R represents a hydrocarbon group containing 1 to 16 carbon atoms or a phenyl group. Among these products, the ones that are particularly preferred are those in which R denotes a C1-C4 alkyl group, more particularly methyl, or a phenyl group.
Among these resins, mention may be made of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by the company General Electric, which are silicones of dimethyl/trimethylsiloxane structure. Mention may also be made of the trimethyl siloxysilicate-type resins sold in particular under the names X22-4914, X21 -5034 and X21 -5037 by the company Shin- Etsu.
The organomodified silicones that may be present in the composition according to the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:
- polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-C24 alkyl groups, such as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils Silwet L 722, L 7500, L 77 and L 71 1 by the company Union Carbide, and the (Ci2)alkylmethicone copolyol sold by the company Dow Corning under the name Q2 5200,
- thiol groups, such as the products sold under the names GP 72 A and GP 71 from the company Genesee,
- alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax 2428, 2434 and 2440 by the company Goldschmidt,
- hydroxylated groups, such as the polyorganosiloxanes containing a hydroxyalkyl function, described in French patent application FR 2 589 476,
- acyloxyalkyl groups, for instance the polyorganosiloxanes described in patent US-A-4 957 732,
- anionic groups of the carboxylic acid type, for instance in the products described in patent EP 186 507 from the company Chisso Corporation, or of the alkylcarboxylic type, such as those present in the product X-22-3701 E from the company Shin-Etsu; 2-hydroxyalkyl sulfonate; 2-hydroxyalkyl thiosulfate such as the products sold by the company Goldschmidt under the names Abil S201 and Abil S255,
- hydroxyacylamino groups, for instance the polyorganosiloxanes described in patent application EP 342 834. Mention may be made, for example, of the product
Q2-8413 from the company Dow Corning.
Among the organomodified silicones, mention may also be made of amino silicones.
The term "amino silicone" is intended to mean any silicone comprising at least one primary, secondary or tertiary amine function or a quaternary ammonium group. The amino silicones that may be used in the cosmetic composition according to the present invention are chosen from:
(a) the compounds corresponding to the following formula (V):
(R1)a(T)3-aSi[OSi(T)2]n[OSi(T)b(R1)2-b]mOSi(T)3-a(R1 )a (V)
in which:
T is a hydrogen atom or a phenyl or hydroxyl (-OH), or CrC8 alkyl, and preferably methyl, or
Ci-C8 alkoxy, preferably methoxy group,
a denotes the number 0 or an integer from 1 to 3, and preferably 0,
b denotes 0 or 1 , and in particular 1 ,
m and n are numbers such that the sum (n + m) can range in particular from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and in particular from 49 to 149, and for m to denote a number from 1 to 2000 and in particular from 1 to 10,
R1 is a monovalent group of formula -CqH2qL in which q is a number from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups:
-N(R2)-CH2-CH2-N(R2)2,
-N(R2)2,
-N+(R2)3 Q-,
-N+(R2) (H)2 Q-,
-N+(R2)2HQ-,
-N(R2)-CH2-CH2-N+(R2)(H)2 Q",
in which R2 may denote a hydrogen atom, a phenyl, benzyl or saturated monovalent hydrocarbon-based group, for example a Ci-C20 alkyl group, and Q" represents a halide ion, for example fluoride, chloride, bromide or iodide.
In particular, the amino silicones corresponding to the definition of formula (V) are chosen from the compounds corresponding to formula (VI) below:
Figure imgf000075_0001
in which R, R' and R", which may be identical or different, denote a C1-C4 alkyl group, preferably CH3; a C1-C4 alkoxy group, preferably methoxy; or OH; A represents a linear or branched, C3-C8 and preferably C3-C6 alkylene group; m and n are integers dependent on the molecular weight and the sum of which is between 1 and 2000.
According to a first possibility, R, R' and R", which may be identical or different, each represent a C1-C4 alkyl group or hydroxyl, A represents a C3 alkylene group and m and n are such that the weight-average molecular weight of the compound is between approximately 5000 and 500 000. The compounds of this type are named "amodimethicone" in the CTFA dictionary.
According to a second possibility, R, R' and R", which may be identical or different, each represent a C1-C4 alkoxy group or hydroxyl, at least one of the groups R and R" is an alkoxy group and A represents a C3 alkylene group. The hydroxyl/alkoxy mole ratio is preferably between 0.2/1 and 0.4/1 and advantageously equal to 0.3/1. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 106. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.
In this category of compounds, mention may be made, inter alia, of the product Belsil® ADM 652 sold by the company Wacker.
According to a third possibility, R and R", which are different, each represent a
C1-C4 alkoxy group or hydroxyl, at least one of the groups R and R" being an alkoxy group, R' representing a methyl group and A representing a C3 alkylene group. The hydroxyl/alkoxy mole ratio is preferably between 1/0.8 and 1/1 .1 and advantageously is equal to 1/0.95. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 200 000. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.
More particularly, mention may be made of the product Fluid WR® 1300 sold by the company Wacker.
Note that the molecular weight of these silicones is determined by gel permeation chromatography (ambient temperature, polystyrene standard, μ styragem columns, eluent THF, flow rate of 1 mm/minute, 200 μΙ of a solution containing 0.5% by weight of silicone in THF are injected, and detection is performed by refractometry and UV-metry).
A product corresponding to the definition of formula (V) is in particular the polymer known in the CTFA dictionary as Trimethylsilyl Amodimethicone, corresponding to formula (VII) below:
(CH3)3 i(CH3 3)/3.
Figure imgf000076_0001
NH.
(VII) in which n and m have the meanings given above in accordance with formula
(VI).
Such compounds are described, for example, in patent EP 95238. A compound of formula (VII) is sold, for example, under the name Q2-8220 by the company OSI.
(b) the compounds corresponding to formula (VIII) below:
Figure imgf000076_0002
(VIII) in which:
R3 represents a monovalent C Ci8 hydrocarbon-based group, and in particular a C1-C18 alkyl or C2-Ci8 alkenyl group, for example methyl,
R4 represents a divalent hydrocarbon-based group, in particular a Ci-Ci8 alkylene group or a divalent Ci-Ci8, for example Ci-C8, alkyleneoxy group,
Q" is a halide ion, in particular chloride,
r represents a mean statistical value from 2 to 20 and in particular from 2 to 8, s represents a mean statistical value from 20 to 200 and in particular from 20 to
50.
Such compounds are described more particularly in patent US 4 185 087.
A compound falling within this class is the product sold by the company Union Carbide under the name Ucar Silicone ALE 56.
(c) quaternary ammonium silicones in particular of formula (IX) below:
Rb OH 2 X R— N— ChL— CH— ChL— R- -Si— O- -Si— R— ChL 2— CHOH— ChL 2—. N - R6 in which:
R6, which may be identical or different, represent a monovalent hydrocarbon- based group having from 1 to 18 carbon atoms, and in particular a C Ci8 alkyl group, a C2-Cis alkenyl group or a ring comprising 5 or 6 carbon atoms, for example methyl,
R5 represents a divalent hydrocarbon-based group, in particular a Ci-Ci8 alkylene group or a divalent Ci-Ci8, for example Ci-C8 alkyleneoxy group linked to the Si by an Si-C bond,
R7, which may be identical or different, each represent a hydrogen atom, a monovalent hydrocarbon-based group containing from 1 to 18 carbon atoms, and in particular a Ci-Ci8 alkyl group, a C2-Ci8 alkenyl group or an -R5-N HCOR6 group;
X" is an anion, such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.),
r represents a mean statistical value from 2 to 200 and in particular from 5 to
100.
These silicones are described, for example, in Application EP-A-0 530 974; d) the amino silicones of formula (X) below:
Figure imgf000078_0001
in which:
- R8, R9, R10 and R11, which may be identical or different, each denote a Ci-C4 alkyl group or a phenyl group,
- R12 denotes a C C4 alkyl group or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number is between 0.01 and 1 meq/g.
When these compounds are used, one particularly advantageous embodiment involves their joint use with cationic and/or non-ionic surfactants.
By way of example, use may be made of the product sold under the name Cationic Emulsion DC939 by Dow Corning, which comprises, aside from amodimethicone, a cationic surfactant, namely trimethylcetylammonium chloride and a non-ionic surfactant of formula Ci3H27-(OC2H4)12-OH, known under the CTFA name Trideceth-12.
Another commercial product that may be used according to the invention is the product sold under the name Dow Corning Q2 7224 by the company Dow Corning, comprising, in combination, trimethylsilyl amodimethicone of formula (X) described above, non-ionic surfactant of formula C8H17-C6H4-(OCH2CH2)4o-OH, known under the CTFA name Octoxynol-40, a second non-ionic surfactant of formula Ci2H25-(OCH2- CH2)6-OH, known under the CTFA name lsolaureth-6, and propylene glycol.
The silicones of the invention may also be silicones grafted with anionic groups, such as the compounds VS 80 or VS 70 sold by the company 3M.
According to the invention, all the silicones can also be used in the form of emulsions, nanoemulsions or microemulsions. The particularly preferred silicones in accordance with the invention are:
- non-volatile silicones chosen from the family of polydialkylsiloxanes with trimethylsilyl end groups, such as oils having a viscosity of between 0.2 and 2.5 m2/s at 25°C, for instance the oils of the DC200 series from Dow Corning, in particular the one with a viscosity of 60 000 cSt, or of the Silbione 70047 and 47 series, and more particularly the oil 70 047 V 500 000 sold by the company Rhodia Chimie, and polydialkylsiloxanes with dimethylsilanol end groups, such as dimethiconols, or polyalkylarylsiloxanes, for instance the oil Silbione 70641 V 200 sold by the company Rhodia Chimie;
- polysiloxanes bearing amine groups such as amodimethicones, trimethylsilyl amodimethicones and polysiloxanes bearing quaternary ammonium groups.
The silicones that are even more particularly preferred in accordance with the invention are polysiloxanes bearing amine groups. The viscosities of the silicones may in particular be determined by the standard
ASTM D445-97 (viscometry).
The conditioning agent(s) may represent from 0.01 % to 10% by weight, preferably from 0.1 % to 5% by weight, more particularly from 0.3% to 5% by weight, and more particularly from 0.3% to 3% by weight, relative to the total weight of the composition C.
Process
The invention also relates to a process for lightening and/or dyeing human keratin fibres, in which the following are applied to said fibres:
a composition A comprising at least one alkaline agent and optionally at least one dyeing agent; and
a composition B comprising at least one chemical oxidizing agent;
- one and/or the other of the two compositions A and B comprising at least one associative thickening polymer,
the compositions A and B being packaged in a device constituted of a container, which is preferably pressurized, comprising at least two compartments a and b separate from one another, the compartment a comprising the composition A and the compartment b comprising the composition B, the device comprising a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to deliver the compositions A and B simultaneously. The mixing of the compositions A and B can be carried out just before the application to the keratin fibres or directly on the keratin fibres, for example during a simultaneous application of the compositions A and B to the hair.
Thus, according to one embodiment, a composition obtained by extemporaneous mixing, at the time of use, of the composition A and of composition B is applied to the keratin fibres.
According to another embodiment, the compositions A and B are applied simultaneously to the keratin fibres (without prior mixing), and then mixed directly on the keratin fibres, for example by massaging.
According to another embodiment, the compositions A and B are applied simultaneously to the keratin fibres, the mixing of the compositions being carried out just before discharge thereof from the device.
The compositions may be applied to wet or dry keratin fibres.
The composition resulting from the mixing is usually left in place on the fibres for a period generally from 1 minute to 1 hour, preferably from 5 minutes to 30 minutes.
The temperature during the treatment process is conventionally between ambient temperature (between 15 and 25°C) and 80°C and preferably between ambient temperature and 60°C.
After the treatment, the human keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.
In one variant of this process, a composition C as defined above, comprising at least one conditioning agent chosen from silicones, cationic polymers and amphoteric polymers, and mixtures thereof, is applied to the keratin fibres after removal of the mixture of the compositions A and B, preferably by rinsing, and optional shampooing followed by rinsing that may occur before the application of the composition C. The application of the composition C may optionally be followed by rinsing, the keratin fibres then being dried or left to dry. The examples that follow serve to illustrate the invention without, however, being limiting in nature.
EXAMPLE
The following compositions are prepared (the amounts are expressed in g% of active material):
Composition A:
AlkyI (C14/C16) Hydroxyethylcellulose (Natrosol Plus 330 0.4
CS from Ashland)
EDTA 0.2
N,N-Bis(2-hydroxyethyl)-p-phenylenediamine sulfate, 1 0.025
H20
1 -3-Hydroxyethyloxy-2,4-diaminobenzene dihydrochloride 0.01
1 -Hydroxy-3-aminobenzene 0.065
1 ,3-Dihydroxybenzene (resorcinol) 0.33
1 ,4-Diaminobenzene 0.35
Sodium sulfite 0.1
Oxyethylenated (4 OE) rapeseed acid amides 3.7
Hexadimethrine chloride (Mexomere PO from Chimex) 1 .2
Trideceth-2 carboxamide MEA (Amidet A15/LAO 55 from 4
Kao)
Oxyethylenated (12 OE) lauryl alcohol 3
Erythorbic acid 0.4
Polyquaternium-6 (Merquat 100 from Nalco) 0.8
Monoethanolamine 4
Sodium cetostearyl sulfate 1 .44
Ammonium hydroxide 3.7
Oxyethylenated (30 OE) oleocetyl alcohol 2
Glycerol 3
Oxyethylenated (2.5 EO) lauryl alcohol 8
Water qs 100 Oxidizing composition B:
Figure imgf000082_0001
Application method:
The compositions A and B are packaged in an aerosol container comprising two flexible pouches and equipped with a diffuser comprising a push-button, and are dispensed simultaneously side by side in 1/1 proportions.
The compositions mix rapidly on the hair and the mixture readily uniformly distributes on the hair. The use qualities are good: good wetting/glidance nature, ease of application, good root adhesion, good consistency on the head, good ease of spreading along the locks of hair.
The hair is then easily rinsed, then washed with a standard shampoo and dried. A strong chestnut brown colouration is obtained.

Claims

1. Device for dispensing a product for dyeing and/or lightening keratin fibres constituted of a container comprising:
i) at least two compartments a and b separate from one another,
the compartment a comprising a composition A comprising at least one alkaline agent and optionally at least one dyeing agent,
the compartment b comprising an oxidizing composition B comprising at least one chemical oxidizing agent,
one and/or the other of the compositions A and B of the two compartments comprising at least one associative thickening polymer;
ii) a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B.
2. Device according to Claim 1 , characterized in that the dyeing agents are chosen from oxidation dye precursors, direct dyes, and mixtures thereof.
3. Device according to Claim 1 or 2, characterized in that the composition A comprises at least one dyeing agent chosen from oxidation dye precursors, preferably chosen from oxidation bases, in particular from para- phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho- aminophenols, heterocyclic bases, and addition salts thereof. 4. Device according to any one of the preceding claims, characterized in that the composition A comprises at least one heterocyclic oxidation base, preferably chosen from:
i) the heterocyclic oxidation bases of formula (I), addition salts thereof and solvates thereof:
Figure imgf000083_0001
in which R-i represents an amino group, a Ci to C4 alkyl group optionally substituted with one or more hydroxyl or amino groups, a Ci to C4 alkoxy group optionally substituted with one or more hydroxyl or amino groups,
ii) the compounds of formula (II) or (III), addition salts thereof and solvates thereof:
Figure imgf000084_0001
in which R2 represents an amino group, a Ci to C4 alkyl group, optionally substituted with one or more hydroxyl or amino groups, a Ci to C4 alkoxy group, optionally substituted with one or more hydroxyl or amino groups; and Z-i represents a covalent bond, an -NR'6(CH2)q- radical or an -0(CH2)p- radical in which R'6 represents a hydrogen atom or a Ci-C6 alkyl radical optionally substituted with one or more hydroxyl groups, p denoting an integer ranging from 0 to 6, q denoting an integer ranging from 0 to 6, and R'i is a cationic radical; and
the radicals R'3, R'4 and R'5, independently, may be a hydrogen atom, an C1-C4 alkyl radical optionally substituted such as methyl, ethyl, hydroxyethyl, aminoethyl, propyl and butyl radicals; and
R'4 and R'5 can together form a partially saturated or unsaturated 5- or 8- membered ring, in particular a cyclopentene or cyclohexene, which is optionally substituted,
iii) the diaminopyrazole derivatives of formula (Γ), addition salts thereof and solvates thereof:
Figure imgf000085_0001
R1 representing a C1-C4 alkyl group which is substituted with one or more hydroxyl or amino groups,
R4 representing an amino group, a C1-C4 alkyl group which is optionally substituted with one or more hydroxyl or amino groups, a C1-C4 alkoxy group which is optionally substituted with one or more hydroxyl or amino groups,
and mixtures thereof.
Device according to any one of the preceding claims, characterized in that the composition A comprises at least one heterocyclic oxidation base, preferably chosen from 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2- [(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol, 2-(4,5-diamino-1 H-pyrazol-1 - yl)ethanol and/or an addition salt thereof or a solvate thereof, and mixtures thereof.
Device according to one of the preceding claims, characterized in that the composition A comprises at least one dyeing agent chosen from direct dyes, which are preferably cationic, preferably chosen from the hydrazono cationic dyes of formulae (Ilia) and (lll'a), the azo cationic dyes (IVa) and (IV'a) and the diazo cationic dyes (Va) below:
Figure imgf000085_0002
in which formulae (Ilia), (lll'a), (IVa), (IV'a) and (Va): Het+ represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferably with one or more (CrC8)alkyl groups such as methyl; Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferably ammonium, particularly tri(Ci- C8)alkylammonium such as trimethylammonium;
Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably with one or more electron-donating groups such as i) optionally substituted (CrC8)alkyl, ii) optionally substituted (CrC8)alkoxy, iii) (di)(Ci-C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci- C8)alkyl-N-aryl(Ci-C8)alkylamino or, as a variant, Ar represents a julolidine group;
Ar' represents an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferably with one or more groups (Ci-C8)alkyl, hydroxyl or (d- C8)alkoxy;
Ar" represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably with one or more (C C8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-C8)alkoxy or phenyl groups; Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-C8)alkyl group, which is optionally substituted, preferably with a hydroxyl group;
or, as a variant, the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar and/or Ra with Rb form, together with the atoms that bear them, a (hetero)cycloalkyl;
particularly, Ra and Rb represent a hydrogen atom or a (CrC4)alkyl group, which is optionally substituted with a hydroxyl group;
An" represents an anionic counterion, such as mesylate or halide.
Device according to any one of the preceding claims, characterized in that the composition A comprises at least one associative thickening polymer.
Device according to any one of the preceding claims, characterized in that the associative thickening polymer(s) is (are) chosen from associative polyurethanes, which are more particularly cationic or non-ionic, associative cellulose derivatives, which are more particularly cationic or non-ionic, associative vinyllactams, associative unsaturated polyacids and more particularly those comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of non-ethoxylated (Cio-
C30) alkyl ester type and copolymers comprising among their monomers an α,β- monoethylenically unsaturated carboxylic acid and an ester of an α,β- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol, associative aminoplast ethers, associative polymers or copolymers comprising at least one ethylenically unsaturated monomer comprising a sulfonic group, alone or as mixtures.
9. Device according to any one of the preceding claims, characterized in that the associative thickening polymer(s) is (are) chosen from associative cellulose derivatives, which are preferably non-ionic, in particular hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22 alkyl groups. 10. Device according to any one of the preceding claims, characterized in that the content of associative thickening polymer(s) represents from 0.01 % to 10% by weight, preferably from 0.05% to 5% by weight, better still from 0.1 % to 2% by weight, relative to the weight of the composition A and/or B. 1 1. Device according to any one of the preceding claims, characterized in that the alkaline agent is chosen from aqueous ammonia and/or at least one alkanolamine and/or at least one basic amino acid, more advantageously from aqueous ammonia and/or at least one alkanolamine. 12. Device according to any one of the preceding claims, characterized in that the chemical oxidizing agent is hydrogen peroxide.
13. Device according to any one of the preceding claims, characterized in that the composition A and/or the composition B comprise(s) one or more surfactants chosen from anionic, amphoteric, zwitterionic, cationic or non-ionic surfactants, and preferentially non-ionic surfactants.
14. Device according to any one of the preceding claims, characterized in that the composition A and/or the composition B comprise(s) at least one non-ionic surfactant, preferably chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 35 mol of ethylene oxide. 15. Device according to one of the preceding claims, characterized in that the composition A comprises at least one anionic surfactant, preferably chosen from (C12- C2o)alkyl sulfates.
16. Device according to one of the preceding claims, in which the composition A and/or B, preferably the composition A, comprises at least one cationic polymer.
17. Device according to one of the preceding claims, in which the composition A and/or B, preferably the composition B, comprises at least one fatty substance, preferably chosen from non-silicone oils of mineral or synthetic origin and fatty alcohols, and mixtures thereof.
18. Device according to one of the preceding claims, in which the container is pressurized. 19. Device according to one of the preceding claims, in which the walls of the container containing the compartments a and b are rigid.
20. Device according to one of the preceding claims, in which the compartments a and b are flexible pouches.
21. Device according to one of the preceding claims, characterized in that the container comprises a dispensing means equipped with at least one dispensing orifice, in communication with the compartments a and b, making it possible to simultaneously deliver the compositions A and B in separate form, by means of at least one dispensing orifice.
22. Device according to one of the preceding claims, in which each compartment is surmounted by a valve. 23. Device according to the preceding claim, in which the dispensing means comprises a single diffuser which caps the two valves.
24. Device according to Claim 22 or 23, in which the diffuser is equipped with two composition conveying pipes, each pipe communicating with the outlet orifice of a valve.
25. Device according to either of Claims 22 and 23, in which the diffuser is equipped with two pipes opening into a mixing chamber equipped with a static mixer, from which a single pipe is directed to a single dispensing/outlet orifice.
26. Process for lightening and/or dyeing human keratin fibres, in which the following are applied to said fibres:
- a composition A comprising at least one alkaline agent and optionally at least one dyeing agent; and
- a composition B comprising at least one chemical oxidizing agent;
one and/or the other of the two compositions comprising at least one associative thickening polymer,
the compositions A and B being packaged in a device as defined in any one of the preceding claims.
27. Kit comprising:
- a device for dispensing a dyeing and/or lightening product as defined in any one of Claims 1 to 25,
- a composition C comprising at least one conditioning agent chosen from silicones, cationic polymers and amphoteric polymers, and mixtures thereof.
PCT/EP2016/080642 2015-12-14 2016-12-12 Device for dispensing a product for dyeing and/or lightening keratin fibres comprising an associative polymer WO2017102650A1 (en)

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