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    • 专利摘要:
    The present invention relates to an anhydrous solid composition for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising a particular chemical oxidizing agent and a polymer comprising at least one vinyl heterocyclic monomer. The present invention also relates to a packaging article containing said composition. The present invention furthermore relates to methods for dyeing keratin fibers using said composition or said article of packaging. The present invention finally relates to the use of said composition or of said packaging article for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair.
    公开号:FR3060360A1
    申请号:FR1662928
    申请日:2016-12-20
    公开日:2018-06-22
    发明作者:Marie Mignon；Chrystel Pourille
    申请人:LOreal SA；
    IPC主号:
    专利说明:

    ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number: 3,060,360 (to be used only for reproduction orders)
    ©) National registration number: 16 62928
    COURBEVOIE © Int Cl 8 : A 61 K8 / 72 (2017.01), A 61 K8 / 41, A 61 Q 5/10
    A1 PATENT APPLICATION
    ©) Date of filing: 20.12.16. ©) Applicant (s): L'OREAL Société anonyme— FR. ©) Priority: @ Inventor (s): MIGNON MARIE and POURILLE CHRYSTEL. (43 / Date of public availability of the request: 22.06.18 Bulletin 18/25. ©) List of documents cited in the report preliminary research: Refer to end of present booklet (© References to other national documents ©) Holder (s): L'OREAL Société anonyme. related: ©) Extension request (s): ©) Agent (s): CASALONGA.
    SOLID ANHYDROUS COMPOSITION FOR COLORING KERATINIC FIBERS COMPRISING A POLYMER COMPRISING AT LEAST ONE VINYL HETEROCYCLIC MONOMER.
    FR 3 060 360 - A1
    The present invention relates to an anhydrous solid composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a particular chemical oxidizing agent and a polymer comprising at least one vinyl heterocyclic monomer.
    The present invention also relates to a packaging article containing said composition.
    The present invention further relates to methods for dyeing keratin fibers using said composition or said conditioning article.
    The present invention finally relates to the use of said composition or of said conditioning article for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    i
    Anhydrous solid composition for dyeing keratin fibers comprising a polymer comprising at least one vinyl heterocyclic monomer
    The present invention relates to an anhydrous solid composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a particular chemical oxidizing agent and a polymer comprising at least one vinyl heterocyclic monomer.
    The present invention also relates to a packaging article containing said composition.
    The present invention further relates to methods for dyeing keratin fibers using said composition or said conditioning article.
    The present invention finally relates to the use of said composition or of said conditioning article for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    Hair coloring, and in particular the masking of gray hair, has long been sought after by many people.
    It is known to dye keratin fibers, in particular human keratin fibers such as the hair, in order to obtain so-called permanent dyes with dye compositions containing oxidation dye precursors, generally called oxidation bases such as ortho- or paraphenylenediamines, ortho- or para-aminophenols or heterocyclic compounds such as pyrazoles, pyrazolinones or pyrazolo-pyridines. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.
    It is also possible to vary the shades obtained with these oxidation bases by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers provides a rich palette of colors for keratin fibers.
    The oxidation dyeing process therefore consists in applying to the keratin fibers, a dye composition comprising oxidation bases or a mixture of oxidation bases and couplers with hydrogen peroxide (H2O2 or hydrogen peroxide) as oxidizing agent, to let diffuse, then to rinse the fibers thus treated.
    The resulting colorings have the advantage of being permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and friction.
    Although the dye compositions can be presented in different galenical forms, such as powders, granules, pastes or creams, they are generally packaged in liquid form. However, solid coloring compositions provide numerous advantages over liquid coloring compositions. Their manufacturing process does not require water, which makes it possible to adopt a more eco-responsible behavior, and can also be miniaturized.
    The formulations in solid form also make it possible to use raw materials which are little or not stable in liquid formulation.
    However, the solid coloring compositions currently on the market present, after several weeks of storage, stability problems, which result in premature oxidation of the dyes and a drop in dye performance once the composition is used. Furthermore, the composition once oxidized tends to darken, which is not appreciated by consumers.
    In order to overcome this stability problem, coloring compositions in solid form have been proposed comprising oxidation dye precursors and sodium percarbonate stabilized by coatings. These coatings make the powder insoluble in water. A foaming lotion is then offered to the user with the coloring composition to allow the powder to be redispersed.
    The final mixture, however, has residual grains and is difficult to apply to keratin fibers, which leads to unsatisfactory coloring.
    In other solid coloring compositions, sodium percarbonate has been replaced by sodium perborate, which is easier to stabilize. However, sodium perborate is less well tolerated by consumers than sodium percarbonate, and has a poorer toxicological profile.
    To date, there is no coloring composition in solid form satisfactory in terms of stability and having a degree of dye quality similar to liquid coloring compositions.
    Thus, there is a real need to provide solid coloring compositions, which do not have the drawbacks mentioned above, i.e. which remain stable over time and retain their coloring properties.
    These compositions must also lead to chromatic, powerful, intense and not very selective colorations, that is to say to colorations which are homogeneous along the keratin fiber.
    The Applicant has surprisingly discovered that a solid coloring composition comprising one or more oxidation bases, one or more specific chemical oxidizing agents, and one or more polymers comprising at least one vinyl heterocyclic monomer makes it possible to achieve the objectives set out above; in particular to obtain a solid coloring composition which is stable over time, and whose coloring properties are maintained even after several months of storage.
    The subject of the present invention is in particular an anhydrous solid composition for dyeing keratin fibers, in particular human keratin fibers, such as the hair, comprising:
    (a) one or more oxidation bases, (b) one or more chemical oxidizing agents chosen from alkali metal percarbonates, alkaline earth metal percarbonates and mixtures thereof, (c) one or more polymers comprising at least one vinyl heterocyclic monomer, and (d) optionally one or more oxidation couplers.
    The presence of a polymer comprising at least one vinyl heterocyclic monomer makes it possible to limit the oxidation of the composition, thereby improving its stability over time. The composition thus stabilized retains its coloring properties.
    Furthermore, the presence of this polymer makes it possible to avoid coating the oxidizing agent. The ready-to-use composition, resulting from the mixture of the anhydrous solid coloring composition according to the invention with a cosmetically acceptable medium, then has a homogeneous texture without residual grains. It is then applied more easily to the keratin fibers and allows a homogeneous covering of the fibers.
    Thus, the anhydrous solid coloring composition according to the invention makes it possible to lead to chromatic, powerful, intense and not very selective coloring, even after several months of storage.
    The present invention also relates to a packaging article comprising:
    i) an envelope defining at least one cavity, the envelope comprising water-soluble and / or liposoluble fibers, preferably water-soluble fibers; and ii) an anhydrous solid coloring composition as defined above;
    it being understood that the anhydrous solid coloring composition is in one of the cavities defined by the envelope i).
    The present invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    - applying to said keratin fibers a ready-to-use composition resulting from the mixture of an anhydrous solid coloring composition, as defined above, and a cosmetically acceptable medium,
    - allow the ready-to-use composition to pause on said keratin fibers,
    - rinse said keratin fibers, and (e) optionally shampoo said keratin fibers, rinse and dry them.
    The present invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    - mix a packaging article, as defined above, with a composition capable of dissolving the envelope of said packaging article,
    - applying the resulting composition to said keratin fibers,
    - allowing said resulting composition to pause on said keratin fibers,
    - rinse said keratin fibers, and
    - optionally shampoo said keratin fibers, rinse and dry them.
    The present application also relates to the use of an anhydrous solid coloring composition, as defined above, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    The present invention also relates to the use of a packaging article, as defined above, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.
    In what follows, and unless otherwise indicated, the limits of a range of values are included in this range, in particular in the expressions "between" and "going from ... to ...".
    Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”.
    The term “keratin materials” preferably denotes human keratin materials, such as the skin, the scalp and human keratin fibers, and more preferably the hair.
    By “anhydrous composition” is meant a composition comprising a water content of less than 3% by weight, preferably less than 1% by weight, relative to the weight of the composition. Preferably, this water content is less than 0.5% by weight, relative to the weight of the composition. More particularly, the water content ranges from 0 to 1% by weight, and preferably from 0 to 0.5% by weight, relative to the total weight of the composition. Finally, more particularly, it does not include water.
    By “solid composition” is meant a composition which may be in the form of powder, paste or particles (for example spherical particles such as small beads).
    By “powder” is meant a composition in powder form, preferably essentially devoid of dust (or fine particles). In other words, the particle size distribution is such that the weight ratio of the particles which have a size less than or equal to 100 micrometers (rate of fines) preferably less than or equal to 65 micrometers (rate of fines) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1% (particle size evaluated using a RETSCH AS 200 DIGIT granulometer; Oscillation height: 1.25 mm / sieving time: 5 minutes). Advantageously, the particle size is between 100pm and 3mm, and more particularly between 65pm and 2mm.
    By “paste” is meant a composition having a viscosity greater than 5 poises and preferably greater than 10 poises, measured at 25 ° C. and at a shear rate of ls 1 ; this viscosity can be determined using a Coneplan rheometer.
    By "particles" is meant small fractional objects formed of solid particles aggregated together, of varying shapes and sizes. They can be regular or irregular in shape. They can be in particular spherical (like granules, granules, beads), square, rectangular, or elongated like sticks. Particularly preferred are spherical particles.
    The size of the particles can be, in its largest dimension, between 0.01 and 5 mm, preferably between 0.1 and 2.5 mm, and better still between 0.5 and 2 mm.
    The anhydrous solid composition according to the invention can be in the form of a compressed solid composition, in particular using a manual or mechanical press.
    Anhydrous solid coloring composition Oxidation bases (a)
    The anhydrous solid coloring composition according to the present invention comprises one or more oxidation bases. Preferably, the oxidation bases are chosen in particular from heterocyclic bases, benzene bases, their addition salts, their solvates and their mixtures.
    The oxidation bases which can be used in the composition of the invention are in particular chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, orthoaminophenols, heterocyclic bases, their addition salts, their solvates and their mixtures.
    Among the para-phenylenediamines which may be mentioned, there are for example para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3dimethyl-para-phenylenediamine, 2,6-dimethyl-paraphenylenediamine , 2,6-diethyl-para-phenylenediamine, 2,5dimethyl-para-phenylenediamine, N, N-dimethyl-paraphenylenediamine, Ν, Ν-diethyl-para-phenylenediamine, N, Ndipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3methylaniline, N, N-bis (3-hydroxyethyl) -para-phenylenediamine, 4-N, N-bis (3-hydroxyethyl) amino-2-methylaniline, 4- N, N-bis (3hydroxyethyl) amino-2-chloroaniline, 2-3-hydroxyethyl-paraphenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - (3-hydroxypropyl) -para-phenylenediamine, 2-hydroxymethylpara-phenylenediamine, N, N-dimethyl-3-methyl-paraphenylenediamine, N-ethyl-N- (3-hydroxyeth yl) -paraphenylenediamine, N- (3, Y-dihydroxypropyl) -para-phenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N-phenyl-paraphenylenediamine, 2-3-hydroxyethyloxy-para- phenylenediamine, the
    2-3-acetylaminoethyloxy-para-phenylenediamine, Ν- (βmethoxyethyl) -para-phenylenedi amine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2 ^ -hydroxyethylamino-5aminotoluene and 3-hydroxy-l - (4'-aminophenyl) pyrrolidine and the corresponding addition salts with an acid.
    Among the aforementioned para-phenylenediamines, particularly preferred are para-phenylenediamine, para-toluenediamine, 2isopropyl-para-phenylenediamine, 2 ^ -hydroxyethyl-paraphenylenediamine, 2 ^ -hydroxyethyloxy-para-phenylenediamine, 2,6 -dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, Nbis ^ -hydroxyethyl) -para-phenylenediamine, 2-chloro-paraphenylenediamine and 2 ^ -acetylaminoethyloxy-paraphenylenediamine and the corresponding addition salts with an acid.
    Among the bis (phenyl) alkylenediamines which may be mentioned, there is for example N, N'-bis ^ -hydroxyethyl) -N, N'bis (4'-aminophenyl) -1,3-diaminopropanol, Ν, Ν '-δΐβζβ3060360 hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (3hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenedi amine, the
    N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'bis (ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenedediine and 1,8-bis ( 2,5-diaminophenoxy) -3,6-dioxaoctane and the corresponding addition salts.
    Among the para-aminophenols which are mentioned, there are for example para-aminophenol, 4-amino-3-methylphenol, 4 amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4 amino-2-aminomethylphenol, 4-amino-2- (3hydroxyethylaminomethyl) phenol and 4-amino-2 -fluorophenol and the corresponding addition salts with an acid.
    Among the ortho-aminophenols which may be mentioned, there are for example 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and the salts thereof. corresponding addition.
    Among the heterocyclic bases which may be mentioned, there are, for example, the pyridine, pyrimidine and pyrazole derivatives.
    Among the pyridine derivatives which may be mentioned, there are the compounds for example described in patents GB 1,026,978 and GB 1,153,196, for example 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3 -aminopyridine and 3,4-diaminopyridine and the corresponding addition salts.
    Other pyridine oxidation bases which are useful in the present invention are the 3-aminopyrazolo [1,5ajpyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples which may be mentioned include pyrazolo [1,5-a] pyrid-3-ylamine, 2acetylaminopyrazolo [1,5-a] pyrid-3-ylamine, 2-morpholin-4ylpyrazolo [1,5- a] pyrid-3-ylamine, 3-aminopyrazolo acid [l, 53060360 ίο
    a] pyridine-2-carboxylic, 2-methoxypyrazolo [1,5-a] pyrid-3ylamine, (3-aminopyrazolo [1,5-a] pyrid-7-yl) methanol, 2- (3aminopyrazolo [l , 5-a] pyrid-5-yl) ethanol, 2- (3-aminopyrazolo [1,5a] pyrid-7-yl) ethanol, (3-aminopyrazolo [1,5-a] pyrid-2-yl ) methanol, 3,6-diaminopyrazolo [1,5-a] pyridine, 3,4-diaminopyrazolo [1,5ajpyridine, pyrazolo [1,5-a] pyridine-3,7-diamine, 7-morpholin -4ylpyrazolo [1,5-a] pyrid-3-ylamine, pyrazolo [1,5-a] pyridine-3,5diamine, 5-morpholin-4-ylpyrazolo [1,5-a] pyrid-3-ylamine , 2 - [(3aminopyrazolo [1,5-a] pyrid-5-yl) (2-hydroxyethyl) -amino] ethanol, 2 [(3-aminopyrazolo [1,5-a] pyrid-7-yl) (2-hydroxyethyl) amino] ethanol, the
    3- aminopyrazolo [1,5-a] pyridin-5-ol, 3-aminopyrazolo [1,5-a] pyridin4- ol, 3-aminopyrazolo [1,5-a] pyridin-6-ol, 3 -aminopyrazolo [1,5a] pyridin-7-ol, 2-3-hydroxyethoxy-3-amino-pyrazolo [1,5ajpyridine; 2- (4-dimethylpiperazinium-1-yl) -3-amino-pyrazolo [1,5ajpyridine; and the corresponding addition salts.
    More particularly, the oxidation bases which are useful in the present invention are chosen from 3-aminopyrazolo [1,5-a] -pyridines and preferably substituted on the carbon atom 2 by:
    a) a (di) (Ci-C6) (alkyl) amino group, said alkyl group being able to be substituted by at least one hydroxy, amino, imidazolium group;
    b) a heterocycloalkyl group containing 5 to 7 members and 1 to 3 heteroatoms, optionally cationic, optionally substituted by one or more (Ci-C6) alkyl groups, such as a di (CiCQalkylpiperazinium group; or
    c) a (Ci-C6) alkoxy group optionally substituted by one or more hydroxy groups such as a β-hydroxyalkoxy group and the corresponding addition salts.
    Among the 3-aminopyrazolo- [1,5-a] -pyridines bases, it is preferable in particular to use 2 [(3-aminopyrazolo [1,5-a] pyridin-2yl) oxy] ethanol, and / or 4 chloride - (3-aminopyrazolo [1,5a] pyridin-2-yl) -1, 1-dimethylpiperazin-1-ium and / or their corresponding addition salts or solvates
    Among the pyrimidine derivatives which may be mentioned, there are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6triaminopyrimidine, 2, 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.
    Among the pyrazole derivatives which may be mentioned, there are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FRA-2 733 749 and DE 195 43 988, such than 4,5-diamino-1-methylpyrazole,
    4.5- diamino-1- (3-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-lmethyl -3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3tert-butyl-l-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (3-hydroxyethyl) -3-methylpyrazole, 4,5diamino-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, 4,5diamino-3-hydroxymethyl-l-isopropylpyrazole, 4,5-diamino-3methyl-l-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-l, 3dimethylpyrazole, 3,4,5 -triaminopyrazole, l-methyl-3,4,5triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole,
    3.5- diamino-4- (3-hydroxyethyl) amino-1-methylpyrazole and the corresponding addition salts. It is also possible to use 4,5-diamino1- (β-methoxy ethyl) pyrazole.
    A 4,5-diaminopyrazole will preferably be used and even more preferably 4,5-diamino-1 - ^ - hydroxyethyl) pyrazole and / or a corresponding salt.
    The pyrazole derivatives which 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 the corresponding addition salts: 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-l-one, la 2 amino-3-ethylamino-6,7-dihydro-lH,5H-pyrazolo [1 , 2-a] pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2a] pyrazol-1-one, 2-amino-3- ( pyrrolidin-1-yl) -6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-l-one, 4,5-diamino-1,2,2-dimethyl-1,2,2dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol3-one, 4,5-diamino-1,2-di- (2-hydroxy ethyl) - 1,2-dihy dropyrazol-3one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-l-one, 2-amino-3-dimethylamino-6,7dihydro-1H , 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8tetrahydro-1H, 6H-pyridazino [l, 2-a] pyrazol-l-one, 4-amino-1,2diethyl-5- (pyrrolid in-l-yl) -1,2-dihydropyrazol-3-one, 4-amino-5- (3dimethylaminopyrrolidin-l-yl) -1,2-diethyl-1,2-dihydropyrazol-3-one, 2 , 3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol1-one.
    hydroxyethyl) pyrazole and / or pyrazolo [1,2-a] pyrazol-1-one
    Preferably, 2,3-diamino-6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-1-one and / or a corresponding salt will be used.
    Preferably, 4,5-diamino-l- (3la 2,3-diamino-6,7-dihydro-1H, 5Het / or 2 [(3-aminopyrazolo [1,5a] pyridin-2-yl) oxy] ethanol and / or 4- (3aminopyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethylpiperazin-1-ium chloride and / or their corresponding salts or solvates as heterocyclic bases.
    In general, the addition salts of the oxidation bases which can be used in the composition according to the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
    Furthermore, the solvates of the oxidation bases represent more particularly the hydrates of said bases and / or the association of said bases with a linear or branched C1 to C 4 alcohol such as methanol, ethanol, isopropanol, n-propanol. Preferably, the solvates are hydrates.
    Preferably, the oxidation base or bases are chosen from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases, their addition salts, their solvates and their mixtures.
    More preferably, the oxidation base or bases are chosen from paraphenylenediamines, their addition salts, their solvates and their mixtures.
    The total amount of the oxidation base (s) present in the anhydrous solid coloring composition according to the present invention preferably ranges from 0.1 to 30% by weight, more preferably from 0.5 to 15% by weight, and better from 1 to 10% by weight, relative to the total weight of the anhydrous solid coloring composition.
    Chemical oxidizing agents (b)
    The anhydrous solid coloring composition according to the present invention further comprises one or more chemical oxidizing agents chosen from alkali metal percarbonates, alkaline earth metal percarbonates and mixtures thereof.
    Preferably, the chemical oxidizing agents present in the anhydrous solid coloring composition according to the invention are anhydrous, and more preferably anhydrous and solid, that is to say in the form of powder, paste or particles (such as beads ).
    Preferably, the chemical oxidizing agent is sodium percarbonate.
    The total amount of the chemical oxidizing agent (s), chosen from alkali metal percarbonates, alkaline earth metal percarbonates and their mixtures, present in the anhydrous solid coloring composition according to the present invention, preferably ranges from 30 to 55% by weight. weight, and more preferably from 35 to 50% by weight, relative to the total weight of the anhydrous solid coloring composition.
    The composition according to the invention may optionally further comprise one or more additional chemical oxidizing agents, different from the chemical oxidizing agents (b), as defined above.
    By "chemical oxidizing agent" is meant according to the invention an oxidizing agent different from air oxygen.
    The additional chemical oxidizing agent (s), optionally present in the anhydrous solid coloring composition according to the invention are preferably anhydrous and more preferably anhydrous and solid, that is to say in the form of powder, paste or particles (such only balls).
    More particularly, the additional anhydrous chemical oxidizing agent (s) are chosen from (i) peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors; (ii) bromates or ferricyanides of alkali metals; (iii) solid chemical oxidizing agents generating hydrogen peroxide such as urea peroxide and polymer complexes which can release hydrogen peroxide, in particular those comprising a vinyl heterocyclic monomer such as polyvinylpyrrolidone / FLCh complexes in particular having in the form of powders, different from the polymer comprising at least one vinyl heterocyclic monomer (c), as defined below; (iv) oxidases producing hydrogen peroxide in the presence of an adequate substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); and their mixtures.
    According to a particular embodiment, the additional chemical oxidizing agent (s) are chosen from the complexes of hydrogen peroxide and of polymer containing as monomer at least one vinyl heterocyclic monomer, different from the polymer comprising at least one vinyl heterocyclic monomer ( c), as defined below.
    More particularly, the vinyl heterocyclic monomer is chosen from monomers comprising a heterocycle having 4 to 6 members, optionally condensed to a benzene ring and comprising from 1 to 4 identical or different intracyclic heteroatoms; the number of intracyclic heteroatoms being less than that of the heterocycle links. Preferably, the number of intracyclic heteroatoms is 1 or 2.
    More particularly, the heteroatom (s) are chosen from sulfur, oxygen, nitrogen, preferably from nitrogen and oxygen. According to an even more advantageous embodiment of the invention, the monomer comprises at least one intracyclic nitrogen atom.
    The vinyl heterocycle can optionally be substituted by one or more C 1 to C 4 , and preferably C 1 to C 2, alkyl groups.
    Preferably, the heterocyclic monomer is chosen from N-vinyl monomers.
    Among the monomers that may be envisaged, there may be mentioned the following monomers, optionally substituted: Nvinylpyrrolidone, vinylcaprolactam, N-vinylpiperidone, N vinyl 3-morpholine, N-vinyl-4-oxazolinone, 2-vinylpyridine, 4vinylpyridine, 2-vinylquinoline, 1-vinylimidazole, 1vinylcarbazole. Preferably, the monomer is optionally substituted N-vinylpyrrolidine.
    According to a particularly advantageous embodiment of the invention, the polymer is a homopolymer.
    However, it is not excluded to use a copolymer. In such a case, the comonomer (s) are chosen from vinyl acetate, (meth) acrylic acids, (meth) acrylic amides, C1 to C4 alkyl esters of substituted (meth) acrylic acid or no.
    The polymer involved in this complex is preferably soluble in water. It can have variable average molecular weights, preferably between 10 3 and 3.10 6 g / mol, and more preferably between 10 3 and 2.10 6 g / mol. It is also possible to use mixtures of such polymers.
    Advantageously, said complex comprises from 10 to 30% by weight of hydrogen peroxide, preferably from 13 to 25% by weight and more preferably from 18 to 22% by weight, relative to the total weight of the complex.
    According to an even more advantageous variant of the invention, in this complex, the molar ratio between the vinyl heterocyclic monomer (s) and the hydrogen peroxide ranges from 0.5 to 2, and preferably from 0.5 to 1.
    This complex is advantageously in the form of a substantially anhydrous powder.
    Complexes of this type are described in particular in US5,008,106, US5,077,047, EP 832846, EP 714919, DE 4344131, DE 19545380 and the other polymer complexes described in US 5,008,093; US 3,376,110; US 5,183,901.
    Examples of complexes include, for example, products of the Peroxydone K-30, Peroxydone K-90, Peroxydone XL10 type as well as the complexes formed with hydrogen peroxide and one of the following polymers of the Plasdone type. K-17, Plasdone K-25, Plasdone K-29/32, Plasdone K-90, Polyplasdone INF-10, Polyplasdone XL-10, Polyplasdone XL, Plasdone S-630, Styleze 2000 Terpolymer, series of Ganex copolymers, marketed by the ISP company.
    Preferably, the composition according to the present invention may comprise one or more additional anhydrous solid chemical oxidants, different from the chemical oxidizing agents (b), chosen from urea peroxide, perborates, persulfates and their mixtures.
    According to a particularly preferred embodiment, the anhydrous solid coloring composition according to the present invention does not comprise an additional chemical oxidizing agent different from the oxidizing agents (b).
    Polymers comprising at least one vinyl heterocyclic monomer (c)
    The anhydrous solid coloring composition according to the present invention further comprises one or more polymers comprising at least one vinyl heterocyclic monomer.
    More particularly, the vinyl heterocyclic monomer is chosen from monomers comprising a heterocycle having 4 to 7 members, and comprising from 1 to 4 identical or different intracyclic heteroatoms, optionally condensed to a benzene ring and / or optionally substituted; the number of intracyclic heteroatoms being less than that of the heterocycle links.
    Preferably, the number of intracyclic heteroatoms is one or two.
    More particularly, the heteroatom (s) are chosen from sulfur, oxygen, nitrogen, and preferably from nitrogen and oxygen.
    According to an even more advantageous embodiment of the invention, the monomer comprises at least one intracyclic nitrogen atom.
    The vinyl heterocycle can optionally be substituted by one or more C 1 to C 4 , and preferably C 1 to C 2, alkyl groups.
    Preferably, the heterocyclic monomer is chosen from N-vinyl monomers.
    Among the heterocyclic vinyl monomers which may be envisaged, the following monomers may advantageously be mentioned, N-vinylpyrrolidone, vinylcaprolactam, Nvinylpiperidone, N vinyl 3-morpholine, N-vinyl-4-oxazolinone, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 1vinylimidazole, 1-vinylcarbazole. Preferably, the monomer is optionally substituted N-vinylpyrrolidone.
    According to a particularly advantageous embodiment of the invention, the polymer is a homopolymer.
    However, it is not excluded to use a copolymer. The copolymer can comprise at least two heterocyclic vinyl monomers as described above, or else at least one heterocyclic vinyl monomer, as described above, and at least one monomer different from the heterocyclic vinyl monomers, as described above.
    In the latter case, the comonomer or comonomers are preferably chosen from vinyl acetate, (meth) acrylic acids, (meth) acrylic amides, C1 to C4 alkyl esters of (meth) acrylic acid substituted or not.
    The polymer comprising at least one heterocyclic vinyl monomer may or may not be crosslinked.
    The polymer comprising at least one vinyl heterocyclic monomer according to the invention is preferably soluble in water. It can have variable average molecular weights, preferably between 10 3 and 3.10 6 g / mol, and more preferably between 10 3 and 2.10 6 g / mol. It is also possible to use mixtures of such polymers.
    Preferably, the polymer comprising at least one vinyl heterocyclic monomer is the homopolymer of vinylpyrrolidone crosslinked or not.
    The total amount of the polymer (s) comprising at least one vinyl heterocyclic monomer, present in the anhydrous solid coloring composition according to the present invention, preferably ranges from 5 to 70% by weight, more preferably from 10 to 60% by weight, and better from 10 to 35% by weight, relative to the total weight of the anhydrous solid coloring composition.
    Oxidation couplers (d)
    The anhydrous solid coloring composition according to the present invention may optionally further comprise one or more oxidation couplers conventionally used for the coloring of keratin fibers.
    Among these oxidation couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers, their addition salts, their solvates and their mixtures.
    By way of example, mention may be made of resorcinol, 2-methyl-5hydroxyethylaminophenol, 2,4-diaminophenoxy ethanol, 1,3dihydroxybenzene, l, 3-dihydroxy-2-methylbenzene, 4-chloro-l, 3dihydroxybenzene , 2,4-diamino-1 - (3-hydroxyethyloxy) benzene, 2-amino-4- (3-hydroxy ethyl amino) -1 - methoxybenzene, 1,3-diaminobenzene, 1,3-bis ( 2,4-diaminophenoxy) propane, 3-ureidoaniline,
    3-ureido-1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, Ι'α-naphthol, 2-methyl-lnaphthol, 6-hydroxyindole, 4-hydroxyindole, 4- hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-Ν- (βhydroxyethyl) amino-3,4-methylenedioxybenzene, 2, 6-bis ^ hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6 -dimethylpyrazolo [1,5-b] -1,4,4-triazole, 2,6dimethyl [3,2-c] -1,4,4-triazole and 6-methylpyrazolo [1,5-a] benzimidazole , 2-methyl-5-aminophenol, 5-Ν- (βhydroxyethyl) amino-2-methylphenol, 3-aminophenol (or metaaminophenol), 3-amino-2-chloro-6-methylphenol, the salts of corresponding addition with an acid and the corresponding mixtures.
    Preferably, the coupler (s) are chosen from metaphenylenediamines, meta-aminophenols, their addition salts and their mixtures, and more preferably from 2,4diaminophenoxyethanol, resorcinol, meta-aminophenol, their addition salts, their solvates and their mixtures.
    The addition salts of the oxidation couplers optionally present in the composition according to the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates , lactates, tosylates, benzenesulfonates, phosphates and acetates, and addition salts with a base such as sodium hydroxide, potash, ammonia, amines or alkanolamines.
    Furthermore, the solvates of the oxidation couplers more particularly represent the hydrates of said couplers and / or the association of said couplers with a linear or branched C1 to C4 alcohol such as methanol, ethanol, isopropanol, n -propanol. Preferably, the solvates are hydrates.
    The total amount of the oxidation coupler (s), when present in the anhydrous solid coloring composition according to the invention, preferably ranges from 0.1 to 25% by weight, more preferably from 0.5 to 20% by weight. weight, and better still from 1 to 19% by weight, relative to the total weight of the anhydrous solid coloring composition.
    Surfactants
    The anhydrous solid coloring composition according to the present invention may optionally further comprise one or more surfactants, preferably chosen from anionic surfactants, amphoteric or zwitterionic surfactants, nonionic surfactants, cationic surfactants and their mixtures.
    By “surfactant” is meant within the meaning of the present invention, an agent comprising at least one hydrophilic group and at least one lipophilic group in its structure, and which is preferably capable of reducing the surface tension of water, and does not comprising in its structure, as possible repeating units, only alkylene oxide units and / or sugar units and / or siloxane units. Preferably, the lipophilic group is a fatty chain comprising from 8 to 30 carbon atoms.
    Preferably, the anhydrous solid coloring composition according to the present invention comprises one or more surfactants chosen from anionic surfactants.
    The term “anionic surfactant” is understood to mean a surfactant comprising only anionic groups as ionic or ionizable groups. These anionic groups are preferably chosen from the groups -C (O) OH, -C (O) O-, -SO3H, S (O) 2 O-, OS (O) 2 OH, -OS (O) 2 O -, -P (O) OH 2 , -P (O) 2 O, -P (O) O 2 -, P (OH) 2 , = P (O) OH, -P (OH) O-, = P (O) O-, = POH, = PO-, the anionic parts comprising a cationic counter ion such as those originating from an alkali metal, an alkaline earth metal, or from an amine or from an ammonium.
    As examples of anionic surfactants which can be used in the composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates , alpha-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyl esters alkyl and polyglycoside-polycarboxylic acids, acyllactylates, salts of D-galactoside-uronic acids, salts of alkyl ether-carboxylic acids, salts of alkyl aryl ether-carboxylic acids, salts of alkyl acids amidoether-carboxylic acids, and the corresponding non-salified forms of all these compounds, the groups a the alkyl and acyl of all these compounds containing from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.
    These compounds can be oxyethylenated and then preferably contain from 1 to 50 ethylene oxide units.
    The salts of C 6 -C 24 alkyl monoesters and of polyglycoside-polycarboxylic acids can be chosen from C 6 -C 24 alkyl polyglycoside citrates, C 6 -C 24 alkyl polyglycosidestartrates and polyglycoside sulfosuccinates C6 to C24 alkyl.
    When the anionic surfactant (s) are in salt form, they can be chosen from alkali metal salts such as the sodium or potassium and preferably sodium salt, ammonium salts, amine salts and in particular amino alcohols or alkaline earth metal salts such as magnesium salts.
    By way of example of amino alcohol salts, mention may in particular be made of the mono-, di- and triethanolamine salts, the mono-, di- or tri-isopropanolamine salts, the 2-amino-2-methyl- salts l-propanol, 2-amino-2-methyl-l, 3-propanediol and tris (hydroxy-methyl) amino methane.
    The alkali or alkaline earth metal salts are preferably used and in particular the sodium or magnesium salts.
    Among the anionic surfactants mentioned, it is preferred to use alkyl (C6-C24) sulfates, alkyl (C6-C24) ethersulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium salts , amino alcohols, and alkaline earth metals, or a mixture of these compounds.
    In particular, it is preferred to use the alkyls (Ci2-C2o) sulfates, the alkyls (Ci2-C 2 o) eth er sul f ates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal salts, ammonium, amino alcohols, and alkaline earth metals, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate, in particular those containing 2.2 moles of ethylene oxide. More preferably the alkyls (Ci2-C2o) sufates such as the alkali metal lauryl sulfate such as sodium.
    Preferably, the anhydrous solid coloring composition according to the present invention comprises one or more surfactants chosen from amphoteric or zwitterionic surfactants.
    The amphoteric or zwitterionic surfactant (s) of the invention are preferably non-silicone, and are in particular derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C8-C2o) alkyl betaines, sulfobetaines, (C8-C2o) alkyl amidoalkyl (C3-C8) betaines and (C8-C2o) alkylamidalkyl (C6-C8) sulfobetaines.
    Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of alkyl (C8-C2o) betaines such as cocobetaine, alkyl (C8-C2o) amidoalkyl (C3-C8) betaines such as cocamidopropylbetaine, and their mixtures. More preferably, the amphoteric or zwitterionic surfactant (s) are chosen from cocamidopropylbetaine and cocobetaine.
    Preferably, the anhydrous solid coloring composition according to the present invention comprises one or more surfactants chosen from cationic surfactants.
    The cationic surfactant (s) which can be used in the composition according to the invention comprise, for example, the primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated, the quaternary ammonium salts, and their mixtures.
    Among the cationic surfactants which may be present in the composition according to the invention, it is more particularly preferred to choose the cetyltrimethylammonium salts, of dipalmitoylethyl and their mixtures, and more behenyltrimethylammonium, behenyltrimethylammonium, hydroxyethylmethylammonium chloride, particularly cetyltrimethylammonium chloride chloride. , dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
    Preferably, the anhydrous solid coloring composition according to the present invention comprises one or more surfactants chosen from nonionic surfactants.
    Examples of nonionic surfactants which can be used in the composition used according to the invention are described for example in Handbook of Surfactants by M.R. PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178.
    As examples of nonionic surfactants, there may be mentioned:
    - oxyalkylenated (C8-C 24) alkyl phenols;
    - Cs to C30 alcohols, saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated;
    - amides, Cs to C30, saturated or unsaturated, linear or branched, oxyalkylenated;
    - esters of Cs to C30 acids, saturated or not, linear or branched, and of polyethylene glycols;
    - esters of Cs to C30 acids, saturated or not, linear or branched, and of polyoxyethylenated sorbitan;
    - fatty acid and sucrose esters (C8-C3o) alkyl, polyglycosides, alkenyl (C8-C3o) poly-glycosides, optionally oxyalkylenated (0 to 10 oxyalkylenated units) and comprising 1 to 15 glucose units, esters of alkyl (CsC3o) glucosides,
    - oxyethylenated vegetable oils, saturated or not;
    - condensates of ethylene oxide and / or propylene oxide, among others, alone or in mixtures;
    - N-alkyl (C8-C3o) glucamine and N-acyl (C8-C 3 o) methylglucamine derivatives;
    - aldobionamides;
    - amine oxides; and
    - oxyethylenated and / or oxypropylenated silicones.
    The surfactants having a number of moles of ethylene oxide and / or propylene advantageously ranging from 1 to 100, more particularly from 2 to 100 and preferably from 2 to 50, more advantageously from 2 to 30. Advantageously, non-ionic surfactants do not include oxypropylene units.
    In accordance with a preferred embodiment of the invention, the nonionic surfactants are chosen from oxyethylenated Cs to C 3 o alcohols comprising from 1 to 100 moles, more particularly from 2 to 100 moles of ethylene oxide ; esters of Cs to C 3 o acids, saturated or unsaturated, linear or branched, and of polyoxyethylenated sorbitan comprising from 1 to 100 moles, better still from 2 to 100 moles of ethylene oxide.
    By way of example of nonionic surfactants mono- or polyglycerolated, use is preferably made of Cs to C40 alcohols, mono- or polyglycerolated.
    In particular, the mono- or polyglycerolated Cs to C40 alcohols preferably correspond to the following formula (A8):
    R29O- [CH2-CH (CH 2 OH) -O] m -H (A8) in which,
    - R29 represents an alkyl or alkenyl radical, linear or branched, in Cs to C40, preferably in Cs to C 3 o; and
    - m represents a number ranging from 1 to 30 and preferably from 1 to 10.
    By way of example of compounds of formula (A8) suitable in the context of the invention, there may be mentioned, lauric alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 LAURYL ETHER), lauric alcohol with 1.5 moles of glycerol, oleic alcohol with 4 moles of glycerol (INCI name: POLYGLYCERYL-4 OLEYL ETHER), oleic alcohol with 2 moles of glycerol (INCI name: POLYGLYCERYL-2 OLEYL ETHER), alcohol cetearyl to 2 moles of glycerol, cetearyl alcohol to 6 moles of glycerol, oleocetyl alcohol to 6 moles of glycerol, and octadecanol to 6 moles of glycerol.
    The alcohol of formula (A8) can represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that in a commercial product can coexist several species of polyglycerolated fatty alcohols in the form of a mixed.
    Among the mono- or poly-glycerol alcohols, it is more particularly preferred to use the alcohol Cs to Cio to one mole of glycerol, the alcohol Cio to C12 to 1 mole of glycerol and the alcohol C12 to 1.5 mole of glycerol.
    Preferably, the nonionic surfactant used in the process of the invention in the composition is a nonionic surfactant mono or polyoxyalkylenated, particularly mono or polyoxyethylenated, mono or polyoxypropylenated, or their combination, more particularly mono or polyoxyethylenated, mono- or polyglycerolated surfactants and alkylpolyglucosides.
    Even more preferably, the nonionic surfactants are chosen from polyoxyethylenated sorbitan esters, polyoxyethylenated fatty alcohols, alkylpolyglucosides and their mixtures.
    More preferably, the anhydrous solid coloring composition according to the present invention comprises one or more surfactants, chosen from anionic surfactants, nonionic surfactants and their mixtures, and more preferably from anionic surfactants and their mixtures.
    Alkaline agents
    The anhydrous solid coloring composition according to the present invention may optionally further comprise one or more alkaline agents.
    The alkaline agent (s) can be chosen from silicates and metasilicates, such as metasilicates of alkali metals; carbonates or hydrogen carbonates of alkali or alkaline earth metals, such as lithium, sodium, potassium, magnesium, calcium or barium; and their mixtures.
    The alkaline agent (s) can also be chosen from ammonium salts, and in particular inorganic ammonium salts.
    Preferably, the ammonium salt or salts are chosen from ammonium halides such as ammonium chloride, ammonium sulphate, ammonium phosphate, ammonium nitrate and their mixtures.
    More preferably, the ammonium salt is ammonium chloride or ammonium sulfate.
    In a preferred embodiment, the anhydrous solid coloring composition according to the present invention comprises one or more alkaline agents.
    Even more preferably, the anhydrous solid coloring composition according to the present invention comprises one or more ammonium salts, preferably chosen from ammonium chloride or ammonium sulfate, and better still ammonium sulfate.
    Thickening polymers
    The anhydrous solid coloring composition according to the present invention may optionally further comprise one or more thickening polymers.
    Advantageously, the thickening polymer (s) are chosen from the following polymers:
    (a) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;
    (b) anionic amphiphilic polymers comprising at least one hydrophilic unit, and at least one fatty chain unit;
    (c) crosslinked acrylic acid homopolymers;
    (d) crosslinked homopolymers of 2-acrylamido-2-methylpropane sulfonic acid and their partially or completely neutralized crosslinked acrylamide copolymers;
    (e) homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide;
    (f) homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride or copolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride and acrylamide; and (g) polysaccharides such as:
    (gl) scleroglucan gums (biopolysaccharide of microbial origin), (g2) gums derived from plant exudates such as gum arabic, Ghatti, Karaya and Tragacanth;
    (g3) celluloses and derivatives;
    (g4) guar gums and derivatives; or (g5) starches or derivatives.
    It should be noted that in the case of the present invention, the thickening polymers have a role on the viscosity of the ready-to-use composition, that is to say of the composition comprising the anhydrous solid coloring composition according to the present invention and a cosmetically acceptable medium.
    According to the invention, the amphiphilic polymers are more particularly hydrophilic polymers capable, in the medium of the composition, and more particularly in an aqueous medium, of reversibly associating with each other or with other molecules.
    Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. By hydrophobic group is meant a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 8 carbon atoms, preferably at least 10 carbon atoms, more preferably from 10 to 30 carbon atoms, especially from 12 to 30 carbon atoms and better still from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. For example, the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.
    Additives
    The anhydrous solid coloring composition according to the present invention may optionally further comprise one or more additives, different from the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric polymers or their mixtures, dandruff agents , antiseborrhoeic agents, hair loss and / or regrowth agents, vitamins and pro-vitamins including panthenol, sunscreens, mineral or organic pigments, sequestering agents, plasticizers, solubilizing agents, acidifying agents , mineral or organic thickening agents, in particular polymeric thickening agents, opacifying or pearlescent agents, antioxidants, hydroxy acids, perfumes, preservatives, pigments and ceramides.
    Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the anhydrous solid coloring composition according to the invention are not, or not substantially, affected by the or the additions envisaged.
    The above additives can generally be present in an amount for each of them between 0 and 20% by weight, relative to the total weight of the anhydrous solid coloring composition.
    Ready-to-use composition
    The present invention also relates to a ready-to-use composition comprising an anhydrous solid coloring composition, as defined above, and a cosmetically acceptable medium. In other words, the ready-to-use composition results from the mixture of an anhydrous solid coloring composition, as defined above, and a cosmetically acceptable medium.
    The total amount of the oxidation base (s) present in the ready-to-use composition according to the present invention preferably ranges from 0.05 to 30% by weight, and more preferably from 0.1 to 10% by weight. weight, relative to the total weight of the ready-to-use composition.
    The total amount of the chemical oxidizing agent (s), chosen from alkali metal percarbonates, alkaline earth metal percarbonates and their mixtures, present in the ready-to-use composition according to the invention, preferably ranges from 5 to 50 % by weight, and more preferably from 10 to 43% by weight, relative to the total weight of the ready-to-use composition.
    The total amount of the polymer or polymers comprising at least one vinyl heterocyclic monomer, present in the ready-to-use composition according to the invention, preferably ranges from 1 to 40% by weight, more preferably from 2.5 to 35% by weight. weight, and better still from 2.5 to 25% by weight, relative to the total weight of the ready-to-use composition.
    The total amount of the coupler (s), when they are present in the ready-to-use composition according to the invention, preferably ranges from 0.01 to 25% by weight, and more preferably from 0.1 to 20% by weight. weight, relative to the total weight of the ready-to-use composition.
    Cosmetically acceptable medium
    The term “cosmetically acceptable medium” means, according to the present application, a medium compatible with keratin fibers, in particular human keratin fibers, such as the hair.
    The cosmetically acceptable medium consists of water or a mixture of water and one or more organic solvents.
    Mention may be made, as organic solvent, of alkanols, linear or branched, of C 2 to C 4 , such as ethanol, isopropanol, tert-butanol or n-butanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
    Article packaging
    The present invention also relates to a packaging article comprising:
    i) an envelope defining at least one cavity, the envelope comprising water-soluble and / or liposoluble fibers, preferably water-soluble fibers; and ii) an anhydrous solid coloring composition as defined above;
    it being understood that the anhydrous solid coloring composition is in one of the cavities defined by the envelope i).
    By “water-soluble” is meant soluble in water, in particular at a rate of at least 10 grams per liter of water, preferably at least 20 g / 1, better at least 50 g / 1, at a lower temperature. or equal to 35 ° C.
    By "liposoluble" is meant soluble in a liquid fatty substance as defined below, in particular at a rate of at least 10 grams per liter of liquid fatty substance in particular in a vegetable or mineral oil such as petrolatum, preferably at least 20 g / 1 in a liquid fatty substance, better still at least 50 g / 1 in a fatty substance, at a temperature less than or equal to 35 ° C.
    The term "temperature less than or equal to 35 ° C." means a temperature not exceeding 35 ° C. but greater than or equal to 0 ° C., for example ranging from more than 1 to 35 ° C., better still from 5 to 30 ° C. and even better from 10 to 30 ° C or 10 to 20 ° C. It is understood that all the temperatures are given at atmospheric pressure
    The packaging article according to the invention is preferably water-soluble or liposoluble at a temperature less than or equal to 35 ° C.
    The packaging article may include one or more cavities, at least one of which contains the anhydrous solid coloring composition as defined above.
    The packaging article preferably comprises a single cavity.
    The envelope may consist of a sheet made of water-soluble and / or liposoluble fibers, folded back on itself or of a first sheet made of water-soluble and / or fat-soluble fibers and covered by a second sheet also made of water-soluble fibers and / or fat-soluble. The ply folded back on itself or the two plies are then hermetically assembled so that the anhydrous solid coloring composition according to the present invention cannot diffuse outside. The anhydrous solid coloring composition is thus enveloped by the envelope i) hermetically. The anhydrous solid coloring composition is distinct from the sheet or the envelope.
    Such an envelope is different from thin water-soluble or liposoluble films in which the anhydrous solid coloring composition would be incorporated into the layer or layers forming the envelope. Compared with these thin water-soluble or liposoluble films, the envelope according to the invention has the advantage of allowing the incorporation of constituents incompatible with it, of being simpler to use because it does not require premixing, neither dissolving the constituents in a solvent, nor heating to evaporate the solvent. The method of manufacturing the packaging article of the invention is also faster and less expensive than the method of manufacturing thin films.
    Furthermore, when the active agents, here in particular the oxidation bases and the couplers, are used in dispersion to form a thin film, this can cause compatibility problems, mechanical problems (film rupture) and impose limits on concentration of active ingredients. In addition, the envelope and the plies useful for the invention have the advantage of allowing greater diversity in the choice of the shape and the appearance of the article because the water-soluble and / or liposoluble sheet (s) can have a variable thickness and density giving access to a wide variety of shapes and sizes, while the thin film is difficult to dry if the thickness is too large, and it is fragile and difficult to handle if the size is too large .
    Advantageously, the envelope or the plies are "deformable to the touch", that is to say in particular that the envelope and the plies deform when they are grasped and pinched between the fingers of a user.
    Preferably, the anhydrous solid coloring composition is present in a cavity generated by at least two plies constituting the envelope and defining between them a cavity, said plies preferably comprising water-soluble fibers.
    According to a particular embodiment of the invention, at least one of the plies of the packaging article consists exclusively of water-soluble fibers, more preferably all the plies of the packaging article of the invention consist exclusively of water-soluble fibers , preferably at a temperature less than or equal to 30 ° C.
    By "fiber" is meant any object whose length is greater than its section. In other words, it is necessary to understand an object of length L and of diameter D such that L is greater and preferably much greater (ie at least 3 times more) than D, D being the diameter of the circle in which is inscribed the fiber section. In particular, the L / D ratio (or form factor) is chosen from the range going from 3.5 to 2500, preferably from 5 to 500, and better still from 5 to 150. The section of a fiber can be any shape, round, serrated or grooved, or even bean-shaped, but also multilobed, in particular trilobed or pentalobate, X-shaped, ribbon, square, triangular, elliptical, or other. The fibers of the invention can be hollow or non-hollow. The fibers used according to the present invention can be of natural, synthetic or even artificial origin. Advantageously, said fibers are of synthetic origin.
    A "natural fiber" is by definition a fiber naturally present in nature, directly or after mechanical and / or physical treatment. This category includes animal fibers such as cellulose fibers, especially extracted from wood, vegetables or algae, from rayon.
    "Artificial fibers" are either completely synthetic or derived from natural fibers which have been subjected to one or more chemical treatments in order to improve in particular the mechanical and / or physico-chemical properties.
    “Synthetic fibers” group together the fibers obtained by chemical synthesis and are generally fibers made up of one or more polymers and / or copolymers, mono- or multi-component, composite or not, which are generally extruded and / or drawn up to 'to the desired fiber diameter.
    Preferably, the fibers of the invention consist of one or more water-soluble polymers.
    The water-soluble polymer (s) of the invention contain water-soluble units in their backbones. The water-soluble units are obtained from one or more water-soluble monomers.
    By "water-soluble monomer" is meant a monomer whose solubility in water is greater than or equal to 1%, preferably greater than or equal to 5% at 25 ° C and at atmospheric pressure (760 mm Hg).
    The said synthetic water-soluble polymer (s) used in the context of the present invention are advantageously obtained from water-soluble monomers comprising at least one double bond. The latter can be chosen from cationic, anionic, nonionic monomers and mixtures thereof.
    As water-soluble monomers capable of being used as precursors of water-soluble units, alone or as a mixture, there may be mentioned by way of examples, the following monomers which can be in free or salified form:
    - (meth) acrylic acid,
    - styrene sulfonic acid,
    - vinylsulfonic acid and (meth) allylsulfonic acid,
    - vinyl phosphonic acid,
    - N-vinylacetamide and N-methyl N-vinylacetamide,
    - N-vinylformamide and N-methyl N-vinylformamide,
    N-vinyllactams comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, Nbutyrolactam and N-vinylcaprolactam,
    - maleic anhydride,
    - itaconic acid,
    - vinyl alcohol of formula CH2 = CHOH,
    the vinyl ethers of formula CH2 = CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons,
    - dimethyldiallyl ammonium halides (chloride), quaternized dimethylaminoethyl methacrylate (MADAME), (meth) acrylamidopropyltrimethylammonium halides (chloride) (APTAC and MAPTAC),
    - methylvinylimidazolium halides (chloride),
    - 2-vinylpyridine and 4-vinylpyridine,
    - acrylonitrile,
    - glycidyl (meth) acrylate,
    - vinyl halides (chloride) and vinylidene chloride,
    - the vinyl monomers of formula (V) below:
    H 2 C = C (R) -C (O) -X (V) in which,
    - R is chosen from H, (Ci-C6) alkyl such as methyl, ethyl and propyl;
    - X is chosen from:
    - alkoxy type -OR 'where R' is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, optionally substituted by at least one halogen atom (iodine, bromine, chlorine, fluorine) ; a sulfonic group (-SO3-), sulfate (SO4-), phosphate (PO4H2); hydroxy (-OH); primary amine (-NH2); secondary (NHRô), tertiary (-NR6R7) or quaternary (-N + RôR7Rs) amine with Rô, R7 and Rs being, independently of one another, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ Rô + R7 + Rs does not exceed 6;
    - the groups -NH 2 , -NHR 'and -NR'R in which R' and R are, independently of one another, hydrocarbon radicals, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms, under provided that the total number of carbon atoms of R '+ R does not exceed 6, said R' and R being optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (OH); sulfonic (-SO3-); sulfate (SO4); phosphate (-PO4H2); primary amine (-NH2); secondary (-NHR6), tertiary (NR6R7) and / or quaternary (-N + R6R7Rs) amine with R6, R7 and Rs being, independently of one another, a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ R ”+ Rô + R7 + Rs does not exceed 6. As compounds corresponding to this formula, mention may be made, for example, of Ν, Ν- dimethylacrylamide, and Ν, Ν-diethylacrylamide; and
    - their mixtures.
    Mention may in particular be made, as anionic monomers, of (meth) acrylic acid, 2-methylamethylpropanesulfonic acid, itaconic acid and their alkali metal, alkaline earth or ammonium salts or those derived from an organic amine such as alkanolamine.
    As non-ionic monomers, mention may in particular be made of (meth) acrylamide, N-vinylformamide, Nvinylacetoamide and hydroxypropyl (meth) acrylate, vinyl alcohol of formula CH2 = CHOH ,.
    The cationic monomers are preferably chosen from quaternary ammonium salts derived from a diallylamine, and those corresponding to the following formula (VI):
    H 2 C = C (Ri) -D-N + R 2 R3R4, X (VI) in which, • Ri represents a hydrogen atom or a methyl group, • R 2 and R3, identical or different, represent an atom of hydrogen or a linear or branched C1-C4 alkyl group, • R4 represents a hydrogen atom, a linear or branched C1-C4 alkyl group or an aryl group, • D represents the following divalent unit: - (Y ) n - (A) - in which:
    Y represents an amide function, an ester (O-C (O) or C (O) -O), a urethane or a urea,
    - A represents a linear or branched, cyclic or acyclic C1 to C10 alkylene group, which may be substituted or interrupted by a divalent aromatic or heteroaromatic group. The alkylene groups can be interrupted by an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom; the alkylene which can be interrupted by a ketone function, an amide, an ester (O-C (O) or C (O) -O), a urethane, or a urea,
    - n is an integer varying from 0 to 1, • X represents an anionic counter ion, such as for example a chloride or a sulfate.
    As examples of water-soluble cationic monomers, mention may be made in particular of the following compounds and their salts: (meth) acrylate of dimethylaminoethyl, of (meth) acryloyloxyethyltrimethylammonium, of (meth) acryloyloxyethyldimethylbenzyl-ammonium, of N- [dimethylaminopropyl] ( meth) acrylamide, of (meth) acryl-amidopropyltrimethylammonium, of (meth) acrylamido-propyldimethylbenzylammonium, of (meth) acrylate of dimethylaminohydroxypropryl, of (meth) acryloyloxyhydroxypropyl-trimethylammonium, of (meth) acryloyloxyhydroxyethylammyl dimethyl.
    Preferably, the polymer useful according to the invention is polymerized from at least one cationic monomer as defined above.
    Preferably, the polymers are polymerized from monomers comprising at least one of the following double bonds:
    - 0 to 30% by mole of acrylic acid,
    - 0 to 95.5% by moles of acrylamide and,
    - 0.5 to 100 mol% of at least one cationic monomer represented in formula (VI) as defined above.
    As polymers which are particularly preferred in the invention, mention may in particular be made of those polymerized from:
    - 10% of acryloyloxyethyldimethylbenzylammonium chloride and 90% of acrylamide,
    - 30% of acryloyloxytrimethylammonium chloride, 50% of acryloyloxyethyldimethylbenzylammonium chloride, and 20% of acrylamide,
    - 10% of acryloyloxyethyltrimethylammonium chloride and 90% of acrylamide,
    30% diallyldimethylammonium chloride and 70% acrylamide, or
    - 30% acrylic acid and 70% acrylamide.
    According to a particular embodiment, the polymers are polymerized from a cationic monomer and acrylic acid, the number of moles of the cationic monomer being greater than the number of moles of acrylic acid.
    As water-soluble polymers obtained from natural products, mention may be made of polysaccharides, i.e. polymers with sugar units.
    By “sugar unit” is meant a unit derived from a carbohydrate of formula C n (H2O) n -i or (CH2O) n which can be optionally modified by substitution and / or by oxidation and / or by dehydration. The sugar units capable of entering into the composition of the polymers of the invention preferably come from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, fructose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid , galactose sulfate, anhydrogalactose sulfate.
    The polymers containing sugar unit (s) according to the invention can be of natural or synthetic origin. They can be non-ionic, anionic, amphoteric or cationic. The basic units of the sugar-based polymers of the invention can be mono- or disaccharides.
    Mention may in particular be made, as polymers capable of being used, of the following native gums, as well as their derivatives:
    a) exudates from trees or shrubs of which:
    - gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);
    - ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);
    - karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);
    tragacanth (or tragacanth) gum (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
    b) gums derived from algae, of which:
    - agar (polymer derived from galactose and anhydrogalactose);
    alginates (polymers of mannuronic acid and glucuronic acid);
    - carrageenans and furcelleranes (polymers of galactose sulfate and anhydrogalactose sulfate);
    c) gums from seeds or tubers of which:
    - guar gum (polymer of mannose and galactose);
    - carob gum (polymer of mannose and galactose);
    - fenugreek gum (polymer of mannose and galactose);
    - tamarind gum (polymer of galactose, xylose and glucose);
    - Konjac gum (glucose polymer and mannose) whose main constituent is glucomannan is a high molecular weight polysaccharide (500,000 <Mglucomannan <2,000,000) composed of units of D-mannose and D-glucose with one branching every 50 or 60 units approximately;
    d) microbial gums, of which:
    - xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid and glucuronic acid);
    - gellan gum (partially acylated glucose polymer, rhamnose and glucuronic acid);
    - scleroglucan gum (glucose polymer);
    - gum of biosaccharides (polymer of galacturonic acid, of fucose and of D-galactose) for example that marketed under the name of FUCOGEL 1.5P of SOLABIA (POLYSACCHARIDE RICH IN FUCOSE (20%) AT 1.1% IN STABILIZED WATER (PHENOXYETHANOL 1.5%)),
    e) plant extracts including:
    - cellulose (glucose polymer);
    - starch (glucose polymer);
    - inulin (polymer of fructose and glucose).
    These polymers can be modified physically or chemically. By way of physical treatment, mention may especially be made of temperature. As chemical treatments, mention may be made of esterification, etherification, amidation and oxidation reactions. These treatments make it possible to lead to polymers which can be nonionic, anionic, cationic or amphoteric.
    Preferably, these chemical or physical treatments are applied to guar gums, carob gums, starches and celluloses.
    The nonionic guar gums which can be used according to the invention can be modified by C 1 to C 6 hydroxylakyl groups. Among the hydroxyalkyl groups, mention may be made of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
    These guar gums are well known in the state of the art and can for example be prepared by reacting oxides of corresponding alkenes such as for example propylene oxides with guar gum, so as to obtain a gum of guar modified by hydroxypropyl groups.
    The rate of hydroxyalkylation preferably varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on guar gum.
    Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.
    Guar gums modified with cationic groups which can more particularly be used according to the invention are guar gums comprising cationic trialkylammonium groups. Preferably, 2 to 30% by number of the hydroxyl functions of these guar gums carry cationic trialkyammonium groups. Even more preferably, 5 to 20% of the number of hydroxyl functions of these guar gums are connected by cationic trialkyammonium groups. Among these trialkylammonium groups, mention may very particularly be made of trimethylammonium and triethylammonium groups. Even more preferably, these groups represent from 5 to 20% by weight relative to the total weight of the modified guar gum.
    According to the invention, guar gums modified with 2,3-epoxypropyl trimethylammonium chloride can be used.
    These guar gums modified by cationic groups are products already known in themselves and are for example described in US Pat. Nos. 3,589,578 and US Pat. No. 4,013,307. Such products are also sold in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company RHODIA CHIMIE.
    As modified locust bean gum, cationic locust bean gum containing hydroxypropyltrimmonium groups such as Catinal CLB 200 offered by the company TOHO can be used.
    The starch molecules used in the present invention can originate from all vegetable sources of starch, in particular cereals and tubers; more particularly it can be starches of corn, rice, cassava, barley, potato, wheat, sorghum, peas, oats, tapioca. It is also possible to use the hydrolysates of the starches mentioned above. The starch is preferably obtained from the potato.
    The starches can be modified chemically or physically, in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.
    More particularly, these reactions can be carried out as follows:
    - pregelatinization by bursting the starch granules (for example drying and cooking in a drying drum);
    - oxidation by strong oxidants leading to the introduction of carboxyl groups in the starch molecule and to the depolymerization of the starch molecule (for example by treating an aqueous solution of starch with sodium hypochlorite);
    - crosslinking by functional agents capable of reacting with the hydroxyl groups of the starch molecules which will thus be linked together (for example with glyceryl and / or phosphate groups);
    - esterification in an alkaline medium for the grafting of functional groups, in particular acyl in C 1 -C 6 (acetyl), hydroxyalkyl in C 1 -C 6 (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.
    It is possible in particular to obtain, by crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-0-P0- (0X) 2 type), diamidon phosphates (of the Am-O-PO- (OX) -O-Am type) or even triamidon (of the Am-0-P0- (0-Am) 2 type) or mixtures thereof; with Am meaning starch and X designating in particular the alkali metals (for example sodium or potassium), the alkaline earth metals (for example calcium, magnesium), the ammonia salts, the salts of amines such as those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1,2-propanediol, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline.
    The phosphorus compounds can be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.
    Diamidon phosphates or compounds rich in diamidon phosphate will preferably be used, such as the product proposed under the references PREJEL VA-70-T AGGL (phosphate of hydroxypropylated cassava gelatinized) or PREJEL TK1 (phosphate of diamidon of cassava gelatinized) or PREJEL 200 (acetylated cassava diamidon phosphate gelatinized) by the company AVEBE or NATIONAL STARCH STRUCTURE ZEA (diamatin phosphate cornified gelatinized).
    A preferred starch is a starch which has undergone at least one chemical modification such as at least one esterification.
    According to the invention, amphoteric starches can also be used, comprising one or more anionic groups and one or more cationic groups. The anionic and cationic groups can be linked to the same reactive site of the starch molecule or to different reactive sites; preferably they are linked to the same reactive site. The anionic groups can be of the carboxylic, phosphate or sulphate type, and preferably carboxylic. The cationic groups can be of primary, secondary, tertiary or quaternary amine type.
    The amphoteric starches are especially chosen from the compounds of the following formulas:
    R 'R
    COOM
    St-O- (CH 2 ) n -N
    C C - COOM / H H
    I H
    HC - C - COOM H H C-C - COOM
    St-O- (CH 2 ) n -N (U)
    R '
    O R 'R
    R '
    St-O-C - C - COOM
    St-O-C - C - COOM (iv) in which:
    • St-0 represents a starch molecule;
    • R, identical or different, represents a hydrogen atom or a methyl radical;
    • R ', identical or different, represents a hydrogen atom, a methyl radical or a group -C (O) -OH;
    • n is an integer equal to 2 or 3;
    • M, identical or different, denotes a hydrogen atom, an alkali or alkaline earth metal such as Na, K, Li, a quaternary ammonium NH4, or an organic amine;
    • R represents a hydrogen atom or a C1 to C8 alkyl radical.
    These compounds are described in particular in US5455340 and US4017460.
    The starches of formulas (II) or (III) are used in particular; and preferably starches modified with 2chloroethylaminodipropionic acid, that is to say starches of formula (II) or (III) in which R, R ', R and M represent a hydrogen atom and n is equal to 2. The preferred amphoteric starch is a starch chloroethylamido dipropionate.
    Celluloses and cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.
    Among these derivatives, a distinction is made between cellulose ethers, cellulose esters and cellulose ether esters.
    Among the cellulose esters, mention may be made of inorganic cellulose esters (cellulose nitrates, sulfates or phosphates), organic cellulose esters (monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates of cellulose) and organic / mixed esters / inorganic cellulose such as acetate butyratesulfates and cellulose acetate propionatesulfates.
    Among the cellulose ester ethers, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulfates.
    Among the nonionic cellulose ethers, mention may be made of alkylcelluloses such as methylcelluloses and ethylcelluloses (for example the standard Ethocel 100 Premium from DOW CHEMICAL); hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR proposed by AQUALON) and hydroxypropylcelluloses (for example Klucel EF from AQUALON); hydroxyalkyl-alkylcellulose mixed celluloses such as hydroxypropyl-methylcelluloses (for example Methocel E4M from DOW CHEMICAL), hydroxyethyl-methylcelluloses, hydroxyethyl-ethylcelluloses (for example Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl-methylcelluloses.
    Among the anionic cellulose ethers, mention may be made of carboxyalkylcelluloses and their salts. As an example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses, as well as their sodium salts.
    Among the cationic cellulose ethers, mention may be made of cross-linked or non-crosslinked quaternized hydroxyethylcelluloses. The quaternizing agent can in particular be diallyldimethylammonium chloride (for example Celquat L200 from NATIONAL STARCH). As another cationic cellulose ether, mention may be made of hydroxyethyl cellulose hydroxypropyltrimethylammonium (for example Ucare polymer JR 400 from AMERCHOL).
    Among the associative polymers with sugar unit (s), mention may be made of celluloses or their derivatives, modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups or their mixtures where the alkyl groups are C8-C22; nonionic alkylhydroxyethylcelluloses such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (C 1 alkyl) sold by the company AQUALON; quaternized (cationic) alkyl hydroxyethylcelluloses such as QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18-B (C12 alkyl) and QUATRISOFT LMX 529-8 (Cis alkyl) sold by the company AMERCHOL, the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (Cis alkyl) sold by the company CRODA and the product SOFTCAT SL 100 sold by the company AMERCHOL; nonionic nonoxynylhydroxyethylcelluloses such as the product Amercell HM-1500 sold by the company Amerchol; non-ionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL.
    As polymers containing sugar unit (s) derived from associative guar, mention may be made of hydroxypropylguars modified by a fatty chain such as the product ESAFLOR HM 22 (modified by a C22 alkyl chain) sold by the company LAMBERTI; the product MIRACARE XC 95-3 (modified by a C14 alkyl chain) and the product RE 205-146 (modified by a C20 alkyl chain) sold by RHODIA CHIMIE.
    The polymer or polymers containing sugar unit (s) of the invention are preferably chosen from guar gums, locust bean gums, xanthan gums, starches and celluloses, in their modified form (derivatives) or not modified.
    Preferably, the polymers containing sugar unit (s) according to the invention are nonionic.
    More preferably, the polymer (s) with sugar unit (s) of the invention are chosen from non-ionic guar gums modified, in particular modified by C 1 to C 6 hydroxyalkyl groups.
    The polymers described above have more particularly a molecular weight by weight greater than 1,000,000 and preferably between 1,000,000 and 50,000,000. The molecular weight is determined by the RSV (Reduced Specifies Viscocity) method as defined in Principles of Polymer Chemistry Cornell University Press, Ithaca, NY 1953 Chapter VII Determination of molecular Weight pp 266316.
    The fibers can be spun, carded or twisted. Advantageously, the fibers used in the context of the present invention are spun. The average diameter of the fibers used according to the present invention, identical or different, is less than 500 μm. Advantageously, such a diameter is less than 200 μm, preferably less than 100 μm, or even less than 50 μm.
    Mention may more particularly be made of water-soluble fibers which include fibers based on Poly VinylAlcohol, fibers of polysaccharides such as glucomannans, starches, celluloses, such as carboxymethylcelluloses, fibers of polyalginic acid, fibers of polylactic acid. , and polyalkyleneoxide fibers, as well as their mixtures. More preferably, the water-soluble fiber or fibers used in the invention are chosen from PVA-based fibers.
    The fibers of the envelope or of the sheets are generally entangled. As indicated above, the term “envelope or web comprising water-soluble fibers” means an envelope or webs which may consist entirely of water-soluble fibers or a web which may comprise both fibers soluble in water. water and water-insoluble fibers at a temperature less than or equal to 35 ° C., the soluble fibers must be in greater quantity than the insoluble fibers. The sheet of fibers must comprise at least 60% by weight of soluble fibers, preferably at least 70% by weight and better still at least 80% by weight relative to the total weight of the fibers. It can thus include, for example, more than
    95% by weight, or even more than 99% by weight and even 100% by weight of water-soluble fibers relative to the total weight of the fibers of the envelope or the layers.
    When the sheet of fibers contains insoluble fibers, these can be of any material usually used as insoluble fibers; it may for example be fibers of silk, cotton, wool, linen, polyamide (Nylon®), polylactic acid, modified cellulose (rayon, viscose, rayon acetate), poly-phenylene terephthalamide, in particular Kevlar®, polyolefin and especially polyethylene or polypropylene, glass, silica, aramid, carbon, especially in graphite form, Teflon®, insoluble collagen, polyesters, polyvinyl chloride or vinylidene, polyethylene terephthalate, fibers formed from a mixture of the above mentioned compounds, such as polyamide / polyester or viscose / polyester fibers.
    In addition, the envelope and the plies of the invention can be woven or non-woven.
    According to a particular embodiment, the envelope and the plies of the invention are woven. In the context of the present invention, a “woven” material results from an organized assembly of fibers, in particular polymeric water-soluble fibers, and more particularly from an interweaving, in the same plane, of said fibers, arranged in the direction of the warp and fibers arranged, perpendicular to the warp fibers, in the weft direction. The bond obtained between these warp and weft fibers is defined by a weave.
    Such a woven material results from an operation aimed at assembling the fibers in an organized manner such as weaving itself, but can also result from knitting.
    More particularly, the two layers or layers comprising the woven polymeric water-soluble fibers which constitute the envelope of the packaging article of the invention do not comprise any other additional layer which is superimposed on them.
    According to another particularly advantageous embodiment of the invention, the envelope and the plies are nonwoven.
    For the purposes of the present invention, the term “nonwoven” means a substrate comprising fibers, in particular polymeric water-soluble fibers, in which the individual fibers are arranged in a disordered manner in a sheet-like structure and which are neither woven, neither knitted. The fibers of the nonwoven are generally bonded together, either under the effect of a mechanical action (for example needling, air jet, water jet, etc.), or under the effect of a thermal action. , or by adding a binder.
    Such a nonwoven is, for example, defined by standard ISO 9092 as a veil or a sheet of fibers oriented directionally or at random, bonded by friction and / or cohesion and / or adhesion, excluding paper and products obtained by weaving, knitting, tufting or sewing incorporating threads or tying filaments.
    A nonwoven differs from paper in the length of the fibers used. In paper, the fibers are shorter. However, there are nonwovens based on cellulosic fiber which are manufactured by the wet process and have short fibers as in paper. The difference between a nonwoven and a paper is usually the lack of hydrogen bonding between the fibers in a nonwoven.
    Very preferably, the fibers used in the context of the present invention are chosen from synthetic fibers such as PVA fibers. In particular, the envelope and plies of the invention are nonwoven, and preferably made of nonwoven PVA fibers.
    To make the non-woven water-soluble layer (s) of the envelope of the packaging article, preferably water-soluble PVA fibers are used at a temperature less than or equal to 35 ° C., such as, for example, the fibers sold. by the Japanese company Kuraray under the name KURALON K-II, and in particular the grade WN2 soluble from 20 ° C. These fibers are described in document EP-A-636716 which teaches the manufacture of PVA fibers soluble in water at temperatures not exceeding 100 ° C., by spinning and stretching the polymer of polyvinyl alcohol in the dry state. or wet in the presence of solvents involved in the solubilization and solidification of the fiber. The fiber thus obtained can lead to the production of woven or non-woven substrates. According to a particular embodiment of the invention, the PVA fibers of the examples of EP-A-636716 are used, in particular Example 2 and Comparative 1: commercial product SOLVRON SS.
    These fibers can also be prepared from a spinning solution, by dissolving a water-soluble PVA-based polymer in a first organic solvent, spinning the solution in a second organic solvent to obtain solidified filaments and the wet drawing of the filaments from which the first solvent is removed, then dried and subjected to a heat treatment. The section of these fibers can be substantially circular. These fibers have a tensile strength of at least 2.7 g / dtex (3 g / d). Application EP-A-0 636 716 describes such water-soluble fibers based on PVA and their manufacturing process. For example, the fibers can also be formed by extrusion and deposited on a conveyor to form a sheet of fibers which is then consolidated by a conventional technique of fiber bonding, such as for example needling, hot bonding, calendering. or the binding by jets of hot air (in English air through bonding), technique in which the water-soluble layer passes in a tunnel where is blown hot air, or hydroliage aiming to bind the fibers under the action of fine jets of water under very high pressure, which cannot be applied to fibers whose dissolution temperature is too low pressure.
    As we have seen above, the invention is not limited to the use of PVA, and fibers made of other water-soluble materials can also be used, provided that these materials dissolve in water having the desired temperature, for example fibers of polysaccharides sold under the name LYSORB by the company LYSAC TECHNOLOGIES, INC or other fibers based on polysaccharide polymers such as glucomannans or starch.
    The layers of the envelope may comprise a mixture of different fibers which are soluble in water at different temperatures (up to 35 ° C).
    The fibers can be composite, and they can comprise, for example, a core and a sheath not having the same nature, for example formed from different grades of PVA.
    According to a particular embodiment of the invention, the ply (s) of the envelope have a nonwoven, comprising water-soluble fibers, alone or as a mixture with insoluble fibers as indicated above, with at most 40% in weight of insoluble fibers relative to the total weight of the fibers constituting the sheet. Preferably, the nonwoven consists essentially of water-soluble fibers, that is to say that it does not contain insoluble fibers.
    The envelope may have any shape suitable for the intended use, for example a rectangular, round or oval shape, and it preferably has dimensions allowing it to be grasped between at least two fingers. Thus, the envelope or the tablecloths may have for example an ovoid shape of about 2 to 10 cm long and about 0.5 to 4 cm wide, or a circular disc shape of about 2 to 10 cm in diameter, or a square shape of about 5 to 15 cm on a side, or a rectangle shape of a length of about 5 to 25 cm, it being understood that it can have any other shape and dimension suitable for the 'intended use.
    Advantageously, the envelope and the plies have a small thickness, the plies being able to consist of several layers. Preferably the thickness of the envelope and the plies ranges from 3 to 99.9% of its other dimensions. This thickness is notably less than 100 mm. The envelope and the layers are thus substantially flat, thin slices.
    The surface delimiting the cavity or cavities has an extent generally less than 625 cm 2 , and for example between 400 cm 2 and 0.025 cm 2 .
    One can for example use an envelope and tablecloths as defined in the French patent application n ° 1 261 120 filed on November 22, 2012.
    The packaging article according to the present invention may comprise one or more plies and water-soluble nonwoven envelope.
    Preferably, the quantity of the envelope present in the packaging article according to the invention is between 0.5 and 20% by weight relative to the total weight of said article; advantageously between 1.0 and 10% by weight, particularly between 2 and 5% by weight; more particularly 3% by weight relative to the total weight of the packaging article.
    The packaging article which may contain the composition according to the invention can be illustrated by the figures la) -le).
    FIG. 1 a) represents a cross section of a particular embodiment of the packaging article comprising the envelope i) constituted by two sheets, preferably water-soluble, 11 and 12 joined together at a peripheral region 14 .
    Preferably the two plies are joined by any suitable fixing means, preferably bonding, welding, in particular heat sealing, in particular by entanglement.
    The first ply 11 also has a free central region D arranged opposite a free central region D of the second ply 12. These two central regions define a central cavity, said cavity contains an anhydrous solid coloring composition as defined above 13 .
    The layers 11 and 12 have a closed outer periphery 15. The shape of the outer periphery 15 is rounded, preferably circular or elliptical, or polygonal, preferably square, rectangular, triangular, and more preferably circular.
    FIG. 1b) represents a top view of the packaging article as described in FIG. la) in which the part D corresponds to the cavity or “central region” in which the anhydrous solid coloring composition 13 is found, and d corresponds to the peripheral region which joins the two layers 11 and 12 in a hermetic manner.
    Figure le) shows a cross section of a particular embodiment of the packaging article comprising an envelope consisting of two plies 11 and 12 preferably water-soluble, and comprising an additional ply 16 preferably water-soluble, and possibly other additional plies 17, preferably water-soluble, which define several cavities in which the ingredients are housed, such as the anhydrous solid coloring composition 13, as defined above, one or more additional chemical oxidizing agents different from the chemical oxidizing agents (b), as defined previously, and / or one or more additives, as defined above, 19, and / or one or more additives different from those introduced into the other cavities 20, as defined above.
    The first ply 11 has a thickness less than its other dimensions, for example less than 10% of its maximum transverse dimension D + 2d.
    The thickness of the first ply 11 is for example less than 10 mm and in particular between 0.1 mm and 3 mm. Its maximum transverse dimension D + d is for example less than 100 mm, and is in particular inclusive between 10 mm and 60 mm.
    The first ply 11 thus forms a layer, for example of nonwoven itself, which may consist of several layers of nonwovens consolidated together.
    The second ply 12 also has a closed outer periphery 15. The outer periphery 15 of the first ply 11 is of identical shape to the outer periphery 15 of the second ply 12.
    The second ply 12 has a thickness less than its other dimensions, for example less than 10% of its maximum transverse dimension D + 2d.
    The thickness of the second ply 12, preferably water-soluble, is for example less than 10 mm and in particular between 0.1 mm and 3 mm. Its maximum transverse dimension D + 2d is less than 100 mm, and is in particular between 10 mm and 60 mm.
    The thickness is advantageously measured according to standard EDANA WSP 120.1 (5).
    The second ply 12 is advantageously a nonwoven.
    The first ply 11 and the second ply 12, which may be identical or of different thicknesses, densities and / or compositions, are preferably water-soluble nonwovens at a temperature less than or equal to 35 ° C. The nonwoven webs and envelope are soluble in an aqueous solution, such as water. The non-woven cover and tablecloths are preferably made of PVA.
    As a variant, the second ply can be formed by the first ply folded back on itself 11 ′ represented by FIG. 1d) in cross section and in figure le) seen from above. The sheet is folded back on itself along the folding axis which defines a cavity in which the anhydrous solid coloring composition 13 'is located, and optionally one or more additional chemical oxidizing agents different from the chemical oxidizing agents (b), such as defined above, and / or one or more additives, as defined above, 19 ′, optionally separated by one or more plies 16 ′ water-soluble. The sheet 11 'once filled with the ingredients 19' and the water-soluble sheet or sheets 16 ', is folded along the axis e, forming a folding zone 15' then joined at a peripheral region 14, hatched part of fig. e), preferably by any suitable fixing means such as gluing, welding, in particular heat sealing, in particular by entanglement. The thickness of the water-soluble sheet 11 ′ and the transverse dimensions meet the same criteria as those defined for the sheet 11 or 12 of FIG. 1b).
    The fibers forming the first ply 11, or 11 ′ and the second ply 12, and the additional plies 16, 16 ’, and 17 are preferably water-soluble, i.e. made up of water-soluble fibers. These fibers are for example water-soluble nonwoven fibers, such as PVA fibers, polysaccharide fibers such as glucomannans or starches or any other polymer or compound capable of forming fibers or threads, obtained for example by extrusion, soluble in water.
    The plies 11, 11 'and 12 and the optional additional plies 16, 16' and 17, preferably of nonwoven fabric generally have a grammage less than or equal to 60 g / m 2 , or even less than or equal to 50 g / m 2 , even better less than or equal to 45 g / m 2 . As a variant, the grammage of at least one layer may be greater than 60 g / m 2 .
    The packaging articles comprising water-soluble fibers according to the invention are preferably soluble in water or in an aqueous composition with a dissolution time of the packaging article, preferably at most one hour.
    Method for preparing the packaging article
    The envelope i) delimits or defines a cavity which is filled with an anhydrous solid coloring composition, as defined above, the article is then closed by folding the envelope i) on itself with its content followed by a assembly at its periphery, for example by gluing or welding, preferably by heat-sealing, or else if the article contains an envelope consisting of two layers, the anhydrous solid coloring composition is deposited on the first layer ii) and optionally one or more chemical oxidizing agents additional, preferably anhydrous solids, different from the chemical oxidizing agents (b) and / or one or more additives iii), the article is closed using a second layer which covers the ingredients ii) and iii) deposited on the first ply and which is assembled for example by gluing or welding at its periphery, preferably by heat sealing at its periphery, so as to obtain an articl hermetic, which does not allow the ingredients ii) and iii) contained in said article to pass into the atmosphere.
    When the envelope and the layers comprise several water-soluble layers of nonwovens, these can be assembled in particular by heat-sealing at their periphery. Preferably the heat-sealing is carried out with entanglement of the fibers of the parts of the envelope to be welded.
    Coloring process
    The present invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    - Apply to said keratin fibers a ready-to-use composition as defined above, that is to say resulting from the mixture of an anhydrous solid coloring composition, as defined above, and a cosmetically acceptable medium
    - allow the ready-to-use composition to pause on said keratin fibers,
    - rinse said keratin fibers, and
    - optionally shampoo said keratin fibers, rinse and dry them.
    The present invention also relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    - mix a packaging article, as defined above, with a composition capable of dissolving the envelope of said packaging article,
    - applying the resulting composition to said keratin fibers,
    - allowing said resulting composition to pause on said keratin fibers,
    - rinse said keratin fibers, and
    - optionally shampoo said keratin fibers, rinse and dry them.
    It is understood that the composition capable of dissolving the envelope depends on the nature of the envelope. In other words, the composition capable of dissolving the envelope is water or an aqueous composition, when the packaging article contains mainly or only a hydrophilic envelope. And, the composition capable of dissolving the envelope is an organic anhydrous composition or an aqueous composition comprising at least one liquid fatty substance or at least one organic solvent different from liquid fatty substances such as lower monoalcohols, for example ethanol, or as polyols, for example propylene glycol or glycerin, when the packaging article mainly or only contains a lipophilic envelope.
    Thus, the aqueous composition can simply be water. The aqueous composition may optionally comprise at least one polar solvent. Among the polar solvents which can be used in this composition, mention may be made of organic compounds which are liquid at room temperature (25 ° C.) and at least partially miscible with water.
    By way of example, there may be mentioned more particularly the alkanols such as ethyl alcohol, isopropyl alcohol, aromatic alcohols such as benzyl alcohol, and phenylethyl alcohol, or also polyols or polyol ethers such as , for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, monoethyl ether or diethylene glycol monobutyl ether.
    More particularly, if one or more solvents are present, their respective content in the aqueous composition varies from 0.5 to 20% by weight, and preferably from 2 to 10% by weight, relative to the weight of said aqueous composition.
    The dilution ratio (expressed by weight) between one or more packaging articles, as defined above, and the composition capable of dissolving the packaging article or articles is preferably between 10/90 and 90/10, and more preferably between 10/90 and 50/50. Even better, this dilution ratio is 20/80.
    When the composition capable of dissolving the article is an aqueous solution of hydrogen peroxide, it preferably has a pH of less than 7. The acid pH guarantees the stability of the hydrogen peroxide in the composition. It can be obtained using acidifying agents such as for example hydrochloric acid, acetic acid, ethydronic acid, phosphoric acid, lactic acid or boric acid, and it can be conventionally adjusted by adding either basifying agents, such as, for example, ammonia, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 1,3-diamino-propane, an alkali (bi) carbonate or ammonium, an organic carbonate such as guanidine carbonate, or alternatively an alkali hydroxide, all these compounds can of course be taken alone or as a mixture.
    The pH of the ready-to-use composition resulting from the mixing of a packaging article, as defined above, with a composition capable of dissolving the envelope of the packaging article is preferably between 7 and 12, and more preferably between 7.5 and 11.
    In particular, the ready-to-use composition used in the coloring process according to the invention is applied to dry or wet keratin fibers.
    The ready-to-use composition is advantageously left to stand on the keratin fibers for a period ranging from 1 minute to 1 hour, and more preferably for a period ranging from 5 to 45 minutes.
    Then, the keratin fibers are rinsed with water. They can optionally be washed with shampoo, followed by rinsing with water, before being dried or left to dry.
    The temperature for implementing the coloring process according to the invention is preferably between room temperature (25 ° C) and 80 ° C, and more preferably between room temperature and 60 ° C.
    use
    The present invention also relates to the use of an anhydrous solid coloring composition, as defined above, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    The present invention also relates to the use of a packaging article, as defined above, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    The following examples serve to illustrate the invention without, however, being limiting in nature.
    EXAMPLES
    In the examples which follow, all the quantities are indicated in percentage by mass of active material relative to the total weight of the composition.
    A. Example 1
    I. Preparation of the compositions
    The coloring composition (A) according to the invention, and the following comparative coloring compositions (A1) and (A2), in the form of an anhydrous powder, were prepared from the ingredients, the contents of which are indicated in the tables below (% in g of active ingredient).
    ATinvention Alcomparative A2comparative Toluene-2,5-diamine sulfate 2 2 2 2,4-diaminophenoxyethanol, HCl 0.029 0.029 0.029 Resorcinol 1 1 1 m-aminophenol 0.2 0.2 0.2 Sodium percarbonate 42.2 42.2 42.2
    Ammonium sulfate 3.6 3.6 3.6 Hydroxypropylated starch phosphate 14.5 14.5 14.5 Sodium metabisulfite 0.4 0.4 0.4 Polyvinylpyrrolidone 17.4 - - Cyclodextrin - 17.4 - Sorbitol - - 17.4 Microcrystalline cellulose 17.7 17.7 17.7 Sodium lauryl sulfate 0.7 0.7 0.7
    II.Evaluation of the stability of the coloring compositions
    2.1. Protocol
    After one month of storage at 45 ° C., each of the compositions (A) to (A2) was mixed with water.
    Then, the stability of each of the compositions (A) to (A2) was evaluated by measuring the percentage of loss of H2O2 by titration of redox with potassium permanganate.
    2.2. Results
    The percentages of loss of H2O2 obtained for each of the compositions, according to the invention (A) and comparative (Al) and (A2), are indicated in the table below.
    ATinvention Alcomparative A2comparative % loss of H2O2 4% 21% 100%
    The results obtained above show that the coloring composition (A), prepared according to the present invention, ie comprising a polymer comprising at least one vinyl heterocyclic monomer (polyvinylpyrrolidone), is more stable over time than the comparative compositions (A1) and (A2) comprising other excipients.
    Indeed, after one month of storage at 45 ° C, only 4% loss of H2O2 is measured in the composition according to the invention. Conversely, the comparative compositions (Al) and (A2) comprising another excipent than polyvinylpyrrolidone lost 21% and 100% of H 2 O 2 respectively .
    III. Dye evaluation of coloring compositions
    3.1. Protocol
    Each of the compositions (A) to (A2) obtained previously, was mixed with water in order to obtain the respective ready-to-use compositions (A) to (A2), in the following proportions:
    - 27.2 g of composition, and
    - qs 100g of water.
    The ready-to-use compositions thus obtained were then applied to locks of 90% white hair, in a bath ratio equal to 5: 1. After a 30-minute break at 27 ° C (thermostatically controlled plate), the locks of hair were rinsed, shampooed and then dried.
    The same protocol was applied from coloring compositions (A) to (A2) stored for 1 month at 45 ° C.
    The color measurements of each of the ready-to-use compositions were evaluated in the CIE L * a * b * system using a MINOLTA CM-3600D spectro-colorimeter.
    In this system L * a * b *, L * represents the intensity of the color, a * indicates Tax of color green / red and b * Tax of color blue / yellow.
    The value of ΔΕ * was calculated from the values of L * a * b * according to the following equation:
    AE * = - ^ (L * -L 0 *) 2 + (a * -a0 *) 2 + (b * -b0 *) 2
    The increase in coloration (ΔΕ *) was calculated on the strands of non-colored hair (Lo *, ao * and bo *) and on the strands of colored hair (L *, a * and b *). The larger the value of ΔΕ *, the better the color rise.
    Then, the stability of the dye performances (diffAE), that is to say the evolution of the dye performances, of the compositions (A) to (A2) was calculated by comparing the increase in the coloration obtained from fresh coloring compositions, ie applied directly after their preparation, (ΔΕ (ΐο)), with the increase in coloration obtained from coloring compositions stored for 1 month at 45 ° C (ΔΕ (timois)) according to the following equation:
    diffAE = (ΔΕ (to)) - (ΔΕ (timois))
    The higher the value of diffAE, the more the dye performance of the coloring composition has been degraded.
    3.2. Results
    The diffAE values obtained for each of the coloring compositions according to the invention (A) and comparative (Al) and (A2) are indicated in the table below.
    ATinvention Alcomparative A2comparative diff ΔΕ 3.5 5.2 15.0
    The results obtained above show that the dyeing properties of the coloring composition (A), prepared according to the present invention, ie comprising a polymer comprising at least one vinyl heterocyclic monomer (polyvinylpyrrolidone), remain more stable over time than the dyeing properties. provided by the comparative compositions (A1) and (A2) each comprising a different excipient than polyvinylpyrrolidone.
    Even after one month of storage at 45 ° C., the composition according to the invention retains its coloring properties, unlike the comparative compositions.
    B. Example 2
    I. Preparation of the compositions
    The coloring composition (B) according to the invention, and the following comparative coloring compositions (B1) to (B3), in the form of an anhydrous powder, were prepared from the ingredients, the contents of which are indicated in the tables below (% in g of active ingredient).
    Binvention Blcomparative B2comparative B3comparative Toluene-2,5-diaminesulfate 3.53 3.53 3.53 3.53 2,4-diaminophenoxyethanol, HCl 0.12 0.12 0.12 0.12 Resorcinol 1.69 1.69 1.69 1.69 m-aminophenol 0.34 0.34 0.34 0.34 Percarbonate ofsodium 44.89 44.89 44.89 44.89 Ammonium sulfate 3.68 3.68 3.68 3.68 Hydroxypropylated starch phosphate 14.71 14.71 14.71 14.71 Metabisulfitesodium 1.47 1.47 1.47 1.47 Polyvinylpyrrolidone 29.58 - - - Talc - 29.58 - - Cyclodextrin - - 29.58 -
    Sodium sulfate - - - 29.58
    II.Evaluation of the stability of the coloring compositions
    2.1. Protocol
    After one month of storage at 45 ° C., each of the compositions (B) to (B3) was mixed with water.
    Then, the stability of each of the compositions (B) to (B3) was evaluated by measuring the percentage of loss of H2O2 by titration of redox with potassium permanganate.
    2.2. Results
    The percentages of loss of H2O2 obtained for each of the compositions, according to the invention (B) and comparative (B1) to (B3), are indicated in the table below.
    Binvention Blcomparative B2comparative B3comparative % loss of H2O2 1.7% 39% 25% 3 8%
    The results obtained above show that the coloring composition (B), prepared according to the present invention, ie comprising a polymer comprising at least one vinyl heterocyclic monomer (polyvinylpyrrolidone), is more stable over time than the comparative compositions (B1) to (B3) comprising other excipients.
    Indeed, after one month of storage at 45 ° C, only 1.7% loss of H2O2 is measured in the composition according to the invention. Conversely, the comparative compositions (B1) to (B3) comprising another excipent than polyvinylpyrrolidone lost respectively 39%, 25% and 38% of H 2 O 2 .
    III. Dye evaluation of coloring compositions
    3.1. Protocol
    Each of the compositions (B) to (B3) obtained previously was mixed with water in order to obtain the respective ready-to-use compositions (B) - (B3), in the following proportions:
    - 27.2 g of composition, and
    - qs 100g of water.
    The ready-to-use compositions thus obtained were then applied to locks of 90% white hair, in a bath ratio equal to 5: 1. After a 30-minute break at 27 ° C (thermostatically controlled plate), the locks of hair were rinsed, then dried.
    The same protocol was applied from coloring compositions (B) to (B3) stored for 1 month at 45 ° C.
    The color measurements of each of the ready-to-use compositions were evaluated in the CIE L * a * b * system using a MINOLTA CM-3600D spectro-colorimeter.
    In this system L * a * b *, L * represents the intensity of the color, a * indicates the axis of color green / red and b * the axis of color blue / yellow.
    The value of ΔΕ * was calculated from the values of L * a * b * according to the following equation:
    AE * = ^ / (L * -L 0 *) 2 + (a * -a0 *) 2 + (b * -b0 *) 2
    The increase in coloration (ΔΕ *) was calculated on the strands of non-colored hair (Lo *, ao * and bo *) and on the strands of colored hair (L *, a * and b *). The larger the value of ΔΕ *, the better the color rise.
    Then, the stability of the dye performances (diffAE), that is to say the evolution of the dye performances, of the compositions (B) to (B3) was calculated by comparing the increase in the coloration obtained from fresh coloring compositions, ie applied directly after their preparation, (ΔΕ (ΐο)), with the increase in coloration obtained from coloring compositions stored for 1 month at 45 ° C (AE (tones)) according to the following equation:
    diff ΔΕ = (ΔΕ * (ΐ 0 )) - (AE * (ti m0 is))
    The higher the value of diff ΔΕ, the more the dye performance of the coloring composition has been degraded.
    3.2. Results
    The diff ΔΕ values obtained for each of the coloring compositions according to the invention (B) and comparative (B1) to (B3) are indicated in the table below.
    Binvention Blcomparative B2comparative B3comparative diff ΔΕ 1.80 17.07 14.75 17.91
    The results obtained above show that the dyeing properties of the coloring composition (B), prepared according to the present invention, ie comprising a polymer comprising at least one vinyl heterocyclic monomer (polyvinylpyrrolidone), remain more stable over time than the dyeing properties. provided by the comparative compositions (B1) to (B3) each comprising a different excipient than polyvinylpyrrolidone.
    Even after one month of storage at 45 ° C., the composition according to the invention retains its coloring properties, unlike the comparative compositions.
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    1. An anhydrous solid composition for dyeing keratin fibers, in particular human keratin fibers, such as the hair, comprising:
    (a) one or more oxidation bases, (b) one or more chemical oxidizing agents chosen from alkali metal percarbonates, alkaline earth metal percarbonates and mixtures thereof, (c) one or more polymers comprising at least one vinyl heterocyclic monomer, and (d) optionally one or more oxidation couplers.
    [2" id="c-fr-0002]
    2. Composition according to Claim 1, characterized in that the oxidation base or bases are chosen from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases, their addition salts, their solvates and their mixtures, and preferably among the paraphenylenediamines, their addition salts, their solvates and their mixtures.
    [3" id="c-fr-0003]
    3. Composition according to Claim 1 or 2, characterized in that the total amount of oxidation base ranges from 0.1 to 30% by weight, preferably from 0.5 to 15% by weight, and more preferably from 1 to 10% by weight, relative to the total weight of the anhydrous solid coloring composition.
    [4" id="c-fr-0004]
    4. Composition according to any one of the preceding claims, characterized in that the total amount of the chemical oxidizing agent (s), chosen from alkali metal percarbonates, alkaline earth metal percarbonates and their mixtures, ranges from 30 to 55% by weight, and preferably from 35 to 50% by weight, relative to the total weight of the anhydrous solid coloring composition.
    [5" id="c-fr-0005]
    5. Composition according to any one of the preceding claims, characterized in that the vinyl heterocyclic monomer is chosen from monomers comprising a heterocycle having from 4 to 7 members, and comprising from 1 to 4 identical or different intracyclic heteroatoms, optionally condensed to a ring benzene and / or optionally substituted; the number of intracyclic heteroatoms being less than that of the heterocycle links.
    [6" id="c-fr-0006]
    6. Composition according to claim 5, characterized in that the vinyl heterocyclic monomer is chosen from N-vinyl monomers, optionally substituted, preferably from Nvinylpyrrolidone, vinylcaprolactam, N-vinylpiperidone, Nvinyl 3-morpholine, N -vinyl-4-oxazolinone, 2-vinylpyridine, 4vinylpyridine, 2-vinylquinoline, 1-vinylimidazole and 1vinylcarbazole, optionally substituted, and more preferably the heterocyclic monomer is N-vinylpyrrolidone, optionally substituted.
    [7" id="c-fr-0007]
    7. Composition according to any one of the preceding claims, characterized in that the polymer comprising at least one vinyl heterocyclic monomer is the homopolymer of polyvinylpyrrolidone crosslinked or not.
    [8" id="c-fr-0008]
    8. Composition according to any one of the preceding claims, characterized in that the total amount of the polymer or polymers comprising at least one vinyl heterocyclic monomer ranges from 5 to 70% by weight, preferably from 10 to 60% by weight, and more preferably from 10 to 35% by weight, relative to the total weight of the anhydrous solid coloring composition.
    [9" id="c-fr-0009]
    9. Composition according to any one of the preceding claims, characterized in that the oxidation coupler (s) are chosen from meta-phenylenediamines, meta3060360 aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers, their salts addition, their solvates and their mixtures.
    [10" id="c-fr-0010]
    10. Composition according to any one of the preceding claims, characterized in that it also comprises one or more surfactants, preferably chosen from anionic surfactants, amphoteric or zwitterionic surfactants, nonionic surfactants, cationic surfactants and their mixtures, and more preferably from anionic surfactants, and their mixtures.
    [11" id="c-fr-0011]
    11. Composition according to any one of the preceding claims, characterized in that it further comprises one or more alkaline agents, preferably chosen from silicates and metasilicates, such as metasilicates of alkali metals; carbonates or hydrogen carbonates of alkali or alkaline earth metals, ammonium salts, and mixtures thereof.
    [12" id="c-fr-0012]
    12. Ready-to-use composition resulting from the mixture of an anhydrous solid coloring composition, as defined in any one of the preceding claims, and of a cosmetically acceptable medium.
    [13" id="c-fr-0013]
    13. Packaging article comprising:
    i) an envelope defining at least one cavity, the envelope comprising water-soluble and / or liposoluble fibers, preferably water-soluble fibers; and ii) an anhydrous solid coloring composition as defined in any one of claims 1 to 11;
    it being understood that the anhydrous solid coloring composition is in one of the cavities defined by the envelope i).
    [14" id="c-fr-0014]
    14. Packaging article according to claim 13, characterized in that the envelope i) consists of two water-soluble or liposoluble sheets (11, 12), preferably water-soluble, joined together at a peripheral region (14) , preferably the two plies being joined by any suitable fixing means, preferably bonding, welding, in particular heat sealing, in particular by entanglement; the first ply (11) further has a free central region (D) disposed opposite a free central region (D) of the second ply 12; these two central regions defining a central cavity, said central cavity containing the anhydrous solid coloring composition (13); the sheets (11, 12) having a closed outer periphery (15) whose shape is rounded, preferably circular or elliptical, or polygonal, preferably square, rectangular, triangular; and more preferably circular.
    [15" id="c-fr-0015]
    15. Packaging article according to claim 14, characterized in that it further comprises a sheet (16), preferably water-soluble, and optionally other (s) sheet (s) water-soluble (s) or liposoluble (s) additional (s) (17), preferably water-soluble (s) which define one or more cavities, separating the anhydrous solid coloring composition (13), one or more additional chemical oxidizing agents different from the chemical oxidizing agents (b) and / or a or more additives (19), and / or one or more additives different from those introduced into the other cavities (20).
    [16" id="c-fr-0016]
    16. Packaging article according to any one of claims 14 or 15, characterized in that the first ply (11), the second ply (12), and possibly the additional plies (16) and (17), have a thickness less than their other dimensions, in particular less than 10% of their maximum transverse dimensions D + 2d; preferably the thickness of the first ply (11) and of the second ply (12) being, in particular less than 10 mm and in particular between 0.1 mm and 3 mm and their maximum transverse dimensions D + 2d being less than 100 mm, and being in particular inclusive between 10 mm and 60 mm, d defining a peripheral region which joins the two plies (11) and (12) hermetically.
    [17" id="c-fr-0017]
    17. Packaging article according to any one of claims 14 to 16, characterized in that the first ply (11) is a nonwoven and the second ply (12) is a nonwoven; said article also has a closed outer periphery (15); the outer periphery (15) of the first layer (11) is identical in shape to the outer periphery (15) of the second layer (12).
    [18" id="c-fr-0018]
    18. Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    applying to said keratin fibers a ready-to-use composition as defined in claim 12, allowing the ready-to-use composition to pause on said keratin fibers,
    - rinse said keratin fibers, and optionally shampoo said keratin fibers, rinse and dry them.
    [19" id="c-fr-0019]
    19. Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising the following successive steps:
    - mixing a packaging article, as defined in any one of claims 13 to 17, with a composition capable of dissolving the envelope of said packaging article,
    - applying the resulting composition to said keratin fibers,
    - allowing said resulting composition to pause on said keratin fibers,
    - rinse said keratin fibers, and
    - optionally shampoo said keratin fibers, rinse and dry them.
    [20" id="c-fr-0020]
    20. Use of an anhydrous solid coloring composition, as defined in any one of claims 1 to 11, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    [21" id="c-fr-0021]
    21. Use of a packaging article, as defined in any one of claims 13 to 17, for the coloring of keratin fibers, and in particular human keratin fibers such as the hair.
    1/2
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    US11090251B2|2021-08-17|
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    EP3558465A1|2019-10-30|
    US20200093729A1|2020-03-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2917973A1|2007-06-29|2009-01-02|Oreal|Anhydrous composition, useful for dyeing human keratin fibers e.g. hair, comprises oxidation dye precursors e.g. para-phenylene diamine, hydrogen peroxide complex and polymer containing heterocyclic vinyl monomer, and alkaline agent|
    FR2917967A1|2007-06-29|2009-01-02|Oreal|Anhydrous powder composition, for dyeing human keratin fibers, preferably hair, comprises oxidation dyes comprising benzene compound; complexes of hydrogen peroxide and polymer comprising vinyl heterocyclic monomer; and alkaline agents|
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    FR3015232A1|2013-12-23|2015-06-26|Oreal|PACKAGING ARTICLE COMPRISING AN ENVELOPE ANHYDROUS COLORING COMPOSITION COMPRISING AN OXIDATION COLOR, USE AND METHOD FOR COLORING KERATIN FIBERS|
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    US5008106A|1989-12-14|1991-04-16|Gaf Chemicals Corporation|Method for reducing the microbial content of surfaces with a microbiocidal, anhydrous complex of PVP-H2 O2|
    US5077047A|1991-04-08|1991-12-31|Isp Investments Inc.|Process for producing PVP-H2O2 products in the form of free-flowing powders|
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    DE4133957A1|1991-10-14|1993-04-15|Wella Ag|HAIR DYE CONTAINING AMINOPYRAZOLE DERIVATIVES AND NEW PYRAZOLE DERIVATIVES|
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    DE4234885A1|1992-10-16|1994-04-21|Wella Ag|Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivatives|
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    US5455340A|1994-02-02|1995-10-03|National Starch And Chemical Investment Holding Corporation|Starches modified with amino-multicarboxylates|
    DE4440957A1|1994-11-17|1996-05-23|Henkel Kgaa|Oxidation dye|
    DE4442900A1|1994-12-02|1996-06-05|Basf Ag|Process for the preparation of powdered hydrogen peroxide polymer complexes|
    FR2733749B1|1995-05-05|1997-06-13|Oreal|COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING DIAMINO PYRAZOLES, DYEING PROCESS, NOVEL DIAMINO PYRAZOLES, AND PREPARATION METHOD THEREOF|
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    FR2801308B1|1999-11-19|2003-05-09|Oreal|KERATINIC FIBER DYEING COMPOSITIONS CONTAINING 3-AMINO PYRAZOLO- [1, (- a] -PYRIDINES, DYEING PROCESS, NEWS 3-AMINO PYRAZOLO- [1,5-a] -PYRIDINES|
    FR2886136B1|2005-05-31|2007-08-10|Oreal|COMPOSITION FOR DYING KERATIN FIBERS COMPRISING AT LEAST ONE DIAMINO-N, N-DIHYDRO-PYRAZOLONE DERIVATIVE AND A CATIONIC OXIDATION DYE|
    EP2011474A1|2007-06-29|2009-01-07|L'Oréal|Wasserfreie Zusammensetzung enthaltend mindestens einen Oxidationsfarbstoff und mindestens einen Komplex von Wasserstoffperoxid mit einem spezifischen Polymer, sowie Färbeverfahren mit dieser Zusammensetzung|
    JP5672255B2|2012-02-21|2015-02-18|新日鐵住金株式会社|Manufacturing method of forged steel roll|FR3089794B1|2018-12-18|2021-01-29|Oreal|Solid composition for dyeing or lightening keratin fibers comprising a phospholipid|
    GB2581870B|2018-12-28|2021-03-31|Henkel Ag & Co Kgaa|Thickening system for a percarbonate-containing colour composition and storage in a multilayer sachet|
    DE102019105179A1|2018-12-28|2020-07-02|Henkel Ag & Co. Kgaa|Thickening system of a percarbonate-containing dye preparation and storage in a multilayer sachet|
    DE102019105176A1|2018-12-28|2020-07-02|Henkel Ag & Co. Kgaa|Powder hair color with percarbonate in a water-soluble film|
    DE102019105165A1|2018-12-28|2020-07-02|Henkel Ag & Co. Kgaa|Thickening system of a dye preparation containing percarbonate|
    WO2020223239A1|2019-04-30|2020-11-05|L'oreal|Dissolvable packages of pre-measured powdered hair bleach|
    法律状态:
    2017-11-13| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-22| PLSC| Publication of the preliminary search report|Effective date: 20180622 |
    2019-11-15| PLFP| Fee payment|Year of fee payment: 4 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 5 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1662928A|FR3060360B1|2016-12-20|2016-12-20|ANHYDROUS SOLID COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A POLYMER COMPRISING AT LEAST ONE VINYL HETEROCYCLIC MONOMER|
    FR1662928|2016-12-20|FR1662928A| FR3060360B1|2016-12-20|2016-12-20|ANHYDROUS SOLID COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING A POLYMER COMPRISING AT LEAST ONE VINYL HETEROCYCLIC MONOMER|
    US16/471,649| US11090251B2|2016-12-20|2017-12-19|Anhydrous solid composition for dyeing keratin fibres comprising a polymer comprising at least one heterocyclic vinyl monomer|
    EP17825199.7A| EP3558465A1|2016-12-20|2017-12-19|Anhydrous solid composition for dyeing keratin fibres comprising a polymer comprising at least one heterocyclic vinyl monomer|
    PCT/EP2017/083442| WO2018114886A1|2016-12-20|2017-12-19|Anhydrous solid composition for dyeing keratin fibres comprising a polymer comprising at least one heterocyclic vinyl monomer|
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