WO2020002521A1 - Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff - Google Patents

Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff Download PDF

Info

Publication number
WO2020002521A1
WO2020002521A1 PCT/EP2019/067199 EP2019067199W WO2020002521A1 WO 2020002521 A1 WO2020002521 A1 WO 2020002521A1 EP 2019067199 W EP2019067199 W EP 2019067199W WO 2020002521 A1 WO2020002521 A1 WO 2020002521A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acid
preferentially
chosen
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2019/067199
Other languages
French (fr)
Inventor
Andrew Greaves
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of WO2020002521A1 publication Critical patent/WO2020002521A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/736—Chitin; Chitosan; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/882—Mixing prior to application
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/884—Sequential application

Definitions

  • the present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application to said keratin fibres a) of at least one monosaccharide, b) of at least one particular polysaccharide, in salified or non-salified form, and c) of at least one dyestuff, followed by a heat treatment of the keratin fibres.
  • the present invention also relates to a composition at acidic pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide bearing amine groups, in salified or non-salified form, and c) at least one dyestuff.
  • C composition at acidic pH
  • the present invention also relates to a kit comprising a multi-compartment device containing a) at least one monosaccharide, b) at least one polysaccharide bearing amine groups, and c) at least one dyestuff, and to a device for heating keratin fibres.
  • Two types of dyeing have essentially been developed for dyeing keratin materials, and in particular human keratin fibres.
  • the first type of dyeing is“permanent” or oxidation dyeing, which uses dyeing compositions containing oxidation dye precursors, generally referred to as oxidation bases.
  • oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
  • the second type of dyeing is "semi-permanent” dyeing or direct dyeing, which consists in applying, to the keratin fibres, direct dyes, which are coloured and colouring molecules that have affinity for said fibres, in leaving them on for a time, and then in rinsing them off.
  • This type of process does not require the use of an oxidizing agent to develop the colouring. However, it is possible to use such an agent in order to obtain, along with the colouring, a lightening effect. This is then referred to as direct dyeing or semi-permanent dyeing under lightening conditions.
  • Permanent or semi-permanent dyeing processes under lightening conditions therefore need to use, with the dye composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases.
  • the colourings thus obtained are only short-lasting. Specifically, given the low interaction between the colouring agents and the fibres, the colourings have a tendency to fade out, or even to disappear, rapidly, with respect to external agents, such as light, sweat, mechanical actions (brushing, styling) and notably after a few shampoo washes.
  • the dyeing power of these compositions may not be entirely satisfactory, or even may be poor, and lead to a restricted range of colours.
  • the colourings may also be too selective, i.e. the difference in colouring is too great along the same keratin fibre that is differently sensitized between its end and its root.
  • a subject of the present patent application is thus a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising:
  • steps (i), (ii) and (iii) may be performed simultaneously or sequentially, before being followed by
  • composition (C) Another subject of the invention is an aqueous composition having an acid pH (pH ⁇ 7), also referred to as composition (C), comprising:
  • Another subject of the invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying to said keratin fibres an aqueous composition (C), as described previously, followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
  • a process for dyeing keratin fibres in particular human keratin fibres such as the hair, comprising a step of applying to said keratin fibres an aqueous composition (C), as described previously, followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
  • the combination of the particular monosaccharide and of the amino polysaccharide makes it possible to form a protective film around the fibres containing the dyestuff.
  • the colourings obtained are more resistant to external agents, and are notably persistent with respect to shampoo washing.
  • the colourings and the treated keratin fibres are also resistant to rubbing and other forms of mechanical attack such as brushing and combing. It should also be noted that the treated keratin fibres do not transfer the colour to tissues and do not stain the scalp.
  • Fibres dyed with the combination of the particular monosaccharide(s), of the amine polysaccharide(s) and of the dyestuff(s) according to the invention make it possible to dye and in addition to improve the cosmetic nature of damaged keratin fibres intrinsically, while at the same time maintaining or even improving the manageability (taming), the frizziness control and/or the persistence of styling of said fibres.
  • This combination also makes it possible to prevent the breakage of natural keratin fibres, while maintaining or even improving the manageability (taming), the frizziness control and/or the persistence of the styling of said fibres.
  • the colourings also have improved colouring properties, notably in terms of intensity, uniformity and persistence, notably with respect to shampoo washing.
  • the present invention relates to a kit comprising:
  • a multi-compartment device comprising a first compartment containing a cosmetic composition (ca) comprising a) one or more monosaccharides; a second compartment containing a cosmetic composition (cb) comprising b) one or more polysaccharides bearing amine group(s) and optionally d) one or more organic or mineral acids; and a third compartment containing a dye composition (cc) comprising c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof; and
  • polysaccharides refers to a polysaccharide sugar which is a polymer constituted of several saccharides bonded together via O-oside bonds, said polymers being constituted of monosaccharide units as defined previously, said monosaccharide units comprising at least 5 carbon atoms, preferably 6; in particular, the monosaccharide units are linked together via a 1,4 or 1,6 bond as a (alpha) or b (beta) anomer, it being possible for each oside unit to be of L or D configuration, and also the salts thereof and the solvates thereof such as the hydrates of said monosaccharides; more particularly, they are polymers formed from a certain number of saccharides (or monosaccharides) having the general formula: -[C x (H 2 0) y )] n - where x is an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is between 5 and 7 inclusive and preferably
  • the term“bearing amine group(s)” means that the monosaccharide(s) a) or polysaccharide(s) b) are substituted with one or more amino group(s) NR I R 2 i.e. at least one of the hydroxyl groups of at least one saccharide unit is replaced with a group NR I R 2 with Ri and R 2 , which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C 6 )alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH 2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C 4 )alkyl group such as benzyl, v) a (hetero)cyclo(C5-C 7 )alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (
  • low molecular weight means that the polysaccharide bearing an amine group has an average molecular weight of less than 400 000 Da;
  • organic or mineral acid salt more particularly means organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid HC1, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 S0 4 , iv) alkylsulfonic acids: Alk-S(0) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(0) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-0-S(0)0H such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid H 3 P0 4 ; ix) triflic acid CF3SO3H and
  • alkyl group or unsaturated C 2 -C 3 o radical being optionally interrupted and/or optionally substituted preferably with one or more hydroxyl groups and not substituted with one or more amino radicals
  • R preferably denoting a (Ci-C 6 )alkyl group optionally interrupted and/or optionally substituted with 1, 2 or 3 hydroxyl groups; preferentially, R represents a (Ci- C 4 )alkyl group such as methyl or ethyl
  • the organic monocarboxylic acids (I) are chosen from acetic acid, glycolic acid and lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid;
  • A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non aromatic polyvalent hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen and/or optionally substituted notably with one or more hydroxyl groups and t represents an integer between 1 and 5 inclusive; preferably, A represents a divalent (Ci-C 6 )alkylene group optionally substituted notably with one or more hydroxyl groups and not substituted with at least one amino radical, and t is equal to 1, 2 or 3, the polycarboxylic acids of formula (II) are preferably chosen from tartaric acid, succinic acid, fumaric acid and citric acid, and mixtures thereof; and
  • amino acids including more carboxylic acid radicals than amino groups, such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; in particular, salts of monocarboxylic acids other than pyrrolidonecarboxylic acid, 100 OE and 500 OE ethoxylated stearic acids, and linoleic acid;
  • an“alkyl radical” is a linear or branched Ci-Cio, preferably Ci-C 6 and in particular Ci-C 4 hydrocarbon-based radical, such as methyl or ethyl, unless otherwise indicated;
  • a (Cx-Cy)alkyl radical is a linear or branched Cx-Cy hydrocarbon-based radical; the expression“optionally interrupted” attributed to the alkyl radical or to the polyvalent hydrocarbon-based group A as defined previously means that said radical may be interrupted with one or more groups or heteroatoms chosen from O, S, CO or combinations thereof such as -CO-O- or -O-CO-, preferably interrupted with one or more non- adjacent oxygen atoms;
  • the expression“optionally substituted” attributed to the alkyl radical or to the polyvalent hydrocarbon-based group A as defined previously means that said radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) Ci-C 4 alkoxy, iii) carboxyl, iv) acylamino, v) amino optionally substituted with one or two identical or different Ci-C 4 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non nitrogen heteroatom;
  • an“alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a linear or branched C 1 -C 10 , preferentially Ci-C 6 and more particularly C 1 -C 4 hydrocarbon-based radical such as methoxy or ethoxy;
  • aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from one of the following atoms or groups:
  • Ci-C 6 preferably Ci-C 4 , alkyl
  • radical R is a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a Ci-C 2 alkyl radical;
  • R represents a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C 1 -C 4 alkyl radical, or a phenyl radical;
  • radicals R which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; - cyano;
  • cyclic or heterocyclic part of a non-aromatic group may be substituted with at least one substituent chosen from the following groups:
  • R-C(O)-N(R’)- - alkylcarbonylamino
  • R-C(O)-N(R’)- a radical atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group
  • the radical R is a Ci-C 2 alkyl group or an amino optionally substituted with one or two identical or different C 1 -C 4 alkyl groups which themselves optionally bear at least one hydroxyl group;
  • R-C(O)-O- - alkylcarbonyloxy
  • R-C(O)-O- the radical R is a C 1 -C 4 alkyl radical or an amino group optionally substituted with one or two identical or different C 1 -C 4 alkyl groups which themselves optionally bear at least one hydroxyl group;
  • R-G-C(O)- - alkoxycarbonyl
  • R-G-C(O)- the radical R is a C 1 -C 4 alkoxy radical and G is an oxygen atom, or an amino group optionally substituted with a C 1 -C 4 alkyl group which itself optionally bears at least one hydroxyl group;
  • a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo groups;
  • an "aryl” radical represents a monocyclic or fused or non-fused polycyclic carbon-based group, comprising from 6 to 22 carbon atoms, at least one ring of which is aromatic; such as phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferentially phenyl;
  • a“heteroaryl radical” represents an optionally cationic, 5- to 22-membered, monocyclic or fused or non-fused polycyclic group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, (benz)imidazolyl, (benzo)bistriazolyl, (benzo)pyrazolyl, (benzo)pyridazinyl, (benzo)quinolyl, (benzo)thiazolyl, (benzo)triazolyl, (benz)oxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, ox
  • heterocyclic radical is a fused or non-fused, 5- to 22-membered monocyclic or polycyclic but non-aromatic radical that may contain one or two unsaturations, including from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium;
  • a“heterocycloalkyl radical” is a heterocyclic radical comprising at least one saturated ring
  • fibres or hair are elastic, have no body, do not hold shape, and the head of hair is flat without volume;
  • the dyeing process according to the present invention comprises a step consisting in applying to keratin fibres a) one or more monosaccharides, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof, also referred to as ingredients a).
  • the monosaccharide(s) a) that may be used according to the present invention may or may not contain amine groups, i.e. they may be chosen from monosaccharides not comprising any amine groups, monosaccharides comprising at least one amine group, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from monosaccharides not comprising any amine groups, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) denote a mixture of monosaccharides, one of which is xylose or the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) denote a single monosaccharide, in particular xylose or the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) are chosen from C 7 monosaccharides: heptoses, such as aldoheptoses and keto heptoses, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) are C 6 monosaccharides: hexoses, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from hexoses of formula (Al), and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof:
  • R a , R b , R d , R e and R f which may be identical or different, represent i) a hydroxyl group, ii) a (Ci-C 4 )alkoxy group, the alkyl chain of which may be optionally substituted, notably with one or more hydroxyl groups, or iii) a carboxyl group; more preferentially, R a , R b , R d , R e and R f represent a hydroxyl group.
  • the monosaccharide(s) a) are chosen from the hexoses of formula (Al) of D configuration, also known as D-glucopyrans, and better still from the hexoses of formula (Al) of b (beta) anomeric configuration.
  • the monosaccharide(s) a) are chosen from hexoses of formula (AG) below, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, preferably D configuration, and the solvates thereof such as hydrates, and mixtures thereof:
  • the monosaccharide(s) a) are advantageously chosen from aldohexoses and ketohexoses, preferably from glucose, galactose, allose, altrose, mannose, gulose, idose and talose, and also the alpha or beta anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof, more preferentially from glucose and galactose, better still glucose, and even better still glucose of D configuration.
  • aldohexoses and ketohexoses preferably from glucose, galactose, allose, altrose, mannose, gulose, idose and talose, and also the alpha or beta anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof, more preferentially from glucose and galactose, better still glucose, and even better still glucose of D configuration.
  • the monosaccharide(s) a) are C5 monosaccharides: pentoses, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from the pentoses of formula (A2), and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof:
  • formula (A2), Rg, Rh, Ri and Rj which may be identical or different, represent i) a hydroxyl group, or ii) a (Ci-C 4 )alkoxy group, the alkyl chain of which may be optionally substituted, notably with one or more hydroxyl groups.
  • the monosaccharide(s) a) are chosen from the pentoses of formula (A2) of D configuration, and better still from the pentoses of formula (A2) of b (beta) anomeric configuration.
  • the monosaccharide(s) a) are chosen from aldopentoses and ketopentoses, and mixtures thereof, and more preferentially xylose, arabinose, lyxose, ribose, ribulose and xylulose, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) are advantageously chosen from monosaccharides not comprising any amine groups, and preferably from xylose and glucose, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from monosaccharides bearing an amine group, i.e. monosaccharides comprising at least one amine group, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from monosaccharides bearing amine group(s), they are preferably salified with a mineral acid such as hydrochloric acid.
  • the monosaccharide(s) a) bear amine group(s) and denote a mixture of monosaccharide(s) bearing amine group(s), one of which is glucosamine or the salts thereof with an organic or mineral acid such as hydrochloric acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) bear amine group(s) and denote a single monosaccharide bearing amine group(s), in particular glucosamine or the salts thereof with an organic or mineral acid or more particularly the mineral acid salts thereof such as the hydrochloric acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) are C 5 monosaccharides bearing amine group(s): pentosamines, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
  • the pentosamines are chosen from aldopentosamines and ketopentosamines such as xylosamine, arabinosamine, lyxosamine, ribosamine, ribulosamine and xylulosamine and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) are chosen from C 7 monosaccharides bearing amine group(s): heptosamines such as aldoheptosamines and ketoheptosamines and also the organic or mineral acid salts thereof, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) are chosen from C 6 monosaccharides: hexosamines and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the monosaccharide(s) a) of the invention are chosen from the hexosamines of formula (A3) below and also the salts thereof with an organic or mineral acid such as hydrochloric acid, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates:
  • R a , R b , R d , R e and R f which may be identical or different, represent (1) a hydroxyl group, (2) a (Ci-C 4 )alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl groups, (3) a carboxyl group, or (4) a group NR I R 2 with Ri and R 2 , which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C 6 )alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH 2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C 4 )alkyl group such as benzyl, v) a (hetero)cyclo(C5-C 7 )alkyl group such as cyclohexyl, morpholinyl, piperazinyl,
  • At least one of the radicals R a , R b , R d , R e and R f represents a group NR I R 2 and preferably at least one of the radicals R a , R b , R d , R e and R f represents a group NR I R 2 and the radicals other than NR I R 2 denote a hydroxyl group.
  • Ri and R 2 are chosen from hydrogen and -C(0)-R’i in which R’i is as defined previously; and more preferentially Ri and R 2 represent i) a hydrogen atom or ii) -C(0)-R’ i, with R’ i representing a (Ci-C 4 )alkyl group such as methyl.
  • R b represents a group NR I R 2 such as NH 2 or -N(H)-C(0)-R’ i with R’i representing a (Ci-C 4 )alkyl group such as methyl, and more preferentially NH 2 , and R a , R d , R e and R f , represent a hydroxyl group.
  • the monosaccharide(s) a) are chosen from the hexosamines of formula (A3) of D configuration, also known as D-glucopyrans, and more preferentially from the hexosamines of formula (A3) of b (beta) anomeric configuration.
  • the monosaccharide(s) a) of the invention are chosen from the hexosamines of formula (A3’) below and also the salts thereof with an organic or mineral acid such as hydrochloric acid, and also the a or b anomers thereof, the optical isomers thereof of L or D, preferably D, configuration, and the solvates thereof such as hydrates, and mixtures thereof:
  • R a , R b , R d , R e and R f are as defined previously for (A3).
  • the monosaccharide(s) a) are advantageously chosen from hexosamines, preferably from aldohexosamines and ketohexosamines, and mixtures thereof, more preferentially from glucosamine, galactosamine, allosamine, altrosamine, mannosamine, gulosamine, idosamine and talosamine, and mixtures thereof.
  • the monosaccharide(s) a) are chosen from glucosamine and galactosamine, and also the salts thereof with an organic or mineral acid such as hydrochloric acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof; more preferentially, the monosaccharide a) is glucosamine, better still glucosamine of D configuration, and even better still glucosamine salified with a mineral acid such as hydrochloric acid.
  • the dyeing process according to the present invention also comprises a step consisting in applying to keratin fibres b) one or more polysaccharides bearing amine group(s), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, also referred to as ingredients b).
  • the polysaccharide(s) bearing amine group(s) b) have an average molecular weight (MW) of less than or equal to 400 kDa and more preferentially less than 200 kDa.
  • MW average molecular weight
  • the polysaccharide(s) bearing amine group(s) b) have a low average molecular weight MW, i.e. they have a molecular weight of less than 100 kDa, preferably less than 40 kDa; more preferentially, they have an average MW of between 1 kDa and 30 kDa and better still between 3 kDa and 28 kDa.
  • the polysaccharide(s) bearing amine group(s) b) are preferably of natural animal or plant origin, or else are derived from synthesis, semisynthesis or biosynthesis.
  • the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing C5-C7 saccharide units bearing amine group(s), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof. More particularly, the polysaccharide(s) bearing amine group(s) b) bear C 6 saccharide unit bearing amine group(s), these polysaccharides bearing amine group(s) are then referred to as polyhexosamines.
  • the saccharide units of the polysaccharide bearing amine group(s) b) are of b (beta) anomeric configuration and/or D configuration.
  • the saccharide units of the polysaccharide bearing amine group(s) b) are connected together between the atoms of carbon 1 of one saccharide unit and of carbon 4 of the other saccharide unit, denoted (l 4).
  • the polysaccharide(s) bearing amine group(s) are preferably chosen from polysaccharides bearing a saccharide unit of formula (B) below, and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof.
  • - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
  • R a , R b and R c which may be identical or different for each saccharide unit, represent (1) a hydroxyl group, (2) a (Ci-C 4 )alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl and/or carboxyl groups, (3) a carboxyl group, or (4) a group NR I R 2 with Ri and R 2 , which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C 6 )alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH 2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C 4 )alkyl group such as benzyl, v) a (hetero)cyclo(C5-C 7 )alkyl group such as cyclohexyl, morpholinyl, piperaziny
  • At least one of the radicals R a , R b or R c of at least one saccharide unit represents a group NR I R 2 and that at least one of the groups NR I R 2 of at least one saccharide unit represents an NH 2 group.
  • Ri and R 2 are chosen from a hydrogen atom and -C(0)-R’i in which R’i is as defined previously; and more preferentially Ri and R 2 represent i) a hydrogen atom or ii) -C(0)-R’ i, with R’ i representing a (Ci-C 4 )alkyl group such as methyl.
  • R a of at least one saccharide unit represents a group NR I R 2 with Ri which represents a hydrogen atom and R 2 is chosen from i) a hydrogen atom or ii) a group -C(0)-R’ i , and R b and R c represent a hydroxyl group, it being understood that at least one of the groups NR I R 2 of at least one saccharide unit represents an NH 2 group.
  • polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing saccharide units of formula (Bl) below, and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof:
  • - R’ represents a hydrogen atom or a (Ci-C 4 )alkylcarbonyl group such as acetyl
  • - R represents a hydrogen atom or a (Ci-C 4 )alkyl group optionally substituted with a carboxyl group such as -CH(C0 2 H)-CH 3 ;
  • - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
  • At least one saccharide unit bears an NH 2 amino group and at least one other saccharide unit bears at least one N(H)-R' group with R' representing a (Ci-C 4 )alkylcarbonyl group such as acetyl CH 3 -C(0)-.
  • the saccharide units of formula (B) or (Bl) are of D configuration, also referred to as D-glucopyran.
  • saccharide units of formula (B) or (Bl) are of b (beta) anomeric configuration.
  • the polysaccharides b) are chosen from the polysaccharides bearing a saccharide unit of formula (B2) below and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
  • R a , R b and R c are as defined for (B) previously; and the radicals R a , R b and R c of each saccharide unit may be identical or different; and
  • - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
  • At least one of the radicals R a , R b or R c of at least one saccharide unit represents a group NR I R 2 , with Ri and R 2 as defined previously for (B), and that at least one of the groups NR I R 2 of at least one saccharide unit represents an NH 2 group; preferably, at least one saccharide unit bears a group R a representing a group -N(H)-R' with R' representing a (Ci-C 4 )alkylcarbonyl group such as acetyl CH 3 -C(0)-.
  • the polysaccharide(s) bearing amine group(s) b) are chosen from chitin and chitosan, and derivatives thereof, and more preferentially chitosan. More particularly, the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing a saccharide unit of formula (B3) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
  • - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
  • At least one saccharide unit bears an NH 2 amino group and at least one other saccharide unit bears a group N(H)-R' with R' representing a (Ci- C 4 )alkylcarbonyl group such as acetyl CH 3 -C(0)-.
  • polysaccharide(s) bearing amine group(s) b) are chosen from the chitosans of formula (B4) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
  • - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
  • - p is greater than 0 and ranges up to 0.5, preferably from 0.05 to 0.3, and better still from 0.1 to 0.20 such as 0.15 with m+p being equal to 1;
  • At least one saccharide unit bears an amino group NH 2 and at least one other saccharide unit bears a group N(H)-R'i with R'i representing a (Ci-C 4 )alkylcarbonyl group such as acetyl CH 3 -C(0)-.
  • the polysaccharide(s) bearing amine group(s) b) are salified, or in salified form, using one or more organic or mineral acids, and preferably using one or more organic acids.
  • organic or mineral acid(s) that may be used correspond to the mineral and organic acids described previously in the section "organic or mineral acid salt”.
  • the polysaccharide(s) bearing amine group(s) b) are salified using one or more organic acid(s) chosen from:
  • R represents a (hetero)aryl radical such as phenyl, a (hetero)aryl(Ci-C 4 )alkyl radical such as benzyl, a (Ci-C3o)alkyl radical or an unsaturated C2-C30 radical (i.e.
  • alkyl or unsaturated C2-C30 radicals being optionally interrupted and/or optionally substituted preferably with one or more hydroxyl groups and not substituted with one or more amino radicals;
  • R preferably denoting a (Ci-C6)alkyl group optionally interrupted and/or optionally substituted with 1, 2 or 3 hydroxyl groups; preferably, R represents a (Ci-C 4 )alkyl group such as methyl or ethyl;
  • A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic polyvalent hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen and/or optionally substituted notably with one or more hydroxyl groups and t represents an integer between 1 and 5 inclusive; preferably, A represents a divalent (Ci-C6)alkylene group optionally substituted notably with one or more hydroxyl groups and not substituted with at least t amino radicals, and t is equal to 1, 2 or 3; and
  • the monocarboxylic organic acids of formula (I) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more preferentially from acetic acid, lactic acid, and mixtures thereof.
  • polycarboxylic acids of formula (II) are chosen from tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, and mixtures thereof.
  • the amino acids including more carboxylic acid radicals than amino groups are chosen from gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and mixtures thereof, and more preferentially gamma-carboxyglutamic acid.
  • the organic acid(s) that may be used are chosen from acetic acid, glycolic acid, lactic acid, tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and mixtures thereof, and preferably, the organic acid is lactic acid.
  • the polysaccharide(s) bearing amine group(s) b) are chosen from chitosans, salified using organic acid, preferentially using monocarboxylic acid of formula (I) as defined previously or polycarboxylic acid of formula (II) as defined previously, even more preferentially salified using carboxylic acid of formula (I) such as lactic acid.
  • the polysaccharide(s) bearing amine group(s) b) denote a mixture of polysaccharide(s) bearing amine group(s), one of which is a chitosan or the organic or mineral acid salts thereof, preferably the salts thereof with an organic acid such as lactic acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the polysaccharide(s) bearing amine group(s) b) denote a single polysaccharide bearing amine group(s), in particular a mixture of chitosan or the organic or mineral acid salts thereof or more particularly the organic acid salts thereof such as the lactic acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the polysaccharide(s) bearing amine group(s) b) denote a single polysaccharide bearing amine group(s), in particular a chitosan or the organic or mineral acid salts thereof or more particularly the organic acid salts thereof such as the lactic acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the dyestuffs in particular a chitosan or the organic or mineral acid salts thereof or more particularly the organic acid salts thereof such as the lactic acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
  • the dyeing process according to the present invention also comprises a step consisting in applying to the keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof, also referred to as ingredients c).
  • the dyestuff(s) are chosen from pigments.
  • pigment is understood to denote a white or coloured solid particle which is naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which is rendered insoluble by formulation in the form of a lake, where appropriate. More particularly, the pigment has little or no solubility in aqueous-alcoholic media.
  • Pigments that may be mentioned include organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a20 371 and ibid, "Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA,
  • They may in particular be monoazo pigments, including b-naphthols, monoazopyrrolone pigments or benzimidazolone pigments; diazo pigments, such as diazodiarylide pigments and bis(N-acetoacetarylide) pigments, or triazo or tetraazo pigments.
  • azo metal complex pigments Mention may also be made of azo metal complex pigments.
  • pigments are also advantageous, namely isoindolinone and isoindoline pigments, phthalocyanine pigments; quinacridone pigments; perinone pigments; perylene pigments; anthraquinone pigments such as hydroxyanthraquinone pigments; aminoanthraquinone pigments including acylaminoanthraquinones and azo anthraquinone pigments; heterocyclic anthraquinones; polycarboxylic anthraquinone pigments, pyranthrone pigments; anthranthrone pigments; diketopyrrolopyrrole (DPP) pigments; thioindigo pigments; dioxazine pigments; triphenylmethane pigments; quinophthalone pigments; and fluorescent pigments.
  • isoindolinone and isoindoline pigments phthalocyanine pigments
  • quinacridone pigments such as hydroxyanthraquinone pigments;
  • the dyes comprise one or more solubilizing groups such as -SO 3 H or -COOH
  • these dyes are made insoluble and consequently pigments by formation of a lake, i.e. by salification (e.g. Na, Ca, St, Ba, etc.) and divided mainly into b-naphthol and 2-hydroxy-3-naphthoic acid pigments "(BON) pigment lakes”.
  • the pigment may be at least partly organic.
  • the pigment is an organic pigment. According to another embodiment of the invention, the pigment is a mineral pigment.
  • the microcapsules according to the invention comprise not more than 80% by weight of pigment relative to the weight of the polymer matrix.
  • they may comprise from 0.5% to 75% by weight, for example from 1% to 70% by weight, notably from 20% to 65% by weight or even from 30% to 60% by weight of pigment relative to the weight of the polymer matrix.
  • the degree of encapsulation depends on the desired modification of the shade and may thus vary significantly according to the effect that it is desired to obtain.
  • pigments that may be used in the present invention, mention may be made of carbon black, titanium oxide, chromium oxide, pigments of D&C or FD&C type and lakes thereof, and especially those known under the names D&C Blue No. 4, D&C Brown No. 1, FD&C Green No. 3, D&C Green No. 5, D&C Green No. 6, FD&C Green No. 8, 20 D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No.
  • lakes examples include lakes based on barium, strontium, calcium or aluminium, or alternatively diketopyrrolopyrroles.
  • pigments with an optical effect such as particles including a natural or synthetic organic or mineral substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being optionally covered with metal substances, for instance aluminium, gold, silver, platinum, copper or bronze, or with metal oxides, for instance titanium dioxide, iron oxide or chromium oxide.
  • a natural or synthetic organic or mineral substrate for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas
  • metal substances for instance aluminium, gold, silver, platinum, copper or bronze, or with metal oxides, for instance titanium dioxide, iron oxide or chromium oxide.
  • They may also be nacres.
  • nacres means iridescent particles, which are notably produced by certain molluscs in their shell, or alternatively which are synthesized.
  • the nacreous pigments may be chosen from mica coated with titanium or with bismuth oxychloride, titanium mica coated with iron oxides, titanium mica coated notably with ferric blue or with chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. Use may also be made of interference pigments, notably liquid- crystal or multilayer pigments.
  • pigments having a structure may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type.
  • pigments having a structure may be, for example, of silica microsphere type containing iron oxide.
  • the pigments in accordance with the invention may be in the form of pigment powder or paste. They may be coated or uncoated.
  • the pigments in accordance with the invention may be chosen, for example, from white or coloured pigments, lakes, pigments with special effects such as nacres or flakes, and mixtures thereof.
  • white or coloured mineral pigments examples include zirconium oxide or cerium oxide, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
  • white or coloured organic pigments examples include nitroso, nitro, azo, xanthene, quinoline, anthraquinone and phthalocyanine compounds, compounds of metallic complex type, and isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
  • the white or coloured organic pigments may be chosen from carmine, carbon blacks such as Black 2, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880,
  • carbon blacks such as Black 2 or lakes such as D&C Red 7.
  • pigment pastes of organic pigments such as the products sold by the company Hoechst under the names:
  • the pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles including:
  • the term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
  • the inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.
  • pigments with special effects refers to pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thus contrast with white or coloured pigments that afford a standard uniform opaque, semi-transparent or transparent shade.
  • pigments with special effects include white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or with chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride.
  • Pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek).
  • Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
  • Quantum dots are luminescent semiconductive nanoparticles that are capable of emitting, under light excitation, radiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they may be manufactured according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein and also in the following publications: Dabboussi B.O. et a ,“(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocrystallites”, Journal of Physical Chemistry B, vol.
  • the pigments in accordance with the invention are preferably coloured pigments.
  • the size of a pigment other than the nacres in solution is generally between
  • 10 nm and 10 pm preferably between 50 nm and 5 pm and even more preferentially between 100 nm and 3 pm.
  • the size of a nacre in solution is generally between 1 and 200 pm, preferably between 1 and 80 pm and even more preferentially between 1 and 50 pm.
  • mineral pigments examples that may be mentioned include titanium dioxide (rutile or anatase) optionally surface-treated and codified in the Color Index under the reference Cl 77891; black, yellow, red and brown iron oxides, codified under the references Cl 77499, 77492 and 77491; manganese violet (Cl 77742); ultramarine blue (Cl 77007); hydrated chromium oxide (Cl 77289); ferric blue (077510).
  • organic pigments that may be mentioned, for example, are the pigment Yellow 3 sold notably under the trade name Jaune Covanor W 1603 by the company Wackherr (Cl 17710), D & C Red No. 19 (Cl 45170), D & C Red No. 9 (Cl 15585), D & C Red No. 21 (Cl 45380), D & C Orange No. 4 (Cl 15510), D & C Orange No. 5 (Cl 45370), D & C Red No. 27 (Cl 45410), D & C Red No. 13 (Cl 15630), D & C Red No. 7 (Cl 15850-1), D & C Red No. 6 (Cl 15850-2), D & C Yellow No.
  • nacreous pigments which may be chosen notably from white nacreous pigments such as mica coated with titanium oxide or bismuth oxide; coloured nacreous pigments such as titanium mica with iron oxides, titanium mica with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also those based on bismuth oxychloride.
  • Pigment pastes of organic pigment are used more particularly, such as the products sold by the company Hoechst under the names:
  • the dyestuff(s) are advantageously chosen from pigments, preferably from white organic pigments, coloured organic pigments, and mixtures thereof, and more preferentially carbon blacks, such as Black 2, lakes, such as D&C Red 7, and mixtures thereof.
  • the dyestuff(s) are chosen from direct dyes.
  • direct dye means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.
  • They may be ionic or nonionic, preferably cationic or nonionic, either as sole dyes.
  • direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.
  • Suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes, alone or as mixtures.
  • the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.
  • the direct dyes comprise at least one quatemized cationic chromophore.
  • acridines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; di
  • cationic azo dyes mention may be made particularly of those resulting from the cationic dyes described in Kirk-Othmer’s Encyclopedia of Chemical Technology,“Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.
  • the direct dye(s) are chosen from cationic dyes known as "basic dyes".
  • cationic quinone dyes those mentioned in the abovementioned Colour Index International are suitable and, among these, mention may be made, inter alia, of the following dyes:
  • azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, for example the following dyes:
  • the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type.
  • the direct dyes are cationic azo dyes, described in EP 850 636, FR 2 788 433, EP 920 856, WO 99/48465, FR 2 757 385, EP 850 637, EP 918 053, WO 97/44004, FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO 01/66646, US 5 708 151, WO 95/01772, WO 515 144, GB 1 195 386, US 3 524 842, US 5 879 413, EP 1 062 940, EP 1 133 976, GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645, Acta Histochem
  • the cationic direct dye(s) comprise(s) a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.
  • cationic radicals are, for example, a cationic radical:
  • an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyry
  • Het + represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (Ci-C 8 ) alkyl group such as methyl;
  • Ar + represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci- Cg)alkyl ammonium, such as trimethylammonium;
  • Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cg)alkyl, ii) optionally substituted (Ci-Cg)alkoxy, iii) (di)(Ci- Cg)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-Cg)alkylamino, v) optionally substituted N-(Ci-Cg)alkyl-N- aryl(Ci-Cg)alkylamino or alternatively Ar represents a julolidine group;
  • Ar represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially by one or more (Ci- Cg)alkyl, hydroxyl, (di)(Ci-Cg)(alkyl)amino, (Ci-Cg)alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (Ci-Cg)alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
  • R a substituent with a substituent of Het + and/or R b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cyclo alkyl; in particular, R a and R b represent a hydrogen atom or a (Ci-C 4 )alkyl group optionally substituted with a hydroxyl group;
  • Q represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
  • R 1 represents a (Ci-C 4 )alkyl group such as methyl
  • R and R which may be identical or different, represent a hydrogen atom or a (Ci-C 4 )alkyl group, such as methyl;
  • R 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs)alkoxy, or (di)(Ci- C 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R 4 is a hydrogen atom,
  • - Z represents a CH group or a nitrogen atom, preferentially CH
  • - Q is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
  • the dyes of formulae (III- 1 ) and (V-l) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
  • a halide such as chloride
  • an alkyl sulfate such as methyl sulfate or mesityl.
  • the direct dyes are fluorescent, i.e. they contain at least one fluorescent chromophore as defined previously.
  • Fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro ⁇ 2-[(2H-pyrrol-2-ylidene-kN)methyl]-lH-pyrrolato-kN ⁇ borons (BODIPY ® ), diketopyrrolopyrroles, fluorindines, (poly)methines (in particular cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxa
  • the fluorescent dye(s) are cationic and comprise at least one quaternary ammonium radical, such as those of formula (VII) below:
  • W + represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (Ci- Cg)alkyl groups, optionally substituted notably with one or more hydroxyl groups;
  • ⁇ Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (Ci-Cg)alkyl, preferably of Ci-C 4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cg)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-Cg)alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(C i -Cgjalkylamino, preferably with the C 1 -C 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocyclo alkyl groups such as piperazinyl, piperidyl
  • m represents an integer between 1 and 4 inclusive, and in particular m has the value 1 or 2; more preferentially 1;
  • R c and R d which may be identical or different, represent a hydrogen atom or an optionally substituted (Ci-Cg)alkyl group, preferentially of Ci-C 4 , or alternatively R c contiguous with W + and/or R contiguous with Ar form, with the atoms that bear them, a (hetero)cycloalkyl; particularly, R c is contiguous with W + and they form a (hetero)cycloalkyl such as cyclohexyl;
  • Q is an organic or mineral anionic counterion as defined previously.
  • a subject of the present invention is also an aqueous composition (C) at acidic pH comprising:
  • ingredients a), b) and c) as defined previously are applied sequentially and are preferably included in three separate compositions (ca), (cb) and (cc).
  • composition (ca) comprises a) one or more monosaccharides as defined previously
  • composition (cb) comprises b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined previously, and optionally c) one more mineral or organic acid(s)
  • composition (cc) comprises one or more dyestuffs as defined previously.
  • compositions (C) and (C) are examples of The mineral or organic acid(s) that may be used in compositions (C) and
  • the content of the monosaccharide(s), present in compositions (C) and (ca), preferably ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and better still from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
  • compositions (C) and (cb) preferably ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and even better still from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
  • the weight ratio of the content of monosaccharide(s) and the amount of polysaccharide(s) bearing amine group(s), present in composition (C) of the invention preferably ranges from 0.5 to 10.
  • compositions (C) and composition(s) (ca), (cb) and/or (cc) are cosmetic compositions, i.e. they contain a physiologically acceptable medium, i.e. a medium that is compatible with human keratin materials such as the skin (of the body, face, area around the eyes, or the scalp), the hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.
  • a physiologically acceptable medium i.e. a medium that is compatible with human keratin materials such as the skin (of the body, face, area around the eyes, or the scalp), the hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.
  • (cc) is advantageously an aqueous medium. It may be constituted, for example, of water or of a mixture of water and of at least one cosmetically acceptable organic solvent.
  • organic solvents examples include C 2 -C 4 lower alcohols, such as ethanol and isopropanol; polyols, notably those containing from 2 to 6 carbon atoms, for instance glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; polyol ethers, for instance 2-butoxyethanol, propylene glycol monomethyl ether and diethylene glycol monomethyl ether or monoethyl ether; and mixtures thereof.
  • C 2 -C 4 lower alcohols such as ethanol and isopropanol
  • polyols notably those containing from 2 to 6 carbon atoms, for instance glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol
  • polyol ethers for instance 2-butoxyethanol, propylene glycol monomethyl ether and diethylene
  • the cosmetic composition(s) (C), (ca), (cb) and/or (cc) each comprise from 50% to 99.8% by weight of water, relative to the weight of each composition.
  • composition(s) (C), (ca), (cb) and/or (cc) of the invention may be adjusted with an organic or mineral acid, or with an alkaline agent chosen from mineral, organic or hybrid alkaline agents or mixtures thereof.
  • the pH values may be adjusted with d) one or more organic or mineral acids as defined previously in the section“Organic or mineral acid salt”.
  • composition (ca) which comprises a) one or more monosaccharides as defined previously, and notably glucose or xylose, is at an acidic pH, i.e. less than 7, in particular less than or equal to 6. More particularly, the pH of composition (ca) is between 2 and 6, preferentially between 2.5 and 5.5 and more preferentially between 3.5 and 5, such as 4.5.
  • the monosaccharide(s) a), present in composition (ca) are in the presence of one or more mineral acid(s), more particularly hydrochloric acid.
  • composition (cb) which comprises b) one or more polysaccharide(s) bearing amine group (s) as defined previously, and in particular a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, such as chitosan, is at an acidic pH, i.e. less than 7, and in particular less than or equal to 6. More particularly, the pH of composition (cb) is between 2 and 6, preferentially between 2.5 and 5.5 and more preferentially between 3.5 and 5, such as 4.5.
  • the polysaccharide(s) bearing amine group(s) b), present in composition (cb), are in the presence of one or more organic acid(s), preferentially chosen from the monocarboxylic acids of formula (I) or the polycarboxylic acids of formula (II) as defined previously, and even more preferentially from the carboxylic acids of formula (I), such as lactic acid.
  • organic acid(s) preferentially chosen from the monocarboxylic acids of formula (I) or the polycarboxylic acids of formula (II) as defined previously, and even more preferentially from the carboxylic acids of formula (I), such as lactic acid.
  • composition (C) comprises:
  • the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
  • composition (C) comprises:
  • polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, more preferentially chitosan, in the presence of one or more mineral acid(s), preferably lactic acid,
  • the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
  • composition (C) comprises:
  • composition (C) optionally one or more mineral or organic acids;
  • the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
  • composition (C) comprises:
  • polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, more preferentially chitosan, and even better still chitosan with an average molecular weight of less than or equal to 400 kDa, in the absence of organic or mineral acid(s), and
  • one or more mineral or organic acids said acid c) preferably being chosen from hydrochloric acid, the organic monocarboxylic acids of formula (I) as defined previously, the polycarboxylic acids of formula (II) as defined previously, and more preferentially from hydrochloric acid, lactic acid, citric acid, fumaric and maleic acid, and mixtures thereof;
  • the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
  • composition (C) comprises one or more monosaccharides a) chosen from monosaccharides bearing an amine group as defined previously.
  • compositions (C), (ca), (cb) and/or (cc) may be adjusted with one or more mineral alkaline agents which are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.
  • mineral alkaline agents which are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.
  • the pH values may also be adjusted with one or more organic alkaline agents which are organic amines, i.e. they contain at least one substituted or unsubstituted amino group.
  • organic alkaline agent(s) are more preferentially chosen from organic amines with a pK b at 25°C of less than 12, preferably of less than 10 and even more advantageously of less than 6. It should be noted that it is the pK b corresponding to the function of highest basicity.
  • the pH values may also be adjusted with one or more hybrid compounds.
  • Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.
  • organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (VIII) below:
  • Ci-C 6 alkylene radical optionally substituted with a hydroxyl group or a Ci-C 6 alkyl radical and/or optionally interrupted with one or more heteroatoms, such as oxygen or NR U ;
  • R x , R y , R z , R 1 and R u which may be identical or different, represent a hydrogen atom, a Ci-C 6 alkyl radical, a Ci-C 6 hydroxyalkyl radical or a Ci-C 6 aminoalkyl radical.
  • composition (C) of the invention may be salified or non-salified.
  • composition (C) corresponds to composition (C) at acidic pH and comprises:
  • composition (C) corresponds to composition (C”) at acidic pH and comprises:
  • compositions (C) and/or (cc) may optionally also comprise one or more additional direct dyes other than the direct dyes mentioned previously.
  • direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than pigments and/or one or more direct dyes that are sparingly soluble or insoluble in aqueous-alcoholic solvents, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes.
  • aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than pigments and/or one or
  • Compositions (C), (ca), (cb) and/or (cc) may also optionally comprise one or more additives other than the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric or zwitterionic surfactants, cationic, anionic, nonionic or amphoteric polymers, or mixtures thereof, other than the polysaccharides of the invention, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, sequestrants, plasticizers, solubilizers, silicones, oils, mineral or organic thickeners, notably polymeric thickeners, antioxidants, hydroxy acids, fragrances, preserving agents and ceramides.
  • additives other than the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric or zwitterionic surfactants
  • compositions according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
  • the above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition comprising same.
  • the process for dyeing keratin fibres, in particular human keratin fibres such as the hair, according to the present invention comprises:
  • steps (i), (ii) and (iii) may be performed simultaneously or sequentially, before being followed by
  • the dyeing process according to the present invention may optionally also comprise a step of drying the keratin fibres.
  • this step of drying the keratin fibres follows steps (i), (ii) and (iii) and precedes the heat treatment step (iv).
  • steps (i), (ii) and (iii) are performed simultaneously, i.e. together.
  • a) the monosaccharide(s) as defined previously, b) the polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined previously, and c) the dyestuff(s) chosen from pigments, direct dyes, and mixtures thereof, as defined previously, are applied together or else the process of the invention comprises a first step of applying to the keratin fibres an aqueous composition (C) as defined previously.
  • the process of the invention comprises a first step consisting in applying to the keratin fibres composition (C) as defined previously, optionally followed by a step of drying said keratin fibres, followed by a step of heat treatment of said keratin fibres at a temperature of greater than 80°C, preferably of between l00°C and 250°C, and preferably with an iron.
  • composition (C) is composition (C) as defined previously.
  • composition (C) represents a composition (C") as defined previously.
  • the process of the invention comprises:
  • a step consisting in simultaneously applying to the keratin fibres a) the monosaccharide(s) as defined previously, b) the polysaccharide(s) bearing amine group(s) as defined previously, and c) the dyestuff(s) chosen from pigments, direct dyes, and mixtures thereof, as defined previously, followed by a leave-on time of between 1 and 60 minutes,
  • the process of the invention comprises:
  • steps (i) and (ii) may be performed simultaneously, before or after step (iii).
  • the process may comprise:
  • a step consisting in applying to said keratin fibres a) one or more monosaccharides as defined previously, and b) one or more polysaccharides bearing amine group(s), in salified or non-salified form, as defined previously,
  • the process may comprise: - a step consisting in applying to said keratin fibres the mixture of compositions (ca) and (cb) as defined previously, followed by a leave-on time of between 1 and 30 minutes,
  • the process may comprise:
  • the process may comprise:
  • the process of the invention does not use oxidized polysaccharide, more generally the process of the invention does not use a compound comprising at least one aldehyde group.
  • composition (cb), (C), (C) or (C") as defined previously does not contain oxidized polysaccharide and more generally composition (cb), (C), (C) or (C") does not contain a compound comprising at least one aldehyde group.
  • the process according to invention may also comprise an additional step of drying the keratin fibres after the application a) of the monosaccharide(s) as defined previously, b) of the polysaccharide(s) bearing amine group(s) as defined previously and/or c) of the dyestuff(s) as defined previously or after application of compositions (C), (C’), (C”), (ca), (cb) and/or (cc) containing same and before the step of heat treatment (iv) of the keratin fibres performed at a temperature of at least 80°C.
  • the process of the invention involves a step of drying the keratin fibres, in particular human keratin fibres such as the hair, before the heat treatment step (iv).
  • the drying step is notably performed using a hairdryer, a hood, or else with a towel, an absorbent or by drying naturally.
  • This drying step is advantageously performed at a temperature ranging from 20 to 70°C.
  • the keratin fibre heat treatment step (iv) of the process of the invention is preferably performed at a temperature of between 80°C and 250°C, it being understood that the temperature is that of the heating means, in particular of the iron, and not the temperature of the keratin fibres.
  • the heat treatment step (iv) is performed on dry keratin fibres.
  • the keratin fibre heat treatment step (iv) is performed at a temperature of at least l00°C, in particular at a temperature of between l00°C and 250°C, inclusive.
  • the keratin fibre heat treatment step (iv) is performed at a temperature ranging from l50°C to 220°C, preferably ranging from l60°C to 220°C, more preferentially ranging from l60°C to 200°C, and even better still ranging from l30°C to l90°C.
  • the heat treatment temperatures correspond to the temperatures of the heating means, in particular of the iron when an iron is used, and not the temperature of the keratin fibres.
  • This heat treatment step (iv) is advantageously performed using an iron.
  • iron means a device for heating keratin fibres by placing said fibres in contact with the heating device.
  • the iron is other than a heating comb.
  • the end of the iron which comes into contact with the keratin fibres generally has two surfaces. These two surfaces may be made of metal or of ceramic. In particular, these two surfaces may be smooth or crimped or curved.
  • the heat treatment step may be performed by means of a straightening iron, a curling iron, a crimping iron or a steam iron such as a Steampod.
  • the heat treatment step is performed by means of a straightening iron.
  • steam irons refers to irons which comprise a device which emits steam and which applies this steam before, during or after the straightening/relaxing.
  • irons that may be used in the process according to the invention, mention may be made of any type of flat hair iron, and in particular, in a non-limiting manner, those described in patents US 5 957 140 and US 5 046 516.
  • the iron may be applied by successive separate strokes lasting a few seconds or by gradual movement or sliding along the keratin fibres, in particular along human keratin fibres such as the hair.
  • the iron is applied in the process according to the invention by a continuous movement from the root to the end of the keratin fibres, notably human keratin fibres such as the hair, in one or more strokes, in particular in one to twenty strokes.
  • Each stroke of the hair iron may last from 2 seconds to 1 minute for a length of the treated keratin fibres of 30 cm ⁇ 3 cm.
  • Step (iv) of heat treatment of the keratin fibres is performed for a time that may range advantageously from 100 milliseconds to 30 minutes, preferably from 1 second to 15 minutes, more preferentially from 2 seconds to 10 minutes, even better still from 3 seconds to 5 minutes and even better still from 4 seconds to 1 minute.
  • the bath ratio of the composition(s) applied before the heat treatment step of the process preferably ranges from 0.1 to 10, and more preferentially from 0.2 to 5.
  • the term "bath ratio" means the ratio between the total weight of the applied composition and the total weight of keratin fibres to be treated.
  • the keratin fibres may be optionally rinsed with water or washed with a shampoo.
  • the keratin fibres are then optionally dried using a hairdryer or a hood or left to dry naturally.
  • the dyeing process is performed one or more times, optionally spaced by one or more cosmetic treatments, preferably spaced by one or more shampoo washes, to treat keratin fibres that have regrown or that have undergone other treatments liable to cause changes in the colouring, or to obtain the desired colour intensity.
  • the process is performed on keratin fibres, in particular human keratin fibres such as the hair, which are notably natural, notably natural hair.
  • a subject of the invention is also a kit comprising:
  • a multi-compartment device comprising a first compartment containing a cosmetic composition (ca) comprising one or more monosaccharides as defined previously; a second compartment containing a cosmetic composition (cb) comprising one or more polysaccharides bearing amine group(s) as defined previously and optionally one or more organic or mineral acids as defined previously; and a third compartment containing a dye composition (cc) comprising one or more dyestuffs as defined previously; and
  • each compartment of the kit may be released either sequentially or simultaneously.
  • composition packaging assembly i.e. the multi-compartment device
  • the composition packaging assembly is, in a known manner, any packaging that is suitable for storing cosmetic compositions (notably a bottle, tube, spray bottle or aerosol bottle).
  • Such a kit allows the process for dyeing keratin fibres according to the invention to be performed.
  • composition (A) and the dye composition (B) according to the present invention were prepared from the ingredients mentioned in the tables below, the contents of which are expressed as weight percentages relative to the total weight of the composition comprising same.
  • composition (A) and the dye composition (B) obtained below are applied according to processes 1 to 9 below:
  • the dye composition (B) is diluted to 10% in water.
  • the solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7- second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B) is diluted to 10% in composition
  • the mixture thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7- second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B) is diluted to 10% in water.
  • the solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood.
  • Composition (A) is then applied to the two locks of hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B) is diluted to 10% in water.
  • the solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood.
  • Composition (A) is then applied to the two locks of hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • composition (A) followed by the leave-on time, drying under a hood and five successive strokes with a straightening iron were repeated three times.
  • the locks of hair of processes 2, 4, 6 and 8 are washed with a shampoo according to the following protocol:
  • the locks are rinsed thoroughly with water at 37°C for 15 seconds.
  • the locks are then washed with a DOP shampoo, in a proportion of 0.4 g of shampoo per gram of hair.
  • the locks are then rinsed with water for 15 seconds, followed by being drained dry, combed and then dried.
  • the colouring obtained by means of the process of the invention does not transfer onto the user’s fingers.
  • the colour of the locks is then evaluated by colorimetry in the CIE L* a* b* system, using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included).
  • L* represents the intensity of the colour
  • a* indicates the green/red colour axis
  • b* the blue/yellow colour axis. The smaller the value of L*, the darker and more powerful the colouring.
  • L*, a* and b* represent the values measured on locks of hair after shampoo washing, namely the locks of hair of processes 2, 4, 6, 8 and 9 mentioned above
  • L0*, aO* and bO* represent the values measured on the respective locks of hair not washed with the shampoo, namely the locks of hair of processes 1, 3, 5 and 7 mentioned above.
  • the value of DE* for process 2 was calculated with L*, a* and b* representing the values obtained for process 2, and L 0 *, a 0 * and b 0 * representing the values obtained for process 1.
  • the colouring obtained by means of the process of the invention is also persistent with respect to shampoo washing at least five times (process 9).
  • compositions Compositions (A’) and (A") and the dye composition (B’) according to the present invention were prepared from the ingredients mentioned in the tables below, the contents of which are expressed as weight percentages relative to the total weight of the composition comprising same.
  • composition (A’) and the dye composition (B’) obtained above are applied according to processes 11 and 13 below.
  • the comparatives were prepared by replacing composition (A') with water according to processes 10 and 12 below.
  • composition (A') and the dye composition (B') obtained above are applied according to processes 15 and 17 below and the comparatives are prepared by replacing composition (A") with water according to processes 14 and 16 below.
  • the dye composition (B') is applied to two locks of natural grey hair at a rate of 1 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two locks of hair at a rate of 3 g of composition per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B') is applied to two locks of natural grey hair at a rate of 1 g of composition per gram of hair.
  • composition (A’) is then applied to the two locks of hair at a rate of 3 g of composition per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B') is applied to two locks of natural grey hair at a rate of 2 g of composition per gram of hair.
  • the locks are dried under a hood. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two locks of hair at a rate of 10 g of composition per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the dye composition (B') is applied to two locks of natural grey hair at a rate of 2 g of composition per gram of hair.
  • composition (A’) is then applied to the two locks of hair at a rate of lOg of composition per gram of hair.
  • the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • dye composition (B') are diluted in 50 g of water, adjusted to pH 3.5 with lactic acid.
  • the mixture thus obtained is applied to two locks of natural grey hair at a rate of 5 g of mixture per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the mixture thus obtained is applied to two locks of natural grey hair at a rate of 5 g of mixture per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the mixture thus obtained is applied to two locks of natural grey hair at a rate of 3g of mixture per gram of hair.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the locks After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
  • the locks are rinsed thoroughly with water at 37°C for 15 seconds.
  • the locks are then washed with a DOP shampoo, in a proportion of 0.4 g of shampoo per gram of hair.
  • the locks are then rinsed with water for 15 seconds, followed by being drained dry, combed and then dried.
  • the colour of the locks and the colour transfer onto a cotton fabric are evaluated visually.
  • the fabric is dragged over the length of the lock using a constant finger pressure and the final colour of the fabric is evaluated.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)

Abstract

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application to said keratin fibres a) of at least one monosaccharide, b) of at least one particular polysaccharide, in salified or non-salified form, and c) of at least one dyestuff, followed by a heat treatment of the keratin fibres. The present invention also relates to a composition at acidic pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide bearing amine group(s), in salified or non-salified form, and c) at least one dyestuff. The present invention also relates to a kit comprising a multi-compartment device containing a) at least one monosaccharide, b) at least one polysaccharide bearing amine group(s), and c) at least one dyestuff, and to a device for heating keratin fibres.

Description

Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff
The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application to said keratin fibres a) of at least one monosaccharide, b) of at least one particular polysaccharide, in salified or non-salified form, and c) of at least one dyestuff, followed by a heat treatment of the keratin fibres.
The present invention also relates to a composition at acidic pH (C) comprising a) at least one monosaccharide, b) at least one polysaccharide bearing amine groups, in salified or non-salified form, and c) at least one dyestuff.
The present invention also relates to a kit comprising a multi-compartment device containing a) at least one monosaccharide, b) at least one polysaccharide bearing amine groups, and c) at least one dyestuff, and to a device for heating keratin fibres.
Many people have sought for a long time to modify the colour of their hair in order, for example, to mask their grey hair.
Two types of dyeing have essentially been developed for dyeing keratin materials, and in particular human keratin fibres.
The first type of dyeing is“permanent” or oxidation dyeing, which uses dyeing compositions containing oxidation dye precursors, generally referred to as oxidation bases. These oxidation bases are colourless or weakly coloured compounds which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or colour modifiers. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
The second type of dyeing is "semi-permanent” dyeing or direct dyeing, which consists in applying, to the keratin fibres, direct dyes, which are coloured and colouring molecules that have affinity for said fibres, in leaving them on for a time, and then in rinsing them off. This type of process does not require the use of an oxidizing agent to develop the colouring. However, it is possible to use such an agent in order to obtain, along with the colouring, a lightening effect. This is then referred to as direct dyeing or semi-permanent dyeing under lightening conditions.
Permanent or semi-permanent dyeing processes under lightening conditions therefore need to use, with the dye composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases.
These conventional dyeing processes can damage the integrity of keratin fibres. Milder solutions, which are also known as makeup solutions and are based on weak physicochemical interactions, make it possible to deposit colouring and/or nacreous agents at the surface without threatening the fibre integrity. Among the colouring agents that may be used in these makeup compositions, pigments and in particular nacres, such as nacres of mica/iron oxide type, have advantageous dyeing properties.
It is currently possible to deposit these colouring agents on fibres to obtain the desired effect. However, the colourings thus obtained are only short-lasting. Specifically, given the low interaction between the colouring agents and the fibres, the colourings have a tendency to fade out, or even to disappear, rapidly, with respect to external agents, such as light, sweat, mechanical actions (brushing, styling) and notably after a few shampoo washes.
Moreover, the dyeing power of these compositions may not be entirely satisfactory, or even may be poor, and lead to a restricted range of colours. The colourings may also be too selective, i.e. the difference in colouring is too great along the same keratin fibre that is differently sensitized between its end and its root.
It is also advantageous to find a means for dyeing damaged keratin fibres by repairing them, that is to say by improving the cosmetic nature of damaged keratin fibres intrinsically, while maintaining or even improving the manageability, the frizziness control and/or the persistence of the styling of said fibres. It is also advantageous to prevent the breakage of natural keratin fibres, while maintaining or even improving the manageability, the frizziness control and/or the persistence of the styling of said fibres.
Finally, added to these drawbacks are the risks of dyeing the user's hands and clothing during the application of these compositions to keratin fibres. Thus, there is a real need to develop a process for dyeing keratin materials, notably keratin fibres, and in particular human keratin fibres such as the hair, which makes it possible to obtain good dyeing properties, notably in terms of intensity, fastness and uniformity, and also satisfactory cosmetic properties, while at the same time preserving the integrity of keratin fibres. The dyeing properties, and notably the intensity, the fastness and the uniformity, must also be persistent with respect to shampoo washing.
Moreover, there is a real need to propose a process that is easy to perform and that avoids any risk of transfer of the colourings onto the user's hands and clothing.
It has been discovered, surprisingly, that combining the applications to keratin fibres of at least one monosaccharide, of at least one particular polysaccharide and of at least one particular dyestuff with a heat treatment of said fibres makes it possible to achieve these objectives; and notably to afford colourings that have good properties, in particular in terms of intensity, uniformity and fastness with respect to external agents, while at the same time respecting the integrity of keratin fibres and avoiding staining users' hands and clothing.
A subject of the present patent application is thus a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising:
(i) a step consisting in applying to said keratin fibres a) one or more monosaccharides,
(ii) a step consisting in applying to said keratin fibres b) one or more polysaccharides bearing amine group(s), in salified or non-salified form; and
(iii) a step consisting in applying to said keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof;
it being understood that steps (i), (ii) and (iii) may be performed simultaneously or sequentially, before being followed by
(iv) a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
Another subject of the invention is an aqueous composition having an acid pH (pH < 7), also referred to as composition (C), comprising:
a) one or more monosaccharide(s),
b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof, and
d) optionally one or more mineral or organic acids.
Another subject of the invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying to said keratin fibres an aqueous composition (C), as described previously, followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
The combination of particular (poly)saccharides with a pigment and/or a direct dye, followed by a heat treatment makes it possible to dye keratin fibres without, however, damaging the fibres or staining the user's hands and clothing.
Moreover, the combination of the particular monosaccharide and of the amino polysaccharide makes it possible to form a protective film around the fibres containing the dyestuff. Thus, the colourings obtained are more resistant to external agents, and are notably persistent with respect to shampoo washing.
The colourings and the treated keratin fibres are also resistant to rubbing and other forms of mechanical attack such as brushing and combing. It should also be noted that the treated keratin fibres do not transfer the colour to tissues and do not stain the scalp.
Fibres dyed with the combination of the particular monosaccharide(s), of the amine polysaccharide(s) and of the dyestuff(s) according to the invention make it possible to dye and in addition to improve the cosmetic nature of damaged keratin fibres intrinsically, while at the same time maintaining or even improving the manageability (taming), the frizziness control and/or the persistence of styling of said fibres. This combination also makes it possible to prevent the breakage of natural keratin fibres, while maintaining or even improving the manageability (taming), the frizziness control and/or the persistence of the styling of said fibres.
The colourings also have improved colouring properties, notably in terms of intensity, uniformity and persistence, notably with respect to shampoo washing.
Finally, the present invention relates to a kit comprising:
- a multi-compartment device comprising a first compartment containing a cosmetic composition (ca) comprising a) one or more monosaccharides; a second compartment containing a cosmetic composition (cb) comprising b) one or more polysaccharides bearing amine group(s) and optionally d) one or more organic or mineral acids; and a third compartment containing a dye composition (cc) comprising c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof; and
- a device for heating the keratin fibres to a temperature of at least 80°C.
Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
In the following text, unless indicated otherwise:
■ the term“monosaccharides” refers to a monosaccharide sugar comprising at least 5 carbon atoms of formula Cx(H20)x with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is between 5 and 7 inclusive, preferably x = 6, they may be of D or L configuration, and of alpha or beta anomer, and also the salts thereof and the solvates thereof such as hydrates;
■ the term“polysaccharides” refers to a polysaccharide sugar which is a polymer constituted of several saccharides bonded together via O-oside bonds, said polymers being constituted of monosaccharide units as defined previously, said monosaccharide units comprising at least 5 carbon atoms, preferably 6; in particular, the monosaccharide units are linked together via a 1,4 or 1,6 bond as a (alpha) or b (beta) anomer, it being possible for each oside unit to be of L or D configuration, and also the salts thereof and the solvates thereof such as the hydrates of said monosaccharides; more particularly, they are polymers formed from a certain number of saccharides (or monosaccharides) having the general formula: -[Cx(H20)y)]n- where x is an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is between 5 and 7 inclusive and preferably x = 6, and y is an integer which represents x - 1, and n is an integer greater than or equal to 2, particularly of between 3 and 3000 inclusive, more particularly between 5 and 2500 and preferentially between 10 and 2300;
■ the term“bearing amine group(s)” means that the monosaccharide(s) a) or polysaccharide(s) b) are substituted with one or more amino group(s) NRIR2 i.e. at least one of the hydroxyl groups of at least one saccharide unit is replaced with a group NRIR2 with Ri and R2, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(C5-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (hetero)cyclo(C5-C7)alkyl(Ci-C4)alkyl group such as cyclohexylmethyl, vii) -C(Y)-(Y')P-R'i with Y and Y’, which may be identical or different, representing an oxygen atom, a sulfur atom or N(R'2), preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined previously, and in particular R'i denoting a (Ci-C6)alkyl group such as methyl. Preferably, Ri and R2 represent a hydrogen atom or a (Ci- C4)alkylcarbonyl group such as acetyl;
the term“low molecular weight” means that the polysaccharide bearing an amine group has an average molecular weight of less than 400 000 Da;
the term“organic or mineral acid salt" more particularly means organic or mineral acid salts in particular chosen from a salt derived from i) hydrochloric acid HC1, ii) hydrobromic acid HBr, iii) sulfuric acid H2S04, iv) alkylsulfonic acids: Alk-S(0)2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(0)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) alkoxysulfinic acids: Alk-0-S(0)0H such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid H3P04; ix) triflic acid CF3SO3H and x) tetrafluoroboric acid HBF4; xi) organic monocarboxylic acids of formula (I)
(I) R-C(0)-OH (I)
in which formula (I):
representing a (hetero)aryl group such as phenyl, a (hetero)aryl(Ci-C4)alkyl group such as benzyl, or (Ci-C3o)alkyl group or an unsaturated C2-C3o radical (i.e. including at least one ethylenic unsaturation, preferably one ethylenic unsaturation), said alkyl group or unsaturated C2-C3o radical being optionally interrupted and/or optionally substituted preferably with one or more hydroxyl groups and not substituted with one or more amino radicals, R preferably denoting a (Ci-C6)alkyl group optionally interrupted and/or optionally substituted with 1, 2 or 3 hydroxyl groups; preferentially, R represents a (Ci- C4)alkyl group such as methyl or ethyl; in particular the organic monocarboxylic acids (I) are chosen from acetic acid, glycolic acid and lactic acid, and mixtures thereof, and more particularly from acetic acid and lactic acid;
xii) the polycarboxylic acids of formula (II) below:
Figure imgf000008_0001
in which formula (II):
A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non aromatic polyvalent hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen and/or optionally substituted notably with one or more hydroxyl groups and t represents an integer between 1 and 5 inclusive; preferably, A represents a divalent (Ci-C6)alkylene group optionally substituted notably with one or more hydroxyl groups and not substituted with at least one amino radical, and t is equal to 1, 2 or 3, the polycarboxylic acids of formula (II) are preferably chosen from tartaric acid, succinic acid, fumaric acid and citric acid, and mixtures thereof; and
xiii) amino acids including more carboxylic acid radicals than amino groups, such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; in particular, salts of monocarboxylic acids other than pyrrolidonecarboxylic acid, 100 OE and 500 OE ethoxylated stearic acids, and linoleic acid;
an“alkyl radical" is a linear or branched Ci-Cio, preferably Ci-C6 and in particular Ci-C4 hydrocarbon-based radical, such as methyl or ethyl, unless otherwise indicated;
a (Cx-Cy)alkyl radical is a linear or branched Cx-Cy hydrocarbon-based radical; the expression“optionally interrupted” attributed to the alkyl radical or to the polyvalent hydrocarbon-based group A as defined previously means that said radical may be interrupted with one or more groups or heteroatoms chosen from O, S, CO or combinations thereof such as -CO-O- or -O-CO-, preferably interrupted with one or more non- adjacent oxygen atoms;
the expression“optionally substituted” attributed to the alkyl radical or to the polyvalent hydrocarbon-based group A as defined previously means that said radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) Ci-C4 alkoxy, iii) carboxyl, iv) acylamino, v) amino optionally substituted with one or two identical or different Ci-C4 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non nitrogen heteroatom;
■ an“alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a linear or branched C1-C10, preferentially Ci-C6 and more particularly C1-C4 hydrocarbon-based radical such as methoxy or ethoxy;
■ when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined hereinabove;
■ the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from one of the following atoms or groups:
- halogen;
- optionally substituted Ci-C6, preferably Ci-C4, alkyl;
- hydroxyl;
- Ci-C2 alkoxy;
- Ci-C4 (poly)hydroxyalkoxy;
- amino;
- 5- or 6-membered heterocycloalkyl;
- 5- or 6-membered heteroaryl, optionally substituted with a (Ci-C4)alkyl radical, preferentially methyl;
- amino substituted with one or two optionally substituted, identical or different Ci-C6 alkyl radicals:
- acylamino (-NR-C(O)-R') in which the radical R is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a Ci-C2 alkyl radical;
- carbamoyl ((R)2N-C(0)-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;
- alkylsulfonylamino (R'-S(0)2-N(R)-) in which the radical R represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C1-C4 alkyl radical, or a phenyl radical;
- aminosulfonyl ((R)2N-S(0)2-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group; - cyano;
- nitro or nitroso; and
- polyhaloalkyl, preferentially trifluoromethyl;
the cyclic or heterocyclic part of a non-aromatic group may be substituted with at least one substituent chosen from the following groups:
- hydroxyl;
- Ci-C4 alkoxy or C2-C4 (poly)hydroxyalkoxy;
- C1-C4 alkyl;
- alkylcarbonylamino (R-C(O)-N(R’)-), in which the radical R’ is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a Ci-C2 alkyl group or an amino optionally substituted with one or two identical or different C1-C4 alkyl groups which themselves optionally bear at least one hydroxyl group;
- alkylcarbonyloxy (R-C(O)-O-), in which the radical R is a C1-C4 alkyl radical or an amino group optionally substituted with one or two identical or different C1-C4 alkyl groups which themselves optionally bear at least one hydroxyl group;
- alkoxycarbonyl (R-G-C(O)-), in which the radical R is a C1-C4 alkoxy radical and G is an oxygen atom, or an amino group optionally substituted with a C1-C4 alkyl group which itself optionally bears at least one hydroxyl group;
a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups;
an "aryl" radical represents a monocyclic or fused or non-fused polycyclic carbon-based group, comprising from 6 to 22 carbon atoms, at least one ring of which is aromatic; such as phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferentially phenyl;
a“heteroaryl radical” represents an optionally cationic, 5- to 22-membered, monocyclic or fused or non-fused polycyclic group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, (benz)imidazolyl, (benzo)bistriazolyl, (benzo)pyrazolyl, (benzo)pyridazinyl, (benzo)quinolyl, (benzo)thiazolyl, (benzo)triazolyl, (benz)oxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthoxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthyl;
a "heterocyclic radical" is a fused or non-fused, 5- to 22-membered monocyclic or polycyclic but non-aromatic radical that may contain one or two unsaturations, including from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium;
a“heterocycloalkyl radical" is a heterocyclic radical comprising at least one saturated ring;
the term“limp” keratin fibres or“limp” hair is understood to mean that said fibres or hair are elastic, have no body, do not hold shape, and the head of hair is flat without volume;
the expression“at least one” is equivalent to“one or more”;
the limits of a range of values are included in that range, notably in the expressions "between... and ..." and "ranging from ... to ..."; and
the term "inclusive" for a range of concentrations means that the limits of that range are included in the defined range. The monosaccharides
The dyeing process according to the present invention comprises a step consisting in applying to keratin fibres a) one or more monosaccharides, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof, also referred to as ingredients a).
The monosaccharide(s) a) that may be used according to the present invention may or may not contain amine groups, i.e. they may be chosen from monosaccharides not comprising any amine groups, monosaccharides comprising at least one amine group, and mixtures thereof.
According to a first variant of the invention, the monosaccharide(s) a) are chosen from monosaccharides not comprising any amine groups, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof. According to a particular form of this variant, the monosaccharide(s) a) denote a mixture of monosaccharides, one of which is xylose or the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
According to another particular form of this variant, the monosaccharide(s) a) denote a single monosaccharide, in particular xylose or the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates.
According to a first embodiment, the monosaccharide(s) a) are chosen from C7 monosaccharides: heptoses, such as aldoheptoses and keto heptoses, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
According to a second preferred embodiment of the invention, the monosaccharide(s) a) are C6 monosaccharides: hexoses, and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
More preferentially, the monosaccharide(s) a) are chosen from hexoses of formula (Al), and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000012_0001
in which formula (Al) Ra, Rb, Rd, Re and Rf, which may be identical or different, represent i) a hydroxyl group, ii) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted, notably with one or more hydroxyl groups, or iii) a carboxyl group; more preferentially, Ra, Rb, Rd, Re and Rf represent a hydroxyl group.
Preferably, the monosaccharide(s) a) are chosen from the hexoses of formula (Al) of D configuration, also known as D-glucopyrans, and better still from the hexoses of formula (Al) of b (beta) anomeric configuration.
Better still, the monosaccharide(s) a) are chosen from hexoses of formula (AG) below, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, preferably D configuration, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000013_0001
in which formula (AG) Ra, Rb, Rd, Re and Rf are as defined previously for (Al).
The monosaccharide(s) a) are advantageously chosen from aldohexoses and ketohexoses, preferably from glucose, galactose, allose, altrose, mannose, gulose, idose and talose, and also the alpha or beta anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof, more preferentially from glucose and galactose, better still glucose, and even better still glucose of D configuration.
According to yet a third particular embodiment, the monosaccharide(s) a) are C5 monosaccharides: pentoses, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof. According to this embodiment, the monosaccharide(s) a) are chosen from the pentoses of formula (A2), and also the a or b anomers thereof, the isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000013_0002
in which formula (A2), Rg, Rh, Ri and Rj, which may be identical or different, represent i) a hydroxyl group, or ii) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted, notably with one or more hydroxyl groups. More preferentially, the monosaccharide(s) a) are chosen from the pentoses of formula (A2) of D configuration, and better still from the pentoses of formula (A2) of b (beta) anomeric configuration.
Preferably, the monosaccharide(s) a) are chosen from aldopentoses and ketopentoses, and mixtures thereof, and more preferentially xylose, arabinose, lyxose, ribose, ribulose and xylulose, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
According to this first variant of the invention, the monosaccharide(s) a) are advantageously chosen from monosaccharides not comprising any amine groups, and preferably from xylose and glucose, and mixtures thereof.
According to a second variant of the invention, the monosaccharide(s) a) are chosen from monosaccharides bearing an amine group, i.e. monosaccharides comprising at least one amine group, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof.
When the monosaccharide(s) a) are chosen from monosaccharides bearing amine group(s), they are preferably salified with a mineral acid such as hydrochloric acid.
According to one particular form of this variant, the monosaccharide(s) a) bear amine group(s) and denote a mixture of monosaccharide(s) bearing amine group(s), one of which is glucosamine or the salts thereof with an organic or mineral acid such as hydrochloric acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to another form of this variant, the monosaccharide(s) a) bear amine group(s) and denote a single monosaccharide bearing amine group(s), in particular glucosamine or the salts thereof with an organic or mineral acid or more particularly the mineral acid salts thereof such as the hydrochloric acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to a first particular embodiment, the monosaccharide(s) a) are C5 monosaccharides bearing amine group(s): pentosamines, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof. According to this particular embodiment of the invention, the pentosamines are chosen from aldopentosamines and ketopentosamines such as xylosamine, arabinosamine, lyxosamine, ribosamine, ribulosamine and xylulosamine and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to a second particular embodiment, the monosaccharide(s) a) are chosen from C7 monosaccharides bearing amine group(s): heptosamines such as aldoheptosamines and ketoheptosamines and also the organic or mineral acid salts thereof, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to yet a third particular embodiment, the monosaccharide(s) a) are chosen from C6 monosaccharides: hexosamines and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
Preferentially, the monosaccharide(s) a) of the invention are chosen from the hexosamines of formula (A3) below and also the salts thereof with an organic or mineral acid such as hydrochloric acid, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates:
Figure imgf000015_0001
in which formula (A3):
- Ra, Rb, Rd, Re and Rf, which may be identical or different, represent (1) a hydroxyl group, (2) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl groups, (3) a carboxyl group, or (4) a group NRIR2 with Ri and R2, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(C5-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (hetero)cyclo(C5-C7)alkyl(Ci- C4)alkyl group such as cyclohexylmethyl, vii) -C(Y)-(Y')P-R'i with Y and Y', which may be identical or different, representing an oxygen atom, a sulfur atom or N(R'2), preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined previously, and in particular R'i denoting a (Ci-C6)alkyl group such as methyl;
it being understood that at least one of the radicals Ra, Rb, Rd, Re and Rf, represents a group NR IR2 and preferably at least one of the radicals Ra, Rb, Rd, Re and Rf represents a group NR IR2 and the radicals other than NR IR2 denote a hydroxyl group.
Preferably, Ri and R2 are chosen from hydrogen and -C(0)-R’i in which R’i is as defined previously; and more preferentially Ri and R2 represent i) a hydrogen atom or ii) -C(0)-R’ i, with R’ i representing a (Ci-C4)alkyl group such as methyl.
Preferably, Rb represents a group NRI R2 such as NH2 or -N(H)-C(0)-R’ i with R’i representing a (Ci-C4)alkyl group such as methyl, and more preferentially NH2, and Ra, Rd, Re and Rf, represent a hydroxyl group.
Preferably, the monosaccharide(s) a) are chosen from the hexosamines of formula (A3) of D configuration, also known as D-glucopyrans, and more preferentially from the hexosamines of formula (A3) of b (beta) anomeric configuration.
Better still, the monosaccharide(s) a) of the invention are chosen from the hexosamines of formula (A3’) below and also the salts thereof with an organic or mineral acid such as hydrochloric acid, and also the a or b anomers thereof, the optical isomers thereof of L or D, preferably D, configuration, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000016_0001
in which formula (A3’) Ra, Rb, Rd, Re and Rf are as defined previously for (A3). The monosaccharide(s) a) are advantageously chosen from hexosamines, preferably from aldohexosamines and ketohexosamines, and mixtures thereof, more preferentially from glucosamine, galactosamine, allosamine, altrosamine, mannosamine, gulosamine, idosamine and talosamine, and mixtures thereof.
Preferably, the monosaccharide(s) a) are chosen from glucosamine and galactosamine, and also the salts thereof with an organic or mineral acid such as hydrochloric acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof; more preferentially, the monosaccharide a) is glucosamine, better still glucosamine of D configuration, and even better still glucosamine salified with a mineral acid such as hydrochloric acid.
The polysaccharides
The dyeing process according to the present invention also comprises a step consisting in applying to keratin fibres b) one or more polysaccharides bearing amine group(s), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, also referred to as ingredients b).
Preferably, the polysaccharide(s) bearing amine group(s) b) have an average molecular weight (MW) of less than or equal to 400 kDa and more preferentially less than 200 kDa.
Advantageously, the polysaccharide(s) bearing amine group(s) b) have a low average molecular weight MW, i.e. they have a molecular weight of less than 100 kDa, preferably less than 40 kDa; more preferentially, they have an average MW of between 1 kDa and 30 kDa and better still between 3 kDa and 28 kDa.
The polysaccharide(s) bearing amine group(s) b) are preferably of natural animal or plant origin, or else are derived from synthesis, semisynthesis or biosynthesis.
According to a particular embodiment of the invention, the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing C5-C7 saccharide units bearing amine group(s), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof. More particularly, the polysaccharide(s) bearing amine group(s) b) bear C6 saccharide unit bearing amine group(s), these polysaccharides bearing amine group(s) are then referred to as polyhexosamines.
According to a particular embodiment, the saccharide units of the polysaccharide bearing amine group(s) b) are of b (beta) anomeric configuration and/or D configuration.
According to a particular embodiment, the saccharide units of the polysaccharide bearing amine group(s) b) are connected together between the atoms of carbon 1 of one saccharide unit and of carbon 4 of the other saccharide unit, denoted (l 4).
According to this embodiment, the polysaccharide(s) bearing amine group(s) are preferably chosen from polysaccharides bearing a saccharide unit of formula (B) below, and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof.
Figure imgf000018_0001
in which formula (B):
- n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
- Ra, Rb and Rc, which may be identical or different for each saccharide unit, represent (1) a hydroxyl group, (2) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl and/or carboxyl groups, (3) a carboxyl group, or (4) a group NRIR2 with Ri and R2, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(C5-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (hetero)cyclo(C5-C7)alkyl(Ci-C4)alkyl group such as cyclohexylmethyl, vii) -C(Y)-(Y')P-R'i with Y and Y', which may be identical or different, representing an oxygen atom, a sulfur atom or N(R'2), preferably oxygen, p = 0 or 1, preferably 0; and R'i and R'2 representing i) to vi) of Ri and R2 defined previously, and in particular R'i denoting a (Ci-C6)alkyl group such as methyl;
it being understood that at least one of the radicals Ra, Rb or Rc of at least one saccharide unit represents a group NRIR2 and that at least one of the groups NRIR2 of at least one saccharide unit represents an NH2 group.
Preferably, Ri and R2 are chosen from a hydrogen atom and -C(0)-R’i in which R’i is as defined previously; and more preferentially Ri and R2 represent i) a hydrogen atom or ii) -C(0)-R’ i, with R’ i representing a (Ci-C4)alkyl group such as methyl.
Preferably, Ra of at least one saccharide unit represents a group NRIR2 with Ri which represents a hydrogen atom and R2 is chosen from i) a hydrogen atom or ii) a group -C(0)-R’ i , and Rb and Rc represent a hydroxyl group, it being understood that at least one of the groups NRIR2 of at least one saccharide unit represents an NH2 group.
More particularly, the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing saccharide units of formula (Bl) below, and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000019_0001
in which formula (Bl):
- R’ represents a hydrogen atom or a (Ci-C4)alkylcarbonyl group such as acetyl
CH3-C(0)-;
- R” represents a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a carboxyl group such as -CH(C02H)-CH3; - n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
it being understood that at least one saccharide unit bears an NH2 amino group and at least one other saccharide unit bears at least one N(H)-R' group with R' representing a (Ci-C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
Preferably, the saccharide units of formula (B) or (Bl) are of D configuration, also referred to as D-glucopyran.
Particularly, the saccharide units of formula (B) or (Bl) are of b (beta) anomeric configuration.
According to a particular embodiment, the polysaccharides b) are chosen from the polysaccharides bearing a saccharide unit of formula (B2) below and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000020_0001
in which formula (B2):
- Ra, Rb and Rc are as defined for (B) previously; and the radicals Ra, Rb and Rc of each saccharide unit may be identical or different; and
- n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
it being understood that at least one of the radicals Ra, Rb or Rc of at least one saccharide unit represents a group NRIR2, with Ri and R2 as defined previously for (B), and that at least one of the groups NRIR2 of at least one saccharide unit represents an NH2 group; preferably, at least one saccharide unit bears a group Ra representing a group -N(H)-R' with R' representing a (Ci-C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
Preferably, the polysaccharide(s) bearing amine group(s) b) are chosen from chitin and chitosan, and derivatives thereof, and more preferentially chitosan. More particularly, the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing a saccharide unit of formula (B3) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000021_0001
in which formula (B3):
- Ri and R2 are as defined in formulae (B) and (B2); and
- n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
it being understood that at least one saccharide unit bears an NH2 amino group and at least one other saccharide unit bears a group N(H)-R' with R' representing a (Ci- C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
More particularly, the polysaccharide(s) bearing amine group(s) b) are chosen from the chitosans of formula (B4) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000021_0002
in which formula (B4): - R'i representing a (Ci-C4)alkyl group such as methyl; and
- n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
- p is greater than 0 and ranges up to 0.5, preferably from 0.05 to 0.3, and better still from 0.1 to 0.20 such as 0.15 with m+p being equal to 1;
it being understood that, in the chitosan, at least one saccharide unit bears an amino group NH2 and at least one other saccharide unit bears a group N(H)-R'i with R'i representing a (Ci-C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
For example, when m = 0.7 and p = 0.3, this means that 70% of the amine groups are free (unsubstituted) and 30% of the amino groups are N-alkyl(Ci- C4)carbonyl groups, in particular N-acetyl groups, corresponding to the chitosan polymer of formula:
Figure imgf000022_0001
with n as defined previously.
Preferably, the polysaccharide(s) bearing amine group(s) b) are salified, or in salified form, using one or more organic or mineral acids, and preferably using one or more organic acids.
The organic or mineral acid(s) that may be used correspond to the mineral and organic acids described previously in the section "organic or mineral acid salt".
Preferably, the polysaccharide(s) bearing amine group(s) b) are salified using one or more organic acid(s) chosen from:
the monocarboxylic acids of formula (I):
R-C(0)-OH (I)
in which formula (I) R represents a (hetero)aryl radical such as phenyl, a (hetero)aryl(Ci-C4)alkyl radical such as benzyl, a (Ci-C3o)alkyl radical or an unsaturated C2-C30 radical (i.e. including at least one ethylenic unsaturation, preferably one ethylenic unsaturation); said alkyl or unsaturated C2-C30 radicals being optionally interrupted and/or optionally substituted preferably with one or more hydroxyl groups and not substituted with one or more amino radicals; R preferably denoting a (Ci-C6)alkyl group optionally interrupted and/or optionally substituted with 1, 2 or 3 hydroxyl groups; preferably, R represents a (Ci-C4)alkyl group such as methyl or ethyl;
- the polycarboxylic acids of formula (II):
Figure imgf000023_0001
in which formula (II) A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic polyvalent hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen and/or optionally substituted notably with one or more hydroxyl groups and t represents an integer between 1 and 5 inclusive; preferably, A represents a divalent (Ci-C6)alkylene group optionally substituted notably with one or more hydroxyl groups and not substituted with at least t amino radicals, and t is equal to 1, 2 or 3; and
- amino acids including more carboxylic acid radicals than amino groups.
Preferably, the monocarboxylic organic acids of formula (I) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof, and more preferentially from acetic acid, lactic acid, and mixtures thereof.
Preferably, the polycarboxylic acids of formula (II) are chosen from tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, and mixtures thereof.
Preferably, the amino acids including more carboxylic acid radicals than amino groups are chosen from gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and mixtures thereof, and more preferentially gamma-carboxyglutamic acid.
More preferentially, the organic acid(s) that may be used are chosen from acetic acid, glycolic acid, lactic acid, tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and mixtures thereof, and preferably, the organic acid is lactic acid. Particularly, the polysaccharide(s) bearing amine group(s) b) are chosen from chitosans, salified using organic acid, preferentially using monocarboxylic acid of formula (I) as defined previously or polycarboxylic acid of formula (II) as defined previously, even more preferentially salified using carboxylic acid of formula (I) such as lactic acid.
According to one particular form of the invention, the polysaccharide(s) bearing amine group(s) b) denote a mixture of polysaccharide(s) bearing amine group(s), one of which is a chitosan or the organic or mineral acid salts thereof, preferably the salts thereof with an organic acid such as lactic acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to another particular form of the invention, the polysaccharide(s) bearing amine group(s) b) denote a single polysaccharide bearing amine group(s), in particular a mixture of chitosan or the organic or mineral acid salts thereof or more particularly the organic acid salts thereof such as the lactic acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates.
According to yet another particular form of the invention, the polysaccharide(s) bearing amine group(s) b) denote a single polysaccharide bearing amine group(s), in particular a chitosan or the organic or mineral acid salts thereof or more particularly the organic acid salts thereof such as the lactic acid salt thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates. The dyestuffs
The dyeing process according to the present invention also comprises a step consisting in applying to the keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof, also referred to as ingredients c).
Preferably, the dyestuff(s) are chosen from pigments.
The term“pigment” is understood to denote a white or coloured solid particle which is naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which is rendered insoluble by formulation in the form of a lake, where appropriate. More particularly, the pigment has little or no solubility in aqueous-alcoholic media. Pigments that may be mentioned include organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a20 371 and ibid, "Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim 10.1002/ 14356007 a20_243.pub3.
Mention may be made especially of azo pigments which contain one or more azo groups A-N=N-B with A representing an optionally substituted (hetero)aryl, B representing optionally substituted (hetero)aryl or -CH[C(0)-R]-C(0)-Xi-A', A' representing an optionally substituted (hetero)aryl and R representing a hydrogen atom or a group (Ci-C6)alkyl, with the groups A, A' and B being (hetero)aryls that do not contain any solubilizing groups such as -S03H or -COOH.
They may in particular be monoazo pigments, including b-naphthols, monoazopyrrolone pigments or benzimidazolone pigments; diazo pigments, such as diazodiarylide pigments and bis(N-acetoacetarylide) pigments, or triazo or tetraazo pigments.
Mention may also be made of azo metal complex pigments.
Other pigments are also advantageous, namely isoindolinone and isoindoline pigments, phthalocyanine pigments; quinacridone pigments; perinone pigments; perylene pigments; anthraquinone pigments such as hydroxyanthraquinone pigments; aminoanthraquinone pigments including acylaminoanthraquinones and azo anthraquinone pigments; heterocyclic anthraquinones; polycarboxylic anthraquinone pigments, pyranthrone pigments; anthranthrone pigments; diketopyrrolopyrrole (DPP) pigments; thioindigo pigments; dioxazine pigments; triphenylmethane pigments; quinophthalone pigments; and fluorescent pigments.
When the dyes comprise one or more solubilizing groups such as -SO3H or -COOH, these dyes are made insoluble and consequently pigments by formation of a lake, i.e. by salification (e.g. Na, Ca, St, Ba, etc.) and divided mainly into b-naphthol and 2-hydroxy-3-naphthoic acid pigments "(BON) pigment lakes".
In the context of the present invention, the pigment may be at least partly organic.
According to one embodiment of the invention, the pigment is an organic pigment. According to another embodiment of the invention, the pigment is a mineral pigment.
The microcapsules according to the invention comprise not more than 80% by weight of pigment relative to the weight of the polymer matrix. In particular, they may comprise from 0.5% to 75% by weight, for example from 1% to 70% by weight, notably from 20% to 65% by weight or even from 30% to 60% by weight of pigment relative to the weight of the polymer matrix.
Needless to say, the degree of encapsulation depends on the desired modification of the shade and may thus vary significantly according to the effect that it is desired to obtain.
As illustrations of pigments that may be used in the present invention, mention may be made of carbon black, titanium oxide, chromium oxide, pigments of D&C or FD&C type and lakes thereof, and especially those known under the names D&C Blue No. 4, D&C Brown No. 1, FD&C Green No. 3, D&C Green No. 5, D&C Green No. 6, FD&C Green No. 8, 20 D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, FD&C Red No. 40, FD&C Red 40 lake, D&C Violet No. 2, Ext. D&C Violet No. 2, FD & C Blue No. 1, D&C Yellow No. 6, FD&C Yellow
No. 6, D&C Yellow No. 7, 25 Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10 or D&C Yellow No. 11, it being understood that when said pigment is not naturally insoluble in the hydrophilic and lipophilic phases usually used in cosmetics, it is used in the form of a corresponding lake, as explained previously.
Examples of lakes that may notably be mentioned include lakes based on barium, strontium, calcium or aluminium, or alternatively diketopyrrolopyrroles.
As further examples of pigments that may be used in the present invention, mention may be made notably of mineral pigments, optionally surface-treated and/or coated, and notably titanium dioxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or alternatively metal powders, for instance aluminium powder, copper powder, gold powder and silver powder.
Mention may also be made of pigments with an optical effect such as particles including a natural or synthetic organic or mineral substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being optionally covered with metal substances, for instance aluminium, gold, silver, platinum, copper or bronze, or with metal oxides, for instance titanium dioxide, iron oxide or chromium oxide.
They may also be nacres.
The term“nacres” means iridescent particles, which are notably produced by certain molluscs in their shell, or alternatively which are synthesized.
The nacreous pigments may be chosen from mica coated with titanium or with bismuth oxychloride, titanium mica coated with iron oxides, titanium mica coated notably with ferric blue or with chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. Use may also be made of interference pigments, notably liquid- crystal or multilayer pigments.
They may also be pigments having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type.
They may also be pigments having a structure that may be, for example, of silica microsphere type containing iron oxide.
As examples of pigments that are most particularly suitable for use in the present invention, mention may be made notably of D&C Red No. 7, titanium oxide, chromium oxide, lakes of the pigments of D&C and FD&C type mentioned above, and especially D&C Red No. 22 lake, Yellow No. 6 lake and FD&C Blue No. 1 lake.
The pigments in accordance with the invention may be in the form of pigment powder or paste. They may be coated or uncoated.
The pigments in accordance with the invention may be chosen, for example, from white or coloured pigments, lakes, pigments with special effects such as nacres or flakes, and mixtures thereof.
Examples of white or coloured mineral pigments that may be mentioned include zirconium oxide or cerium oxide, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
Examples of white or coloured organic pigments that may be mentioned include nitroso, nitro, azo, xanthene, quinoline, anthraquinone and phthalocyanine compounds, compounds of metallic complex type, and isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds. In particular, the white or coloured organic pigments may be chosen from carmine, carbon blacks such as Black 2, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880,
17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in patent FR 2 679 771.
Preferably, carbon blacks such as Black 2 or lakes such as D&C Red 7. Use may also be made of pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:
- Cosmenyl Yellow IOG: Yellow 3 pigment (Cl 11710);
- Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);
- Cosmenyl Orange GR: Orange 43 pigment (Cl 71105);
- Cosmenyl Red R: Red 4 pigment (Cl 12085);
- Cosmenyl Carmine FB: Red 5 pigment (Cl 12490);
- Cosmenyl Violet RL: Violet 23 pigment (Cl 51319);
- Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74160);
- Cosmenyl Green GG: Green 7 pigment (Cl 74260);
- Cosmenyl Black R: Black 7 pigment (Cl 77266).
The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles including:
- an inorganic core,
- at least one binder for fixing the organic pigments to the core, and
- at least one organic pigment at least partially covering the core.
The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium. Among the organic dyes, mention may be made of cochineal carmine.
Mention may be made, as examples of lakes, of the products known under the following names: D & C Red 21 (Cl 45 380), D & C Orange 5 (Cl 45 370), D & C Red 27 (Cl 45 410), D & C Orange 10 (Cl 45 425), D & C Red 3 (Cl 45 430), D & C Red 7 (Cl 15 850:1), D & C Red 4 (Cl 15 510), D & C Red 33 (Cl 17 200), D & C Yellow 5 (Cl 19 140), D & C Yellow 6 (Cl 15 985), D & C Green (Cl 61 570), D & C Yellow 1 O (Cl 77 002), D & C Green 3 (Cl 42 053) or D & C Blue 1 (Cl 42 090).
The term“pigments with special effects” refers to pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thus contrast with white or coloured pigments that afford a standard uniform opaque, semi-transparent or transparent shade.
Examples of pigments with special effects that may be mentioned include white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as mica coated with titanium and with iron oxides, mica coated with titanium and especially with ferric blue or with chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride.
Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
Quantum dots are luminescent semiconductive nanoparticles that are capable of emitting, under light excitation, radiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they may be manufactured according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein and also in the following publications: Dabboussi B.O. et a ,“(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocrystallites”, Journal of Physical Chemistry B, vol. 101, 1997, pages 9463-9475, and Peng, Xiaogang et al., “Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photo stability and electronic accessibility”, Journal of the American Chemical Society, vol. 119, No. 30, pages 7019-7029.
The pigments in accordance with the invention are preferably coloured pigments.
The variety of pigments used makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic or interference effects.
The size of a pigment other than the nacres in solution is generally between
10 nm and 10 pm, preferably between 50 nm and 5 pm and even more preferentially between 100 nm and 3 pm. The size of a nacre in solution is generally between 1 and 200 pm, preferably between 1 and 80 pm and even more preferentially between 1 and 50 pm.
Among the mineral pigments, examples that may be mentioned include titanium dioxide (rutile or anatase) optionally surface-treated and codified in the Color Index under the reference Cl 77891; black, yellow, red and brown iron oxides, codified under the references Cl 77499, 77492 and 77491; manganese violet (Cl 77742); ultramarine blue (Cl 77007); hydrated chromium oxide (Cl 77289); ferric blue (077510).
Among the organic pigments that may be mentioned, for example, are the pigment Yellow 3 sold notably under the trade name Jaune Covanor W 1603 by the company Wackherr (Cl 17710), D & C Red No. 19 (Cl 45170), D & C Red No. 9 (Cl 15585), D & C Red No. 21 (Cl 45380), D & C Orange No. 4 (Cl 15510), D & C Orange No. 5 (Cl 45370), D & C Red No. 27 (Cl 45410), D & C Red No. 13 (Cl 15630), D & C Red No. 7 (Cl 15850-1), D & C Red No. 6 (Cl 15850-2), D & C Yellow No. 5 (Cl 19140), D & C Red No. 36 (Cl 12085), D & C Orange No. 10 (Cl 45425), D & C Yellow No. 6 (Cl 15985), D & C Red No. 30 (Cl 73360), D & C Red No. 3 (Cl 45430), carbon black (Cl 77266) and lakes based on cochineal carmine (Cl 75470).
It is also possible to use nacreous pigments, which may be chosen notably from white nacreous pigments such as mica coated with titanium oxide or bismuth oxide; coloured nacreous pigments such as titanium mica with iron oxides, titanium mica with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also those based on bismuth oxychloride.
Pigment pastes of organic pigment are used more particularly, such as the products sold by the company Hoechst under the names:
- Cosmenyl Yellow 10G: Yellow 3 pigment (Cl 11710);
- Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);
- Cosmenyl Orange GR: Orange 43 pigment (Cl 71105)
- Cosmenyl Red R: Red 4 pigment (Cl 12085)
- Cosmenyl Carmine FB: Red 5 pigment (Cl 12490)
- Cosmenyl Violet RL: Violet pigment 23 (Cl 51319)
- Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74260)
- Cosmenyl Green GG: Green 7 pigment (Cl 74260)
- Cosmenyl Black R: Black 7 pigment (Cl 77266)
The dyestuff(s) are advantageously chosen from pigments, preferably from white organic pigments, coloured organic pigments, and mixtures thereof, and more preferentially carbon blacks, such as Black 2, lakes, such as D&C Red 7, and mixtures thereof.
Preferably, the dyestuff(s) are chosen from direct dyes.
The term "direct dye" means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.
They may be ionic or nonionic, preferably cationic or nonionic, either as sole dyes.
These direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.
Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes, and natural direct dyes, alone or as mixtures.
Preferentially, the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group. According to a particular embodiment of the invention, the direct dyes comprise at least one quatemized cationic chromophore.
Mention may be made, as direct dye according to the invention, of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines, such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids, such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines, such as dimethines of stilbene or styryl types; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, in particular nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines; thioindigos; thiopyronines; triarylmethanes or xanthenes.
For the cationic azo dyes, mention may be made particularly of those resulting from the cationic dyes described in Kirk-Othmer’s Encyclopedia of Chemical Technology,“Dyes, Azo”, J. Wiley & Sons, updated on 19 April 2010.
Among the azo dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.
According to a preferred embodiment of the invention, the direct dye(s) are chosen from cationic dyes known as "basic dyes".
Among the azo dyes described in the Colour Index International 3rd edition, mention may be made notably of the following compounds:
- Basic Red 22
- Basic Red 76
- Basic Yellow 57
- Basic Brown 16 - Basic Brown 17.
Among the cationic quinone dyes, those mentioned in the abovementioned Colour Index International are suitable and, among these, mention may be made, inter alia, of the following dyes:
- Basic Blue 22
- Basic Blue 99.
Among the azine dyes that are suitable for use, mention may be made of those listed in the Colour Index International, for example the following dyes:
- Basic Blue 17
- Basic Red 2.
Among the cationic triarylmethane dyes that may be used according to the invention, mention may be made, in addition to those listed in the Colour Index, of the following dyes:
- Basic Green 1
- Basic Violet 3
- Basic Violet 14
- Basic Blue 7
- Basic Blue 26.
Mention may also be made of the cationic dyes described in the documents US 5 888 252, EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. Mention may also be made of those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons.
Preferably, the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type.
According to a particular embodiment, the direct dyes are cationic azo dyes, described in EP 850 636, FR 2 788 433, EP 920 856, WO 99/48465, FR 2 757 385, EP 850 637, EP 918 053, WO 97/44004, FR 2 570 946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO 01/66646, US 5 708 151, WO 95/01772, WO 515 144, GB 1 195 386, US 3 524 842, US 5 879 413, EP 1 062 940, EP 1 133 976, GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chim. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211 ; Rev. Roum. Chim. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9), 600-3;
Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233- 4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11(3), 163-72.
Preferably, the cationic direct dye(s) comprise(s) a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.
These cationic radicals are, for example, a cationic radical:
- bearing an exocyclic (di/tri)(C i -C8)alkylammonium charge, or
- bearing an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bistetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium.
Mention may be made of the hydrazono cationic dyes of formulae (III) and (IV) and the azo cationic dyes of formulae (V) and (VI) below:
Het+-C(Ra)=N-N(Rb)-Ar, Q Het+-N(Ra)-N=C(Rb)-Ar, Q
(III) (IV)
Het+-N=N-Ar, Q Ar+-N=N-Ar”, Q
(V) (VI) in which formula (III) to (VI): • Het+ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferentially with at least one (Ci-C8) alkyl group such as methyl;
• Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci- Cg)alkyl ammonium, such as trimethylammonium;
• Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cg)alkyl, ii) optionally substituted (Ci-Cg)alkoxy, iii) (di)(Ci- Cg)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-Cg)alkylamino, v) optionally substituted N-(Ci-Cg)alkyl-N- aryl(Ci-Cg)alkylamino or alternatively Ar represents a julolidine group;
• Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially by one or more (Ci- Cg)alkyl, hydroxyl, (di)(Ci-Cg)(alkyl)amino, (Ci-Cg)alkoxy or phenyl groups;
• Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-Cg)alkyl group, which is optionally substituted, preferentially with a hydroxyl group;
• or else the Ra substituent with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cyclo alkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
• Q represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (III) to (VI) as defined previously. More particularly, the cationic direct dyes of formulae (III) to (VI) bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO
95/01772 and EP 714 954. Preferentially the following direct dyes:
Figure imgf000035_0001
(III-1) (V-l)
in which formulae (III- 1 ) and (V-l):
- R1 represents a (Ci-C4)alkyl group such as methyl;
- R and R , which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl; and
- R4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs)alkoxy, or (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferentially CH,
- Q is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
In particular, the dyes of formulae (III- 1 ) and (V-l) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
Figure imgf000036_0001
Basic Red 51 Basic Orange 31 Basic Yellow 87 with Q' being an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.
According to a particular embodiment of the invention, the direct dyes are fluorescent, i.e. they contain at least one fluorescent chromophore as defined previously. Fluorescent dyes that may be mentioned include the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-lH-pyrrolato-kN}borons (BODIPY®), diketopyrrolopyrroles, fluorindines, (poly)methines (in particular cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes and xanthenes.
Mention may also be made of the fluorescent dyes described in the documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO
95/15144 and EP 714 954 and those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann’s Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in the handbook— "A Guide to Fluorescent Probes and Labeling Technologies", lOth Ed., Molecular Probes/In vitrogen - Oregon 2005, circulated on the Internet or in the preceding printed editions.
According to a preferred variant of the invention, the fluorescent dye(s) are cationic and comprise at least one quaternary ammonium radical, such as those of formula (VII) below:
W+-[C(Rc)=C(Rd)]m -Ar, Q
(VII)
in which formula (VII):
• W+ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more (Ci- Cg)alkyl groups, optionally substituted notably with one or more hydroxyl groups;
· Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (Ci-Cg)alkyl, preferably of Ci-C4 such as methyl; iii) one or more hydroxyl groups; iv) one or more (Ci-Cg)alkoxy groups such as methoxy; v) one or more hydroxy(Ci-Cg)alkyl groups such as hydroxyethyl, vi) one or more amino groups or (di)(C i -Cgjalkylamino, preferably with the C1-C4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocyclo alkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;
• m’ represents an integer between 1 and 4 inclusive, and in particular m has the value 1 or 2; more preferentially 1;
• Rc and Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (Ci-Cg)alkyl group, preferentially of Ci-C4, or alternatively Rc contiguous with W+ and/or R contiguous with Ar form, with the atoms that bear them, a (hetero)cycloalkyl; particularly, Rc is contiguous with W+ and they form a (hetero)cycloalkyl such as cyclohexyl;
• Q is an organic or mineral anionic counterion as defined previously.
Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions comprising these natural dyes and in particular henna-based poultices or extracts. The compositions
A subject of the present invention is also an aqueous composition (C) at acidic pH comprising:
a) one or more monosaccharide(s) as defined previously,
b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined previously,
c) one or more dyestuffs, as defined previously, and
d) optionally one or more mineral or organic acids, preferably other than the following acids: aspartic acid.
According to a particular embodiment of the invention, ingredients a), b) and c) as defined previously are applied sequentially and are preferably included in three separate compositions (ca), (cb) and (cc). In other words, composition (ca) comprises a) one or more monosaccharides as defined previously, composition (cb) comprises b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined previously, and optionally c) one more mineral or organic acid(s), and composition (cc) comprises one or more dyestuffs as defined previously.
The mineral or organic acid(s) that may be used in compositions (C) and
(cb) of the invention correspond to the mineral and organic acids described previously in the "organic or mineral acid salt” section.
The content of the monosaccharide(s), present in compositions (C) and (ca), preferably ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and better still from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
The content of polysaccharide(s) bearing amine group(s), present in compositions (C) and (cb), preferably ranges from 0.01% to 20% by weight, more preferentially from 0.05% to 10% by weight and even better still from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
The weight ratio of the content of monosaccharide(s) and the amount of polysaccharide(s) bearing amine group(s), present in composition (C) of the invention, preferably ranges from 0.5 to 10.
The content of the dyestuff(s), chosen from pigments and direct dyes, and mixtures thereof, present in compositions (C) and (cc), preferably ranges from 0.05% to 30% by weight and more preferentially from 0.5% to 10% by weight relative to the total weight of the composition comprising same.
Composition (C) and composition(s) (ca), (cb) and/or (cc) are cosmetic compositions, i.e. they contain a physiologically acceptable medium, i.e. a medium that is compatible with human keratin materials such as the skin (of the body, face, area around the eyes, or the scalp), the hair, the eyelashes, the eyebrows, bodily hair, the nails or the lips.
The cosmetically acceptable medium of composition(s) (C), (ca), (cb) and/or
(cc) is advantageously an aqueous medium. It may be constituted, for example, of water or of a mixture of water and of at least one cosmetically acceptable organic solvent.
Examples of organic solvents that may be mentioned include C2-C4 lower alcohols, such as ethanol and isopropanol; polyols, notably those containing from 2 to 6 carbon atoms, for instance glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol or diethylene glycol; polyol ethers, for instance 2-butoxyethanol, propylene glycol monomethyl ether and diethylene glycol monomethyl ether or monoethyl ether; and mixtures thereof.
Preferably, the cosmetic composition(s) (C), (ca), (cb) and/or (cc) each comprise from 50% to 99.8% by weight of water, relative to the weight of each composition.
The pH values of the composition(s) (C), (ca), (cb) and/or (cc) of the invention may be adjusted with an organic or mineral acid, or with an alkaline agent chosen from mineral, organic or hybrid alkaline agents or mixtures thereof.
The pH values may be adjusted with d) one or more organic or mineral acids as defined previously in the section“Organic or mineral acid salt”.
Preferably, composition (ca) which comprises a) one or more monosaccharides as defined previously, and notably glucose or xylose, is at an acidic pH, i.e. less than 7, in particular less than or equal to 6. More particularly, the pH of composition (ca) is between 2 and 6, preferentially between 2.5 and 5.5 and more preferentially between 3.5 and 5, such as 4.5.
Preferably, the monosaccharide(s) a), present in composition (ca) are in the presence of one or more mineral acid(s), more particularly hydrochloric acid.
Preferably, composition (cb) which comprises b) one or more polysaccharide(s) bearing amine group (s) as defined previously, and in particular a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, such as chitosan, is at an acidic pH, i.e. less than 7, and in particular less than or equal to 6. More particularly, the pH of composition (cb) is between 2 and 6, preferentially between 2.5 and 5.5 and more preferentially between 3.5 and 5, such as 4.5.
Preferably, the polysaccharide(s) bearing amine group(s) b), present in composition (cb), are in the presence of one or more organic acid(s), preferentially chosen from the monocarboxylic acids of formula (I) or the polycarboxylic acids of formula (II) as defined previously, and even more preferentially from the carboxylic acids of formula (I), such as lactic acid.
According to a first particular embodiment of the invention, composition (C) comprises:
a) one or more monosaccharides as defined previously, preferably glucose or xylose, in the presence of one or more mineral acid(s), preferably hydrochloric acid, and b) one or more polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide comprising saccharide units of formula (B), (Bl), (B2) or (B3) or (B4) as defined previously, more preferentially chitosan, and even better still chitosan with an average molecular weight of less than or equal to 400 kDa, in the presence of one or more mineral acid(s), preferably lactic acid,
c) one or more dyestuff(s) as defined previously, and
d) optionally one or more mineral or organic acids;
the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
According to a second particular embodiment of the invention, composition (C) comprises:
a) one or more monosaccharides as defined previously, preferably glucose or xylose, in the absence of organic or mineral acid(s), and
b) one or more polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, more preferentially chitosan, in the presence of one or more mineral acid(s), preferably lactic acid,
c) one or more dyestuff(s) as defined previously, and
d) optionally one or more mineral or organic acids;
the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
According to a third particular embodiment of the invention, composition (C) comprises:
a) one or more monosaccharides as defined previously, preferably glucose or xylose, in the presence of one or more mineral acid(s), preferably hydrochloric acid, and b) one or more polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide comprising saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, more preferentially chitosan, and even better still chitosan with an average molecular weight of less than or equal to 400 kDa, in the absence of organic or mineral acid(s),
c) one or more dyestuff(s) as defined previously, and
d) optionally one or more mineral or organic acids; the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
According to a fourth particular embodiment of the invention, composition (C) comprises:
a) one or more monosaccharides as defined previously, preferably glucose or xylose, in the absence of mineral acid(s),
b) one or more polysaccharide(s) bearing amine group(s) as defined previously, preferably a polysaccharide bearing saccharide units of formula (B), (Bl), (B2), (B3) or (B4) as defined previously, more preferentially chitosan, and even better still chitosan with an average molecular weight of less than or equal to 400 kDa, in the absence of organic or mineral acid(s), and
c) one or more dyestuff(s) as defined previously, and
d) one or more mineral or organic acids, said acid c) preferably being chosen from hydrochloric acid, the organic monocarboxylic acids of formula (I) as defined previously, the polycarboxylic acids of formula (II) as defined previously, and more preferentially from hydrochloric acid, lactic acid, citric acid, fumaric and maleic acid, and mixtures thereof;
the pH of said composition (C) is acidic, i.e. less than 7, preferably less than or equal to 6, more preferentially between 2 and 6, even better still between 2.5 and 5.5 and even more preferentially between 3.5 and 5, such as 4.5.
According to a fifth particular embodiment of the invention, composition (C) comprises one or more monosaccharides a) chosen from monosaccharides bearing an amine group as defined previously.
The pH values of compositions (C), (ca), (cb) and/or (cc) may be adjusted with one or more mineral alkaline agents which are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.
The pH values may also be adjusted with one or more organic alkaline agents which are organic amines, i.e. they contain at least one substituted or unsubstituted amino group. The organic alkaline agent(s) are more preferentially chosen from organic amines with a pKb at 25°C of less than 12, preferably of less than 10 and even more advantageously of less than 6. It should be noted that it is the pKb corresponding to the function of highest basicity.
The pH values may also be adjusted with one or more hybrid compounds. Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.
The organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (VIII) below:
R \ / RZ
N -W- N
Ry /
Figure imgf000043_0001
(VIII)
in which formula (VIII):
- W is a divalent Ci-C6 alkylene radical optionally substituted with a hydroxyl group or a Ci-C6 alkyl radical and/or optionally interrupted with one or more heteroatoms, such as oxygen or NRU;
- Rx, Ry, Rz, R1 and Ru, which may be identical or different, represent a hydrogen atom, a Ci-C6 alkyl radical, a Ci-C6 hydroxyalkyl radical or a Ci-C6 aminoalkyl radical.
The polysaccharide(s) bearing amine group(s), present in composition (C) of the invention, may be salified or non-salified.
According to a first variant of the invention, composition (C) corresponds to composition (C) at acidic pH and comprises:
a) one or more monosaccharides as defined previously;
b) one or more salified polysaccharides bearing amine group(s) as defined previously, preferably with an average molecular weight of less than or equal to 400 kDa;
c) one or more dyestuffs as defined previously; and
d) optionally one or more mineral or organic acids.
According to another variant of the invention, composition (C) corresponds to composition (C”) at acidic pH and comprises:
a) one or more monosaccharide(s) as defined previously; b) one or more non-salified polysaccharides bearing amine group(s) as defined previously, preferably with an average molecular weight of less than or equal to 400 kDa;
c) one or more dyestuff(s) as defined previously; and
d) optionally one or more mineral or organic acids.
Compositions (C) and/or (cc) may optionally also comprise one or more additional direct dyes other than the direct dyes mentioned previously.
These direct dyes are chosen, for example, from those conventionally used in direct dyeing, and among which mention may be made of any commonly used aromatic and/or non-aromatic dye such as neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, natural direct dyes other than pigments and/or one or more direct dyes that are sparingly soluble or insoluble in aqueous-alcoholic solvents, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine direct dyes, and fluorescent dyes.
Among the natural direct dyes, mention may be made of lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts may also be used.
Compositions (C), (ca), (cb) and/or (cc) may also optionally comprise one or more additives other than the compounds of the invention and among which mention may be made of cationic, anionic, nonionic, amphoteric or zwitterionic surfactants, cationic, anionic, nonionic or amphoteric polymers, or mixtures thereof, other than the polysaccharides of the invention, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, sequestrants, plasticizers, solubilizers, silicones, oils, mineral or organic thickeners, notably polymeric thickeners, antioxidants, hydroxy acids, fragrances, preserving agents and ceramides.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the compositions according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s). The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition comprising same. Process for dyeing keratin fibres
The process for dyeing keratin fibres, in particular human keratin fibres such as the hair, according to the present invention comprises:
(i) a step consisting in applying to said keratin fibres a) one or more monosaccharides,
(ii) a step consisting in applying to said keratin fibres b) one or more polysaccharides bearing amine group(s), in salified or non-salified form; and
(iii) a step consisting in applying to said keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof;
it being understood that steps (i), (ii) and (iii) may be performed simultaneously or sequentially, before being followed by
(iv) a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
The dyeing process according to the present invention may optionally also comprise a step of drying the keratin fibres. When it is present, this step of drying the keratin fibres follows steps (i), (ii) and (iii) and precedes the heat treatment step (iv).
According to a first particular embodiment of the process of the invention, steps (i), (ii) and (iii) are performed simultaneously, i.e. together. In other words, a) the monosaccharide(s) as defined previously, b) the polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined previously, and c) the dyestuff(s) chosen from pigments, direct dyes, and mixtures thereof, as defined previously, are applied together or else the process of the invention comprises a first step of applying to the keratin fibres an aqueous composition (C) as defined previously.
Preferably, the process of the invention comprises a first step consisting in applying to the keratin fibres composition (C) as defined previously, optionally followed by a step of drying said keratin fibres, followed by a step of heat treatment of said keratin fibres at a temperature of greater than 80°C, preferably of between l00°C and 250°C, and preferably with an iron.
According to a first advantageous variant of the invention, composition (C) is composition (C) as defined previously. According to another advantageous variant of the invention, composition (C) represents a composition (C") as defined previously.
In other words, according to a first variant of this embodiment, the process of the invention comprises:
- a step consisting in simultaneously applying to the keratin fibres a) the monosaccharide(s) as defined previously, b) the polysaccharide(s) bearing amine group(s) as defined previously, and c) the dyestuff(s) chosen from pigments, direct dyes, and mixtures thereof, as defined previously, followed by a leave-on time of between 1 and 60 minutes,
- optionally followed by a step of drying said keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature of greater than or equal to 80°C, preferably of between l00°C and 250°C.
According to a second variant of this embodiment, the process of the invention comprises:
- a step consisting in applying to the keratin fibres a composition (C), (C’) or (C”) as defined previously, followed by a leave-on time of between 1 and 60 minutes,
- optionally followed by a step of drying said keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature of greater than or equal to 80°C, preferably of between l00°C and 250°C.
According to a second embodiment of the invention, steps (i) and (ii) may be performed simultaneously, before or after step (iii). In other words, according to a first variant of this embodiment, the process may comprise:
- a step consisting in applying to said keratin fibres a) one or more monosaccharides as defined previously, and b) one or more polysaccharides bearing amine group(s), in salified or non-salified form, as defined previously,
- optionally followed by a step of drying the keratin fibres,
- followed by a step consisting in applying to said keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof, as defined previously,
- optionally followed by a step of drying the keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
According to a second variant of this embodiment, the process may comprise: - a step consisting in applying to said keratin fibres the mixture of compositions (ca) and (cb) as defined previously, followed by a leave-on time of between 1 and 30 minutes,
- optionally followed by a step of drying the keratin fibres,
- followed by a step consisting in applying to said keratin fibres composition (cc) as defined previously, followed by a leave-on time of between 1 and 30 minutes,
- optionally followed by a step of drying the keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
According to a third variant of this embodiment, the process may comprise:
- a step consisting in applying to said keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof, as defined previously,
- optionally followed by a step of drying the keratin fibres,
- followed by a step consisting in applying to said keratin fibres a) one or more monosaccharides as defined previously, and b) one or more polysaccharides bearing amine group(s), in salified or non-salified form, as defined previously,
- optionally followed by a step of drying the keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
According to a fourth variant of this embodiment, the process may comprise:
- a step consisting in applying to said keratin fibres composition (cc) as defined previously, followed by a leave-on time of between 1 and 30 minutes,
- optionally followed by a step of drying the keratin fibres,
- followed by a step consisting in applying to said keratin fibres the mixture of compositions (ca) and (cb) as defined previously, followed by a leave-on time of between 1 and 30 minutes,
- optionally followed by a step of drying the keratin fibres,
- followed by a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
According to a particular variant of the invention, the process of the invention does not use oxidized polysaccharide, more generally the process of the invention does not use a compound comprising at least one aldehyde group. According to a preferred embodiment of the invention, composition (cb), (C), (C) or (C") as defined previously does not contain oxidized polysaccharide and more generally composition (cb), (C), (C) or (C") does not contain a compound comprising at least one aldehyde group.
The process according to invention may also comprise an additional step of drying the keratin fibres after the application a) of the monosaccharide(s) as defined previously, b) of the polysaccharide(s) bearing amine group(s) as defined previously and/or c) of the dyestuff(s) as defined previously or after application of compositions (C), (C’), (C”), (ca), (cb) and/or (cc) containing same and before the step of heat treatment (iv) of the keratin fibres performed at a temperature of at least 80°C.
Preferably, the process of the invention involves a step of drying the keratin fibres, in particular human keratin fibres such as the hair, before the heat treatment step (iv).
The drying step is notably performed using a hairdryer, a hood, or else with a towel, an absorbent or by drying naturally. This drying step is advantageously performed at a temperature ranging from 20 to 70°C.
The keratin fibre heat treatment step (iv) of the process of the invention is preferably performed at a temperature of between 80°C and 250°C, it being understood that the temperature is that of the heating means, in particular of the iron, and not the temperature of the keratin fibres.
According to a preferred form of the invention, the heat treatment step (iv) is performed on dry keratin fibres.
Preferably, the keratin fibre heat treatment step (iv) is performed at a temperature of at least l00°C, in particular at a temperature of between l00°C and 250°C, inclusive.
Advantageously, the keratin fibre heat treatment step (iv) is performed at a temperature ranging from l50°C to 220°C, preferably ranging from l60°C to 220°C, more preferentially ranging from l60°C to 200°C, and even better still ranging from l30°C to l90°C.
It is understood that the heat treatment temperatures correspond to the temperatures of the heating means, in particular of the iron when an iron is used, and not the temperature of the keratin fibres.
This heat treatment step (iv) is advantageously performed using an iron. For the purposes of the present invention, the term "iron" means a device for heating keratin fibres by placing said fibres in contact with the heating device.
For the purposes of the present invention, the iron is other than a heating comb.
The end of the iron which comes into contact with the keratin fibres generally has two surfaces. These two surfaces may be made of metal or of ceramic. In particular, these two surfaces may be smooth or crimped or curved.
The heat treatment step may be performed by means of a straightening iron, a curling iron, a crimping iron or a steam iron such as a Steampod. Preferably, the heat treatment step is performed by means of a straightening iron.
For the purposes of the present invention, the term“steam irons” refers to irons which comprise a device which emits steam and which applies this steam before, during or after the straightening/relaxing.
As examples of irons that may be used in the process according to the invention, mention may be made of any type of flat hair iron, and in particular, in a non-limiting manner, those described in patents US 5 957 140 and US 5 046 516.
The iron may be applied by successive separate strokes lasting a few seconds or by gradual movement or sliding along the keratin fibres, in particular along human keratin fibres such as the hair.
Preferably, the iron is applied in the process according to the invention by a continuous movement from the root to the end of the keratin fibres, notably human keratin fibres such as the hair, in one or more strokes, in particular in one to twenty strokes. Each stroke of the hair iron may last from 2 seconds to 1 minute for a length of the treated keratin fibres of 30 cm ± 3 cm.
Step (iv) of heat treatment of the keratin fibres is performed for a time that may range advantageously from 100 milliseconds to 30 minutes, preferably from 1 second to 15 minutes, more preferentially from 2 seconds to 10 minutes, even better still from 3 seconds to 5 minutes and even better still from 4 seconds to 1 minute.
The bath ratio of the composition(s) applied before the heat treatment step of the process preferably ranges from 0.1 to 10, and more preferentially from 0.2 to 5.
For the purposes of the present invention, the term "bath ratio" means the ratio between the total weight of the applied composition and the total weight of keratin fibres to be treated. After the heat treatment step (iv) of the process, the keratin fibres may be optionally rinsed with water or washed with a shampoo. The keratin fibres are then optionally dried using a hairdryer or a hood or left to dry naturally.
According to a particular embodiment of the invention, the dyeing process is performed one or more times, optionally spaced by one or more cosmetic treatments, preferably spaced by one or more shampoo washes, to treat keratin fibres that have regrown or that have undergone other treatments liable to cause changes in the colouring, or to obtain the desired colour intensity.
According to one embodiment of the invention, the process is performed on keratin fibres, in particular human keratin fibres such as the hair, which are notably natural, notably natural hair.
The kit
A subject of the invention is also a kit comprising:
- a multi-compartment device comprising a first compartment containing a cosmetic composition (ca) comprising one or more monosaccharides as defined previously; a second compartment containing a cosmetic composition (cb) comprising one or more polysaccharides bearing amine group(s) as defined previously and optionally one or more organic or mineral acids as defined previously; and a third compartment containing a dye composition (cc) comprising one or more dyestuffs as defined previously; and
- a device for heating the keratin fibres to a temperature of greater than or equal to 80°C, preferably between l00°C and 250°C.
The contents of each compartment of the kit may be released either sequentially or simultaneously.
The composition packaging assembly, i.e. the multi-compartment device, is, in a known manner, any packaging that is suitable for storing cosmetic compositions (notably a bottle, tube, spray bottle or aerosol bottle).
Such a kit allows the process for dyeing keratin fibres according to the invention to be performed.
The examples that follow serve to illustrate the invention without, however, being limiting in nature. EXAMPLES
Example 1 1) Preparation of the compositions
Composition (A) and the dye composition (B) according to the present invention were prepared from the ingredients mentioned in the tables below, the contents of which are expressed as weight percentages relative to the total weight of the composition comprising same.
Figure imgf000051_0001
Figure imgf000051_0002
2) Protocol
Composition (A) and the dye composition (B) obtained below are applied according to processes 1 to 9 below:
Processes 1 and 2 (comparative)
At the time of use, the dye composition (B) is diluted to 10% in water.
The solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7- second strokes with a straightening iron at a temperature of l90°C.
Processes 3 and 4 (invention)
At the time of use, the dye composition (B) is diluted to 10% in composition
(A).
The mixture thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7- second strokes with a straightening iron at a temperature of l90°C.
Processes 5 and 6 (invention)
At the time of use, the dye composition (B) is diluted to 10% in water.
The solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood.
Composition (A) is then applied to the two locks of hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Processes 7, 8 and 9 (invention)
At the time of use, the dye composition (B) is diluted to 10% in water.
The solution thus obtained is applied to two locks of sensitized hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood.
Composition (A) is then applied to the two locks of hair at a rate of 0.5 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
The application of composition (A) followed by the leave-on time, drying under a hood and five successive strokes with a straightening iron were repeated three times. On conclusion of each of the processes mentioned above, the locks of hair of processes 2, 4, 6 and 8 are washed with a shampoo according to the following protocol:
The locks are rinsed thoroughly with water at 37°C for 15 seconds. The locks are then washed with a DOP shampoo, in a proportion of 0.4 g of shampoo per gram of hair. The locks are then rinsed with water for 15 seconds, followed by being drained dry, combed and then dried.
This protocol is repeated five times for the lock of process 9. 3) Qualitative results
The colour of the locks and the colour transfer onto the fingers are evaluated visually. The results are given in the table below.
Figure imgf000053_0001
Figure imgf000054_0002
The results obtained above show that the process of the invention gives the hair a black colouring that is persistent with respect to shampoo washing, and does so for up to five shampoo washes (process 9), unlike the comparative processes not involving any monosaccharide or any polysaccharide bearing amine group(s).
Moreover, the colouring obtained by means of the process of the invention does not transfer onto the user’s fingers.
4) Quantitative results
The colour of the locks is then evaluated by colorimetry in the CIE L* a* b* system, using a Minolta CM 3600 spectrocolorimeter (illuminant D65, angle 10°, specular component included).
In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis. The smaller the value of L*, the darker and more powerful the colouring.
The smaller the value of a*, the greener the colour and the higher the value of a*, the redder the colour.
The smaller the value of b*, the bluer the colour and the higher the value of b*, the yellower the colour.
The colour buildup, corresponding to the variation in colouring between the locks of hair before and after the treatment or dyeing, is defined by (DE*) according to the following equation:
Figure imgf000054_0001
In this equation, L*, a* and b* represent the values measured on locks of hair after shampoo washing, namely the locks of hair of processes 2, 4, 6, 8 and 9 mentioned above, and L0*, aO* and bO* represent the values measured on the respective locks of hair not washed with the shampoo, namely the locks of hair of processes 1, 3, 5 and 7 mentioned above.
In other words, the value of DE* for process 2 was calculated with L*, a* and b* representing the values obtained for process 2, and L0*, a0* and b0* representing the values obtained for process 1.
The lower the value of DE*, the greater the resistance of the colourings with respect to shampoo washing. The colorimetric values obtained after dyeing the locks by means of processes 1 to 9 are given in the table below.
Figure imgf000055_0001
The results obtained above show that the colouring obtained by means of the process of the invention, using a monosaccharide, a polysaccharide bearing amine group(s) and a dyestuff, is resistant to shampoo washing, unlike the colouring obtained via the comparative process not involving a monosaccharide or a polysaccharide bearing amine group(s).
The colouring obtained by means of the process of the invention is also persistent with respect to shampoo washing at least five times (process 9).
Example 2
1) Preparation of the compositions Compositions (A’) and (A") and the dye composition (B’) according to the present invention were prepared from the ingredients mentioned in the tables below, the contents of which are expressed as weight percentages relative to the total weight of the composition comprising same.
Figure imgf000056_0001
Figure imgf000056_0002
2) Protocol
Composition (A’) and the dye composition (B’) obtained above are applied according to processes 11 and 13 below. The comparatives were prepared by replacing composition (A') with water according to processes 10 and 12 below.
Composition (A') and the dye composition (B') obtained above are applied according to processes 15 and 17 below and the comparatives are prepared by replacing composition (A") with water according to processes 14 and 16 below.
Process 10 (comparative)
The dye composition (B') is applied to two locks of natural grey hair at a rate of 1 g of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two locks of hair at a rate of 3 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 11 (invention)
The dye composition (B') is applied to two locks of natural grey hair at a rate of 1 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood. Composition (A’) is then applied to the two locks of hair at a rate of 3 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 12 (comparative)
The dye composition (B') is applied to two locks of natural grey hair at a rate of 2 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood. Water, adjusted to pH 3.5 with lactic acid, is then applied to the two locks of hair at a rate of 10 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 13 (invention)
The dye composition (B') is applied to two locks of natural grey hair at a rate of 2 g of composition per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood. Composition (A’) is then applied to the two locks of hair at a rate of lOg of composition per gram of hair. After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C. Process 14 (comparative)
At the time of use, 20 g of dye composition (B') are diluted in 50 g of water, adjusted to pH 3.5 with lactic acid.
The mixture thus obtained is applied to two locks of natural grey hair at a rate of 5 g of mixture per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 15 (invention)
At the time of use, 20 g of dye composition (B') are diluted in 50 g of composition (A").
The mixture thus obtained is applied to two locks of natural grey hair at a rate of 5 g of mixture per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 16 (comparative)
At the time of use, 10 g of dye composition (B') are diluted in 50 g of water, adjusted to pH 3.5 with lactic acid.
The mixture thus obtained is applied to two locks of natural grey hair at a rate of 3g of mixture per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
Process 17 (invention)
At the time of use, 10 g of dye composition (B') are diluted in 50 g of composition (A"). The mixture thus obtained is applied to two locks of natural grey hair at a rate of 3 g of mixture per gram of hair.
After a leave-on time of 5 minutes at 33°C, the locks are dried under a hood, and are then each subjected to five successive 7-second strokes with a straightening iron at a temperature of l90°C.
On conclusion of each of the processes mentioned above, a lock of hair of each process was washed with a shampoo according to the following protocol:
The locks are rinsed thoroughly with water at 37°C for 15 seconds. The locks are then washed with a DOP shampoo, in a proportion of 0.4 g of shampoo per gram of hair. The locks are then rinsed with water for 15 seconds, followed by being drained dry, combed and then dried.
3) Qualitative results
The colour of the locks and the colour transfer onto a cotton fabric are evaluated visually.
The fabric is dragged over the length of the lock using a constant finger pressure and the final colour of the fabric is evaluated.
The results are given in the table below.
Figure imgf000059_0001
Figure imgf000060_0001
The results obtained above show that the process of the invention gives the hair a red colouring that is persistent with respect to shampoo washing, unlike the comparative processes not involving any monosaccharide or any polysaccharide bearing amine group(s).
Moreover, the colouring obtained by means of the process of the invention does not transfer onto fabric. 4) Quantitative results
The colorimetric values obtained after dyeing and shampooing the locks by means of processes 10 to 17 are given in the table below.
Figure imgf000061_0001
The results obtained above show that the colouring obtained by means of the process of the invention, using a monosaccharide, a polysaccharide bearing amine group(s) and a dyestuff, is resistant to shampoo washing, unlike the colouring obtained via the comparative process not involving a monosaccharide or a polysaccharide bearing amine group(s).

Claims

1. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising:
(i) a step consisting in applying to said keratin fibres a) one or more monosaccharides,
(ii) a step consisting in applying to said keratin fibres b) one or more polysaccharides bearing amine group(s), in salified or non-salified form; and
(iii) a step consisting in applying to said keratin fibres c) one or more dyestuffs chosen from pigments and direct dyes, and mixtures thereof;
it being understood that steps (i), (ii) and (iii) may be performed simultaneously or sequentially, before being followed by
(iv) a step of heat treatment of said keratin fibres at a temperature greater than or equal to 80°C, preferably with an iron.
2. Process according to Claim 1, characterized in that the monosaccharide(s) a) are chosen from hexoses and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof; and preferably from the hexoses of formula (Al) below and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000062_0001
in which formula (Al):
- Ra, Rb, Rd, Re and Rf, which may be identical or different, represent i) a hydroxyl group, ii) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted, notably with one or more hydroxyl groups, or iii) a carboxyl group; preferably, Ra, Rb, Rd, Re and Rf represent a hydroxyl group; and more preferentially, (Al) represents (AG):
Figure imgf000063_0001
in which formula (A ) Ra, Rb, Rd, Re and Rf are as defined previously for (Al).
3. Process according to Claim 1 or 2, characterized in that the monosaccharide(s) a) are chosen from aldohexoses, ketohexoses, and mixtures thereof, preferably from glucose, galactose, allose, altrose, mannose, gulose, idose, talose, and mixtures thereof, more preferentially from glucose and galactose, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof; better still, the monosaccharide a) is glucose, and even better still glucose of D configuration.
4. Process according to Claim 1, characterized in that the monosaccharide(s) a) are chosen from monosaccharides bearing amine group(s), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates; preferably from monosaccharides bearing amine group(s) salified with a mineral acid such as hydrochloric acid.
5. Process according to the preceding claim, characterized in that the monosaccharide(s) a) are chosen from the hexosamines of formula (A3) below and also the salts thereof with an organic or mineral acid such as hydrochloric acid, and also the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates:
Figure imgf000064_0001
in which formula (A3):
- Ra, Rb, Rd, Re and Rf, which may be identical or different, represent (1) a hydroxyl group, (2) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl groups, (3) a carboxyl group, or (4) a group NR IR2 with Ri and R2, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(C5-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (hetero)cyclo(C5-C7)alkyl(Ci- C4)alkyl group such as cyclohexylmethyl, vii) -C(Y)-(Y’)P-R’ i with Y and Y’, which may be identical or different, representing an oxygen atom, a sulfur atom or N(R’2), preferably oxygen, p = 0 or 1, preferably 0; and R’ i and R’2 representing i) to vi) of Ri and R2 defined previously, and in particular R’ i denoting a (Ci-C6)alkyl group such as methyl;
it being understood that at least one of the radicals Ra, Rb, Rd, Re and Rf, represents a group NR IR2 and preferably at least one of the radicals Ra, Rb, Rd, Re and Rf represents a group NR IR2 and the radicals other than NR IR2 denote a hydroxyl group, and more preferentially (A3) represents (A3’):
Figure imgf000064_0002
in which formula (A3’) Ra, Rb, Rd, Re and Rf are as defined previously for (A3).
6. Process according to the preceding Claim 4 or 5, characterized in that the monosaccharide(s) a) are chosen from aldohexosamines, ketohexosamines, and mixtures thereof, preferably from glucosamine, galactosamine, allosamine, altrosamine, mannosamine, gulosamine, idosamine, talosamine, and mixtures thereof, more preferentially from glucosamine and galactosamine, and also the salts thereof with an organic or mineral acid such as hydrochloric acid, the a or b anomers thereof, the optical isomers thereof of L or D configuration and the solvates thereof such as hydrates, and mixtures thereof; better still, the monosaccharide a) is glucosamine, even better still glucosamine of D configuration, and even more particularly glucosamine salified with a mineral acid such as hydrochloric acid.
7. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) b) are chosen from C6 saccharide units bearing amine group(s); preferably, the saccharide units of the polysaccharide bearing amine group(s) are of b (beta) anomeric configuration and/or D configuration; more preferentially, the saccharide units of the polysaccharide bearing amine group(s) are connected together in (l 4).
8. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing saccharide units of formula (B), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, and the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000065_0001
in which formula (B):
- n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
- Ra, Rb and Rc, which may be identical or different for each saccharide unit, represent (1) a hydroxyl group, (2) a (Ci-C4)alkoxy group, the alkyl chain of which may be optionally substituted notably with one or more hydroxyl and/or carboxyl groups, (3) a carboxyl group, or (4) a group NRIR2 with Ri and R2, which may be identical or different, representing i) a hydrogen atom, ii) a (Ci-C6)alkyl group that is optionally substituted, preferably with one or more hydroxyl or NH2 groups, iii) an aryl group such as phenyl, iv) an aryl(Ci-C4)alkyl group such as benzyl, v) a (hetero)cyclo(C5-C7)alkyl group such as cyclohexyl, morpholinyl, piperazinyl, piperidyl, vi) a (hetero)cyclo(C5-C7)alkyl(Ci-C4)alkyl group such as cyclohexylmethyl, vii) a group -C(Y)-(Y’)P-R’ i with Y and Y’, which may be identical or different, representing an oxygen atom, a sulfur atom or N(R’2), p is equal to 0 or 1, and R’i and R’2 representing i) to vi) of Ri and R2 defined previously,
it being understood that at least one of the radicals Ra, Rb or Rc of at least one saccharide unit represents a group NRIR2 and that at least one of the groups NRIR2 of at least one saccharide unit represents an NH2 group.
9. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) are chosen from polysaccharides bearing saccharide units of formula (Bl), and also the organic or mineral acid salts thereof, the a or b anomers thereof, the optical isomers thereof of L or D configuration, the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000066_0001
in which formula (Bl):
(i) R’ represents a hydrogen atom or a (Ci-C4)alkylcarbonyl group such as acetyl CH3-C(0)-;
(ii) R” represents a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a carboxyl group such as -CH(C02H)-CH3; and
(iii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300; it being understood that at least one saccharide unit bears an NH2 amino group and at least one other saccharide unit bears a group N(H)-R' with R' representing a (Ci- C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
10. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) b) are chosen from polysaccharides bearing saccharide units of formula (B3), and also the organic or mineral acid salts thereof, the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000067_0001
in which formula (B3):
(i) Ri and R2 are as defined in Claim 8; and
(ii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
it being understood that at least one saccharide unit bears an NH2 amino group and at least one other saccharide unit bears a group N(H)-R' with R' representing a (Ci- C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
11. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) b) are chosen from the chitosans of formula (B4), and also the organic or mineral acid salts thereof, the solvates thereof such as hydrates, and mixtures thereof:
Figure imgf000068_0001
in which formula (B4):
(i) R'i representing a (Ci-C4)alkyl group such as methyl; and
(ii) p is greater than 0 and ranges up to 0.5, preferably from 0.05 to 0.3, and more preferentially from 0.1 to 0.20 such as 0.15 with m+p being equal to 1;
(iii) n is an integer greater than or equal to 2, preferably between 3 and 3000, more preferentially between 5 and 2500, and better still between 10 and 2300;
it being understood that at least one saccharide unit bears an NH2 amino group and at least one other saccharide unit bears a group N(H)-R'i with R'i representing a (Ci- C4)alkylcarbonyl group such as acetyl CH3-C(0)-.
12. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group)s) b) are salified with one or more organic acid(s), preferably chosen from:
- the monocarboxylic acids of formula (I):
R-C(0)-OH (I)
in which formula (I), R represents a (hetero)aryl radical such as phenyl, a (hetero)aryl(Ci-C4)alkyl radical such as benzyl, a (Ci-C3o)alkyl radical or an unsaturated C2-C30 radical, said alkyl or unsaturated C2-C30 radicals being optionally interrupted and/or optionally substituted, preferably with one or more hydroxyl groups and not substituted with one or more amino radicals;
- the polycarboxylic acids of formula (II):
Figure imgf000069_0001
in which formula (II), A represents a saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic polyvalent hydrocarbon-based group comprising from 1 to 30 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen and/or optionally substituted notably with one or more hydroxyl groups and t represents an integer between 1 and 5 inclusive; and
- amino acids including more carboxylic acid radicals than amino groups.
13. Process according to the preceding claim, characterized in that the organic acid(s) are chosen from acetic acid, glycolic acid, lactic acid, tartaric acid, succinic acid, fumaric acid, maleic acid, citric acid, gamma-carboxyglutamic acid, aspartic acid, glutamic acid, and mixtures thereof, and preferably, the organic acid is lactic acid.
14. Process according to any one of the preceding claims, characterized in that the polysaccharide(s) bearing amine group(s) b) have an average molecular weight MW of less than or equal to 400 kDa, preferably less than 200 kDa, more preferentially less than 100 kDa, even better still less than 40 kDa, even better still between 1 kDa and 30 kDa inclusive, more even more preferentially between 3 kDa and 28 kDa.
15. Process according to any one of the preceding claims, characterized in that the dyestuff(s) are chosen from pigments, preferably from white organic pigments, coloured organic pigments, and mixtures thereof, and more preferentially carbon blacks, such as Black 2, lakes, such as D&C Red 7, and mixtures thereof.
16. Process according to any one of the preceding claims, characterized in that steps (i), (ii) and (iii) are performed simultaneously or by applying to the keratin fibres an aqueous composition (C) at acidic pH comprising a) one or more monosaccharide(s), b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, c) one or more dyestuffs chosen from pigments, direct dyes, and mixtures thereof, and optionally d) one or more organic or mineral acid(s).
17. Process according to any one of Claims 1 to 15, characterized in that steps (i) and (ii) are performed simultaneously, before or after step (iii).
18. Process according to any one of Claims 1 to 15, characterized in that steps (i), (ii) and (iii) are applied sequentially.
19. Process according to the preceding claim, characterized in that the monosaccharide(s), the polysaccharide(s) bearing amine group(s) and the dyestuff(s) are respectively included in three distinct compositions (ca), (cb) and (cc).
20. Process according to Claim 16 or 19, characterized in that the content of the monosaccharide(s), present in the composition (C) or in the composition (ca), ranges from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight and more preferentially from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
21. Process according to any one of Claims 16, 19 and 20, characterized in that the content of the polysaccharide(s) bearing amine group(s), present in the composition (C) or in the composition (cb), ranges from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight and more preferentially from 0.1% to 5% by weight, relative to the total weight of the composition comprising same.
22. Process according to any one of the preceding claims, characterized in that step (iv) of heat treatment of the keratin fibres is performed at a temperature of at least l00°C, preferably at a temperature ranging from 100 to 250°C; more preferentially from 150 to 220°C, even better still from 160 to 220°C, even better still from 160 to 200°C, and even more preferentially from 130 to l90°C.
23. Process according to any one of the preceding claims, characterized in that it comprises a step of drying the keratin fibres before the heat treatment step (iv), said drying step being performed using a hairdryer, a hood, or else with a towel, an absorbent or by natural drying; the drying step is preferably performed at a temperature ranging from 20°C to 70°C.
24. Cosmetic composition (C), at acidic pH, comprising:
a) one or more monosaccharide(s) as defined in any one of Claims 1 to 6 and 20, b) one or more polysaccharide(s) bearing amine group(s), in salified or non-salified form, as defined in any one of Claims 1, 7 to 11 and 21,
c) one or more dyestuff(s) as defined in either of Claims 1 and 15; and
d) and optionally one or more mineral or organic acid(s), as defined in either of Claims 12 and 13.
25. Kit comprising:
- a multi-compartment device comprising a first compartment containing a cosmetic composition (ca) comprising a) one or more monosaccharide(s) as defined in any one of Claims 1 to 6 and 20; a second compartment containing a cosmetic composition (cb) comprising b) one or more polysaccharide(s) bearing amine group(s) as defined in any one of Claims 1, 7 to 11 and 21, and optionally c) one or more organic or mineral acids as defined in either of Claims 12 and 13; and a third compartment containing a dye composition (cc) comprising one or more dyestuffs as defined in either of Claims 1 and 15; and
- a device for heating the keratin fibres to a temperature of at least 80°C.
PCT/EP2019/067199 2018-06-29 2019-06-27 Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff Ceased WO2020002521A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1856006A FR3083106B1 (en) 2018-06-29 2018-06-29 PROCESS FOR COLORING KERATINIC FIBERS USING A MONOSACCHARIDE, A POLYSACCHARIDE WITH AMINO GROUPS AND A COLORING MATTER
FR1856006 2018-06-29

Publications (1)

Publication Number Publication Date
WO2020002521A1 true WO2020002521A1 (en) 2020-01-02

Family

ID=65031333

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/067199 Ceased WO2020002521A1 (en) 2018-06-29 2019-06-27 Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff

Country Status (2)

Country Link
FR (1) FR3083106B1 (en)
WO (1) WO2020002521A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024223198A1 (en) * 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa Leave-in dyeing method for keratin fibres comprising the application of a dyeing agent including chitosan, pigment, acid and water and subsequent heating
WO2025021351A1 (en) * 2023-07-27 2025-01-30 Henkel Ag & Co. Kgaa Improvement of the washing fastness of keratin fibers dyed with direct dyes by means of a sealing process using chitosan
WO2025257372A1 (en) * 2024-06-13 2025-12-18 L'oreal Process for dyeing keratin fibres using a compound containing acetoacetate functions, a (poly)amine compound and a direct dye
WO2026002418A1 (en) * 2024-06-27 2026-01-02 Henkel Ag & Co. Kgaa Method for dyeing keratin fibres, comprising the use of a dye having a film-forming polymer and a dyeing compound, and the use of an aftertreatment agent having a film-forming polymer

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102023203838A1 (en) * 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa Process for coloring keratin fibers, comprising the application of a colorant containing chitosan and coloring compound and the application of a post-treatment agent containing protein hydrolysate and/or amino acid
DE102023203837A1 (en) * 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa A method for dyeing keratin fibers, comprising the application of a dye containing chitosan and coloring compound and the application of a shampoo
DE102023203839A1 (en) * 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa Method for dyeing keratin fibers comprising the application of an alkaline pretreatment agent and the application of a dye containing chitosan and coloring compound

Citations (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB738585A (en) 1952-07-17 1955-10-19 May & Baker Ltd Improvements in or relating to tetrazolium compounds
FR1221122A (en) 1958-02-25 1960-05-31 Thera Chemie G M B H Hair dye products
FR1516943A (en) 1966-01-10 1968-02-05 Oreal Basic dyes suitable for dyeing hair
FR1540423A (en) 1966-07-25 1968-09-27 Oreal New dyes, their manufacturing processes and their applications
FR1560664A (en) 1967-02-22 1969-03-21
FR1567219A (en) 1967-03-01 1969-05-16
GB1195386A (en) 1966-08-05 1970-06-17 Sandoz Ltd Water-Soluble Cationic Monoazo-Dyestuffs and their manufacture and use
US3524842A (en) 1967-08-04 1970-08-18 Durand & Huguenin Ag Water-soluble cationic phenylazo-naphthol dyestuffs containing a quaternary ammonium group
FR2189006A1 (en) 1972-06-19 1974-01-25 Oreal
FR2275462A1 (en) 1974-06-21 1976-01-16 Ici Ltd PROCESS FOR PREPARING BIPYRIDILIUM COMPOUNDS AND PRODUCTS OBTAINED
FR2285851A1 (en) 1974-09-27 1976-04-23 Oreal 3-AMINO PYRIDINE DERIVATIVES AND TINCTORIAL COMPOSITIONS CONTAINING THEM
DE2538363A1 (en) 1974-08-30 1976-05-13 Oreal COLORING AGENTS CONTAINING QUATERNAER AZO COLORS DERIVED FROM 2-AMINOPYRIDINE
FR2570946A1 (en) 1984-10-01 1986-04-04 Oreal NOVEL KERATIN FIBER DYEING COMPOSITIONS CONTAINING AZOIC DYE, PROCESS FOR PREPARING THE DYE AND IMPLEMENTING SAID COMPOSITIONS FOR DYING KERATIN FIBERS
US5046516A (en) 1988-10-31 1991-09-10 George Barradas Hair curling iron
FR2679771A1 (en) 1991-08-01 1993-02-05 Oreal USE FOR TEMPORARY DYING OF KERATINIC FIBERS OF AN INSOLUBLE PIGMENT OBTAINED BY OXIDIZING POLYMERIZATION OF INDOLIC DERIVATIVES.
DE4137005A1 (en) 1991-11-11 1993-05-13 Bitterfeld Wolfen Chemie Hair dye contg. bis:cationic diazo dye contg. tri:azo gps. - giving uniform colour from hair roots to tips without dyeing scalp
DE4220388A1 (en) 1992-06-22 1993-12-23 Bitterfeld Wolfen Chemie Cationic azo dyes - for keratin materials showing improved evenness
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
WO1997044004A1 (en) 1996-05-23 1997-11-27 L'oreal Direct capillary dyeing composition comprising a cross-linked polymer with acrylic and alkyl c10-c30 acrylate units
FR2757385A1 (en) 1996-12-23 1998-06-26 Oreal KERATIN FIBER OXIDATION DYEING COMPOSITION AND DYEING METHOD USING THE SAME
EP0850637A1 (en) 1996-12-23 1998-07-01 L'oreal Composition for the oxidative dyeing of keratinic fibres and dyeing process using this composition
EP0860636A1 (en) 1997-02-20 1998-08-26 Hutchinson Tight connection between conduits
US5879413A (en) 1996-11-27 1999-03-09 Warner-Jenkinson Europe Limited Cationic diazo dyes for the dyeing of hair
US5888252A (en) 1993-11-30 1999-03-30 Ciba Specialty Chemicals Corporation Processes for dyeing keratin-containing fibres with cationicazo dyes
EP0918053A1 (en) 1997-11-21 1999-05-26 L'oreal Azo compounds, their use for dyeing, compositions containing them and dyeing processes
EP0920856A1 (en) 1997-12-05 1999-06-09 L'oreal Process for direct dying of keratinous fibres in two steps with the help of direct basic dyes
US5957140A (en) 1998-11-19 1999-09-28 Mcgee; Robert J. Hair styling iron for straightening and curling
WO1999048465A1 (en) 1998-03-20 1999-09-30 L'oreal Oxidation dyeing composition for keratinous fibres containing a 3-aminopyridine azo derivative and dyeing method using said composition
US5990479A (en) 1997-11-25 1999-11-23 Regents Of The University Of California Organo Luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes
FR2788433A1 (en) 1999-01-19 2000-07-21 Oreal USE OF CATIONIC PHENYL-AZO-BENZENIC COMPOUNDS IN KERATIN FIBER DYE, TINCTORIAL COMPOSITIONS AND DYEING PROCESSES
EP1062940A1 (en) 1998-02-10 2000-12-27 Yamahatsu Sangyo Kaisha, Ltd. A permanent wave agent composition having dyeing effect and method for dyeing hair using the same
US6225198B1 (en) 2000-02-04 2001-05-01 The Regents Of The University Of California Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process
WO2001066646A1 (en) 2000-03-09 2001-09-13 Ciba Specialty Chemicals Holding Inc. A method of colouring hair using cationic dyes
EP1133976A2 (en) 2000-03-17 2001-09-19 Kao Corporation Hair dye composition
EP1133975A2 (en) 2000-03-17 2001-09-19 Kao Corporation Hair dye composition
EP1184426A2 (en) 2000-09-01 2002-03-06 Toda Kogyo Corporation Composite particles, process for producing the same, and pigment, paint and resin composition using the same
WO2003029359A1 (en) 2001-09-24 2003-04-10 Ciba Specialty Chemicals Holdings Inc. Cationic reactive dyes
US7815900B1 (en) * 2000-07-11 2010-10-19 L'ORéAL S.A. Use of C3-C5 monosaccharides to protect keratinous fibers
US20120064182A1 (en) * 2009-01-30 2012-03-15 Beiersdorf Ag Cosmetic or dermatological preparation comprising collagen, chitosan, glycosylaminoglycan and cell growth promoting peptide and/or cellular complex
FR3004943A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION COMPRISING HENNE AND / OR INDIGO, OIL AND SACCHARIDE, AND CAPILLARY COLORING METHOD IMPLEMENTING THE SAME
US20180049964A1 (en) * 2015-03-12 2018-02-22 L'oreal Process for protecting and repairing keratin fibres, based on oxidized polysaccharide and on (poly)saccharide with amine group

Patent Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB738585A (en) 1952-07-17 1955-10-19 May & Baker Ltd Improvements in or relating to tetrazolium compounds
FR1221122A (en) 1958-02-25 1960-05-31 Thera Chemie G M B H Hair dye products
FR1516943A (en) 1966-01-10 1968-02-05 Oreal Basic dyes suitable for dyeing hair
FR1540423A (en) 1966-07-25 1968-09-27 Oreal New dyes, their manufacturing processes and their applications
GB1195386A (en) 1966-08-05 1970-06-17 Sandoz Ltd Water-Soluble Cationic Monoazo-Dyestuffs and their manufacture and use
FR1560664A (en) 1967-02-22 1969-03-21
FR1567219A (en) 1967-03-01 1969-05-16
US3524842A (en) 1967-08-04 1970-08-18 Durand & Huguenin Ag Water-soluble cationic phenylazo-naphthol dyestuffs containing a quaternary ammonium group
FR2189006A1 (en) 1972-06-19 1974-01-25 Oreal
FR2275462A1 (en) 1974-06-21 1976-01-16 Ici Ltd PROCESS FOR PREPARING BIPYRIDILIUM COMPOUNDS AND PRODUCTS OBTAINED
DE2527638A1 (en) 1974-06-21 1976-05-06 Ici Ltd PROCESS FOR PRODUCING DIPYRIDILIUM COMPOUNDS
DE2538363A1 (en) 1974-08-30 1976-05-13 Oreal COLORING AGENTS CONTAINING QUATERNAER AZO COLORS DERIVED FROM 2-AMINOPYRIDINE
FR2285851A1 (en) 1974-09-27 1976-04-23 Oreal 3-AMINO PYRIDINE DERIVATIVES AND TINCTORIAL COMPOSITIONS CONTAINING THEM
FR2570946A1 (en) 1984-10-01 1986-04-04 Oreal NOVEL KERATIN FIBER DYEING COMPOSITIONS CONTAINING AZOIC DYE, PROCESS FOR PREPARING THE DYE AND IMPLEMENTING SAID COMPOSITIONS FOR DYING KERATIN FIBERS
US5046516A (en) 1988-10-31 1991-09-10 George Barradas Hair curling iron
FR2679771A1 (en) 1991-08-01 1993-02-05 Oreal USE FOR TEMPORARY DYING OF KERATINIC FIBERS OF AN INSOLUBLE PIGMENT OBTAINED BY OXIDIZING POLYMERIZATION OF INDOLIC DERIVATIVES.
DE4137005A1 (en) 1991-11-11 1993-05-13 Bitterfeld Wolfen Chemie Hair dye contg. bis:cationic diazo dye contg. tri:azo gps. - giving uniform colour from hair roots to tips without dyeing scalp
DE4220388A1 (en) 1992-06-22 1993-12-23 Bitterfeld Wolfen Chemie Cationic azo dyes - for keratin materials showing improved evenness
WO1995001772A1 (en) 1993-07-05 1995-01-19 Ciba-Geigy Ag Process for dyeing keratin-containing fibres
WO1995015144A1 (en) 1993-11-30 1995-06-08 Ciba-Geigy Ag Cationic dyes for keratin-containing fibres
US5888252A (en) 1993-11-30 1999-03-30 Ciba Specialty Chemicals Corporation Processes for dyeing keratin-containing fibres with cationicazo dyes
US5708151A (en) 1994-11-03 1998-01-13 Ciba Specialty Chemicals Corporation Cationic imidazole azo dyes
EP0714954A2 (en) 1994-11-03 1996-06-05 Ciba-Geigy Ag Cationic iminazoleazodyestuffs
WO1997044004A1 (en) 1996-05-23 1997-11-27 L'oreal Direct capillary dyeing composition comprising a cross-linked polymer with acrylic and alkyl c10-c30 acrylate units
US5879413A (en) 1996-11-27 1999-03-09 Warner-Jenkinson Europe Limited Cationic diazo dyes for the dyeing of hair
EP0850636A1 (en) 1996-12-23 1998-07-01 L'oreal Composition for the oxidative dyeing of keratinic fibres and dyeing process using this composition
EP0850637A1 (en) 1996-12-23 1998-07-01 L'oreal Composition for the oxidative dyeing of keratinic fibres and dyeing process using this composition
FR2757385A1 (en) 1996-12-23 1998-06-26 Oreal KERATIN FIBER OXIDATION DYEING COMPOSITION AND DYEING METHOD USING THE SAME
EP0860636A1 (en) 1997-02-20 1998-08-26 Hutchinson Tight connection between conduits
EP0918053A1 (en) 1997-11-21 1999-05-26 L'oreal Azo compounds, their use for dyeing, compositions containing them and dyeing processes
US5990479A (en) 1997-11-25 1999-11-23 Regents Of The University Of California Organo Luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes
EP0920856A1 (en) 1997-12-05 1999-06-09 L'oreal Process for direct dying of keratinous fibres in two steps with the help of direct basic dyes
EP1062940A1 (en) 1998-02-10 2000-12-27 Yamahatsu Sangyo Kaisha, Ltd. A permanent wave agent composition having dyeing effect and method for dyeing hair using the same
WO1999048465A1 (en) 1998-03-20 1999-09-30 L'oreal Oxidation dyeing composition for keratinous fibres containing a 3-aminopyridine azo derivative and dyeing method using said composition
US5957140A (en) 1998-11-19 1999-09-28 Mcgee; Robert J. Hair styling iron for straightening and curling
FR2788433A1 (en) 1999-01-19 2000-07-21 Oreal USE OF CATIONIC PHENYL-AZO-BENZENIC COMPOUNDS IN KERATIN FIBER DYE, TINCTORIAL COMPOSITIONS AND DYEING PROCESSES
US6225198B1 (en) 2000-02-04 2001-05-01 The Regents Of The University Of California Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process
WO2001066646A1 (en) 2000-03-09 2001-09-13 Ciba Specialty Chemicals Holding Inc. A method of colouring hair using cationic dyes
EP1133976A2 (en) 2000-03-17 2001-09-19 Kao Corporation Hair dye composition
EP1133975A2 (en) 2000-03-17 2001-09-19 Kao Corporation Hair dye composition
US7815900B1 (en) * 2000-07-11 2010-10-19 L'ORéAL S.A. Use of C3-C5 monosaccharides to protect keratinous fibers
EP1184426A2 (en) 2000-09-01 2002-03-06 Toda Kogyo Corporation Composite particles, process for producing the same, and pigment, paint and resin composition using the same
WO2003029359A1 (en) 2001-09-24 2003-04-10 Ciba Specialty Chemicals Holdings Inc. Cationic reactive dyes
US20120064182A1 (en) * 2009-01-30 2012-03-15 Beiersdorf Ag Cosmetic or dermatological preparation comprising collagen, chitosan, glycosylaminoglycan and cell growth promoting peptide and/or cellular complex
FR3004943A1 (en) * 2013-04-26 2014-10-31 Oreal COMPOSITION COMPRISING HENNE AND / OR INDIGO, OIL AND SACCHARIDE, AND CAPILLARY COLORING METHOD IMPLEMENTING THE SAME
US20180049964A1 (en) * 2015-03-12 2018-02-22 L'oreal Process for protecting and repairing keratin fibres, based on oxidized polysaccharide and on (poly)saccharide with amine group

Non-Patent Citations (25)

* Cited by examiner, † Cited by third party
Title
"Kirk-Othmer Encyclopedia of Chemical Technology", 1993, WILEY AND SONS, article "Dyes and Dye Intermediates"
"Kirk-Othmer's Encyclopedia of Chemical Technology", 19 April 2010, J. WILEY & SONS, article "Dyes, Azo"
"Molecular Probes/Invitrogen - Oregon", 2005, article "A Guide to Fluorescent Probes and Labeling Technologies"
"Pigments, Inorganic, 1. General", 2009, WILEY-VCH VERLAG GMBH & CO. KGAA
"Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG GMBH & CO. KGAA, article "Pigment organics"
ACTA HISTOCHEM, vol. 61, no. 1, 1978, pages 48 - 52
ANN. CHIM. (ROME, vol. 65, no. 5-6, 1975, pages 305 - 14
CHIM. IND. (MILAN, vol. 56, no. 9, 1974, pages 600 - 3
DABBOUSSI B.O. ET AL.: "CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocrystallites", JOURNAL OF PHYSICAL CHEMISTRY B, vol. 101, 1997, pages 9463 - 9475
DATABASE GNPD [online] MINTEL; 19 August 2008 (2008-08-19), ANONYMOUS: "Watering Whip", XP055588681, retrieved from www.gnpd.com Database accession no. 960436 *
DATABASE GNPD [online] MINTEL; 23 January 2014 (2014-01-23), ANONYMOUS: "Wrinkle and Pore Refining Treatment", XP055588622, retrieved from www.gnpd.com Database accession no. 2300850 *
DATABASE GNPD [online] MINTEL; 7 August 2014 (2014-08-07), ANONYMOUS: "Volume Shampoo", XP055588683, retrieved from www.gnpd.com Database accession no. 2587533 *
DYES PIGM, vol. 11, no. 3, 1989, pages 163 - 72
DYES PIGM, vol. 19, no. 1, 1992, pages 69 - 79
GER. MONATSH., vol. 106, no. 3, 1975, pages 643 - 8
JOURNAL OF THE CHINESE CHEMICAL SOCIETY (TAIPEI, vol. 45, no. 1, 1998, pages 209 - 211
K. VENKATARAMAN: "The Chemistry of Synthetic Dyes", vol. 1-7, 1952, ACADEMIC PRESS
KHIM. TEKHNOL., vol. 22, no. 5, 1979, pages 548 - 53
LIHUA JIANYAN, HUAXUE FENCE, vol. 29, no. 4, 1993, pages 233 - 4
MRL BULL. RES. DEV., vol. 6, no. 2, 1992, pages 21 - 7
PENG, XIAOGANG ET AL.: "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 119, no. 30, pages 7019 - 7029
REV. ROUM. CHIM., vol. 33, no. 4, 1988, pages 377 - 83
TEXT. RES. J., vol. 54, no. 2, 1984, pages 105 - 7
TSITOLOGIYA, vol. 10, no. 3, 1968, pages 403 - 5
ZH. OBSHCH. KHIM., vol. 40, no. 1, 1970, pages 195 - 202

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024223198A1 (en) * 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa Leave-in dyeing method for keratin fibres comprising the application of a dyeing agent including chitosan, pigment, acid and water and subsequent heating
DE102023203833A1 (en) 2023-04-26 2024-10-31 Henkel Ag & Co. Kgaa Leave-on dyeing process for keratin fibers comprising the application of a dye containing chitosan, pigment, acid and water and subsequent heating
WO2025021351A1 (en) * 2023-07-27 2025-01-30 Henkel Ag & Co. Kgaa Improvement of the washing fastness of keratin fibers dyed with direct dyes by means of a sealing process using chitosan
WO2025257372A1 (en) * 2024-06-13 2025-12-18 L'oreal Process for dyeing keratin fibres using a compound containing acetoacetate functions, a (poly)amine compound and a direct dye
FR3163260A1 (en) * 2024-06-13 2025-12-19 L'oreal A process for coloring keratin fibers using an acetoacetate compound, a (poly)amine compound, and a direct dye
WO2026002418A1 (en) * 2024-06-27 2026-01-02 Henkel Ag & Co. Kgaa Method for dyeing keratin fibres, comprising the use of a dye having a film-forming polymer and a dyeing compound, and the use of an aftertreatment agent having a film-forming polymer

Also Published As

Publication number Publication date
FR3083106B1 (en) 2020-10-02
FR3083106A1 (en) 2020-01-03

Similar Documents

Publication Publication Date Title
WO2020002521A1 (en) Process for dyeing keratin fibres using a monosaccharide, a polysaccharide bearing amine groups and a dyestuff
EP2651374B1 (en) Process for dyeing keratin fibres using a direct dye bearing a disulfide/thiol/protected thiol function and water vapour
EP2259766A2 (en) Composition for dyeing keratin fibres comprising at least one direct dye comprising a disulphide/protected-thiol function and at least one siliceous compound comprising a thiol function and method using the composition
WO2015097308A1 (en) Dyeing process using an insoluble substrate bearing at least one direct dye and an aqueous composition
EP3459520A1 (en) Hair dyeing composition
CN113784701B (en) Method for dyeing keratin materials using direct dyes and unsaturated heterocyclic salts and compositions containing said direct dyes and unsaturated heterocyclic salts
JP7436487B2 (en) Methods for dyeing keratin materials using direct dyes and aliphatic ammonium salts, and compositions containing them
EP3986366B1 (en) Composition comprising at least one alkoxysilane, at least one non-amino silicone and water, the alkoxysilane/non-amino silicone mass ratio ranging from 95/5 to 5/95
EP3621583A1 (en) Fluorescent direct dye bearing an aliphatic chain and a disulfide/thiol/protected-thiol function for dyeing keratin materials
EP4452211B1 (en) Process for removing makeup from keratin fibres which have been treated beforehand with a composition comprising a photocrosslinkable polymer
WO2020260486A1 (en) Process for dyeing keratin fibers using a particular cyclic polycarbonate, a compound comprising at least one amine group and a coloring agent, composition and device
US12233146B2 (en) Process for dyeing keratin fibers using a direct dye and a saccharinate salt and composition comprising them
WO2015097310A1 (en) Lightening dyeing process using a substrate bearing at least one oxidizing agent and an aqueous composition comprising one or more direct dyes
WO2021259810A1 (en) Composition for simultaneous bleaching and dyeing of keratin fibers, comprising a particular heterocyclic salt, and process using this composition
EP4452216A1 (en) Composition comprising a photocrosslinkable polymer having a hydrophobic group and a coloring agent
WO2020127247A1 (en) Process for dyeing keratin materials using a direct dye and a saturated heterocyclic salt, and composition comprising same
BR112021011868B1 (en) PROCESS FOR DYEING KERATIN MATERIALS, COMPOSITION AND MULTI-COMPARTMENT DEVICE
BR112021011892B1 (en) PROCESS FOR DYEING KERATIN MATERIALS AND COMPOSITION

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19733495

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19733495

Country of ref document: EP

Kind code of ref document: A1