WO2012084472A1 - Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat - Google Patents
Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat Download PDFInfo
- Publication number
- WO2012084472A1 WO2012084472A1 PCT/EP2011/071743 EP2011071743W WO2012084472A1 WO 2012084472 A1 WO2012084472 A1 WO 2012084472A1 EP 2011071743 W EP2011071743 W EP 2011071743W WO 2012084472 A1 WO2012084472 A1 WO 2012084472A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radical
- alkyl
- optionally substituted
- amino
- group
- Prior art date
Links
- NOUSSFBVCNPNKZ-UHFFFAOYSA-N CCOc1n[n](ccc(N(C)C)c2)c2c1N Chemical compound CCOc1n[n](ccc(N(C)C)c2)c2c1N NOUSSFBVCNPNKZ-UHFFFAOYSA-N 0.000 description 1
- ZNDQIUSCKRUQMO-UHFFFAOYSA-N CCc(c1c2N)ccc(C)[n]1nc2N1CCN(CCO)CC1 Chemical compound CCc(c1c2N)ccc(C)[n]1nc2N1CCN(CCO)CC1 ZNDQIUSCKRUQMO-UHFFFAOYSA-N 0.000 description 1
- GJXXUAQAMXLLMO-UHFFFAOYSA-N CN(C)CCCNc1n[n](ccc(N(C)C)c2)c2c1N Chemical compound CN(C)CCCNc1n[n](ccc(N(C)C)c2)c2c1N GJXXUAQAMXLLMO-UHFFFAOYSA-N 0.000 description 1
- DJGKEEHHEOWBJD-UHFFFAOYSA-N CN(C)c(c1c2N)ccc[n]1nc2OCCN(CC1)CC1[N+](C)(C)C Chemical compound CN(C)c(c1c2N)ccc[n]1nc2OCCN(CC1)CC1[N+](C)(C)C DJGKEEHHEOWBJD-UHFFFAOYSA-N 0.000 description 1
- PGNKPLGYGMTFIC-UHFFFAOYSA-N Cc(ccc1c2N)c(C)[n]1nc2OC Chemical compound Cc(ccc1c2N)c(C)[n]1nc2OC PGNKPLGYGMTFIC-UHFFFAOYSA-N 0.000 description 1
- AXAKBJAUNWYERJ-UHFFFAOYSA-N Cc(ccc1c2N)c(C)[n]1nc2OCCN(CC1)CC1[N+](C)(C)C Chemical compound Cc(ccc1c2N)c(C)[n]1nc2OCCN(CC1)CC1[N+](C)(C)C AXAKBJAUNWYERJ-UHFFFAOYSA-N 0.000 description 1
- QBVZZWPOGALAFB-UHFFFAOYSA-N Cc(ccc1c2[NH-])c(C)[n]1nc2OCC[N+]1(C)CCCCC1 Chemical compound Cc(ccc1c2[NH-])c(C)[n]1nc2OCC[N+]1(C)CCCCC1 QBVZZWPOGALAFB-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1c(*)[n]2nc(**)c(N)c2c(**)c1C Chemical compound Cc1c(*)[n]2nc(**)c(N)c2c(**)c1C 0.000 description 1
- RDNFFBNXDHRBEU-UHFFFAOYSA-N Nc1c(ccc2c3CCC2)[n]3nc1NCCC[n]1cncc1 Chemical compound Nc1c(ccc2c3CCC2)[n]3nc1NCCC[n]1cncc1 RDNFFBNXDHRBEU-UHFFFAOYSA-N 0.000 description 1
- VMWKFCDPBMAKCU-UHFFFAOYSA-N Nc1c(ccc2c3CCC2)[n]3nc1NCCc1ccncc1 Chemical compound Nc1c(ccc2c3CCC2)[n]3nc1NCCc1ccncc1 VMWKFCDPBMAKCU-UHFFFAOYSA-N 0.000 description 1
- APUNYLHYCLCTOM-UHFFFAOYSA-N Nc1c(ccc2c3CCC2)[n]3nc1OCCc1ccncc1 Chemical compound Nc1c(ccc2c3CCC2)[n]3nc1OCCc1ccncc1 APUNYLHYCLCTOM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
- A61K8/315—Halogenated hydrocarbons
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
-
- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/24—Thermal properties
-
- 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
Definitions
- One subject of the invention is a process for dyeing keratin fibres, especially the hair, using i) at least one hydroxybenzaldehyde derivative, ii) at least one oxidizing agent, and Hi) at least one alkalinizing agent in the presence of heat.
- This dyeing process makes it possible to obtain colorations that are chromatic, intense, deep and long-lasting even in the absence of oxidation bases such as para-phenylenediamines and para-aminophenols, or of active CH compounds.
- oxidation bases such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds.
- oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, give rise to coloured compounds via a process of oxidative condensation.
- couplers or coloration modifiers the latter being chosen especially from aromatic mefa-diamines, mefa-aminophenols, mefa-di phenols and certain heterocyclic compounds such as indole compounds having light stability and stability to shampooing.
- This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with hydrogen peroxide (H 2 0 2 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres.
- hydrogen peroxide H 2 0 2 or aqueous hydrogen peroxide solution
- the colorations resulting therefrom are permanent, strong and resistant to external agents, especially to light, adverse weather conditions, washing, perspiration and rubbing.
- Derivatives of 5,6-dihydroxyindoles are also capable of generating deep shades by "autoxidation" , but the resulting colorations are not always satisfactory, especially in terms of chromaticity, strength, remanence or change in colour after shampooing and exposure to light.
- the conventional dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane nitrobenzene type or natural dyes.
- These dyes which are coloured and colouring molecules that have an affinity for the fibres, are applied to the keratin fibres for a time necessary for obtaining the desired coloration, then rinsed.
- the colorations resulting therefrom are chromatic colorations that are, however, only temporary or semi-permanent since the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor fastness with respect to washing or perspiration.
- One known variant is to apply to keratin fibres, instead of direct dyes, dye precursors that form the colour in situ via a chemical reaction.
- aromatic aldehyde/ketone precursors have been described that condense with active CH precursors to form, in situ, the direct dye after release of water.
- These direct dyes are also light-sensitive due to the low resistance of the chromophore to photochemical attack, and lead to fading of the coloration of the hair over time. These dyes do not make it possible to obtain satisfactory colorations, especially in terms of remanence.
- R 1 , R 2 , R 3 , R 4 and R 5 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- M + representing a cationic counterion such as an alkali metal or alkaline-earth metal, or an ammonium
- a carbamoyl -0-C(0)-NR a R b with R a and R which may be identical or different, representing a hydrogen atom or a linear or branched (CrC 5 )alkyl group; particularly -0-C(0)-NH 2 ;
- an amido -C(0)-NR 6 R 7 or -NR 6 -C(0)-R 7 with R 6 and R 7 which may be identical or different, representing a hydrogen atom or a (CrC 5 )alkyl group, particularly -C(0)-NH 2 ;
- R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 form, together with the carbon atoms to which they are attached, a 6-membered (hetero)aryl group such as phenyl;
- R 1 or R 3 represents a hydroxyl group; with, when R 1 represents a hydroxyl group, then R 2 or R 3 or R 4 or R 5 represents a hydrogen atom; and when R 3 represents a hydroxyl group then R 1 or R 2 or R 4 or R 5 represents a hydrogen atom;
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of ingredients i), ii) and Hi), or of the total weight of the composition(s) used in the process.
- Another subject of the invention is a cosmetic composition for dyeing keratin fibres, comprising:
- the pH of the composition is above 7 and preferably between 7.5 and 12;
- the compound(s) of formula (I) comprise at least one of the two radicals R 1 or R 3 which represents a hydroxyl group; with, when R 1 represents a hydroxyl group, then R 2 or R 3 or R 4 or R 5 represents a hydrogen atom; and when R 3 represents a hydroxyl radical then R 1 or R 2 or R 4 or R 5 represents a hydrogen atom;
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the ingredients ii) and Hi), and
- the alkalinizing agent Hi is other than monoethanolamine
- hydroxybenzaldehyde derivative of formula (I) represents a compound chosen from 4-hydroxy-3-methoxybenzaldehyde and 2-hydroxy-3- methoxybenzaldehyde, which is in the presence of 2-aminophenol, 2,5- diaminotoluene sulphate; then the alkalinizing agent Hi) is other than ammonium hydroxide.
- Another subject of the invention relates to a multicompartment device comprising the ingredients i) to Hi) as defined previously.
- composition and dyeing process of the invention have the advantage of dyeing human keratin fibres, with strong, chromatic dyeing results that are resistant to washing, perspiration, sebum and light, and that are moreover long-lasting, without impairing said fibres. Furthermore, the colorations obtained using the process give uniform colours from the root to the end of a fibre (little coloration selectivity).
- the shades obtained after dyeing with the composition or the process of the invention are very intense, in particular at a temperature above room temperature, preferably at a temperature between 45°C and 80°C.
- the colorations obtained with the composition or the process of the invention are compatible with conventional oxidation conditions for lightening hair.
- the colorations are particularly persistent with regard to shampooing operations.
- the "a/yr radical represents a fused or nonfused monocyclic or polycyclic carbon-based group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl; preferably, the aryl radical is a phenyl;
- heteroaryr radical represents a fused or nonfused, optionally cationic, 5- to 22- membered monocyclic or polycyclic group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulphur and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl,
- R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(CrC 8 )alkyl group such as methyl;
- R a heteroaryl substituent as defined previously and R + an ammonium R a R b c N + -, phosphonium R a R b R c P + - or ammonium RaR b RcN + -(CrC 6 )alkylamino group with R a , R b and R c , which may be identical or different, representing a hydrogen atom or a (d-C 8 )alkyl group such as methyl; the "aryP' or "heteroaryP' radical or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
- a C 1 -C16 and preferably C C C 8 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C C 2 alkoxy, (poly)hydroxy(C 2 -C 4 )alkoxy, acylamino, amino substituted with two, identical or different, C C 4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocycle optionally comprising another heteroatom that is identical to or different from nitrogen;
- halogen atom such as chlorine, fluorine or bromine
- a 5- or 6-membered heterocycloalkyl radical such as cyclohexyl
- an optionally cationic 5- or 6-membered heteroaryl radical preferentially imidazolium, optionally substituted with a (C C 4 )alkyl radical, preferentially methyl;
- one amino group optionally substituted with one or two optionally substituted C C 3 alkyl radicals said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7- membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen;
- radical R is a hydrogen atom or a (C C 4 )alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a (CrC 2 )alkyl radical;
- R 2 N-C(0)- in which the radicals R, which may be identical or different, represent a hydrogen atom or a (C C 4 )alkyl radical optionally bearing at least one hydroxyl group;
- R'-S(0) 2 -N(R)- in which the radical R represents a hydrogen atom or a C C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a (Ci-C 4 )alkyl radical, or a phenyl radical;
- R 2 N-S(0) 2 - in which the radicals R, which may be identical or different, represent a hydrogen atom or a (C C 4 )alkyl radical optionally bearing at least one hydroxyl group;
- an "alky radical is a saturated, linear or branched C Ci 6 , preferably C C 8 hydrocarbon-based radical such as methyl or ethyl;
- the expression "optionally substituted” attributed to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the following groups: i) hydroxyl, ii) (C C 4 )alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different (d-C 6 )alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N + R'R"R"', An " for which R', R" and R'", which may be identical or different, represent a hydrogen atom or a (CrC 6 )alkyl group
- R representing a hydrogen atom, a (C C 6 ) alkyl group, or aryl group or electron- withdrawing group, in particular those that are electron-withdrawing via an -M mesomeric effect such as cyano -CN or -C(0)OR' with R' representing a C C 6 alkyl group or a hydrogen atom;
- Het + representing a cationic heteroaryl group with an endocyclic cationic charge, i.e. the charge of which is included in the aromaticity of said heteroaryl and which is stabilized via a mesomeric effect;
- the active methylene compound is in particular of formula (ll 2 ) below:
- ⁇ R' represents an optionally substituted (d-C 6 )alkyl group
- ⁇ 2 represents a heteroaryl group with an endocyclic cationic charge comprising from 5 to 13 ring members, which may possibly also comprise the cationic nitrogen atom, and comprising from 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulphur, and which bears, on a carbon atom of the heteroaryl, a group R-CH 2 - with R representing a hydrogen atom or a (CrC 6 )alkyl or aryl group; such as imidazolium, oxazolium, thiazolium, pyridinium, pyrimidinium such as 2- oxopyrimidinium, quinolinium, the group R-CH 2 - being at position 2 or 4 of the pyridinium or quinolinium or at position 2, 4 or 5 of the imidazolium, oxazolium or thiazolium group, or at position 4 and 6 of the pyrimidinium such as 2- oxopyrimidinium;
- One particular embodiment of the invention relates to hydroxybenzaldehyde derivatives or mixtures thereof of formula (I) in which at least one of the two radicals R 1 and/or R 3 represent(s) a hydroxyl group and in which R 1 , R 2 , R 3 , R 4 and R 5 represent, independently of one another, a hydrogen or halogen atom, preferably a chlorine atom or a group chosen from:
- R 1 and R 2 , or R 2 and R 3 , or R 3 and R 4 form, together with the carbon atoms to which they are attached, an aromatic ring containing 6 carbon atoms;
- R 1 represents a hydroxyl group
- R 2 or R 3 or R 4 or R 5 represents a hydrogen atom
- R 3 represents a hydroxyl group
- R 4 or R 5 represents a hydrogen atom.
- the derivatives of formula (I) are chosen from compounds 1_ to 10 as defined in the preceding table.
- hydroxybenzaldehyde derivatives or mixtures thereof are chosen from those of formula (II):
- R'i represents a hydrogen atom or a hydroxyl group
- R' 2 represents a hydrogen atom, or a group chosen from a hydroxyl, a carboxaldehyde, a linear or branched C C 4 alkyl and a linear or branched C C 4 alkoxy;
- R' 4 represents a hydrogen atom or a group chosen from a hydroxyl, a linear or branched C C 4 alkyl and a linear or branched C C 4 alkoxy;
- R' 5 represents a hydrogen atom or a hydroxyl group
- the preferred compounds (II) are the following:
- the hydroxybenzaldehyde derivative(s) of formula (I) are synthetic, natural, or are found in natural extracts.
- hydroxybenzaldehydes such as vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3- hydroxy-4-methoxybenzaldehyde) or ethyl vanillin (4-hydroxy-3-ethoxybenzaldehyde) derived from extract of vanilla or Vanilla planifolia or Vanilla tahitensis, protocatechualdehyde derived from extract of Cassia garrettiana, gallaldehyde derived from extract of Boletus scaber.
- the derivative(s) of formula (I) are present in the composition or in the process without the presence of oxidizing agent or coupler.
- oxidation dyes are present optionally with couplers.
- the coloration observed is compatible with conventional oxidation conditions for lightening hair.
- the coloration is persistent with regard to shampooing operations.
- the derivative(s) of formula (I) are at a total concentration that is at least 10 times higher than the concentration of other oxidation dyeing precursors, for instance the bases and couplers optionally present in the mixture.
- the hydroxybenzaldehyde derivative(s) or mixtures thereof of formula (I) exist in the composition or in the process according to the invention at a concentration of greater than 1 g per 100 g (%) relative to the total weight of the composition containing the hydroxybenzaldehyde derivative(s) or the extract(s) comprising them, particularly between between 1 g % and 10 g % and preferably between 1 g % and 5 g %.
- said process uses a chemical oxidizing agent.
- chemical oxidizing agent is understood to mean an oxidizing agent other than the oxygen from the air.
- alkali metal or quaternary ammonium persalts such as perborates, persulphates, percarbonates, peroxodiphosphates or Oxone®;
- the oxidizing agent is particularly chosen from sodium perborate, sodium persulphate, potassium persulphate, ammonium persulphate, sodium percarbonate and potassium percarbonate;
- aliphatic C C 6 and aromatic C6-C20 organic peracids such as performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid;
- the oxidizing agent is particularly peracetic acid;
- organic peroxides such as dioxirane, C C 6 alkyl peroxides, benzoyl peroxide, peroxo(CrC 6 )alkyl carboxylates, bis(tri)(CrC 6 )alkylsilyl peroxides such as bis(trimethylsilyl) peroxide, C C 6 alkyl peroxydicarbonates, and sodium nonanoyloxybenzene sulphonate as described in patents WO 1995/000625 and US 4 412 934;
- organic peroxides such as dioxirane, C C 6 alkyl peroxides, benzoyl peroxide, peroxo(CrC 6 )alkyl carboxylates, bis(tri)(CrC 6 )alkylsilyl peroxides such as bis(trimethylsilyl) peroxide, C C 6 alkyl peroxydicarbonates, and sodium nonanoyloxybenzene sulphonate as described in patents
- oxidizing anions such as nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates and periodates;
- the oxidizing agent is particularly chosen from an alkali metal hypochlorite or periodate such as sodium hypochlorite or sodium periodate;
- N-oxy (NO ) radicals such as the 2,2,6,6-tetra(CrC 6 )alkylpiperidinooxy or 2,2,6,6-tetra(Ci-C 6 )alkylmorpholinooxy radical, nitrosodisulphonate Fremy salts and morpholine N-oxide; the oxidizing agent is particularly chosen from the 2,2,6,6-tetramethylpiperidyloxy radical.
- multivalent iodine derivatives such as iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinanes, alkyls and benzoyl hypoiodites;
- the oxidizing agent is chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid and Dess-Martin periodinane;
- the optional supports for these oxidizing agents a) to h) may be chosen from silica, alumina, charcoal and charged or neutral polymers; i) hydrogen peroxides or system(s) that generate hydrogen peroxide such as:
- polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H 2 0 2 in particular in the form of powders, and the other polymeric complexes described in US 5 008 093; US 3 376 1 10; US 5 183 901 ; i-3) oxidases that produce hydrogen peroxide in the presence of a suitable substrate
- glucose for example glucose in the case of glucose oxidase or uric acid with uricase
- metal peroxides that generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide;
- chemical oxidizing agent(s) is (are) chosen from i) hydrogen peroxide or systems that generate hydrogen peroxide. More particularly H 2 0 2 .
- the process uses one or more system(s) that generate hydrogen peroxide, chosen from i) urea peroxide, i-2) polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H 2 0 2 ; i-3) oxidases; i-5) perborates and i-6) percarbonates.
- composition according to the invention comprises hydrogen peroxide.
- composition(s) comprising the hydrogen peroxide or the generator(s) of hydrogen peroxide may also contain various adjuvants conventionally used in hair dye compositions and as defined hereinbelow under the heading "cosmetic composition”.
- the hydrogen peroxide or the system(s) that generate hydrogen peroxide that is (are) used preferably represent from 0.001 % to 12% by weight expressed as hydrogen peroxide relative to the total weight of the composition(s) containing it or them.
- the process of the invention or the composition of the invention contains hydrogen peroxide or an aqueous hydrogen peroxide solution at the 20-volume concentration of between 1 g and 70 g per 100 g (%) of the composition containing said peroxide; preferably between 3 g % and 50 g % and especially between 3 g % and 50 g %.
- the alkalinizing agent present in the composition according to the invention or used in the dyeing process according to the invention as a fourth ingredient Hi) is an agent for increasing the pH of the composition(s) in which it is present.
- the alkalinizing agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.
- said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii), amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (III) below:
- W is a divalent (C Cio)alkylene group optionally interrupted by at least one heteroatom such as O, S, NR e , and/or said alkylene group is optionally substituted with at least one hydroxyl group or a (C C 4 )alkyl radical;
- R a , Rb, R c , R d and R e which may be identical or different, represent a hydrogen atom, (C C 4 )alkyl or C C 4 hydroxyalkyl, preferably a propylene group.
- the mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals from groups III,
- the hydroxide may be formed in situ, for instance guanidine hydroxide, by reacting calcium hydroxide and guanidine carbonate.
- bicarbonates also known as hydrogen carbonates, of the following formulae:
- the alkalinizing agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates; preferentially alkali metal (bi)carbonates.
- alkali metal or alkaline-earth metal (bi)carbonates Mention may be made of Na, K, Mg and Ca carbonates or hydrogen carbonates and mixtures thereof, and in particular sodium hydrogen carbonate.
- These hydrogen carbonates may originate from a natural water, for example spring water from the Vichy basin or from La Roche Posay or Badoit water (cf. for example, patent document FR 2 814 943).
- sodium carbonate [497-19-8] Na 2 C0 3
- sodium hydrogen carbonate or sodium bicarbonate [144-55-8] NaHC0 3
- sodium dihydrogen carbonate Na(HC0 3 ) 2 .
- the alkalinizing agent(s) Hi) are chosen from i) bicarbonates, particularly alkali metal or ammonium bicarbonates, ii) aqueous ammonia, iii) alkanolamines such as ethanolamine or 2-amino-2-methyl-1-propanol, more preferably aqueous ammonia.
- the alkalinizing agent(s) as defined previously preferably represent(s) from 10 "3 to 2.5x 10 "1 mol per 100 g (%) of the composition containing said alkalinizing agents. Particularly from 0.05 to 0.5 mol% preferably from 0.1 to 0.25 g % by weight of the composition.
- optionally sulphate salt :
- the process or the composition according to the invention may contain at least one (di)sulphate.
- sulphates is understood to mean the salts derived from sulphuric acid H 2 S0 4 , the sulphate ion of which is S0 4 2" (See “Sulfites, Thiosulfates, and Dithionites” in Ullmann's Encyclopedia of Industrial Chemistry; 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim - http://onlinelibrary.wiley.com/doi/10.1002/14356007.a25_477/pdf).
- the pH of the sulphates according to the invention is neutral or even slightly acid (pH between 7 and 6.6).
- the sulphates are sulphates of formula M 2 S0 3 or M'S0 3 or a hydrogen sulphate of formula MHS0 3 with M representing an alkali metal such as Na or K or (di)(CrC 6 )(alkyl)ammonium or tri(C C 6 )alkylammonium such as NH 4 + , or else disulphates of formula M'S 2 0 5 with M' representing an alkaline-earth metal.
- the sulphates of the invention are in particular salts of alkali metals or alkaline-earth metals or ammonium, (di)(CrC 6 )alkylammonium or tri(CrC 6 )alkylammonium; preferably the cationic counterion of the sulphate is chosen from sodium and potassium, and ammonium.
- the sulphate salts according to the invention are chosen from:
- the sulphate salt(s) used in the composition or in the process of the invention represent from 0.001 % to 10% by weight approximately, of the total weight of the composition(s) containing this or these sulphate salts, and more preferably still from 0.05% to 0.1 % by weight approximately.
- optionally one or more mordants one or more mordants
- the composition according to the invention may contain at least one mordant or the process of the invention may involve a supplementary step with at least one mordant.
- mordant is understood to mean a mordanting agent conventionally used in the textile industry and which is cosmetically acceptable, preferably in the form of metal salts such as iron, aluminium, titanium, calcium, manganese, copper, zinc and strontium salts.
- the mordant may be iron sulphate, manganese gluconate, copper sulphate, zinc gluconate, calcium chloride, magnesium chloride, potassium titanyl oxalate or strontium acetate.
- the mordant used is iron sulphate.
- the mordants are particularly found in the composition in proportions between 0.001 % and 10% relative to the total weight of the composition containing them.
- neither the dyeing process nor the composition of the invention use or contain a mordanting agent.
- water is preferably included in the process of the invention. It may originate from the moistening of the keratin fibres and/or from the composition(s) comprising compounds i) to Hi) as defined previously or from one or more other compositions. Preferably, the water comes from at least one composition comprising at least one compound chosen from i) to Hi) as defined previously.
- cosmetic compositions :
- compositions according to the invention are cosmetically acceptable, i.e. they comprise a dye support that generally contains water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
- organic solvent means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it.
- organic solvents examples include C C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
- C C 4 lower alkanols such as ethanol and isopropanol
- polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
- the organic solvents are present in proportions preferably of between 1 % and 40% by weight approximately and even more preferentially between 5% and 30% by weight approximately relative to the total weight of the dye composition.
- composition(s) of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.
- adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwit
- Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and mineral or organic thickeners.
- the above adjuvants are generally present in an amount for each of them of between
- ingredients i) to Hi) as defined previously or the cosmetic composition according to the invention comprising ingredients i) to Hi) as defined previously may also use or comprise one or more additional direct dyes.
- 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 o/f 70-diphenols, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine and methine cyanine direct dyes, and fluorescent dyes. All these additional dyes are other than the ortho-diphenol derivatives according to the invention.
- the additional direct dye(s) used in the composition(s) preferably represent from 0.001 % to 10% by weight approximately, of to the total weight of the composition(s) containing them, and even more preferentially from 0.05% to 5% by weight approximately.
- compositions of the process using ingredients i) to Hi) as defined previously or the cosmetic composition according to the invention comprising ingredients i) to Hi) as defined previously may also use or comprise one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.
- oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
- couplers mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
- the process of the invention, nor the composition of the invention contain a coupler, especially mefa-aminophenols.
- the process or the composition of the invention use or contain at least one oxidation dye, and bases and couplers, chosen from:
- Ri, R ⁇ , R3 and R 4 which may be identical or different, represent:
- a linear or branched C C 6 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a radical OR 5 , a radical NR 6 R7, a carboxyl radical, a sulphonyl radical, a carboxamido radical CONR 6 R7, a sulphonamido radical S0 2 NR 6 R7, a heteroaryl, an aryl optionally substituted with a (CrC 4 )alkyl group, a hydroxyl, a C C 2 alkoxy, an amino or a (di)alkyl(CrC 2 )amino;
- an aryl radical optionally substituted with one or more of a (C C 4 )alkyl, a hydroxyl, a C1-C2 alkoxy, an amino or a (di)(CrC 2 )alkylamino;
- R 3 and R 4 may also represent a hydrogen atom
- R 5 , R 6 and R 7 which may be identical or different, represent a hydrogen atom; a linear or branched C C 4 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a hydroxyl, a C C 2 alkoxy, a carboxamido CONR 8 Rg, a sulphonyl S0 2 R 8 , an aryl optionally substituted with a (C C 4 )alkyl, a hydroxyl, a C C 2 alkoxy, an amino, a (di)alkyl(C C 2 )amino; an aryl optionally substituted with a (C C 4 )alkyl, a hydroxyl, a C C 2 alkoxy, an amino or a (di)alkyl(d- C 2 )amino;
- R 6 and R 7 which may be identical or different, may also represent a carboxamido radical CONR 8 Rg; or a sulphonyl S0 2 R 8 ;
- R 8 and R 9 which may be identical or different, represent a hydrogen atom; a linear or branched C C 4 alkyl radical which is optionally substituted with one or more of a hydroxyl or a C C 2 alkoxy;
- Ri and R 2 on the one hand, and R 3 and R 4 , on the other hand, may form, with the nitrogen atoms to which they are attached, a saturated or unsaturated 5- or 7- membered heterocycle which is optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino, (di)(C C 4 )alkylamino, hydroxyl, carboxyl, carboxamido and (C C 2 )alkoxy radicals, C C 4 alkyl radicals optionally substituted with one or more hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl or sulphonyl radicals;
- R 3 and R 4 may also form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which can be replaced with an optionally substituted oxygen or nitrogen atom;
- Zi and Z 2 independently represent: i) a single covalent bond, ii) a divalent radical chosen from an oxygen atom and a radical -NR 6 (R 7 ) P -
- R 6 represents a hydrogen atom or a C C 6 alkyl radical, or R 6 , with R ⁇ respectively R 2 , form, together with the nitrogen atom to which they are attached, a substituted or unsubstituted, saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, optionally containing one or more heteroatoms or groups selected from N, O, S, S0 2 and -CO-, it being possible for the heterocycle to be cationic and/or substituted with a cationic or noncationic radical,
- -NR 6 R7- is a cationic radical in which R 6 and R 7 independently represent an alkyl radical
- o Zi may also represent a divalent radical -S-, -SO- or -S0 2 - when is a methyl radical;
- Ri and R 2 independently represent a hydrogen or halogen atom, or a group chosen from:
- a C1-C10 alkyl radical which is optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO and S0 2 ,
- a 5- to 8-membered ring which is substituted or unsubstituted, saturated, unsaturated or aromatic and optionally comprises one or more heteroatoms or groups selected from N, O, S, S0 2 and -CO-, it being possible for the ring to be cationic and/or substituted with a cationic radical,
- R 2 when Zi, respectively Z 2 , represents a covalent bond, then respectively R 2 , may also represent:
- R and R' independently represent a hydrogen atom or an optionally substituted C C 6 alkyl radical
- R 3 , R 4 and R 5 which may be identical or different, represent:
- Ci-C 6 dialkylamino radical in which the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which may contain one or more heteroatoms or groups selected from N, O, S, S0 2 and CO, it being possible for the heterocycle to be cationic and/or substituted with a cationic radical;
- R 3, R 4 and R 5 may form, in pairs, a saturated or unsaturated ring
- o X represents an anionic counterion or group of anions making it possible to ensure the electronegativity of the derivative of formula (V),
- Zi represents an oxygen atom or a group N R 6 , when Zi represents N R 6 then and R 6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, saturated or unsaturated or aromatic 5- to 8-membered heterocycle;
- Zi may also represent a divalent radical S, SO or S0 2 when represents CH 3 ; o Ri and R 6 independently represent:
- substituent an optionally substituted C1-C10 alkyl radical, it being possible for the substituent to be an optionally substituted, saturated or unsaturated or aromatic 5- to 8- membered (hetero)cycle;
- R ⁇ , R3, R4 and R 5 independently represent:
- R 9 and R 10 representing an optionally substituted, linear or branched C C 6 alkyl
- Rn and R 12 which may be identical or different, representing an optionally substituted, linear or branched C C 6 alkyl, it being possible for Rn and R 12 to form, together with the nitrogen atom to which they are attached, a saturated or unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from N, O, S, S0 2 and CO, the heterocycle being optionally substituted;
- R ⁇ , R3, R 4 , R5 may form, in pairs, with the adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle;
- o Zi is an oxygen atom or a group NR 2 ;
- R 2 is a hydrogen atom or a linear or branched C C 4 alkyl radical, a benzyl radical or an acetyl radical;
- Ri is a saturated, linear or branched C 1 -C 10 alkyl radical, which is substituted with or interrupted by a cationic radical, optionally interrupted by one or more oxygen atoms and/or by one or more groups N R 2 , optionally substituted with one or more radicals chosen from hydroxyl, alkoxy and C C 4 hydroxyalkyl radicals, or is a saturated or unsaturated or aromatic cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C C 4 alkyl, hydroxyl, Ci-C 4 alkoxy, amino, (C C 4 )alkylamino, di(C C 4 )alkylamino, thio, (C C 4 )alkylthio, carboxyl, (C C 4 )alkylcarbonyl, sulphonyl, amido and C C 4 hydroxyalkyl radicals; when Zi represents NR 2 then
- ⁇ Ri and R 2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C 1 -C 10 alkyl radicals and hydroxyl, C C 4 alkoxy, amino, (C C 4 )alkylamino, di(C
- ⁇ Ri and R 2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated noncationic 5- to 8-membered heterocycle substituted with a cationic radical and optionally substituted with one or more radicals chosen from C 1 -C 10 alkyl radicals and hydroxyl, C C 4 alkoxy, amino, (C C 4 )alkylamino, di(C C 4 )alkylamino, thio, (C C 4 )alkylthio, carboxyl, (C C 4 )alkylcarbonyl, sulphonyl, amido and C C 4 hydroxyalkyl radicals;
- R is chosen from a hydrogen atom, halogens selected from fluorine, chlorine and bromine, linear or branched C C 4 alkyl radicals and carboxyl (-COOH) and (Ci-C 4 )alkoxycarbonyl radicals;
- An- represents an anionic counterion or group of anions.
- the oxidation base(s) present in the composition(s) are each generally present in an amount of between 0.001 % and 10% by weight, of the total weight of the corresponding composition(s).
- the oxidation bases in particular aromatic amines such as para- phenylenediamines and/or para-aminophenols are present in the composition of the invention or are used in the process of the invention, they are in amounts such that the ratio of the amount of hydroxybenzaldehyde derivatives of formula (I) as defined previously/the amount of oxidation base is at least greater than 5; preferably greater than 20.
- the dyeing process and the composition according to the invention do not comprise oxidation bases, in particular para- phenylenediamines and/or para-aminophenols.
- the cosmetic composition(s) of the invention may be in various galenic forms, such as a powder, a lotion, a foam, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres. They may also be packaged in a propellant-free pump-action bottle or under pressure in an aerosol container in the presence of a propellant and form a foam. pH of the composition(s)
- the pH of the composition(s) containing Hi) the alkalinizing agent(s) is above 7 and preferably between 8 and 12. It is particularly between 8 and 10.
- the pH of the composition(s) containing the oxidizing agent is preferably below 7, more particularly between 1 and 5.
- composition(s) that contain(s) the hydroxybenzaldehyde derivative(s) of formula (I) as defined previously and that contain(s) no alkalinizing agent are at a pH of below 7 and preferably of between 3 and 6.5.
- compositions containing the sulphate salt(s) that contain or do not contain alkalinizing agent are at a pH of above 7 and preferably of between 8 and 12.
- compositions may be adjusted to the desired value by means of acidifying or alkalinizing agents usually used in the dyeing of keratin fibres as defined in "// J alkalinizing agent' above, or alternatively using standard buffer systems.
- acidifying agents of the compositions mention may particularly be made of those chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulphuric acid H 2 S0 4 , iv) alkylsulphonic acids: Alk-S(0) 2 OH such as methylsulphonic acid and ethylsulphonic acid; v) arylsulphonic acids: Ar-S(0) 2 OH such as benzenesulphonic acid and toluenesulphonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) phosphoric acid H 3 P0 4 ; xi) acetic acid CH 3 C(0)OH; xii) triflic acid CF 3 S0 3 H; and xiii) tetrafluoroboric acid HBF 4 .
- the process of the invention does not use an active CH compound, and the composition according to the invention does not contain an active CH compound.
- the dyeing process is carried out:
- composition(s) by applying to the keratin fibres, in one or more steps, one or more cosmetic compositions containing the following ingredients, taken together or separately in said composition(s):
- the pH of the composition comprising the ingredient(s) iii) is basic i.e. above 7; preferably between 7.5 and 12; and
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the composition(s) comprising the ingredients i), ii) and iii); and
- the waiting time between the steps of applying the compositions comprising the ingredient(s) i), ii) and/or iii) is set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more particularly between 15 and 45 minutes.
- the keratin fibres may or may not be moistened beforehand.
- the chemical oxidizing agent(s) such as hydrogen peroxide ii) are either in a mixture with the ingredients i), or are applied in a composition without the other ingredients ii) and iii).
- One particular embodiment of the invention relates to dyeing processes with step a) that is carried out in one or two application steps.
- step a) of the process for dyeing keratin fibres is carried out by applying to the keratin fibres the preferably aqueous, cosmetic composition according to the invention comprising:
- oxidizing agent preferably a chemical oxidizing agent
- composition preferably does not contain an active CH compound
- the pH of the composition is basic i.e. above 7; preferably between 7.5 and 12;
- the compound(s) of formula (I) comprise at least one of the two radicals R 1 or R 3 which represents a hydroxyl group; with, when R 1 represents a hydroxyl radical, then R 2 or R 3 or R 4 or R 5 represents a hydrogen atom; and when R 3 represents a hydroxyl radical then R 1 or R 2 or R 4 or R 5 represents a hydrogen atom;
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the composition comprising the ingredients i) to Hi).
- the waiting time after application is generally set at between 5 minutes and 24 hours, particularly between 10 and 120 minutes and more particularly between 15 and 60 minutes, especially between 15 and 45 minutes.
- step a) of the process for dyeing keratin fibres is performed in two steps.
- step a) involves applying to said fibres a cosmetic composition comprising the ingredients i), ii) as defined previously, and then, in a second step, a cosmetic composition comprising the ingredient Hi) as defined previously is applied to said fibres, it being understood that at least one of the two cosmetic compositions is aqueous.
- step a) firstly comprises applying to said fibres a composition comprising the ingredients i) and Hi) as defined previously, and then, in a second step, a second cosmetic composition comprising the ingredient(s) ii) as defined previously is applied to said fibres, it being understood that preferably at least one of the two compositions is aqueous.
- said step a) ends with the treatment of the keratin fibres with the ingredient Hi).
- the application temperature of step a) of the process of the invention is generally between room temperature (15°C to 25°C) and 150°C and particularly between 15°C and 85°C, and preferably between 20°C and 60°C. If the application is carried out at a temperature above the temperature of 30°C, then it is possible to do away with step b) of the process of the invention. According to one preferred embodiment of the invention, the application of the composition(s) according to step a) of the process is carried out at room temperature, i.e. at 25°C.
- step b) of the process of the invention after application of the composition(s) according to step a) of the process of I'invention, the hair is subjected to a heat treatment by heating at a temperature above room temperature, i.e. above 30°C, particularly at a temperature between 35°C and 80°C. More particularly between 40°C and 50°C, such as 45°C.
- step b) of the process of the invention may be performed using a a hairstyling hood, a hairdryer or an infrared ray emitter or other standard heating appliances.
- heating iron at a temperature of between 60°C and 220°C and preferably between 120°C and 200°C.
- One advantageous aspect relates to the dyeing process as described previously, preceded by one or more mordanting steps by pretreating the keratin fibres with at least one mordant as defined previously (see “v) optionally one or more mordant(s)").
- the mordant(s) are especially in a cosemtic composition and are applied at least 5 minutes before the implementation of the dyeing process comprising the ingredients i) to Hi) as defined previously.
- the mordant used is particularly iron sulphate.
- Another advantageous aspect relates to the dyeing process as described previously, followed by post-treatment steps such as shampooing using a standard shampoo, rinsing, for example with water, and/or drying the keratin fibres by heat treatment as defined below.
- the dyeing process according to the invention is carried out in one step by applying to the keratin fibres the composition according to the invention comprising the ingredients i) to Hi) as defined previously, followed by post-treatment steps of rinsing, for example with water, of shampooing with a standard shampoo, and/or drying the keratin fibres.
- compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and especially of compositions present in dyeing kits.
- kits Another subject of the invention is a multicompartment dyeing device or "kit".
- this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which the ingredients i) at least one hydroxybenzaldehyde derivative of formula (I), as defined previously, ii) at least one chemical oxidizing agent such as hydrogen peroxide and Hi) at least one alkalinizing agent as defined previously are distributed.
- the kit comprises three compartments, the first two compartments comprising, respectively, the powdered ingredients i) and Hi) as defined previously and the third compartment containing an aqueous composition such as water.
- the compound(s) ii) are hydrogen peroxide precursors.
- the kit comprises four compartments, the first three compartments comprising, respectively, the powdered ingredients i), ii) and Hi) as defined previously and the fourth compartment containing an aqueous composition such as water.
- kits comprising three compartments, one of which contains at least one aqueous composition, and comprising an ingredient i) to Hi) as defined previously.
- Another preferred embodiment concerns a device comprising three compartments: (a) a first compartment contains a composition containing:
- a second compartment contains a composition containing:
- At least one chemical oxidizing agent such as hydrogen peroxide
- a third compartment contains Hi) at least one alkalinizing agent as defined previously.
- kits that contain, in a first compartment, a composition comprising compounds i) and iii) as defined previously and, in a second compartment, a composition comprising compound ii) at least one chemical oxidizing agent such as hydrogen peroxide as defined previously.
- the device according to the invention also comprises an additional composition (c) comprising one or more treating or mordanting agents.
- compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means, which may be identical or different, such as fine brushes, coarse brushes or sponges.
- the device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913.
- composition for 100 g Composition for 100 g:
- composition is applied with a bath ratio of 1 g of hair per 5 g of composition.
- the locks of hair are grey containing 90% natural white (90% NW) hairs.
- the composition is left on the lock for 15 or 30 minutes at 45°C.
- the locks are then rinsed, shampooed and dried with a hairdryer. Colorimetric results:
- the coloration of the hair is evaluated visually and read on a Minolta spectrocolorimeter (CM3600d, illuminant D65, angle 10°, SCI values) for the L*, a*, b* colorimetric measurements.
- CM3600d Minolta spectrocolorimeter
- L* represents the intensity of the colour
- a* indicates the green/red colour axis
- b* the blue/yellow colour axis.
- the lower the value of L the darker or more intense the colour.
- L*, a* and b* represent the values measured after dyeing natural hair containing 90% white hairs
- L* 0 , a 0 * and b 0 * represent the values measured for natural hair containing 90% untreated hairs.
- the coloration is very persistent with regard to washing operations and light.
- alkaline agent ethanolamine, or sodium hydoxide, or arginine, or sodium bicarbonate, or ammonium bicarbonate or 2-amino-2-methyl-1-propanol
- the above composition is applied with a bath ratio of 1 g of hair per 5 g of composition.
- the locks of hair are grey containing 90% natural white (90% NW) hairs.
- the composition is left on the lock for 30 minutes at 45°C.
- the locks are then rinsed, shampooed and dried with a hairdryer.
- composition for 100g is a composition for 100g:
- the above composition is applied with a bath ratio of 1 g of hair per 5 g of composition.
- the locks of hair are grey containing 90% natural white (90% NW) hairs.
- the composition is left on the lock for 30 minutes at 45°C.
- the locks are then rinsed, shampooed and dried with a hairdryer.
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)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
Abstract
One subject of the invention is a process for dyeing keratin fibres, especially the hair, using i)at least one hydroxybenzaldehyde derivative, ii)at least one oxidizing agent, and iii) at least one alkalinizing agent in the presence of heat. Another subject of the invention is a cosmetic composition for dyeing keratin fibres comprising the ingredients i)to iii)as defined previously. Another subject of the invention is a multicompartment device comprising the ingredients i),ii)and iii). This dyeing process makes it possible to obtain better colorations that are chromatic, intense and long-lasting without the use of oxidation bases such as para-phenylenediamines and para-aminophenols.
Description
PROCESS FOR DYEING KERATIN FIBRES USING HYDROXYBENZALDEHYDE DERIVATIVES, OXIDIZING AGENTS AND ALKALINIZING AGENTS IN THE PRESENCE
OF HEAT One subject of the invention is a process for dyeing keratin fibres, especially the hair, using i) at least one hydroxybenzaldehyde derivative, ii) at least one oxidizing agent, and Hi) at least one alkalinizing agent in the presence of heat. This dyeing process makes it possible to obtain colorations that are chromatic, intense, deep and long-lasting even in the absence of oxidation bases such as para-phenylenediamines and para-aminophenols, or of active CH compounds.
It is known practice to obtain "permanent" colorations with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, 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 coloration modifiers, the latter being chosen especially from aromatic mefa-diamines, mefa-aminophenols, mefa-di phenols and certain heterocyclic compounds such as indole compounds having light stability and stability to shampooing.
This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with hydrogen peroxide (H202 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. The colorations resulting therefrom are permanent, strong and resistant to external agents, especially to light, adverse weather conditions, washing, perspiration and rubbing.
Derivatives of 5,6-dihydroxyindoles are also capable of generating deep shades by "autoxidation" , but the resulting colorations are not always satisfactory, especially in terms of chromaticity, strength, remanence or change in colour after shampooing and exposure to light.
To attain deep shades, the presence of para-phenylenediamine oxidation bases is virtually indispensable.
It is also known to dye keratin fibres with dye compositions containing direct dyes. The conventional dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane nitrobenzene type or natural dyes. These dyes, which are coloured and colouring molecules that have an affinity for the fibres, are applied to the keratin fibres for a time necessary for obtaining the desired coloration, then rinsed. The colorations resulting therefrom are chromatic colorations that are, however, only temporary or semi-permanent since the nature of the interactions that bind the direct dyes to the keratin fibre and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power and their poor fastness with respect to washing or perspiration. One known variant is to apply to keratin fibres, instead of direct
dyes, dye precursors that form the colour in situ via a chemical reaction. For example, in patents US 6,790,239 and US 6,770, 102, and international patent applications WO 2006/131 163 and WO 2006/002710 aromatic aldehyde/ketone precursors have been described that condense with active CH precursors to form, in situ, the direct dye after release of water. These direct dyes are also light-sensitive due to the low resistance of the chromophore to photochemical attack, and lead to fading of the coloration of the hair over time. These dyes do not make it possible to obtain satisfactory colorations, especially in terms of remanence.
Other documents mention the use of 2-hydroxy- or 4-hydroxy-3-methoxybenzaldehyde for colouring the hair in the presence of oxidation bases of 2-aminophenol type and 2,5- diaminotoluene type (FR 2 462 907 and of DE 28 30 497 - Schwarzkopf).
There is thus a real need to find new means of dyeing keratin fibres that make it possible to obtain uniform, strong and/or chromatic colorations with deep shades, ideally without conventional aromatic amines such as para-phenylenediamines and para- aminophenols, which would be light-fast, resistant to adverse weather conditions, persistent with regard to washing operations and perspiration, which do not stain and are sufficiently stable in the presence of oxidizing agents such as an aqueous hydrogen peroxide solution in order to be able to obtain a simultaneous lightening of the fibre with the aformentioned advantages.
This objective is achieved by the present invention, one subject of which is a process for dyeing keratin fibres, comprising:
a) the application to the keratin fibres of:
i) nic
(I) in which formula (I):
R1, R2, R3, R4 and R5, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
■ a hydroxy I;
■ a linear or branched (d-C5)alkyl which is optionally substituted, especially
by at least one hydroxyl group;
■ a linear or branched (d-C5)alkoxy;
■ a carboxyl -C(0)-OH or carboxylate -C(0)-0", M+ ; with M+ representing a cationic counterion such as an alkali metal or alkaline-earth metal, or an ammonium;
■ a carbamoyl -0-C(0)-NRaRb with Ra and R , which may be identical or different, representing a hydrogen atom or a linear or branched (CrC5)alkyl group; particularly -0-C(0)-NH2;
■ an amido -C(0)-NR6R7 or -NR6-C(0)-R7 with R6 and R7, which may be identical or different, representing a hydrogen atom or a (CrC5)alkyl group, particularly -C(0)-NH2;
■ an ester -C(0)-0-R8 or -0-C(0)-R8, with R8 representing a (C C5)alkyl group, particularly -C(0)-0-R8;
■ a (CrC5)alkylcarbonyl;
■ a carboxaldehyde -C(0)H; and
■ an amino NRaRb with Ra and R , as defined previously;
■ or else R1 and R2, or R2 and R3, or R3 and R4 form, together with the carbon atoms to which they are attached, a 6-membered (hetero)aryl group such as phenyl;
on condition that at least one of the two radicals R1 or R3 represents a hydroxyl group; with, when R1 represents a hydroxyl group, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl group then R1 or R2 or R4 or R5 represents a hydrogen atom;
ii) at least one chemical oxidizing agent; and
Hi) at least one alkalinizing agent;
b) then a heat treatment of the keratin fibres at a temperature above 30°C, preferably between 30°C and 80°C;
it being understood that the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of ingredients i), ii) and Hi), or of the total weight of the composition(s) used in the process.
Another subject of the invention is a cosmetic composition for dyeing keratin fibres, comprising:
i) at least one derivative of formula (I), as defined previously;
ii) at least one chemical oxidizing agent; and
Hi) at least one alkalinizing agent;
it being understood that:
the pH of the composition is above 7 and preferably between 7.5 and 12;
the compound(s) of formula (I) comprise at least one of the two radicals R1 or R3 which represents a hydroxyl group; with, when R1 represents a hydroxyl group, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl radical then R1 or R2 or R4 or R5 represents a hydrogen atom;
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the ingredients ii) and Hi), and
when the hydroxybenzaldehyde derivative of formula (I) represents a compound chosen from 3,4-dihydroxybenzaldehyde; 4-hydroxy-2-methoxybenzaldehyde; 3,5-dimethoxybenzaldehyde; 4-hydroxy-1-naphthaldehyde; 3,5-dimethyl-4- hydroxybenzaldehyde, then the alkalinizing agent Hi) is other than monoethanolamine; and
when the hydroxybenzaldehyde derivative of formula (I) represents a compound chosen from 4-hydroxy-3-methoxybenzaldehyde and 2-hydroxy-3- methoxybenzaldehyde, which is in the presence of 2-aminophenol, 2,5- diaminotoluene sulphate; then the alkalinizing agent Hi) is other than ammonium hydroxide.
Another subject of the invention relates to a multicompartment device comprising the ingredients i) to Hi) as defined previously.
The composition and dyeing process of the invention have the advantage of dyeing human keratin fibres, with strong, chromatic dyeing results that are resistant to washing, perspiration, sebum and light, and that are moreover long-lasting, without impairing said fibres. Furthermore, the colorations obtained using the process give uniform colours from the root to the end of a fibre (little coloration selectivity). The shades obtained after dyeing with the composition or the process of the invention are very intense, in particular at a temperature above room temperature, preferably at a temperature between 45°C and 80°C.
Moreover, the colorations obtained with the composition or the process of the invention are compatible with conventional oxidation conditions for lightening hair. The colorations are particularly persistent with regard to shampooing operations.
Unless otherwise indicated in the present invention it is understood that:
- the "a/yr radical represents a fused or nonfused monocyclic or polycyclic carbon-based group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl; preferably, the aryl radical is a phenyl;
- a "heteroaryr radical represents a fused or nonfused, optionally cationic, 5- to 22- membered monocyclic or polycyclic group, comprising from 1 to 6 heteroatoms chosen
from nitrogen, oxygen, sulphur and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyrimidyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and the ammonium salts thereof; a "cationic heteroaryl radicar is a heteroaryl group as defined previously, which comprises an endocyclic or exocyclic cationic group,
o when the charge is endocyclic, it is included in the electron derealization via the mesomeric effe inium, imidazolium or indolinium group:
with R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(CrC8)alkyl group such as methyl;
when the charge is exocyclic, it is not included in the electron derealization via the mesomeric effect, for example it is an ammonium or phosphonium substituent R+ such as trimethylammonium, which is outside the heteroaryl such as pyridyl, indolyl or imidazol
with R a heteroaryl substituent as defined previously and R+ an ammonium RaRb cN+-, phosphonium RaRbRcP+- or ammonium RaRbRcN+-(CrC6)alkylamino group with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom or a (d-C8)alkyl group such as methyl; the "aryP' or "heteroaryP' radical or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
• a C1-C16 and preferably C C8 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C C2 alkoxy, (poly)hydroxy(C2-C4)alkoxy, acylamino, amino substituted with two, identical or different, C C4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the
nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocycle optionally comprising another heteroatom that is identical to or different from nitrogen;
a halogen atom such as chlorine, fluorine or bromine;
a hydroxyl group;
a (CrC2)alkoxy radical;
a (CrC2)alkylthio radical;
a (poly)hydroxy(C2-C4)alkoxy radical;
an amino radical;
a 5- or 6-membered heterocycloalkyl radical such as cyclohexyl;
an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (C C4)alkyl radical, preferentially methyl;
an amino radical substituted with one or two identical or different (d-C6)alkyl radicals, optionally substituted with at least:
i) one hydroxyl group;
ii) one amino group optionally substituted with one or two optionally substituted C C3 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7- membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen;
-N(R)-C(0)-R' in which the radical R is a hydrogen atom or a (C C4)alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a (CrC2)alkyl radical;
R2N-C(0)- in which the radicals R, which may be identical or different, represent a hydrogen atom or a (C C4)alkyl radical optionally bearing at least one hydroxyl group;
R'-S(0)2-N(R)- in which the radical R represents a hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a (Ci-C4)alkyl radical, or a phenyl radical;
R2N-S(0)2- in which the radicals R, which may be identical or different, represent a hydrogen atom or a (C C4)alkyl radical optionally bearing at least one hydroxyl group;
a carboxylic radical in acid or salified (preferably with an alkali metal or a substituted or unsubstituted ammonium) form;
a cyano group;
a polyhaloalkyi group containing from 1 to 6 carbon atoms and comprising from 1 to 6 identical or different halogen atoms, the polyhaloalkyi group is, for example, trifluoromethyl;
- an "alky radical is a saturated, linear or branched C Ci6, preferably C C8 hydrocarbon-based radical such as methyl or ethyl;
the expression "optionally substituted" attributed to the alkyl radical implies that said alkyl radical may be substituted with one or more radicals chosen from the following groups: i) hydroxyl, ii) (C C4)alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different (d-C6)alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N+R'R"R"', An" for which R', R" and R'", which may be identical or different, represent a hydrogen atom or a (CrC6)alkyl group, or alternatively -N+R'R"R"' forms a heteroaryl such as imidazolium optionally substituted with a (C C6)alkyl group, and An" represents the counterion of the organic or mineral acid or of the corresponding halide; preferably when the alkyl radical is optionally substituted, it is substituted with at least one hydroxyl, especially hydroxymethyl, group; an "alkoxy" radical is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a linear or branched C Ci6 and preferentially C C8 hydrocarbon-based radical; an "alkylthio" radical is an alkyl-S- radical for which the alkyl radical is a linear or branched C Ci6 and preferentially C C8 hydrocarbon-based radical; an "active CH" or "active methylene" compound is a reactive compound that contains a "CH" or "methylene" group which may readily lose or release a proton from said CH or methylene group, i.e. for which the carbon atom that bears the proton of the CH or methylene is directly bonded to an electron-deficient cationic heteroaryl group:
(
with
• R representing a hydrogen atom, a (C C6) alkyl group, or aryl group or electron- withdrawing group, in particular those that are electron-withdrawing via an -M mesomeric effect such as cyano -CN or -C(0)OR' with R' representing a C C6 alkyl group or a hydrogen atom;
• Het+ representing a cationic heteroaryl group with an endocyclic cationic charge, i.e. the charge of which is included in the aromaticity of said heteroaryl and which is stabilized via a mesomeric effect;
(II2)
in which formula (ll2):
■ R' represents an optionally substituted (d-C6)alkyl group;
■ 2 represents a heteroaryl group with an endocyclic cationic charge comprising from 5 to 13 ring members, which may possibly also comprise the cationic nitrogen atom, and comprising from 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulphur, and which bears, on a carbon atom of the heteroaryl, a group R-CH2- with R representing a hydrogen atom or a (CrC6)alkyl or aryl group; such as imidazolium, oxazolium, thiazolium, pyridinium, pyrimidinium such as 2- oxopyrimidinium, quinolinium, the group R-CH2- being at position 2 or 4 of the pyridinium or quinolinium or at position 2, 4 or 5 of the imidazolium, oxazolium or thiazolium group, or at position 4 and 6 of the pyrimidinium such as 2- oxopyrimidinium;
- the limit values delimiting the extent of a range of values are included in this range of values; and
- the expression "at least' is understood to mean "one or more". i) hydroxybenzaldehyde derivative of formula (I)
One particular embodiment of the invention relates to hydroxybenzaldehyde derivatives or mixtures thereof of formula (I) in which at least one of the two radicals R1 and/or R3 represent(s) a hydroxyl group and in which R1 , R2, R3, R4 and R5 represent, independently of one another, a hydrogen or halogen atom, preferably a chlorine atom or a group chosen from:
■ a hydroxyl;
■ a linear or branched C C4 alkyl;
■ a linear or branched C C4 alkoxy, preferably a methoxy radical;
■ a carboxyl -C(0)-OH;
■ a carboxaldehyde -C(0)H; and
■ a di(Ci-C4)alkylamino; or else
■ R1 and R2, or R2 and R3, or R3 and R4 form, together with the carbon atoms to which they are attached, an aromatic ring containing 6 carbon atoms;
on the condition that when R1 represents a hydroxyl group, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl group then R1 or R2 or
R4 or R5 represents a hydrogen atom.
The advantageous compounds of (I) of the invention are those from the table below:
Preferably, the derivatives of formula (I) are chosen from compounds 1_ to 10 as defined in the preceding table.
According to one particular embodiment of the invention that makes it possible to obtain intense, deep colorations, the hydroxybenzaldehyde derivatives or mixtures thereof are chosen from those of formula (II):
(II)
in which formula (II):
> R'i represents a hydrogen atom or a hydroxyl group;
> R'2 represents a hydrogen atom, or a group chosen from a hydroxyl, a carboxaldehyde, a linear or branched C C4 alkyl and a linear or branched C C4 alkoxy;
> R'4 represents a hydrogen atom or a group chosen from a hydroxyl, a linear or branched C C4 alkyl and a linear or branched C C4 alkoxy;
> R'5 represents a hydrogen atom or a hydroxyl group;
with, more particularly:
R'i = OH and R'5 = OH or a linear or branched C C5 alkoxy; and/or
R'2 = OH or C(0)H and R'4 = OH or a linear or branched C C5 alkoxy; and R' or R'2 or R'4 or R'5 denotes a hydrogen atom.
The preferred compounds (II) are the following:
and/or the organic or mineral base salts thereof and/or solvates thereof.
According to the invention, the hydroxybenzaldehyde derivative(s) of formula (I) are synthetic, natural, or are found in natural extracts. For example, mention may be made of hydroxybenzaldehydes such as vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3- hydroxy-4-methoxybenzaldehyde) or ethyl vanillin (4-hydroxy-3-ethoxybenzaldehyde) derived from extract of vanilla or Vanilla planifolia or Vanilla tahitensis, protocatechualdehyde derived from extract of Cassia garrettiana, gallaldehyde derived from extract of Boletus scaber.
According to one embodiment, the derivative(s) of formula (I) are present in the composition or in the process without the presence of oxidizing agent or coupler.
According to another embodiment, oxidation dyes are present optionally with couplers.
The coloration observed is compatible with conventional oxidation conditions for lightening hair. The coloration is persistent with regard to shampooing operations.
In the latter variant, the derivative(s) of formula (I) are at a total concentration that is at least 10 times higher than the concentration of other oxidation dyeing precursors, for instance the bases and couplers optionally present in the mixture.
Preferably, the hydroxybenzaldehyde derivative(s) or mixtures thereof of formula (I) exist in the composition or in the process according to the invention at a concentration of greater than 1 g per 100 g (%) relative to the total weight of the composition containing the hydroxybenzaldehyde derivative(s) or the extract(s) comprising them, particularly between
between 1 g % and 10 g % and preferably between 1 g % and 5 g %. ii) chemical oxidizing agent
According to the dyeing process of the invention, said process uses a chemical oxidizing agent. The expression "chemical oxidizing agent" is understood to mean an oxidizing agent other than the oxygen from the air.
The expression "chemical oxidizing agent" is understood more particularly to mean:
a) ozone;
b) alkali metal or quaternary ammonium persalts such as perborates, persulphates, percarbonates, peroxodiphosphates or Oxone®; the oxidizing agent is particularly chosen from sodium perborate, sodium persulphate, potassium persulphate, ammonium persulphate, sodium percarbonate and potassium percarbonate;
c) aliphatic C C6 and aromatic C6-C20 organic peracids, and the percarboxylate forms thereof, such as performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid; the oxidizing agent is particularly peracetic acid;
d) organic peroxides such as dioxirane, C C6 alkyl peroxides, benzoyl peroxide, peroxo(CrC6)alkyl carboxylates, bis(tri)(CrC6)alkylsilyl peroxides such as bis(trimethylsilyl) peroxide, C C6 alkyl peroxydicarbonates, and sodium nonanoyloxybenzene sulphonate as described in patents WO 1995/000625 and US 4 412 934;
e) oxidizing anions such as nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates and periodates; the oxidizing agent is particularly chosen from an alkali metal hypochlorite or periodate such as sodium hypochlorite or sodium periodate;
f) stable N-oxy (NO ) radicals such as the 2,2,6,6-tetra(CrC6)alkylpiperidinooxy or 2,2,6,6-tetra(Ci-C6)alkylmorpholinooxy radical, nitrosodisulphonate Fremy salts and morpholine N-oxide; the oxidizing agent is particularly chosen from the 2,2,6,6-tetramethylpiperidyloxy radical.
g) multivalent iodine derivatives such as iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinanes, alkyls and benzoyl hypoiodites;
more preferentially, the oxidizing agent is chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid and Dess-Martin periodinane;
h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N-hydroxyphthalimide, alkyl nitrites;
the optional supports for these oxidizing agents a) to h) may be chosen from silica, alumina, charcoal and charged or neutral polymers;
i) hydrogen peroxides or system(s) that generate hydrogen peroxide such as:
i-1 ) urea peroxide;
i-2) polymeric complexes that can release hydrogen peroxide, such as polyvinylpyrrolidone/H202 in particular in the form of powders, and the other polymeric complexes described in US 5 008 093; US 3 376 1 10; US 5 183 901 ; i-3) oxidases that produce hydrogen peroxide in the presence of a suitable substrate
(for example glucose in the case of glucose oxidase or uric acid with uricase);
i-4) metal peroxides that generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide;
i-5) perborates; or
i-6) percarbonates.
More particularly the chemical oxidizing agent(s) is (are) chosen from i) hydrogen peroxide or systems that generate hydrogen peroxide. More particularly H202.
According to one preferred embodiment of the invention, the process uses one or more system(s) that generate hydrogen peroxide, chosen from i) urea peroxide, i-2) polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H202; i-3) oxidases; i-5) perborates and i-6) percarbonates.
More preferably, the composition according to the invention comprises hydrogen peroxide.
Moreover, the composition(s) comprising the hydrogen peroxide or the generator(s) of hydrogen peroxide may also contain various adjuvants conventionally used in hair dye compositions and as defined hereinbelow under the heading "cosmetic composition".
According to one particular embodiment of the invention, the hydrogen peroxide or the system(s) that generate hydrogen peroxide that is (are) used preferably represent from 0.001 % to 12% by weight expressed as hydrogen peroxide relative to the total weight of the composition(s) containing it or them. More particularly, the process of the invention or the composition of the invention contains hydrogen peroxide or an aqueous hydrogen peroxide solution at the 20-volume concentration of between 1 g and 70 g per 100 g (%) of the composition containing said peroxide; preferably between 3 g % and 50 g % and especially between 3 g % and 50 g %.
Hi) alkalinizing agent
The alkalinizing agent present in the composition according to the invention or used in the dyeing process according to the invention as a fourth ingredient Hi) is an agent for increasing the pH of the composition(s) in which it is present. The alkalinizing agent is a Bronsted, Lowry or Lewis base. It may be mineral or organic.
Particularly, said agent is chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii), amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and viii) the compounds of formula (III) below:
in which formula (III) W is a divalent (C Cio)alkylene group optionally interrupted by at least one heteroatom such as O, S, NRe, and/or said alkylene group is optionally substituted with at least one hydroxyl group or a (C C4)alkyl radical; Ra, Rb, Rc, Rd and Re, which may be identical or different, represent a hydrogen atom, (C C4)alkyl or C C4 hydroxyalkyl, preferably a propylene group.
The mineral or organic hydroxides are preferably chosen from a) hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal, for instance sodium hydroxide or potassium hydroxide, c) hydroxides of a transition metal, such as hydroxides of metals from groups III,
IV, V and VI, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.
The hydroxide may be formed in situ, for instance guanidine hydroxide, by reacting calcium hydroxide and guanidine carbonate.
The term "(bi)carbonates i)" means:
a) carbonates of alkali metals (Met2 +, C03 2"), of alkaline-earth metals (Met'2+, C03 2") of ammonium ((R"4N+)2, C03 2") or of phosphonium ((R"4P+)2, C03 2") with Met' representing an alkaline-earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom, an optionally substituted (CrC6)alkyl group such as a hydroxyethyl group),
and
b) bicarbonates, also known as hydrogen carbonates, of the following formulae:
> R'+, HC03 " with R' representing a hydrogen atom, an alkali metal, an ammonium group R"4N+- or a phosphonium group R"4P+- where R", which may be identical or different, represent a hydrogen atom, an optionally substituted (CrC6)alkyl group such as a hydroxyethyl group and, when R' represents a hydrogen atom, the hydrogen carbonate is then known as a dihydrogen carbonate (C02, H20); and
> Met'2+ (HC03 ")2 with Met' representing an alkaline-earth metal.
More particularly, the alkalinizing agent is chosen from alkali metal or alkaline-earth metal (bi)carbonates; preferentially alkali metal (bi)carbonates.
Mention may be made of Na, K, Mg and Ca carbonates or hydrogen carbonates and mixtures thereof, and in particular sodium hydrogen carbonate. These hydrogen carbonates may originate from a natural water, for example spring water from the Vichy basin or from La Roche Posay or Badoit water (cf. for example, patent document FR 2 814 943). In particular, mention may be made of sodium carbonate [497-19-8] = Na2C03, sodium hydrogen carbonate or sodium bicarbonate [144-55-8] = NaHC03, and sodium dihydrogen carbonate = Na(HC03)2.
According to one particularly advantageous embodiment, the alkalinizing agent(s) Hi) are chosen from i) bicarbonates, particularly alkali metal or ammonium bicarbonates, ii) aqueous ammonia, iii) alkanolamines such as ethanolamine or 2-amino-2-methyl-1-propanol, more preferably aqueous ammonia.
The alkalinizing agent(s) as defined previously preferably represent(s) from 10"3 to 2.5x 10"1 mol per 100 g (%) of the composition containing said alkalinizing agents. Particularly from 0.05 to 0.5 mol% preferably from 0.1 to 0.25 g % by weight of the composition. iv) optionally sulphate salt:
The process or the composition according to the invention may contain at least one (di)sulphate. The term "sulphates" is understood to mean the salts derived from sulphuric acid H2S04, the sulphate ion of which is S04 2" (See "Sulfites, Thiosulfates, and Dithionites" in Ullmann's Encyclopedia of Industrial Chemistry; 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim - http://onlinelibrary.wiley.com/doi/10.1002/14356007.a25_477/pdf). The pH of the sulphates according to the invention is neutral or even slightly acid (pH between 7 and 6.6).
According to another preferred embodiment of the invention, the sulphates are sulphates of formula M2S03 or M'S03 or a hydrogen sulphate of formula MHS03 with M representing an alkali metal such as Na or K or (di)(CrC6)(alkyl)ammonium or tri(C C6)alkylammonium such as NH4 +, or else disulphates of formula M'S205 with M' representing an alkaline-earth metal.
The sulphates of the invention are in particular salts of alkali metals or alkaline-earth metals or ammonium, (di)(CrC6)alkylammonium or tri(CrC6)alkylammonium; preferably the cationic counterion of the sulphate is chosen from sodium and potassium, and ammonium.
Preferably, the sulphate salts according to the invention are chosen from:
a) ammonium sulphate [10196-04-0]: (NH4)2S03;
b) sodium sulphate [7757-83-7]: Na2S03; and
c) sodium hydrogen sulphate [7631-90-5]: NaHS03. According to one preferred embodiment of the invention, the sulphate salt(s) used in the composition or in the process of the invention represent from 0.001 % to 10% by weight
approximately, of the total weight of the composition(s) containing this or these sulphate salts, and more preferably still from 0.05% to 0.1 % by weight approximately. v) optionally one or more mordants
The composition according to the invention may contain at least one mordant or the process of the invention may involve a supplementary step with at least one mordant. The term "mordant" is understood to mean a mordanting agent conventionally used in the textile industry and which is cosmetically acceptable, preferably in the form of metal salts such as iron, aluminium, titanium, calcium, manganese, copper, zinc and strontium salts. By way of example, the mordant may be iron sulphate, manganese gluconate, copper sulphate, zinc gluconate, calcium chloride, magnesium chloride, potassium titanyl oxalate or strontium acetate. Preferably, the mordant used is iron sulphate.
The mordants are particularly found in the composition in proportions between 0.001 % and 10% relative to the total weight of the composition containing them.
According to another particular embodiment of the invention, neither the dyeing process nor the composition of the invention use or contain a mordanting agent. water:
According to one embodiment of the invention, water is preferably included in the process of the invention. It may originate from the moistening of the keratin fibres and/or from the composition(s) comprising compounds i) to Hi) as defined previously or from one or more other compositions. Preferably, the water comes from at least one composition comprising at least one compound chosen from i) to Hi) as defined previously. cosmetic compositions:
The cosmetic compositions according to the invention are cosmetically acceptable, i.e. they comprise a dye support that generally contains water or a mixture of water and of one or more organic solvents or a mixture of organic solvents.
The term "organic solvent" means an organic substance that is capable of dissolving or dispersing another substance without chemically modifying it. Organic solvents:
Examples of organic solvents that may be mentioned include C C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol.
The organic solvents are present in proportions preferably of between 1 % and 40% by
weight approximately and even more preferentially between 5% and 30% by weight approximately relative to the total weight of the dye composition.
Adjuvants:
The composition(s) of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.
Said adjuvants are preferably chosen from surfactants such as anionic or nonionic surfactants or mixtures thereof and mineral or organic thickeners.
The above adjuvants are generally present in an amount for each of them of between
0.01 % and 40% by weight relative to the weight of the composition, and preferably between 0.1 % and 20% by weight relative to the weight of the composition.
Needless to say, a person skilled in the art will take care to select this or these additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) that is (are) useful in the dyeing process in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).
Additional dyes:
The process using ingredients i) to Hi) as defined previously or the cosmetic composition according to the invention comprising ingredients i) to Hi) as defined previously may also use or comprise one or more additional direct dyes. 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 o/f 70-diphenols, neutral, acidic or cationic quinone and in particular anthraquinone direct dyes, azine, triarylmethane, indoamine, methine, styryl, porphyrin, metalloporphyrin, phthalocyanine and methine cyanine direct dyes, and fluorescent dyes. All these additional dyes are other than the ortho-diphenol derivatives according to the invention.
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 in particular henna-based poultices or extracts, may also be used.
The additional direct dye(s) used in the composition(s) preferably represent from 0.001 % to 10% by weight approximately, of to the total weight of the composition(s) containing them, and even more preferentially from 0.05% to 5% by weight approximately.
The compositions of the process using ingredients i) to Hi) as defined previously or the
cosmetic composition according to the invention comprising ingredients i) to Hi) as defined previously may also use or comprise one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.
Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
Among these couplers, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof. According to one particular embodiment of the invention, neither the process of the invention, nor the composition of the invention contain a coupler, especially mefa-aminophenols.
More particularly, the process or the composition of the invention use or contain at least one oxidation dye, and bases and couplers, chosen from:
• 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one and also salts thereof such as 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one dimethanesulphonate;
• diamino-N,N-dihydropyrazolone derivatives of formula (IV) or an addition salt thereof:
(IV)
in which formula (IV):
Ri, R∑, R3 and R4, which may be identical or different, represent:
- a linear or branched C C6 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a radical OR5, a radical NR6R7, a carboxyl radical, a sulphonyl radical, a carboxamido radical CONR6R7, a sulphonamido radical S02NR6R7, a heteroaryl, an aryl optionally substituted with a (CrC4)alkyl group, a hydroxyl, a C C2 alkoxy, an amino or a (di)alkyl(CrC2)amino;
- an aryl radical optionally substituted with one or more of a (C C4)alkyl, a hydroxyl, a C1-C2 alkoxy, an amino or a (di)(CrC2)alkylamino;
- a 5- or 6-membered heteroaryl radical which is optionally substituted with one or more radicals selected from a (C C4)alkyl and a (C C2)alkoxy;
R3 and R4 may also represent a hydrogen atom;
R5, R6 and R7, which may be identical or different, represent a hydrogen atom; a linear or branched C C4 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a hydroxyl, a C C2 alkoxy, a carboxamido CONR8Rg, a sulphonyl S02R8, an aryl optionally substituted with a (C C4)alkyl, a hydroxyl, a C C2 alkoxy, an amino, a (di)alkyl(C C2)amino; an aryl optionally substituted with a (C C4)alkyl, a hydroxyl, a C C2 alkoxy, an amino or a (di)alkyl(d-
C2)amino;
R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8Rg; or a sulphonyl S02R8;
R8 and R9, which may be identical or different, represent a hydrogen atom; a linear or branched C C4 alkyl radical which is optionally substituted with one or more of a hydroxyl or a C C2 alkoxy;
Ri and R2, on the one hand, and R3 and R4, on the other hand, may form, with the nitrogen atoms to which they are attached, a saturated or unsaturated 5- or 7- membered heterocycle which is optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino, (di)(C C4)alkylamino, hydroxyl, carboxyl, carboxamido and (C C2)alkoxy radicals, C C4 alkyl radicals optionally substituted with one or more hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl or sulphonyl radicals;
R3 and R4 may also form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which can be replaced with an optionally substituted oxygen or nitrogen atom;
More particularly the derivatives of formula (IV) or the addition salts thereof are chosen from:
4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4-amino-5-methylamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4-amino-5-dimethylamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4-amino-5-(2-hydroxyethyl)amino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4-amino-5-(pyrrolidin-1-yl)-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4-amino-5-(piperidin-1-yl)-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4-amino-5-methylamino-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4-amino-5-dimethylamino-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4-amino-5-(2-hydroxyethyl)amino-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4-amino-5-(pyrrolidin-1-yl)-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4-amino-5-(piperidin-1-yl)-1 ,2-bis(2-hydroxyethyl)-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1 ,2-phenyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1-ethyl-2-methyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-2-ethyl-1-methyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1-phenyl-2-methyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-1-(2-hydroxyethyl)-2-methyl-1 ,2-dihydropyrazol-3-one;
4,5-diamino-2-(2-hydroxyethyl)-1-methyl-1 ,2-dihydropyrazol-3-one;
2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-methylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-dimethylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-ethylamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-isopropylarnino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-(2-hydroxypropyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-bis(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2-amino-3-(3-hydroxypyrrolidin-1-yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2- amino-3-(piperidin-1-yl)-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2,3-diamino-6-methyl-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2,3-diamino-6-dimethyl-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one;
2,3-diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2-a]pyrazol-1-one;
2,3-diamino-5,8-dihydro-1 H,6H-pyridazino[1 ,2-a]pyrazol-1-one;
salts of 4-(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)-1 ,1-dimethylpiperazin-1-ium, especially the halides such as 4-(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)-1 , 1-dimethylpiperazin-1- ium hydrochloride chloride; and
3- aminopyrazolo[1 ,5-a]pyridine derivatives of formula (V) below and also the salts and solvates thereof:
in which formula (V):
o Zi and Z2 independently represent: i) a single covalent bond, ii) a divalent radical chosen from an oxygen atom and a radical -NR6(R7)P-
- with p = 0 or 1 with, when p is equal to 0 then R6 represents a hydrogen atom or a C C6 alkyl radical, or R6, with R^ respectively R2, form, together with the nitrogen atom to which they are attached, a substituted or unsubstituted, saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, optionally containing one or more heteroatoms or groups selected from N, O, S, S02 and -CO-, it being possible for the heterocycle to be cationic and/or substituted with a cationic or noncationic radical,
- when p is equal to 1 then -NR6R7- is a cationic radical in which R6 and R7 independently represent an alkyl radical,
o Zi may also represent a divalent radical -S-, -SO- or -S02- when is a methyl radical;
it being understood that at least one of Z-i and Z2 is other than a single covalent bond, o Ri and R2 independently represent a hydrogen or halogen atom, or a group chosen
from:
a C1-C10 alkyl radical which is optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO and S02,
a C1-C10 alkyl radical which is substituted and/or interrupted by a cationic radical, - an SO3H radical,
a 5- to 8-membered ring which is substituted or unsubstituted, saturated, unsaturated or aromatic and optionally comprises one or more heteroatoms or groups selected from N, O, S, S02 and -CO-, it being possible for the ring to be cationic and/or substituted with a cationic radical,
when Zi, respectively Z2, represents a covalent bond, then respectively R2, may also represent:
an optionally substituted C C6 alkylcarbonyl radical;
a radical -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR' in which R and R' independently represent a hydrogen atom or an optionally substituted C C6 alkyl radical;
o R3, R4 and R5, which may be identical or different, represent:
a hydrogen atom;
a hydroxyl radical;
a Ci-C6 alkoxy radical;
- a Ci-C6 alkylthio radical;
an amino radical;
a monoalkylamino radical;
a Ci-C6 dialkylamino radical in which the alkyl radicals may form, with the nitrogen atom to which they are attached, a saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, which may contain one or more heteroatoms or groups selected from N, O, S, S02 and CO, it being possible for the heterocycle to be cationic and/or substituted with a cationic radical;
an optionally substituted C C6 alkylcarbonyl radical;
- a radical -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR' with R and R' as defined previously;
a halogen;
- a radical -NHSO3H;
an optionally substituted C C4 alkyl radical;
an optionally substituted, saturated or unsaturated or aromatic carbon-based ring;
R 3, R4 and R5, may form, in pairs, a saturated or unsaturated ring;
o X represents an anionic counterion or group of anions making it possible to ensure the electronegativity of the derivative of formula (V),
with the condition that at least one of the groups Zi, Ri, Z2, and R2 represents a cationic radical.
More particularly the derivatives of formula (V) or the addition salts thereof are chosen from:
3-(3-Aminopyrazolo[1 ,5-a]pyridin-2-yl)-1 -methyl-3H-imidazol-1 -ium
[2-(3-Aminopyrazolo[1 ,5-a]pyridin-2-ylamino)ethyl]-ethyldimethylammonium
inopyrazolo[1 ,5-a]pyridin-2-yl)oxy]-N,N,N-trimethylethanaminium
1-{2-[(3-aminopyrazo 1-methylpyrrolidinium
1-{2-[(3-aminopyraz 1-methylpiperidinium
4-{2-[(3-aminopyrazolo methylmorpholin-4-ium
N-{2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethyl}-N-isopropyl-N-methylpropan-2- aminium
-[3-(3-Aminopyrazolo[1 ,5-a]pyridin-2-yloxy)propyl]-1-methyl-3H-imidazol-1-iurTi
4-(3-Aminopyrazolo ethyl[1 ,4]diazepan-1-iurri
[2-(3-Amino-67-dimethylpyrazolo[1 ,5-a]pyridin-2-ylamino)ethyl]trimethylammonium
4-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)-1 , 1-dimethylpiperazin-1-ium
4-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)-1 -(2-hydroxyethyl)-1 -methylpiperazin-1 -ium
[1-(3-Amino-67-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)pyrrolidin-3-yl]trimethylammonium
{1-[2-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yloxy)ethyl]pyrrolidir
trimethylammonium
1-{2-[(3-amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethyl}-1-
-{2-[(3-amino-67-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethyl}-4-methylmorpholin-
4-ium
2-[(3-amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)oxy]-N,N,N- trimethylethanaminium
N-{2-[(3-amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethyl}-N-isopropyl-N-
[3-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yloxy)propyl]trimethyl- ammonium
2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)oxy]-N,N,N- trimethylethanaminium
-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]-N,N,N-
-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]-N,N,N-
-{2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]ethyl}-
1-{3-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2- yl)amino]propyl}-3-methyl-1 H-imidazol-3-ium
-{2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]ethyl}-
1 -methylpyrrolidinium
-{2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]ethyl}-
4-{2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]ethyl}-
N-{2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-yl)amino]ethyl}-
N-is inium
[1-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yl)pyrrolidin-3-yl](2-hydroxyethyl)- dimethylammonium
{1-[2-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yloxy)ethyl]pyrrolidir
trimethylammonium
[3-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-ylamino)propyl]- trimethylammonium
[3-(3-Amino-4-dimethylaminopyrazolo[1 ,5-a]pyridin-2-ylamino)propyl]- trimethylammonium
-(3-Amino-4-dimethylaminopyrazolo[1 ,5-a]pyridin-2-yl)-1-methylpiperazin-1-ium
[1-(3-Amino-4-dimethylaminopyrazolo[1 ,5-a]pyridin-2-yl)pyrrolidi
trimethylammonium
3-[2-(3-Amino-4-dimethylaminopyrazolo[1 ,5-a]pyridin-2-yloxy)ethyl]- 1-met yl-3H-imidazol-1-i
{1 -[2-(3-Amino-4-dimethylaminopyrazolo[1 ,5-a]pyridin-2-yloxy)ethyl]pyrrolidi
trimethylammonium
(3-Amino-2-methoxypyrazolo[1 ,5-a]pyridin-4-yl)trimethylammonium
• salts of 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol, especially 2-[(3-amino- pyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol hydrochloride; and
• derivatives of a 3-aminopyrazolo[1 ,5-a]pyridine derivative of formula (VI) and also the salts and solvates there
in which formula (VI):
o Zi represents an oxygen atom or a group N R6, when Zi represents N R6 then and R6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, saturated or unsaturated or aromatic 5- to 8-membered heterocycle;
Zi may also represent a divalent radical S, SO or S02 when represents CH3; o Ri and R6 independently represent:
- a hydrogen atom;
- an optionally substituted C1-C10 alkyl radical, it being possible for the substituent to be an optionally substituted, saturated or unsaturated or aromatic 5- to 8- membered (hetero)cycle;
- an optionally substituted, saturated or unsaturated or aromatic 5- to 8-membered
(hetero)cycle; o R∑, R3, R4 and R5 independently represent:
■ a hydrogen atom;
■ an optionally substituted C C4 alkyl radical;
■ a group chosen from NH2, NHR10, NRn R12, OH or OR9, with R9 and R10 representing an optionally substituted, linear or branched C C6 alkyl, Rn and R12, which may be identical or different, representing an optionally substituted, linear or branched C C6 alkyl, it being possible for Rn and R12 to form, together with the nitrogen atom to which they are attached, a saturated or unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from N, O, S, S02 and CO, the heterocycle being optionally substituted;
o R∑, R3, R4, R5, may form, in pairs, with the adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle;
(3-Aminopyrazolo[1 ,5-a]pyridin-2-ylamino)methanol
2-pyrrolidin-1 -ylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-(3-Dimethylaminopyrrolidin-1 -yl)pyrazolo[1 ,5-a]pyridin-3-ylamine
2-[1 ,4]Diazepan-1 -ylpyrazolo[1 ,5-a]pyridin-3-ylamine
1 -[4-(3-Aminopyrazolo ,4]diazepam-1 -yiethanone
-[2-(3-Dimethylaminopyrrolidin-1 -yl)ethoxy]-6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-Methoxy-6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-Ethoxy-6,7-dimethylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-(3-Amino-6,7-dimethylpyrazolo[1 ,5-a]pyridin-2-yloxy)ethanol
6,7-Dimethyl-2-methylsulphanylpyrazolo[1 ,5-a]pyridin-3-ylamine
N-5,N-5-Dimethyl-2-(4-methylpiperazin-1 -yl)pyrazolo[1 ,5-a]pyridine-3,5-diamine
2-Ethoxy-N-5,N-5-dimethylpyrazolo[1 ,5-a]pyridine-3,5-diamine
4-Ethyl-2-methoxy-7-methylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-Ethoxy-4-ethyl-7-methylpyrazolo[1 ,5-a]pyridin-3-ylamine
4-Ethyl-2-isopropoxy-7-methylpyrazolo[1 ,5-a]pyridin-3-ylamine
2-(3-Amino-4-ethyl-7-methylpyrazolo[1 ,5-a]pyridin-2-yloxy)ethanol
4-Et yl-2-methanesulphonyl-7-methylpyrazolo[1 ,5-a]pyridin-3-ylamine
N2-methyl-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridine-2,3-diamine
2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2- yl)amino]ethanol
2,2'-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-
1-(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-
2-(4-methylpiperazin-1-yl)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
2-[4-(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2-
N2-[2-(dimethylamino)ethyl]-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
N2-[3-(1 H-imidazol-1-yl)propyl]-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
pyridin-2-ylethyl)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridine-
pyridin-3-ylethyl)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridine-
pyridin-4-ylethyl)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridine-
N2-(2-piperidin-1-ylethyl)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
2-[2-(dimethylamino)ethoxy]-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
2-(2-pyrrolidin-1-ylethoxy)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
2-(2-piperidin-1-ylethoxy)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-
-(2-pyridin-2-ylethoxy)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin
-(2-pyridin-3-ylethoxy)-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin
3-amine
2-methoxy-7,8-dihydr [1 ,5-a]pyridin-3-amine
2-ethoxy-7,8-dihydro 1 ,5-a]pyridin-3-amine
2-[(3-amino-7,8-dihydro-6H-cyclopenta[e]pyrazolo[1 ,5-a]pyridin-2- yl)oxy]ethanol
5-[(2-hydroxyethyl)amino]-2-methylphenol;
3,4-dihydro-2H-1 ,4-benzoxazin-6-ol;
3-amino-2-chloro-6-methylphenol;
2-aminopyridin-3-ol;
2-methylbenzene-1 ,3-diol;
2-(2,4-diaminophenoxy)ethanol hydrochloride; and
cationic aminopyridine derivatives of general formula (VII), addition salts thereof with an acid and solvates thereof:
(VII)
in which formula (VII) the group bears the cationic charge,
o Zi is an oxygen atom or a group NR2;
R2 is a hydrogen atom or a linear or branched C C4 alkyl radical, a benzyl radical or an acetyl radical;
Ri is a saturated, linear or branched C1-C10 alkyl radical, which is substituted with or interrupted by a cationic radical, optionally interrupted by one or more oxygen atoms and/or by one or more groups N R2, optionally substituted with one or more radicals chosen from hydroxyl, alkoxy and C C4 hydroxyalkyl radicals, or is a saturated or unsaturated or aromatic cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C C4 alkyl, hydroxyl, Ci-C4 alkoxy, amino, (C C4)alkylamino, di(C C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals; when Zi represents NR2 then
■ Ri and R2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C1-C10 alkyl radicals and hydroxyl, C C4 alkoxy, amino, (C C4)alkylamino, di(C
C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals, it being possible for this heterocycle to contain one or more heteroatoms chosen from N or O, preferably N, or
■ Ri and R2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated noncationic 5- to 8-membered heterocycle substituted with a cationic radical and optionally substituted with one or more radicals chosen from C1-C10 alkyl radicals and hydroxyl, C C4 alkoxy, amino, (C C4)alkylamino, di(C C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals;
R is chosen from a hydrogen atom, halogens selected from fluorine, chlorine and bromine, linear or branched C C4 alkyl radicals and carboxyl (-COOH) and (Ci-C4)alkoxycarbonyl radicals;
An- represents an anionic counterion or group of anions.
More particularly the derivatives of formula (VII) or the addition salts thereof are chosen from:
2-[(3,5-diaminopyridin-2-yl)amino]-N, N, N-trimethylethanammonium,
2-[(3,5-diaminopyridin-2-yl)(methyl)amino]-N, N, N-trimethylethanammonium, 1 -{2-[(3,5-diaminopyridin-2-yl)amino]ethyl}-1 -methylpiperidinium,
1 -(3,5-diaminopyridin-2-yl)-N, N, N-trimethylpyrrolidin-3-ammonium,
1 -{3-[(3,5-diaminopyridin-2-yl)amino]propyl}-3-(2-hydroxyethyl)-1 H-imidazol-3- ium,
1 -{3-[(3,5-diaminopyridin-2-yl)amino]propyl}-1 -methylpiperidinium,
1 -{2-[(3,5-diaminopyridin-2-yl)amino]ethyl}-1 -methylpyrrolidinium,
1 -{3-[(3,5-diaminopyridin-2-yl)amino]propyl}-1 -methylpyrrolidinium,
1 -{2-[(3,5-diaminopyridin-2-yl)amino]ethyl}-3-methyl-1 H-imidazol-3-ium,
4-{3-[(3,5-diaminopyridin-2-yl)amino]propyl}-4-methylmorpholin-4-ium 4-{2-[(3,5-diaminopyridin-2-yl)amino]ethyl}-4-methylmorpholin-4-ium, 1-[2-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)ethyl]-1-methylpiperi 1-[2-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)ethyl]-1-methylpyrroli
1- [2-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)ethyl]-3-methyl-1 H-i
3- ium,
4- [2-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)ethyl]-4-methylmorp ium,
2- ({2-[(3,5-diaminopyridin-2-yl)arnino]ethyl}arnino)-N,N,N- trimethylethanammonium, 3-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)- N,N,N-trimethylpropan-1 -ammonium,
2- {2-[(3,5-diaminopyridin-2-yl)amino]ethoxy}-N,N,N-trimethylethanammonium,
3- {2-[(3,5-diaminopyridin-2-yl)amino]ethoxy}-N,N,N-trimethylpropan-1 -ammonium, 1-(2-{2-[(3,5-diaminopyridin-2-yl)amino]ethoxy}ethyl)-1-methylpiperidinium, 1-(2-{2-[(3,5-diaminopyridin-2-yl)amino]ethoxy}ethyl)-1-methylpyrrolidinium, 1-{3-[(3,5-diaminopyridin-2-yl)amino]propyl}-3-methyl-1 H-imidazol-3-ium, 1-[3-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)propyl]-3-methyl-1 H-imidazol-
3- ium,
4- [3-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)propyl]-1 , 1- dimethylpiperazin-1-ium,
1-(3-{2-[(3,5-diaminopyridin-2-yl)amino]ethoxy}propyl)-1-methylpiperidinium,
4-[3-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)propyl]-4-methylmorpholin-4- ium,
3-({2-[(3,5-diaminopyridin-2-yl)amino]ethyl}amino)-N-ethyl-N-methyl-N- propylpropan-1 -ammonium,
3-[(3,5-diaminopyridin-2-yl)amino]-N,N,N-trimethylpropan-1 -ammonium, 3-[(3,5-diaminopyridin-2-yl)(methyl)amino]-N,N,N-trimethylpropan-1 -ammonium,
3- [(3,5-diaminopyridin-2-yl)oxy]-N,N,N-trimethylpropan-1 -ammonium, 1-{2-[(3,5-diaminopyridin-2-yl)amino]ethyl}-3-(2-hydroxyethyl)-1 H-imidazol-3-ium,
4- (3,5-diaminopyridin-2-yl)-1-(2-hydroxyethyl)-1-methylpiperazin-1-ium, 4-(3,5-diaminopyridin-2-yl)-1 , 1-bis(2-hydroxyethyl)piperazin-1-ium,
4-(3,5-diaminopyridin-2-yl)-(2-trimethylethan)-morpholin-ammonium,
4-(3,5-diaminopyridin-2-yl)-(2-methyldiethylethan)-morpholin-ammonium, 4-(3,5-diaminopyridin-2-yl)morpholin}2-1 , 1 dimethylpyrrolidinium,
(3,5-diaminopyridin-2-yl)-3-trimethyl piperidin-ammonium,
(3,5-diaminopyridin-2-yl)-4-trimethyl piperidin-ammonium, and
4-(3,5-diaminopyridin-2-yl)-1 , 1-dimethylpiperazin-1-ium.
The oxidation base(s) present in the composition(s) are each generally present in an amount of between 0.001 % and 10% by weight, of the total weight of the corresponding composition(s).
When the oxidation bases, in particular aromatic amines such as para- phenylenediamines and/or para-aminophenols are present in the composition of the invention or are used in the process of the invention, they are in amounts such that the ratio of the amount of hydroxybenzaldehyde derivatives of formula (I) as defined previously/the amount of oxidation base is at least greater than 5; preferably greater than 20.
According to one preferred embodiment of the invention, the dyeing process and the composition according to the invention do not comprise oxidation bases, in particular para- phenylenediamines and/or para-aminophenols. The cosmetic composition(s) of the invention may be in various galenic forms, such as a powder, a lotion, a foam, a cream or a gel, or in any other form that is suitable for dyeing keratin fibres. They may also be packaged in a propellant-free pump-action bottle or under pressure in an aerosol container in the presence of a propellant and form a foam. pH of the composition(s)
The pH of the composition(s) containing Hi) the alkalinizing agent(s) is above 7 and preferably between 8 and 12. It is particularly between 8 and 10.
If the composition(s) contain(s) no alkalinizing agent, the pH of the composition(s) containing the oxidizing agent, such as hydrogen peroxide or the system that generates hydrogen peroxide, is preferably below 7, more particularly between 1 and 5.
Preferably, the composition(s) that contain(s) the hydroxybenzaldehyde derivative(s) of formula (I) as defined previously and that contain(s) no alkalinizing agent are at a pH of below 7 and preferably of between 3 and 6.5.
According to one particular embodiment of the invention, the compositions containing the sulphate salt(s) that contain or do not contain alkalinizing agent are at a pH of above 7 and preferably of between 8 and 12.
The pH of these compositions may be adjusted to the desired value by means of acidifying or alkalinizing agents usually used in the dyeing of keratin fibres as defined in "// J alkalinizing agent' above, or alternatively using standard buffer systems.
Among the acidifying agents of the compositions, mention may particularly be made of those chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulphuric acid H2S04, iv) alkylsulphonic acids: Alk-S(0)2OH such as methylsulphonic acid and ethylsulphonic acid; v) arylsulphonic acids: Ar-S(0)2OH such as benzenesulphonic acid and toluenesulphonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) phosphoric acid H3P04; xi) acetic acid CH3C(0)OH; xii) triflic acid CF3S03H; and xiii) tetrafluoroboric acid HBF4.
Dyeing process according to steps a) and b)
Preferably, the process of the invention does not use an active CH compound, and the
composition according to the invention does not contain an active CH compound.
According to one particular embodiment of the invention, the dyeing process is carried out:
a) by applying to the keratin fibres, in one or more steps, one or more cosmetic compositions containing the following ingredients, taken together or separately in said composition(s):
i) at least one hydroxybenzaldehyde derivative of formula (I) as defined previously; ii) at least one oxidizing agent, preferably a chemical oxidizing agent; and
iii) at least one alkalinizing agent;
it being understood that:
the pH of the composition comprising the ingredient(s) iii) is basic i.e. above 7; preferably between 7.5 and 12; and
the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the composition(s) comprising the ingredients i), ii) and iii); and
b) by heat treatment of the keratin fibres at a temperature above 30°C.
The waiting time between the steps of applying the compositions comprising the ingredient(s) i), ii) and/or iii) is set at between 3 and 120 minutes, preferentially between 10 and 60 minutes and more particularly between 15 and 45 minutes.
The keratin fibres may or may not be moistened beforehand.
More particularly, in the process of the invention, the chemical oxidizing agent(s) such as hydrogen peroxide ii) are either in a mixture with the ingredients i), or are applied in a composition without the other ingredients ii) and iii).
One particular embodiment of the invention relates to dyeing processes with step a) that is carried out in one or two application steps.
According to one particular embodiment of the invention, step a) of the process for dyeing keratin fibres is carried out by applying to the keratin fibres the preferably aqueous, cosmetic composition according to the invention comprising:
i) at least one derivative of formula (I), as defined previously;
ii) at least one oxidizing agent, preferably a chemical oxidizing agent; and
iii) at least one alkalinizing agent;
it being understood that:
the composition preferably does not contain an active CH compound;
- the pH of the composition is basic i.e. above 7; preferably between 7.5 and 12; the compound(s) of formula (I) comprise at least one of the two radicals R1 or R3 which represents a hydroxyl group; with, when R1 represents a hydroxyl radical, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl radical then R1 or R2 or R4 or R5 represents a hydrogen atom;
- the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the composition comprising the ingredients i)
to Hi).
The waiting time after application is generally set at between 5 minutes and 24 hours, particularly between 10 and 120 minutes and more particularly between 15 and 60 minutes, especially between 15 and 45 minutes.
According to another particular embodiment of the invention, step a) of the process for dyeing keratin fibres is performed in two steps.
In a first variant, step a) involves applying to said fibres a cosmetic composition comprising the ingredients i), ii) as defined previously, and then, in a second step, a cosmetic composition comprising the ingredient Hi) as defined previously is applied to said fibres, it being understood that at least one of the two cosmetic compositions is aqueous.
In a second variant of the process for dyeing keratin fibres, step a) firstly comprises applying to said fibres a composition comprising the ingredients i) and Hi) as defined previously, and then, in a second step, a second cosmetic composition comprising the ingredient(s) ii) as defined previously is applied to said fibres, it being understood that preferably at least one of the two compositions is aqueous.
According to one preferred dyeing process of the invention, said step a) ends with the treatment of the keratin fibres with the ingredient Hi).
The application temperature of step a) of the process of the invention is generally between room temperature (15°C to 25°C) and 150°C and particularly between 15°C and 85°C, and preferably between 20°C and 60°C. If the application is carried out at a temperature above the temperature of 30°C, then it is possible to do away with step b) of the process of the invention. According to one preferred embodiment of the invention, the application of the composition(s) according to step a) of the process is carried out at room temperature, i.e. at 25°C.
In step b) of the process of the invention, after application of the composition(s) according to step a) of the process of I'invention, the hair is subjected to a heat treatment by heating at a temperature above room temperature, i.e. above 30°C, particularly at a temperature between 35°C and 80°C. More particularly between 40°C and 50°C, such as 45°C.
In practice, the heat treatment operation of step b) of the process of the invention may be performed using a a hairstyling hood, a hairdryer or an infrared ray emitter or other standard heating appliances.
It is possible to use, both as heating means and as hair straightening means, a heating iron at a temperature of between 60°C and 220°C and preferably between 120°C and 200°C.
One advantageous aspect relates to the dyeing process as described previously, preceded by one or more mordanting steps by pretreating the keratin fibres with at least one mordant as defined previously (see "v) optionally one or more mordant(s)"). The mordant(s) are especially in a cosemtic composition and are applied at least 5 minutes before the implementation of the dyeing process comprising the ingredients i) to Hi) as defined
previously. The mordant used is particularly iron sulphate.
Another advantageous aspect relates to the dyeing process as described previously, followed by post-treatment steps such as shampooing using a standard shampoo, rinsing, for example with water, and/or drying the keratin fibres by heat treatment as defined below.
Preferably, the dyeing process according to the invention is carried out in one step by applying to the keratin fibres the composition according to the invention comprising the ingredients i) to Hi) as defined previously, followed by post-treatment steps of rinsing, for example with water, of shampooing with a standard shampoo, and/or drying the keratin fibres.
In all the particular embodiments and variants of the processes described previously, the compositions mentioned are ready-to-use compositions that may result from the extemporaneous mixing of two or more compositions and especially of compositions present in dyeing kits.
Dyeing device or "kit":
Another subject of the invention is a multicompartment dyeing device or "kit". Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which the ingredients i) at least one hydroxybenzaldehyde derivative of formula (I), as defined previously, ii) at least one chemical oxidizing agent such as hydrogen peroxide and Hi) at least one alkalinizing agent as defined previously are distributed.
According to a first variant, the kit comprises three compartments, the first two compartments comprising, respectively, the powdered ingredients i) and Hi) as defined previously and the third compartment containing an aqueous composition such as water. In this case, the compound(s) ii) are hydrogen peroxide precursors.
Or else the kit comprises four compartments, the first three compartments comprising, respectively, the powdered ingredients i), ii) and Hi) as defined previously and the fourth compartment containing an aqueous composition such as water.
Another variant concerns a kit comprising three compartments, one of which contains at least one aqueous composition, and comprising an ingredient i) to Hi) as defined previously.
Another preferred embodiment concerns a device comprising three compartments: (a) a first compartment contains a composition containing:
i) at least one hydroxybenzaldehyde derivative of formula (I) as defined previously; and
(b) a second compartment contains a composition containing:
ii) at least one chemical oxidizing agent such as hydrogen peroxide;
(c) a third compartment contains Hi) at least one alkalinizing agent as defined previously.
In this other embodiment, at least one of the three compositions is preferably aqueous and the hydroxybenzaldehyde derivative(s) of formula (I) may be in powder form.
Among the two-compartment kits, it is also possible to have kits that contain, in a first compartment, a composition comprising compounds i) and iii) as defined previously and, in a second compartment, a composition comprising compound ii) at least one chemical oxidizing agent such as hydrogen peroxide as defined previously.
According to one variant, the device according to the invention also comprises an additional composition (c) comprising one or more treating or mordanting agents.
The compositions of the device according to the invention are packaged in separate compartments, optionally accompanied by suitable application means, which may be identical or different, such as fine brushes, coarse brushes or sponges.
The device mentioned above may also be equipped with a means for dispensing the desired mixture on the hair, for instance the devices described in patent FR 2 586 913.
EXAMPLES OF DYEING
EXAMPLE A :
The following composition was prepared: Composition for 100 g:
3 g of hydroxybenzaldehyde compound i) according to the invention;
5 g of 20% aqueous ammonia;
30 g of 20-volume aqueous hydrogen peroxide solution;
62 g of water.
The above composition is applied with a bath ratio of 1 g of hair per 5 g of composition. The locks of hair are grey containing 90% natural white (90% NW) hairs. The composition is left on the lock for 15 or 30 minutes at 45°C. The locks are then rinsed, shampooed and dried with a hairdryer. Colorimetric results:
The coloration of the hair is evaluated visually and read on a Minolta spectrocolorimeter (CM3600d, illuminant D65, angle 10°, SCI values) for the L*, a*, b* colorimetric measurements.
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 lower the value of L, the darker or more intense the colour. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.
The variation in coloration between the dyed locks of natural white hair that are untreated (control) and after treatment are defined by (ΔΕ*) according to the following equation:
ΔΕ* = J(L * -L0*)2 + (a* - a0 *)2 + (b* -b0 *)2
In this equation, L*, a* and b* represent the values measured after dyeing natural hair containing 90% white hairs, and L*0, a0* and b0* represent the values measured for natural hair containing 90% untreated hairs.
The higher the value of ΔΕ, the greater the difference in colour between the control locks and the dyed locks.
The coloration is very persistent with regard to washing operations and light.
EXAMPLE B:
The following composition was prepared:
Composition for 100 g:
- 1.5 g of hydroxybenzaldehyde compound i) according to the invention;
- 1 g of alkaline agent (ethanolamine, or sodium hydoxide, or arginine, or sodium bicarbonate, or ammonium bicarbonate or 2-amino-2-methyl-1-propanol);
- 30 g of 20-volume aqueous hydrogen peroxide solution; and
- 67.5 g of water.
The above composition is applied with a bath ratio of 1 g of hair per 5 g of composition. The locks of hair are grey containing 90% natural white (90% NW) hairs. The composition is left on the lock for 30 minutes at 45°C. The locks are then rinsed, shampooed and dried with a
hairdryer.
EXAMPLE C:
The following composition was prepared:
Composition for 100g:
- 1 g of hydroxybenzaldehyde compound i) according to the invention;
- 2 g of 20% aqueous ammonia;
- 12 g of 20-volume aqueous hydrogen peroxide solution; and
- 85 g of water.
The above composition is applied with a bath ratio of 1 g of hair per 5 g of composition. The locks of hair are grey containing 90% natural white (90% NW) hairs. The composition is left on the lock for 30 minutes at 45°C. The locks are then rinsed, shampooed and dried with a hairdryer.
Hydroxybenzaldehyde Structures Visual results
compound i)
1 Brown
3 0 Brown
HO^
4 Dark brown
7 Dark pink
OH
9 OH Brown
HO^^^OH
Claims
1. Process for dyeing keratin fibres, comprising:
a) the application to the keratin fibres of:
i) rganic or
(I)
in which formula (I):
R1, R2, R3, R4 and R5, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
■ a hydroxyl;
■ an optionally substituted linear or branched (d-C5)alkyl;
■ a linear or branched (CrC5)alkoxy;
■ a carboxyl -C(0)-OH or carboxylate -C(0)-0", M+ ; with M+ representing a cationic counterion such as an alkali metal or alkaline-earth metal, or an ammonium;
■ a carbamoyl -0-C(0)-NRaRb with Ra and R , which may be identical or different, representing a hydrogen atom or a linear or branched (CrC5)alkyl group; particularly -0-C(0)-NH2;
■ an amido -C(0)-NR6R7 or -NR6-C(0)-R7 with R6 and R7, which may be identical or different, representing a hydrogen atom or a (CrC5)alkyl group, particularly -C(0)-NH2;
■ an ester -C(0)-0-R8 or -0-C(0)-R8, with R8 representing a (C C5)alkyl group, particularly -C(0)-0-R8;
■ a (CrC5)alkylcarbonyl;
■ a carboxaldehyde -C(0)H; and
■ an amino NRaRb with Ra and R , as defined previously;
■ or else R1 and R2, or R2 and R3, or R3 and R4 form, together with the carbon atoms to which they are attached, a 6-membered (hetero)aryl group such as phenyl;
on condition that at least one of the two radicals R1 or R3 represents a hydroxyl group; with, when R1 represents a hydroxyl group, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl group then R1 or R2 or R4 or R5 represents a hydrogen atom;
ii) at least one chemical oxidizing agent; and Hi) at least one alkalinizing agent;
b) then a heat treatment of the keratin fibres at a temperature above 30°C;
it being understood that the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of ingredients i), ii) and Hi), or of the total weight of the composition(s) used in the process.
2. Dyeing process according to the preceding claim, in which the hydroxybenzaldehyde derivative(s) of formula (I) contain at least one of the two radicals R1 and/or R3 which represent(s) a hydroxyl group and R1, R2, R3, R4 and R5 represent, independently of one another, a hydrogen or halogen atom, or a group chosen from:
■ a hydroxyl;
■ a linear or branched C C4 alkyl;
■ a linear or branched C C4 alkoxy;
■ a carboxyl -C(0)-OH;
■ a carboxaldehyde -C(0)H; and
■ a di(Ci-C4)alkylamino; or else
■ R1 and R2, or R2 and R3, or R3 and R4 form, together with the carbon atoms to which they are attached, an aromatic ring containing 6 carbon atoms;
on the condition that when R1 represents a hydroxyl group then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl group then R1 or R2 or R4 or R5 represents a hydrogen atom.
3. Dyeing process according to either one of the preceding claims, in which the hydroxybenzaldehyde derivative(s) of formula (I) or mixtures thereof are chosen from those of formula (II):
(II)
which formula (II):
> R'i represents a hydrogen atom or a hydroxyl group;
> R'2 represents a hydrogen atom, or a group chosen from a hydroxyl, a carboxaldehyde, a linear or branched C C4 alkyl and a linear or branched C C4 alkoxy;
> R'4 represents a hydrogen atom or a group chosen from a hydroxyl, a linear or branched C C4 alkyl and a linear or branched C C4 alkoxy;
> R'5 represents a hydrogen atom or a hydroxyl group;
4. Dyeing process according to Claim 1 or 2, in which the hydroxybenzaldehyde derivative(s) of formula (I) or mixtures thereof are chosen from those of formula (II):
(II)
in which formula (II):
R = OH and R'5 = OH or a linear or branched d-C5 alkoxy; and/or
- R'2 = OH or C(0)H and R'4 = OH or a linear or branched C C5 alkoxy;
and R'i or R'2 or R'4 or R'5 denotes a hydrogen atom.
5. Dyeing process according to any one of the preceding claims, in which the hydroxybenzaldehyde derivative(s) of formula (I) or mixtures thereof are chosen from those from the table below:
and/or the organic or mineral base salts thereof and/or solvates thereof.
6. Dyeing process according to the preceding claim, in which the hydroxybenzaldehyde derivative(s) of formula (I) or mixtures thereof are chosen from compounds 1_ to 10 and particularly 1 , 3, 4, 7 and 9.
7. Dyeing process according to any one of the preceding claims, in which ii) the chemical oxidizing agent(s) are chosen from: a) ozone;
b) alkali metal or quaternary ammonium persalts, persulphates, percarbonates, peroxodiphosphates or Oxone®;
c) aliphatic C C6 and aromatic C6-C20 organic peracids, and the percarboxylate forms thereof;
d) organic peroxides;
e) oxidizing anions;
f) stable N-oxy (NO ) radicals;
g) multivalent iodine derivatives;
h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N-hydroxyphthalimide, alkyl nitrites;
the optional supports for these oxidizing agents a) to h) may be chosen from silica, alumina, charcoal and charged or neutral polymers;
i) hydrogen peroxide or system(s) that generate hydrogen peroxide
such as:
1) urea peroxide;
2) polymeric complexes that can release hydrogen peroxide;
i-3) oxidases that produce hydrogen peroxide in the presence of a suitable substrate;
4) metal peroxides that generate hydrogen peroxide in water, for instance calcium peroxide or magnesium peroxide;
i-5) perborates; or
i-6) percarbonates.
8. Dyeing process according to any one of the preceding claims, in which ii) the chemical oxidizing agent(s) is (are) chosen from hydrogen peroxide.
9. Dyeing process according to the preceding claim, in which the hydrogen peroxide is at a 20-volume concentration of between 1 g and 70 g per 100 g (%) of the composition containing said peroxide; preferably between 3 g % and 50 g % and especially between 3 g % and 50 g %.
10. Dyeing process according to any one of the preceding claims, in which Hi) the alkalinizing agent(s) is (are) chosen from: a) (bi)carbonates, b) aqueous ammonia, c) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and derivatives thereof, d) oxyethylenated and/or oxypropylenated ethylenediamines, e) mineral or organic hydroxides, f) alkali metal silicates such as sodium metasilicates, g) amino acids, preferably basic amino acids such as arginine, lysine, ornithine, citrulline and histidine, and h) the compounds of formula (III) below: R
in which formula (III) W is a divalent (C Cio)alkylene group optionally interrupted by at least one heteroatom such as O, S, NRe, and/or said alkylene group is optionally substituted with at least one hydroxyl group or a (C C4)alkyl radical; Ra, Rb, Rc, Rd and Re, which may be identical or different, represent a hydrogen atom, (C C4)alkyl or C C4 hydroxyalkyl.
11. Dyeing process according to any one of the preceding claims, in which Hi) the alkalinizing agent is aqueous ammonia.
12. Dyeing process according to any one of the preceding claims, which does not use para-phenylenediamines or ara-aminophenols.
13. Dyeing process according to any one of the preceding claims, which uses at least one oxidation dye, base and/or coupler, chosen from:
· 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one and also the salts thereof such as dimethanesulphonate;
diamino-N,N-dihydropyrazolone derivatives of formula (IV) or an addition salt thereof:
- a linear or branched C C6 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a radical OR5, a radical NR6R7, a carboxyl radical, a sulphonyl radical, a carboxamido radical CONR6R7, a sulphonamido radical S02NR6R7, a heteroaryl, an aryl optionally substituted with a (Ci-C4)alkyl group, a hydroxyl, a C C2 alkoxy, an amino or a (di)(CrC2)alkylamino;
- an aryl radical optionally substituted with one or more of a (C C4)alkyl, a hydroxyl, a Ci-C2 alkoxy, an amino or a (di)(CrC2)alkylamino;
- a 5- or 6-membered heteroaryl radical which is optionally substituted with one or more radicals selected from a (C C4)alkyl and a (CrC2)alkoxy;
R3 and R4 may also represent a hydrogen atom;
R5, R6 and R7, which may be identical or different, represent a hydrogen atom; a linear or branched C C4 alkyl radical which is optionally substituted with one or more radicals selected from the group consisting of a hydroxyl, a C C2 alkoxy, a carboxamido CONR8Rg, a sulphonyl S02R8, an aryl optionally substituted with a (C C4)alkyl, a hydroxyl, a C C2 alkoxy, an amino, a (di)alkyl(CrC2)amino; an aryl optionally substituted with a (C C4)alkyl, a hydroxyl, a C C2 alkoxy, an amino or a (di)alkyl(d- C2)amino;
R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9; or a sulphonyl S02R8;
R8 and R9, which may be identical or different, represent a hydrogen atom; a linear or branched C C4 alkyl radical which is optionally substituted with one or more of a hydroxyl or a C C2 alkoxy;
Ri and R2, on the one hand, and R3 and R4, on the other hand, may form, with the nitrogen atoms to which they are attached, a saturated or unsaturated 5- or 7- membered heterocycle which is optionally substituted with one or more radicals selected from the group consisting of halogen atoms, amino, (di)(C C4)alkylamino, hydroxyl, carboxyl, carboxamido and (C C2)alkoxy radicals, C C4 alkyl radicals optionally substituted with one or more hydroxyl, amino, (di)alkylamino, alkoxy, carboxyl or sulphonyl radicals;
R3 and R4 may also form, together with the nitrogen atom to which they are attached, a 5- or 7-membered heterocycle, the carbon atoms of which can be replaced with an optionally substituted oxygen or nitrogen atom;
salts of 4-(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)-1 , 1-dimethylpiperazin-1-ium, especially the halides such as hydrochloride chloride;
3-aminopyrazolo[1 ,5-a]pyridine derivatives of formula (V) below and also the salts and solvates thereof:
which formula (V):
Zi and Z2 independently represent: i) a single covalent bond, ii) a divalent radical chosen from an oxygen atom and a radical -NR6(R )P-,
with p = 0 or 1 with, when p is equal to 0 then R6 represents a hydrogen atom or a C C6 alkyl radical, or R6, with R^ respectively R2, form, together with the nitrogen atom to which they are attached, a substituted or unsubstituted, saturated or unsaturated, aromatic or nonaromatic, 5- to 8-membered heterocycle, optionally containing one or more heteroatoms or groups selected from N, O, S, S02 and -CO-, it being possible for the heterocycle to be cationic and/or substituted with a cationic or noncationic radical, when p is equal to 1 then -NR6R7- is a cationic radical in which R6 and R7 independently represent an alkyl radical,
o Zi may also represent a divalent radical -S-, -SO- or -S02- when is a methyl radical;
it being understood that at least one of Z-i and Z2 is other than a single covalent bond, o Ri and R2 independently represent a hydrogen or halogen atom, or a group chosen from: a C1-C10 alkyl radical which is optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO and S02,
a C1-C10 alkyl radical which is substituted and/or interrupted by a cationic radical, an SO3H radical,
a 5- to 8-membered ring which is substituted or unsubstituted, saturated or unsaturated or aromatic and optionally contains one or more heteroatoms or groups selected from N, O, S, S02 and -CO-, it being possible for the ring to be cationic and/or to be substituted with a cationic radical,
when Zi, respectively Z2, represents a covalent bond, then R^ respectively R2, may also represent:
an optionally substituted C C6 alkylcarbonyl radical;
- a radical -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR' in which R and R' independently represent a hydrogen atom or an optionally substituted C C6 alkyl radical;
o R3, R4 and R5, which may be identical or different, represent:
a hydrogen atom;
- a hydroxyl radical;
a Ci-C6 alkoxy radical;
a Ci-C6 alkylthio radical;
an amino radical;
a monoalkylamino radical;
- a Ci-C6 dialkylamino radical in which the alkyl radicals may form, with the nitrogen to which they are attached, a saturated or unsaturated, aromatic or nonaromatic,
5- to 8-membered heterocycle, which may contain one or more heteroatoms or groups selected from N, O, S, S02 and CO, it being possible for the heterocycle to be cationic and/or substituted with a cationic radical;
- an optionally substituted C C6 alkylcarbonyl radical;
a radical -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR' with R and R' as defined previously;
a halogen;
a radical -NHSO3H;
- an optionally substituted C C4 alkyl radical;
an optionally substituted, saturated or unsaturated or aromatic carbon-based ring; R3, R4 and R5, may form, in pairs, a saturated or unsaturated ring;
X represents an anionic counterion or group of anions making it possible to ensure the electronegativity of the derivative of formula (V),
with the condition that at least one of the groups Zi , Ri , Z2, and R2 represents a cationic radical:
salts of 2-[(3-aminopyrazolo[1 ,5-a]pyridin-2-yl)oxy]ethanol, especially hydrochloride; derivatives of a 3-aminopyrazolo[1 ,5-a]pyridine derivative of formula (VI) and also the salts and solvates there
in which formula (VI):
o Zi represents an oxygen atom or a group N R6, when Zi represents N R6 then and R6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, saturated or unsaturated or aromatic 5- to 8-membered heterocycle;
Zi may also represent a divalent radical S, SO or S02 when represents CH3; o Ri and R6 independently represent:
- a hydrogen atom;
- an optionally substituted C1-C10 alkyl radical, it being possible for the substituent to be an optionally substituted, saturated or unsaturated or aromatic 5- to 8- membered (hetero)cycle;
- an optionally substituted, saturated or unsaturated or aromatic 5- to 8-membered (hetero)cycle; o R∑, R3, R4 and R5 independently represent:
» a hydrogen atom;
■ an optionally substituted C C4 alkyl radical;
■ a group chosen from N H2, N H R10, N Rn R12, OH or OR9, with R9 and R10 representing an optionally substituted, linear or branched C C6 alkyl, Rn and R12, which may be identical or different, representing an optionally substituted, linear or branched C C6 alkyl, it being possible for Rn and R12 to form, together with the nitrogen atom to which they are attached, a saturated or unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from N , O, S, S02 and CO, the heterocycle being optionally substituted;
o R2, R3, R4, R5, may form, in pairs, with the adjacent radicals, an optionally substituted, saturated or unsaturated (hetero)cycle; • 5-[(2-hydroxyethyl)amino]-2-methylphenol;
• 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol;
• 3-amino-2-chloro-6-methylphenol;
• 2-aminopyridin-3-ol;
· 2-methylbenzene-1 ,3-diol;
• 2-(2,4-diaminophenoxy)ethanol hydrochloride; and
• cationic aminopyridine derivatives of general formula (VII), addition salts thereof with an acid and solvates thereof:
(VII)
in which formula (VII) the group bears the cationic charge,
o Zi is an oxygen atom or a group NR2;
R2 is a hydrogen atom or a linear or branched C C4 alkyl radical, a benzyl radical or an acetyl radical;
Ri is a saturated, linear or branched C1-C10 alkyl radical, which is substituted with or interrupted by a cationic radical, optionally interrupted by one or more oxygen atoms and/or by one or more groups NR2, optionally substituted with one or more radicals chosen from hydroxyl, alkoxy and C C4 hydroxyalkyl radicals, or is a saturated or unsaturated or aromatic cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C C4 alkyl, hydroxyl, Ci-C4 alkoxy, amino, (C C4)alkylamino, di(C C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals; when Zi represents NR2 then
■ Ri and R2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated cationic 5- to 8-membered heterocycle optionally substituted with one or more radicals chosen from C1-C10 alkyl radicals and hydroxyl, C C4 alkoxy, amino, (C C4)alkylamino, di(C C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals, it being possible for this heterocycle to contain one or more heteroatoms chosen from N or O, preferably N, or
■ Ri and R2 may form, together with the nitrogen atom to which they are attached, a saturated or unsaturated noncationic 5- to 8-membered heterocycle substituted with a cationic radical and optionally substituted with one or more radicals chosen from C1-C10 alkyl radicals and hydroxyl, C C4 alkoxy, amino, (C C4)alkylamino, di(Ci-C4)alkylamino, thio, (C C4)alkylthio, carboxyl, (C C4)alkylcarbonyl, sulphonyl, amido and C C4 hydroxyalkyl radicals;
■ R is chosen from a hydrogen atom, halogens selected from fluorine, chlorine and bromine, linear or branched C C4 alkyl radicals and carboxyl (-COOH) and (Ci-C4)alkoxycarbonyl radicals; and
■ An" represents an anionic counterion or group of anions.
14. Dyeing process according to any one of the preceding claims, which does not use an activated-CH compound.
15. Cosmetic composition comprising:
i) at least one derivative of formula (I), as defined in any one of Claims 1 to 6;
ii) at least one chemical oxidizing agent as defined in any one of Claims 1 and 7 to 9; and
Hi) at least one alkalinizing agent as defined in any one of Claims 1 , 10 and 1 1 ;
it being understood that:
the pH of the composition is above 7;
the compound(s) of formula (I) comprise at least one of the two radicals R1 or R3 which represents a hydroxyl group; with, when R1 represents a hydroxyl group, then R2 or R3 or R4 or R5 represents a hydrogen atom; and when R3 represents a hydroxyl radical then R1 or R2 or R4 or R5 represents a hydrogen atom;
the total concentration of hydroxybenzaldehyde derivatives of formula (I) is greater than 1 % relative to the total weight of the ingredients ii) and Hi) and
when the hydroxybenzaldehyde derivative of formula (I) represents a compound chosen from 3,4-dihydroxybenzaldehyde; 4-hydroxy-2-methoxybenzaldehyde;
3,5-dimethoxybenzaldehyde; 4-hydroxy-1-naphthaldehyde; 3,5-dimethyl-4- hydroxybenzaldehyde, then the alkalinizing agent Hi) is other than monoethanolamine; and
when the hydroxybenzaldehyde derivative of formula (I) represents a compound chosen from 4-hydroxy-3-methoxybenzaldehyde and 2-hydroxy-3- methoxybenzaldehyde, which is in the presence of 2-aminophenol, 2,5- diaminotoluene sulphate; then the alkalinizing agent Hi) is other than ammonium hydroxide.
16. Multicompartment device comprising from 2 to 4 compartments containing from 2 to 4 compositions in which the ingredients i), ii), Hi) as defined in any one of Claims 1 to 14 are distributed, said compositions being aqueous or pulverulent, with at least one of these compositions being aqueous.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180061028.0A CN103249455B (en) | 2010-12-20 | 2011-12-05 | Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1060792A FR2968949B1 (en) | 2010-12-20 | 2010-12-20 | PROCESS FOR COLORING KERATIN FIBERS FROM HYDROXYBENZALDEHYDE DERIVATIVES, OXIDIZING AGENTS, ALKALINIZING AGENTS IN THE PRESENCE OF HEAT |
FR1060792 | 2010-12-20 | ||
FR1150071A FR2969923B1 (en) | 2011-01-05 | 2011-01-05 | PROCESS FOR COLORING KERATIN FIBERS FROM HYDROXYBENZALDEHYDE DERIVATIVES, OXIDIZING AGENTS, ALKALINIZING AGENTS IN THE PRESENCE OF HEAT |
FR1150071 | 2011-01-05 | ||
US201161430266P | 2011-01-06 | 2011-01-06 | |
US61/430,266 | 2011-01-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012084472A1 true WO2012084472A1 (en) | 2012-06-28 |
Family
ID=45540847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/071743 WO2012084472A1 (en) | 2010-12-20 | 2011-12-05 | Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN103249455B (en) |
WO (1) | WO2012084472A1 (en) |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3376110A (en) | 1967-01-30 | 1968-04-02 | Gen Aniline & Film Corp | Solid stabilized hydrogen peroxide compositions |
DE2830497B1 (en) | 1978-07-12 | 1980-01-17 | Schwarzkopf Gmbh Hans | Process for dyeing human hair and means for carrying it out |
DE2932489B1 (en) * | 1979-08-10 | 1980-06-04 | Schwarzkopf Gmbh Hans | Process for dyeing human hair and means for carrying it out |
FR2480599A1 (en) * | 1980-04-17 | 1981-10-23 | Oreal | USE OF HYDROXYL DERIVATIVES OF BENZALDEHYDE FOR THE COLORING OF KERATIN FIBERS, PROCESS AND COMPOSITION IMPLEMENTING THEM |
US4412934A (en) | 1982-06-30 | 1983-11-01 | The Procter & Gamble Company | Bleaching compositions |
FR2586913A1 (en) | 1985-09-10 | 1987-03-13 | Oreal | PROCESS FOR FORMING IN IN SITU A COMPOSITION CONSISTING OF TWO PARTS CONDITIONED SEPARATELY AND DISPENSING ASSEMBLY FOR IMPLEMENTING SAID METHOD |
US5008093A (en) | 1989-11-08 | 1991-04-16 | Gaf Chemicals Corporation | Anhydrous complexes of PVP and hydrogen peroxide |
US5183901A (en) | 1992-01-24 | 1993-02-02 | Isp Investments Inc. | Urea-hydrogen peroxide-polyvinylpyrrolidone |
WO1995000625A1 (en) | 1993-06-25 | 1995-01-05 | The Procter & Gamble Company | Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate |
FR2814943A1 (en) | 2000-10-09 | 2002-04-12 | Oreal | Coloring composition for skin and keratin fibers, comprises color precursor and catalytic system containing salts or oxides of manganese and-or zinc and alkaline hydrocarbonates |
WO2003090700A1 (en) * | 2002-04-26 | 2003-11-06 | Wella Aktiengesellschaft | Agents for oxidatively dying keratin fibers |
DE10241076A1 (en) * | 2002-09-05 | 2004-03-11 | Henkel Kgaa | Agent for dyeing keratin fibers |
US6770102B1 (en) | 1999-08-05 | 2004-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Agent for dying keratin fibers |
US6790239B1 (en) | 1999-10-23 | 2004-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Agent for coloring keratin containing fibers |
WO2006002710A1 (en) | 2004-06-29 | 2006-01-12 | Georg Menshen Gmbh & Co. Kg | Closure for a container |
WO2006131163A1 (en) | 2005-06-08 | 2006-12-14 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent composition for dyeing keratin fibres |
WO2007019930A1 (en) * | 2005-08-15 | 2007-02-22 | Henkel Kommanditgesellschaft Auf Aktien | Agent for dyeing keratinous fibres |
EP2014275A2 (en) * | 2007-06-15 | 2009-01-14 | Henkel AG & Co. KGaA | Kit for preparing storage-stable formulations |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10354812A1 (en) * | 2003-11-21 | 2006-08-17 | Henkel Kgaa | Method for coloring keratin-containing fibers |
-
2011
- 2011-12-05 WO PCT/EP2011/071743 patent/WO2012084472A1/en active Application Filing
- 2011-12-05 CN CN201180061028.0A patent/CN103249455B/en not_active Expired - Fee Related
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3376110A (en) | 1967-01-30 | 1968-04-02 | Gen Aniline & Film Corp | Solid stabilized hydrogen peroxide compositions |
DE2830497B1 (en) | 1978-07-12 | 1980-01-17 | Schwarzkopf Gmbh Hans | Process for dyeing human hair and means for carrying it out |
DE2932489B1 (en) * | 1979-08-10 | 1980-06-04 | Schwarzkopf Gmbh Hans | Process for dyeing human hair and means for carrying it out |
FR2462907A1 (en) | 1979-08-10 | 1981-02-20 | Schwarzkopf Gmbh Hans | PROCESS FOR DYING NATURAL HAIR AND AGENT FOR CARRYING OUT THE PROCESS |
FR2480599A1 (en) * | 1980-04-17 | 1981-10-23 | Oreal | USE OF HYDROXYL DERIVATIVES OF BENZALDEHYDE FOR THE COLORING OF KERATIN FIBERS, PROCESS AND COMPOSITION IMPLEMENTING THEM |
US4412934A (en) | 1982-06-30 | 1983-11-01 | The Procter & Gamble Company | Bleaching compositions |
FR2586913A1 (en) | 1985-09-10 | 1987-03-13 | Oreal | PROCESS FOR FORMING IN IN SITU A COMPOSITION CONSISTING OF TWO PARTS CONDITIONED SEPARATELY AND DISPENSING ASSEMBLY FOR IMPLEMENTING SAID METHOD |
US5008093A (en) | 1989-11-08 | 1991-04-16 | Gaf Chemicals Corporation | Anhydrous complexes of PVP and hydrogen peroxide |
US5183901A (en) | 1992-01-24 | 1993-02-02 | Isp Investments Inc. | Urea-hydrogen peroxide-polyvinylpyrrolidone |
WO1995000625A1 (en) | 1993-06-25 | 1995-01-05 | The Procter & Gamble Company | Granular laundry detergent compositions containing lipase and sodium nonanoyloxybenzene sulfonate |
US6770102B1 (en) | 1999-08-05 | 2004-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Agent for dying keratin fibers |
US6790239B1 (en) | 1999-10-23 | 2004-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Agent for coloring keratin containing fibers |
FR2814943A1 (en) | 2000-10-09 | 2002-04-12 | Oreal | Coloring composition for skin and keratin fibers, comprises color precursor and catalytic system containing salts or oxides of manganese and-or zinc and alkaline hydrocarbonates |
WO2003090700A1 (en) * | 2002-04-26 | 2003-11-06 | Wella Aktiengesellschaft | Agents for oxidatively dying keratin fibers |
DE10241076A1 (en) * | 2002-09-05 | 2004-03-11 | Henkel Kgaa | Agent for dyeing keratin fibers |
WO2006002710A1 (en) | 2004-06-29 | 2006-01-12 | Georg Menshen Gmbh & Co. Kg | Closure for a container |
WO2006131163A1 (en) | 2005-06-08 | 2006-12-14 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent composition for dyeing keratin fibres |
WO2007019930A1 (en) * | 2005-08-15 | 2007-02-22 | Henkel Kommanditgesellschaft Auf Aktien | Agent for dyeing keratinous fibres |
EP2014275A2 (en) * | 2007-06-15 | 2009-01-14 | Henkel AG & Co. KGaA | Kit for preparing storage-stable formulations |
Non-Patent Citations (1)
Title |
---|
"Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG GMBH & CO. KGAA, article "Sulfites, Thiosulfates, and Dithionites" |
Also Published As
Publication number | Publication date |
---|---|
CN103249455B (en) | 2017-04-19 |
CN103249455A (en) | 2013-08-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8888866B2 (en) | Dyeing process using a natural dye on keratin fibres that have undergone permanent reshaping | |
US20090320216A1 (en) | Fluorescent entity, dyeing composition containing at least one fluorescent entity, and method for lightening keratin materials using said at least one fluorescent entity | |
WO2012084473A1 (en) | Process for dyeing keratin fibres using resorcinol derivatives, sulfate salts, an oxidizing agent and a basifying agent | |
US8597373B2 (en) | Hair dyeing process using a composition comprising at least one indole or indoline compound, a metal salt, hydrogen peroxide and a basifying agent | |
FR2954121A1 (en) | COLORING AND / OR DECOLOURING AGENT OF TWO - PART KERATIN FIBERS, COMPRISING A PARTICULAR FOLDER AND A REDUCTONE. | |
FR2984148A1 (en) | OXIDATION COLORING PROCESS USING A BODY-RICH COMPOSITION AND METAL CATALYSTS, AND APPROPRIATE DEVICE | |
FR3030244A1 (en) | COLORING COMPOSITION COMPRISING A PARA-PHENYLENEDIAMINE OXIDATION BASE AND A PARTICULAR COUPLER | |
FR3030243A1 (en) | COLORING COMPOSITION COMPRISING A PARA-PHENYLENEDIAMINE OXIDATION BASE AND A HETEROCYCLIC OXIDATION BASE | |
EP3229756B1 (en) | Hair dyeing process using at least one dye, a titanium salt and an anionic thickening polymer | |
US8518126B2 (en) | Hair dyeing process using a chromene or chromane dye | |
FR2902323A1 (en) | Coloring of keratinous fibers comprising applying a mixture of a composition comprising a coupler e.g. 6-chloro-2-methyl-5-aminophenol and oxidation base such as diamino-N,N-dihydro-pyrazolone and a tinctorial composition | |
EP3373902B1 (en) | Cationic direct dye comprising an aliphatic chain and bearing a disulfide/thiol/protected-thiol function for dyeing keratin fibres | |
FR2926983A1 (en) | Composition, useful for oxidation coloring of keratin fibers, preferably human hair, comprises 3-amino 2-methylamino 6-methoxypyridine, oxidation dyes and polyols compound | |
WO2018229296A1 (en) | Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye | |
KR20190087532A (en) | A method of dyeing keratin fibers using at least one specific triarylmethane dye and at least one fluorescent dye | |
FR2954101A1 (en) | COLORING AND / OR DECOLOURING AGENT FOR KERATINIC FIBERS INTO TWO OR MORE PARTS, COMPRISING AN ALKALINE REVERSE EMULSION. | |
FR2919500A1 (en) | Composition, useful for dyeing keratin fibers, preferably human keratin fibers such as hair, comprises cationic cellulose ether, 2,3-diaminopyrazolone derivatives, and second oxidation dyes | |
US7585332B2 (en) | Composition containing a styryl or imine type dye and a thiol compound, hair coloring process and device | |
FR2971158A1 (en) | Lightening or dyeing keratinous fibers, in presence of oxidizing agent, comprises applying formulation comprising composition of e.g. fatty substance, composition of e.g. ammonium (bi)carbonate and composition of e.g. oxidizing agent | |
KR20190087531A (en) | A method of dyeing keratin fibers using at least one specific 2-azo (benz) imidazolium dye and at least one fluorescent dye | |
FR3037239A1 (en) | CAPILLARY COLORING PROCESS USING TITANIUM SALT, OXIDATION COLOR, AND INTERMEDIATE RINSE | |
EP3558462B1 (en) | Process for dyeing and relaxing curls of keratin fibres, using reducing agents and hair dyes, and associated kit | |
WO2012084472A1 (en) | Process for dyeing keratin fibres using hydroxybenzaldehyde derivatives, oxidizing agents and alkalinizing agents in the presence of heat | |
EP2488152A2 (en) | Composition comprising at least one 1,8-dihydroxynaphthalene derivative and at least one basifying agent different from aqueous ammonia, process for dyeing keratin fibres using the composition | |
FR2940056A1 (en) | Coloring keratin fibers, preferably human keratin fibers such as hair, comprises applying on the fibers a composition comprising e.g. surfactants, cosmetic composition comprising e.g. direct dyes and composition comprising oxidizing agent |
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: 11813673 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: 11813673 Country of ref document: EP Kind code of ref document: A1 |