EP0954275A1 - Composition de teinture d'oxydation des fibres keratiniques comprenant un derive de paraphenylenediamine et procede de teinture mettant en oeuvre cette composition - Google Patents

Composition de teinture d'oxydation des fibres keratiniques comprenant un derive de paraphenylenediamine et procede de teinture mettant en oeuvre cette composition

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Publication number
EP0954275A1
EP0954275A1 EP97912242A EP97912242A EP0954275A1 EP 0954275 A1 EP0954275 A1 EP 0954275A1 EP 97912242 A EP97912242 A EP 97912242A EP 97912242 A EP97912242 A EP 97912242A EP 0954275 A1 EP0954275 A1 EP 0954275A1
Authority
EP
European Patent Office
Prior art keywords
composition
formula
acid
paraphenylenediamine
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97912242A
Other languages
German (de)
French (fr)
Inventor
Marie-Pascale Audousset
Jean Cotteret
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of EP0954275A1 publication Critical patent/EP0954275A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • 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

Definitions

  • the subject of the invention is a composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one derivative of paraphenylenediamine suitably selected as oxidation base, in association with at at least one coupler of the meta-aminophenol or meta-diphenol type suitably selected, as well as the dyeing process using this composition.
  • oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds
  • couplers or color modifiers the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols
  • compositions for the oxidation dyeing of keratinous fibers containing, as the oxidation base, parapnenylenediamines substituted in position 2 such as for example the ⁇ o 2- ⁇ -mesylam ⁇ noethyloxy paraphenylenediamine, optionally in combination with one or more couplers of the meta-aminophenol type such as Dar for example 5-am ⁇ no 2-methyl phenol metapnenylenediamine or meta- ⁇ iphenol in order to obtain, in an oxidizing alkaline medium, blue shades olus OR less purple very bright
  • the colors obtained with these compositions are however not entirely satisfactory in particular with regard to the behavior of these colors with regard to the various aggressions that can occur with the hair and in particular with respect to perspiration and the permanent
  • the oresente invention aims to proDose new co ⁇ roosiiions DOU ⁇ the oxidation dyeing of keratin fibers and in particular ⁇ es human keratin flora such as the hair which have very good dyeing properties
  • the first object of the invention is therefore a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comorend in a medium suitable for dyeing
  • - R represents a hydrogen atom, a mesyl, carbamoyl or acetyl radical
  • - n is an integer between 1 and 4 inclusive
  • R. represents a hydroxyl radical or an NHR group where R denotes a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C monohydroxyalkyl or C 2 -C polyhydroxyalkyl,
  • the colors obtained with the above compositions have good dyeing power and excellent resistance properties both with respect to atmospheric agents such as light and bad weather and with respect to perspiration and the various treatments which may undergo the hair (shampoos, permanent deformations)
  • the subject of the invention is also a process for the oxidation dyeing of keratin fibers using this composition.
  • addition salts with an acid which can be used in the context of the dye compositions of the invention can in particular be chosen from hydrochlorides, hydrobromides, sulfates and tartrates
  • paraphenylenediamine derivatives of formula (I) above there may be mentioned more particularly 2- ⁇ -mesylam ⁇ noethyloxy paraphenylenediamine, 2- ⁇ -ure ⁇ doethyloxy paraDhenylenediamine, 2- ⁇ -acetylam ⁇ noethyloxy paraDhenylenediamine, 2- ⁇ -am ⁇ noethyloxy paraphenylene ⁇ iamine and their addition salts with an acid
  • couplers of formula (II) above there may be mentioned more particularly meta-aminophenol, 5-am ⁇ no 2-methoxy phenol, 5-am ⁇ no 2- ( ⁇ -hydroxyethyloxy) phenol, 5-am ⁇ no 2- methyl phenol, 5-N- ( ⁇ -hydroxyethyl) am ⁇ no 2-methyl phenol, 5-N- ( ⁇ -hydroxypropylam ⁇ no) 2-methyl phenol, 1, 3-d ⁇ hydroxy benzene, 2-methyl 1, 3- dehydroxy benzene, ⁇ -chloro 1, 3-d ⁇ hydroxy benzene, and their addition salts with an acid
  • the Daraphenylenediamine derivative (s) of formula (I) according to the invention and / or their addition salt (s) with an acid preferably represent from 0 0005 to 10% by weight approximately of the total weight of the dye composition, and even more preferably from 0.05 to 7% by weight approximately
  • the coupler (s) of formula (II) according to the invention and / or their addition salt (s) with an acid preferably represent from 0.0001 to 5% in DOids approximately of the total weight of the dye composition, and even more oreferential from 0.005 to 3% in DOids approximately
  • the medium suitable for dyeing is generally constituted by water or by a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water.
  • organic solvent mention may, for example, be made of lower alkanols, C- j -C i, such as ethanol and isopropanol, glycerol, glycols and glycol liners such as 2-butoxyethanol DroDyleneglycol, monoethyl etner and mc n omethyléther diethylene ⁇ ue and aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products e * their melan ⁇ es
  • the solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
  • the pH of the dye composition as defined above is generally between 5 and 12 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.
  • acidifying agents there may be mentioned, by way of examples, mineral or organic acids such as hydrochloric acid, orthophosphonic acid, carboxylic acids such as tart ⁇ que acid, citric acid, lactic acid, sulfonic acids
  • basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and t ⁇ thanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below
  • R. R 3 in which R is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in C, -C 4 , R ,, R 5 , R- and R , identical or different, represent a hydrogen atom , an alkyl radical in C.-C. or C 4 -C 4 hydroxyalkyl
  • the dye composition in accordance with the invention May also contain, in addition to the dyes defined above, other bases for oxidation different from the derivatives, this paraohenylene ⁇ iamine ⁇ e formula (I) in accordance with the invention and / or other couplers different from the ae thread formers according to the invention and / or direct dyes, in particular to modify the nuances or to enrich them with reflections
  • the dye composition according to the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair such as anionic, cationic, non-lonic, arriDhoteric surfactants or mixtures thereof, anionic, cationic, non-polymeric -ionic, amphoteric or their mixtures, mineral or organic thickening agents, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones , film-forming agents, preserving agents, opacifying agents
  • the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • the subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.
  • the dye composition is applied to the fibers to be dyed such that they are defined orecedemme ⁇ t the color being revealed at neutral pH aci ⁇ e or alkaline using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.
  • the pH resulting from the mixture of the dye composition and the oxidizing composition is between 5 and 12 approximately.
  • the dye composition described above is mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration
  • an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration
  • the mixture obtained is then applied to the keratin fibers and left to stand for 3 to 40 to 5 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, wash with shampoo, rinse again and dry
  • the oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for> the oxidation state of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates Hydrogen peroxide is particularly preferred.
  • the pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 2 and 12 approximately and even more preferably between 5 and 1 1 It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above
  • the oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
  • composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • Another object of the invention is a device with several compartments or "kit” for dyeing or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above
  • These devices can be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices described in patent FR-A-2,586,913 in the name of the applicant
  • each dye composition contains the same molar amount of coupler as well as the same molar amount of oxidation base, namely 3 10 "3 moles
  • each dye composition was mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3
  • a color is defined by the expression HV / C in which the three parameters respectively designate the hue or Hue 0 (H), the intensity or Value (V) and the purity or Chromaticity (C), the forward slash is just a convention and does not indicate a ratio
  • the locks of hair dyed from batch A were subjected to a test of resistance to perm.
  • the locks of hair from batch A were immersed for 5 minutes in an oxidizing solution (consisting of a hydrogen peroxide solution at 8 volumes and of pH 3) at a rate of 2 g of oxidizing solution per lock of 1 g
  • the locks were then rinsed with water and then dried for 1 hour at 60 ° C.
  • ⁇ E represents the difference in color between two wicks ⁇ H ⁇ V and ⁇ C represent the variation in absolute value of the parameters HV and C and Co represents the purity of the wick with respect to which one wishes to evaluate the difference in color
  • the color degradation ( ⁇ E) is all the more important as the figure indicates is high
  • compositions 1 and 3 in accordance with the invention that is to say containing the combination of a paraphenylenediamine derivative of formula (I) and of a coupler of formula (II) lead to colorings which are much better resistant to perm than the colors obtained with compositions 2 and 4 which are not part of the invention because they contain
  • compositions 2 and 4 of the prior art are by example described in patent application FR-A-2 364 888
  • the locks of hair dyed from batch B were subjected to a test of resistance to perspiration To do this, the batch B hair strands were immersed in a crystallizing dish covered with a watch glass and containing a synthetic sweat solution of the following composition •
  • the dyed hair strands of lot B were allowed to stay in this synthetic sweat solution for 48 hours at 37 ° C. The strands were then rinsed and then dried.
  • the color of the locks of batch B was then evaluated again in the MUNSELL system using a CM 2002 MINOLTA colo ⁇ meter so as to determine the degradation of the colorations after this test of resistance to perspiration.
  • the difference in color between two locks was calculated by applying the NICKERSON formula as described above.
  • compositions 1 and 3 in accordance with the invention that is to say containing the association of a paraphenylenediamine derivative of formula (I) and of a coupler of formula (II) lead to resistant coloring. much better at transpiration than the colorings obtained with comDositions 2 and ⁇ which are not part of the invention because they contain the association of a paraphenylenediamine derivative of formula (I) in accordance with the invention and of a coupler which does not correspond to the formula (II) of the invention
  • compositions 2 and 4 of the prior art are, for example, approved in patent application FR-A-2 364

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

Abstract

The invention concerns an oxidation dyeing composition for human keratinous fibers, in particular human keratinous fibers such as hair, containing at least one paraphenylenediamine derivative of formula (I) oxidation base, in combination with at least one meta-aminophenol or meta-diphenol coupling agent, as well as the dyeing method using this composition.

Description

COMPOSITION DE TEINTURE D'OXYDAΗON DES FIBRES KERAΗNIQUES COMPRENANT UN DERIVE DE PARAPHENYLENEDIAMINE ET PROCEDE DE TEINTURE METTANT EN OEUVRE CETTE COMPOSITIONKERAΗNIC FIBER OXIDATIVE DYE COMPOSITION COMPRISING A PARAPHENYLENEDIAMINE DERIVATIVE AND DYEING METHOD USING THE SAME
L'invention a pour objet une composition pour la teinture d'oxydation des fibres kératiniques, en particulier des fibres kératiniques humaines telles que les cheveux, comprenant au moins un dérivé de paraphénylènediamine convenablement sélectionné à titre de base d'oxydation, en association avec au moins un coupleur de type méta-aminophénol ou méta-diphénol convenablement sélectionné, ainsi que le procédé de teinture mettant en oeuvre cette composition.The subject of the invention is a composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one derivative of paraphenylenediamine suitably selected as oxidation base, in association with at at least one coupler of the meta-aminophenol or meta-diphenol type suitably selected, as well as the dyeing process using this composition.
Il est connu de teindre les fibres kératiniques et en particulier les cheveux humains avec des compositions tinctoriales contenant des précurseurs de colorant d'oxydation, en particulier des ortho ou paraphénylènediamines, des ortho ou paraaminophénols, appelés généralement bases d'oxydation Les précurseurs de colorants d'oxydation, ou bases d'oxydation, sont des composés incolores ou faiblement colorés qui, associés à des produits oxydants, peuvent donner naissance par un processus de condensation oxydative à des composés colorés et colorantsIt is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular ortho or paraphenylenediamines, ortho or paraaminophenols, generally called oxidation bases. oxidation, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds
On sait également que l'on peut faire varier les nuances obtenues avec ces bases d'oxydation en les associant à des coupleurs ou modificateurs de coloration, ces derniers étant choisis notamment parmi les métadiamines aromatiques, les métaaminophénols, les métadiphénolsWe also know that we can vary the shades obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols
La variété des molécules mises en jeu au niveau des bases d'oxydation et des coupleurs, permet l'obtention d'une riche palette de couleursThe variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors
La coloration dite "permanente" obtenue grâce à ces colorants d'oxydation, doit Dar ailleurs satisfaire un certain nombre d'exigences Ainsi, elle doit être sans inconvénient sur le plan toxicologique elle doit permettre d obtenir des nuances dans l'intensité souhaitée et présenter une bonne tenue face aux agents extérieurs (lumière intempéries lavage, ondulation permanente transDiration frottements)The so-called "permanent" coloration obtained thanks to these oxidation dyes must, moreover, satisfy a certain number of requirements. Thus, it must be without drawback from a toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents (bad weather washing, permanent ripple transDiration friction)
Il a déjà ete propose, notamment dans la demande αe brevet français FR-A-2 364 888 des compositions pour la teinture d'oxydation des fibres kératiniques renfermant a titre de base d'oxydation des parapnenylenediamines substituées en position 2 telles que par exemple la ιo 2-β-mesylamιnoethyloxy paraphénylènediamine, éventuellement en association avec un ou plusieurs coupleurs de type meta-aminophenol tel que Dar exemple le 5-amιno 2-methyl phénol metapnenylenediamine ou meta-αiphenol afin d'obtenir en milieu alcalin oxydant, des colorations aux nuances bleues olus OU moins pourpres très lumineuses Les colorations obtenues avec ces compositions ne sont toutefois pas entièrement satisfaisantes notamment en ce qui concerne la tenue de ces colorations vis a vis des diverses agressions que peuvent SUDIΓ les cheveux et en particulier vis a vis αe la transpiration et αe la permanenteIt has already been proposed, in particular in French patent application FR-A-2 364 888, compositions for the oxidation dyeing of keratinous fibers containing, as the oxidation base, parapnenylenediamines substituted in position 2 such as for example the ιo 2-β-mesylamιnoethyloxy paraphenylenediamine, optionally in combination with one or more couplers of the meta-aminophenol type such as Dar for example 5-amιno 2-methyl phenol metapnenylenediamine or meta-αiphenol in order to obtain, in an oxidizing alkaline medium, blue shades olus OR less purple very bright The colors obtained with these compositions are however not entirely satisfactory in particular with regard to the behavior of these colors with regard to the various aggressions that can occur with the hair and in particular with respect to perspiration and the permanent
n La oresente invention vise a proDoser de nouvelles coπroosiiions DOU Γ la coloration d oxydation des fibres kératiniques et en particulier αes flores kératiniques humaines telles que les cheveux qui présentent de très bonnes propriétés tinctorialesn The oresente invention aims to proDose new coπroosiiions DOU Γ the oxidation dyeing of keratin fibers and in particular αes human keratin flora such as the hair which have very good dyeing properties
:-> Ainsi la demanderesse vient maintenant de découvrir qu'il est possible d ootenir de nouvelles teintures particulièrement résistantes qui engenαrent des co'orations intenses en associant: -> Thus the plaintiff has now discovered that it is possible to obtain new particularly resistant dyes which generate intense coorations by associating
- au noms un dérive de paraDhenylenediamine de formule (I) αetinie d-apres et/ou I un de ses sels d addit'on avec un acide - au moins un coupleur de formule (II) définie ci-apres et/ou l'un de ses sels d'addition avec un acide,- in the names a derivative of paraDhenylenediamine of formula (I) αetinie d-apres and / or I one of its addit'on salts with an acid at least one coupler of formula (II) defined below and / or one of its addition salts with an acid,
Cette découverte est a la base de la présente inventionThis discovery is the basis of the present invention
L'invention a donc pour premier objet une composition pour la teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisée par le fait qu'elle comorend dans un milieu approprie pour la teintureThe first object of the invention is therefore a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comorend in a medium suitable for dyeing
- au moins une base d'oxydation choisie parmi les dérives de paraphénylènediamine de formule (I) suivante et leurs sels d'addition avec un acide- at least one oxidation base chosen from the derivatives of paraphenylenediamine of formula (I) below and their addition salts with an acid
αans laquelle in which
- R représente un atome d'hydrogène, un radical mesyle, carbamoy'le ou acetyle,- R represents a hydrogen atom, a mesyl, carbamoyl or acetyl radical,
- n est un nombre entier compris entre 1 et 4 inclusivement ,- n is an integer between 1 and 4 inclusive,
- au moins un coupleur choisi parmi les composes de formule (I I) suivante et leu-s sels d addition avec un acide dans laquelle :- at least one coupler chosen from the compounds of formula (II) below and their addition salts with an acid in which :
- R. représente un radical hydroxyle ou un groupement NHR où R désigne un atome d'hydrogène, un radical alkyle en C,-C4, monohydroxyalkyle en C.-C. ou polyhydroxyalkyle en C2-C ,- R. represents a hydroxyl radical or an NHR group where R denotes a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C monohydroxyalkyl or C 2 -C polyhydroxyalkyl,
- R3 représente un atome d'hydrogène, un radical alkyle en C,-C4 l alcoxy en C C. OU un atome d'halogène choisi parmi le chlore, le brome et le fluor ; étant entendu que lorsque n = 2, que R, représente un radical mésyle, que R3 représente un radical mέthyle en position 6, et que R2 représente un groupement NHR , alors R. est différent d'un atome d'hydrogène.- R 3 represents a hydrogen atom, an alkyl radical in C, -C 4 l alkoxy in C C. OR a halogen atom chosen from chlorine, bromine and fluorine; it being understood that when n = 2 that R represents a mesyl radical, that R 3 represents a methyl radical in position 6, and that R 2 represents an NHR group, then R. is different from a hydrogen atom.
Les colorations obtenues avec les compositions ci-dessus présentent une bonne puissance tinctoriale et d'excellentes propriétés de résistance à la fois vis à vis des agents atmosphériques tels que la lumière et les intempéries et vis à vis de la transpiration et des différents traitements que peuvent subir les cheveux (shampooings, déformations permanentes)The colors obtained with the above compositions have good dyeing power and excellent resistance properties both with respect to atmospheric agents such as light and bad weather and with respect to perspiration and the various treatments which may undergo the hair (shampoos, permanent deformations)
L'invention a également pour objet un procédé de teinture d'oxydation des fibres kératiniques mettant en oeuvre cette composition.The subject of the invention is also a process for the oxidation dyeing of keratin fibers using this composition.
Les sels d'addition avec un acide utilisables dans le cadre des compositions tinctoriales de l'invention peuvent être notamment choisis parmi les chlorhydrates, les bromhydrates, les sulfates et les tartratesThe addition salts with an acid which can be used in the context of the dye compositions of the invention can in particular be chosen from hydrochlorides, hydrobromides, sulfates and tartrates
Parmi les dérivés de paraphénylènediamine de formule (I) ci-dessus, on peut plus particulièrement citer la 2-β-mésylamιnoéthyloxy paraphénylènediamine, la 2-μ-uréιdoéthyloxy paraDhénylènediamine, la 2-β-acétylamιnoéthyloxy paraDhenylènediamine, la 2-β-amιnoéthyloxy paraphényleneαiamine et leur sels d'addition avec un acideAmong the paraphenylenediamine derivatives of formula (I) above, there may be mentioned more particularly 2-β-mesylamιnoethyloxy paraphenylenediamine, 2-μ-ureιdoethyloxy paraDhenylenediamine, 2-β-acetylamιnoethyloxy paraDhenylenediamine, 2-β-amιnoethyloxy paraphenyleneαiamine and their addition salts with an acid
Parmi les coupleurs de formule (II) ci-dessus, on peut plus particulièrement citer le méta-aminophénol, le 5-amιno 2-méthoxy phénol, le 5-amιno 2-(β-hydroxyéthyloxy) phénol, le 5-amιno 2-méthyl phénol, le 5-N-(β-hydroxyéthyl)amιno 2-méthyl phénol, le 5-N-(γ-hydroxypropylamιno) 2-méthyl phénol, le 1 ,3-dιhydroxy benzène, le 2-méthyl 1 ,3-dιhydroxy benzène, le ^-chloro 1 ,3-dιhydroxy benzène, et leurs sels d'addition avec un acideAmong the couplers of formula (II) above, there may be mentioned more particularly meta-aminophenol, 5-amιno 2-methoxy phenol, 5-amιno 2- (β-hydroxyethyloxy) phenol, 5-amιno 2- methyl phenol, 5-N- (β-hydroxyethyl) amιno 2-methyl phenol, 5-N- (γ-hydroxypropylamιno) 2-methyl phenol, 1, 3-dιhydroxy benzene, 2-methyl 1, 3- dehydroxy benzene, ^ -chloro 1, 3-dιhydroxy benzene, and their addition salts with an acid
Le ou les dérives de Daraphénylenediamine de formule (I) conforme a l'invention et/ou leur(s) sels d'addition avec un acide représentent de préférence de 0 0005 à 10 % en poids environ du poids total de la composition tinctoriale, et encore plus préférentiellement de 0,05 à 7 % en poids environThe Daraphenylenediamine derivative (s) of formula (I) according to the invention and / or their addition salt (s) with an acid preferably represent from 0 0005 to 10% by weight approximately of the total weight of the dye composition, and even more preferably from 0.05 to 7% by weight approximately
Le ou les coupleurs de formule (II) conforme à l'invention et/ou leur(s) sels d'addition avec un acide représentent de préférence de 0,0001 a 5 % en DOids environ du poids total de la composition tinctoriale, et encore plus oreferentiellemeπt de 0,005 a 3 % en DOids environThe coupler (s) of formula (II) according to the invention and / or their addition salt (s) with an acid preferably represent from 0.0001 to 5% in DOids approximately of the total weight of the dye composition, and even more oreferential from 0.005 to 3% in DOids approximately
Le milieu approprié pour la teinture (ou support) est généralement constitue par de l'eau ou par un mélange d'eau et d'au moins un solvant organique pour solubiliser les composes qui ne seraient pas suffisamment solubles dans l'eau A titre de solvant organique, on peut par exemple citer les alcanols inférieurs en C-j -C i, tels que l'éthanol et l'isopropanol , le glycérol , les glycols et etners de glycols comme le 2-butoxyéthanol le DroDyleneglycol, le monoéthyletner et le mcnomethyléther du diethyleneglycol, ainsi αue les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, les produits analogues e* leurs melanαes Les solvants peuvent être présents dans des proportions de préférence comprises entre 1 et 40 % en poids environ par rapport au poids total de la composition tinctoriale, et encore plus préférentiellement entre 5 et 30 % en poids environThe medium suitable for dyeing (or support) is generally constituted by water or by a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. organic solvent, mention may, for example, be made of lower alkanols, C- j -C i, such as ethanol and isopropanol, glycerol, glycols and glycol liners such as 2-butoxyethanol DroDyleneglycol, monoethyl etner and mc n omethyléther diethylene αue and aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products e * their melanαes The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
Le pH de la composition tinctoriale telle que définie précédemment est généralement compris entre 5 et 12 environ II peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniquesThe pH of the dye composition as defined above is generally between 5 and 12 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.
Parmi les agents acidifiants, on peut citer, a titre d'exemples, les acides minéraux ou organiques comme l'acide chlorhydπque, l'acide orthophosphoπque, les acides carboxyliques comme l'acide tartπque, l'acide citrique, l'acide lactique, les acides sulfoniquesAmong the acidifying agents, there may be mentioned, by way of examples, mineral or organic acids such as hydrochloric acid, orthophosphonic acid, carboxylic acids such as tartπque acid, citric acid, lactic acid, sulfonic acids
Parmi les agents alcalinisants, on peut citer, à titre d'exemples, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et tπέthanolamines ainsi que leurs dérives, les hydroxydes de sodium ou de potassium et les composes de formule (III) suivanteAmong the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and tπέthanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below
R5 R7 R 5 R 7
^ N - R - N (m)^ N - R - N (m)
R. R3 dans laquelle R est un reste propylène éventuellement substitue par un groupement hydroxyle ou un radical alkyle en C,-C4 , R,, R5, R- et R=, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C.-C. ou hydroxyalkyle en C,-C4 R. R 3 in which R is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in C, -C 4 , R ,, R 5 , R- and R =, identical or different, represent a hydrogen atom , an alkyl radical in C.-C. or C 4 -C 4 hydroxyalkyl
La comDosition tinctoriale conforme a l'invention Deut encore contenir en plus des colorants définis ci-dessus d'autres bases d'oxydation différentes des dérives ce paraohényleneαiamine αe formule (I) conforme a l'invention et/ou d'autres coupleurs différents des coucleurs αe formule fil) conforme a l'invention et/ou des colorants directs, notamment pour modifier les nuances ou les enrichir en refletsThe dye composition in accordance with the invention May also contain, in addition to the dyes defined above, other bases for oxidation different from the derivatives, this paraohenyleneαiamine αe formula (I) in accordance with the invention and / or other couplers different from the ae thread formers according to the invention and / or direct dyes, in particular to modify the nuances or to enrich them with reflections
La composition tinctoriale selon l'invention peut également renfermer divers 5 adjuvants utilises classiquement dans les compositions pour la teinture des cheveux tels que des agents tensio-actifs anioniques, cationiques, non- loniques, arriDhoteres ou leurs mélanges, des polymères anioniques, cationiques, non-ioniques, amphotères ou leurs mélanges, des agents épaississants minéraux ou organiques, des agents antioxydants, des agents de ι o pénétration, des agents séquestrants, des parfums, des tampons, des agents dispersants, des agents de conditionnement tels que par exemple des silicones, des agents filmogenes, des agents conservateurs, des agents opacifiantsThe dye composition according to the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair such as anionic, cationic, non-lonic, arriDhoteric surfactants or mixtures thereof, anionic, cationic, non-polymeric -ionic, amphoteric or their mixtures, mineral or organic thickening agents, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones , film-forming agents, preserving agents, opacifying agents
Bien entendu, l'nomme de l'art veillera a choisir le ou les éventuels comDosés b complémentaires mentionnes ci-avant, de manière telle que les propriétés avantageuses attachées intrinsèquement a la composition tinctoriale selon l'invention ne soient pas, ou substantiellement Das, altérées par la ou les adjonctions envisagéesOf course, the person skilled in the art will take care to choose the possible additional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered by the planned addition (s)
:i La comDosition tinctoriale selon l'invention peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains: i The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
L'invention a également pour objet un procédé de teinture des fibres kératiniques et en particulier des fibres kératiniques humaines telles αue les cheveux mettant en oeuvre la composition tinctoriale telle que αefinie précédemmentThe subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.
• i Selon ce proceαe, on applique sur les fibres a colorer la comDosition tinctoriale telle αue définie orecedemmeπt la couleur étant révélée a pH aciαe neutre ou alcalin à l'aide d'un agent oxydant qui est ajouté juste au moment de l'emploi à la composition tinctoriale ou qui est présent dans une composition oxydante appliquée simultanément ou séquentiellement de façon séparée. • i According to this proceαe, the dye composition is applied to the fibers to be dyed such that they are defined orecedemmeπt the color being revealed at neutral pH aciαe or alkaline using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.
5 Selon une forme de réalisation préférée de l'invention, le pH résultant du mélange de la composition tinctoriale et de la composition oxydante est compris entre 5 et 12 environ.According to a preferred embodiment of the invention, the pH resulting from the mixture of the dye composition and the oxidizing composition is between 5 and 12 approximately.
Selon une forme de mise en oeuvre particulièrement préférée du procédé de o teinture selon l'invention, on mélange, au moment de l'emploi, la composition tinctoriale décrite ci-dessus avec une composition oxydante contenant, dans un milieu approprié pour la teinture, au moins un agent oxydant présent en une quantité suffisante pour développer une coloration Le mélange obtenu est ensuite appliqué sur les fibres kératiniques et on laisse poser pendant 3 à 40 5 minutes environ, de préférence 5 à 30 minutes environ, après quoi on rince, on lave au shampooing, on rince à nouveau et on sècheAccording to a particularly preferred embodiment of the dyeing process according to the invention, the dye composition described above is mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 40 to 5 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, wash with shampoo, rinse again and dry
L'agent oxydant présent dans la composition oxydante telle que définie ci-dessus peut être choisi parmi les agents oxydants classiquement utilisés pour > la te'nture d'oxydation des fibres kératiniques, et parmi lesquels on peut citer le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels tels que les perborates et persulfates Le peroxyde d'hydrogène est particulièrement préféré.The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for> the oxidation state of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates Hydrogen peroxide is particularly preferred.
Le pH de la composition oxydante renfermant l'agent oxydant tel que défini ci-dessus est tel qu'après mélange avec la composition tinctoriale, le pH de la composition résultante appliquée sur les fibres kératiniques varie de préférence entre 2 et 12 environ et encore plus préférentiellement entre 5 et 1 1 II est ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques et tels que définis précédemment La composition oxydante telle que définie ci-dessus peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux et tels que définis précédemmentThe pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 2 and 12 approximately and even more preferably between 5 and 1 1 It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
La composition qui est finalement appliquée sur les fibres kératiniques peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humainsThe composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
Un autre objet de l'invention est un dispositif a plusieurs compartiments ou "kit" de teinture ou tout autre système de conditionnement a plusieurs compartiments dont un premier compartiment renferme la composition tinctoriale telle que définie ci-dessus et un second compartiment renferme la comϋosition oxydante telle que définie ci-dessus Ces dispositifs peuvent être équiDes d'un moyen permettant de délivrer sur les cheveux le mélange souhaite, tel que les dispositifs décrits dans le brevet FR-A-2 586 913 au nom de la demanderesseAnother object of the invention is a device with several compartments or "kit" for dyeing or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above These devices can be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices described in patent FR-A-2,586,913 in the name of the applicant
Les exemples qui suivent sont destines à illustrer l'invention sans pour autant en limiter la portée The examples which follow are intended to illustrate the invention without however limiting its scope
EXEMPLESEXAMPLES
EXEMPLES 1 à 4 COMPARATIFSEXAMPLES 1 to 4 COMPARATIVE
On a préparé les compositions tinctoriales suivantes (teneurs en grammes)The following dye compositions were prepared (contents in grams)
exemple ne faisant pas partie de l'inventionexample not part of the invention
suoDort de teinture communcommon dye suoDort
Ethanol à 96° 18 0 gEthanol at 96 ° 18 0 g
Sel oentasodique de l'acide diéthylenetπaminopentacetiquε 1 08 gOentasodium salt of diethylenetπaminopentacetic acid 1 08 g
Mé:aoιsulfιte αe sodium en solution aqueuse, à 35 % de M A 0 58 gMé: aoιsulfιte αe sodium in aqueous solution, 35% M A 0 58 g
Ammoniaque à 20 % de NH3 1 0 0 g Il est important de noter que chaque composition tinctoriale contient la même quantité molaire de coupleur ainsi que la même quantité molaire de base d'oxydation, à savoir 3 10"3 moleAmmonia at 20% NH 3 1 0 0 g It is important to note that each dye composition contains the same molar amount of coupler as well as the same molar amount of oxidation base, namely 3 10 "3 moles
n Au moment de l'emploi, on a mélangé chaque composition tinctoriale avec une quantité égale d'une composition oxydante constituée par une solution d'eau oxygénée à 20 volumes (6 % en poids) et présentant un pH d'environ 3n At the time of use, each dye composition was mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3
Chaque mélange obtenu a été appliqué pendant 30 minutes sur deux lots de î o mèches de cheveux gris naturels à 90 % de blancs (lot A et lot B) Les mèches de cheveux ont ensuite été rincées, lavées avec un shampooing standard puis séchéesEach mixture obtained was applied for 30 minutes to two lots of natural gray hair strands with 90% white hairs (lot A and lot B). The hair strands were then rinsed, washed with a standard shampoo and then dried.
La couleur des mèches (lot A et lot B) a ensuite été évaluée dans le système 15 MUNSELL au moyen d'un colonmetre CM 2002 MINOLTA (Norme ASTM D 1535-68)The color of the locks (lot A and lot B) was then evaluated in the MUNSELL system using a CM 2002 MINOLTA colonometer (ASTM standard D 1535-68).
Selon la notation MUNSELL, une couleur est définie par l'expression H V / C dans laquelle les trois paramètres désignent respectivement la teinte ou Hue 0 (H), l'intensité ou Value (V) et la pureté ou Chromaticité (C), la barre oblique de cette expression est simplement une convention et n'indique pas un ratioAccording to the MUNSELL notation, a color is defined by the expression HV / C in which the three parameters respectively designate the hue or Hue 0 (H), the intensity or Value (V) and the purity or Chromaticity (C), the forward slash is just a convention and does not indicate a ratio
Résistance à la permanente :Resistance to perm:
Les mèches de cheveux teintes du lot A ont été soumises à un test de 5 résistance à la permanenteThe locks of hair dyed from batch A were subjected to a test of resistance to perm.
Pour ce faire, les mèches de cheveux du lot A ont été immergées pendant 10 minutes dans une solution de réducteur a raison de 2 g de la solution réductrice suivante par mèche de 1 g 0 Solution réductriceTo do this, the locks of hair from batch A were immersed for 10 minutes in a reducing solution at the rate of 2 g of the following reducing solution per lock of 1 g 0 Reducing solution
- Acide thioglycolique 6,7 g- Thioglycolic acid 6.7 g
- Dithioglycolate de diammonium a 48 % dans l'eau 5,0 g- 48% diammonium dithioglycolate in water 5.0 g
- Agent alca nisant q s pH = 7,9- Agent alca nisant q s pH = 7.9
- Eau déminéralisée q s p 100,0 g- Demineralized water q s p 100.0 g
Apres rinçage, les mèches de cheveux du lot A ont ete immergées pendant 5 minutes dans une solution oxydante (constituée par une solution de peroxyde d'hydrogène a 8 volumes et de pH 3) a raison de 2 g de solution de oxydante par mèche de 1 gAfter rinsing, the locks of hair from batch A were immersed for 5 minutes in an oxidizing solution (consisting of a hydrogen peroxide solution at 8 volumes and of pH 3) at a rate of 2 g of oxidizing solution per lock of 1 g
Les mèches ont ensuite ete rincées a l'eau puis sechees pendant 1 heure a 60 °CThe locks were then rinsed with water and then dried for 1 hour at 60 ° C.
La couleur des mèches de cheveux du lot A a ete ensuite évaluée a nouveau dans le système MUNSELL au moyen d'un coloπmetre CM 2002 MINOLTAThe color of the locks of hair in batch A was then evaluated again in the MUNSELL system by means of a CM 2002 MINOLTA colometer.
La différence entre la couleur de la mèche avant la permanente et la couleur de la mèche aores la permanente a ete calculée en appliquant la formule de NIC ERSONThe difference between the color of the wick before the perm and the color of the wick before the perm was calculated using the NIC ERSON formula
ΔE = 0,4 CoΔH + 6ΔV + 3 ΔCΔE = 0.4 CoΔH + 6ΔV + 3 ΔC
telle que décrite par exemple dans "Couleur, Industrie et Technique" pages 14-17 vol n° 5 , 1978as described for example in "Color, Industry and Technology" pages 14-17 vol n ° 5, 1978
Dans cette formule ΔE représente la différence de couleur entre deux mèches ΔH ΔV et ΔC reDresentent la variation en valeur absolue des paramètres H V et C et Co représente la pureté de la mèche par rapport a laquelle on désire évaluer la différence de couleur La dégradation de couleur (ΔE) est d'autant plus importante que le chiffre indique est élevéIn this formula ΔE represents the difference in color between two wicks ΔH ΔV and ΔC represent the variation in absolute value of the parameters HV and C and Co represents the purity of the wick with respect to which one wishes to evaluate the difference in color The color degradation (ΔE) is all the more important as the figure indicates is high
Les résultats sont donnés dans le tableau I ci-dessousThe results are given in Table I below.
Couleur desColor of
EXEMPLE Couleur des cheveux Dégradation de la cheveux avant après couleur la permanente la permanente ΔH ΔV ΔC ΔEEXAMPLE Hair color Degradation of the hair before after color the perm the perm ΔH ΔV ΔC ΔE
(*) Exemple ne faisant pas partie de l'invention( * ) Example not part of the invention
!0 Ces résultats montrent que les compositions 1 et 3 conformes à l'invention, c'est à dire contenant l'association d'un dérivé de paraphénylènediamine de formule (I) et d'un coupleur de formule (II) conduisent à des colorations résistant beaucoup mieux à la permanente que les colorations obtenues avec les compositions 2 et 4 qui ne font pas partie de l'invention car elles contiennent! 0 These results show that compositions 1 and 3 in accordance with the invention, that is to say containing the combination of a paraphenylenediamine derivative of formula (I) and of a coupler of formula (II) lead to colorings which are much better resistant to perm than the colors obtained with compositions 2 and 4 which are not part of the invention because they contain
15 l'association d'un dérivé de paraphénylènediamine de formule (1) conforme à l'invention et d'un coupleur ne répondant pas à la formule (II) de l'invention Ces compositions 2 et 4 de l'art antérieur sont par exemple décrites dans la demande de brevet FR-A-2 364 88815 the combination of a para-phenylenediamine derivative of formula (1) according to the invention and of a coupler not corresponding to formula (II) of the invention These compositions 2 and 4 of the prior art are by example described in patent application FR-A-2 364 888
o Résistance à la transpiration :o Resistance to perspiration:
Les mèches de cheveux teintes du lot B ont été soumises à un test de résistance à la transpiration Pour ce faire, les mèches de cheveux du lot B ont été immergées dans un cristallisoir recouvert d'un verre de montre et renfermant une solution de sueur synthétique de composition suivante • The locks of hair dyed from batch B were subjected to a test of resistance to perspiration To do this, the batch B hair strands were immersed in a crystallizing dish covered with a watch glass and containing a synthetic sweat solution of the following composition •
- NaCI 1 g- NaCI 1 g
- Hydrogénophosphate de potassium 0, 1 g- Potassium hydrogen phosphate 0, 1 g
- Histidine 0,025 g- Histidine 0.025 g
- Acide lactique q s pH 3,2- Lactic acid q s pH 3.2
- Eau distillée q s p 100 g- Distilled water q s p 100 g
On a laissé séjourner les mèches de cneveux teints du lot B dans cette solution de sueur synthétique pendant 48 heures à 37° C Les mèches ont ensuite été rincées puis séchéesThe dyed hair strands of lot B were allowed to stay in this synthetic sweat solution for 48 hours at 37 ° C. The strands were then rinsed and then dried.
La couleur des mèches du lot B a été ensuite évaluée à nouveau dans le système MUNSELL au moyen d'un coloπmètre CM 2002 MINOLTA de façon a déterminer la dégradation des colorations après ce test de résistance à la transpirationThe color of the locks of batch B was then evaluated again in the MUNSELL system using a CM 2002 MINOLTA coloπmeter so as to determine the degradation of the colorations after this test of resistance to perspiration.
La différence de couleur entre deux mèches (ici, avant et après le traitement simulant une transpiration) a été calculée en appliquant la formule de NICKERSON telle que décrite précédemmentThe difference in color between two locks (here, before and after the treatment simulating sweating) was calculated by applying the NICKERSON formula as described above.
Les résultats sont donnés dans le tableau II ci-après Couleur des Couleur des Dégradation de laThe results are given in Table II below. Color of Color of Degradation of
EXEMPLE cheveux avant cheveux après couleur transpiration transpiration ΔH ΔV I ΔC | ΔEEXAMPLE hair before hair after color perspiration perspiration ΔH ΔV I ΔC | ΔE
Exemple ne faisant pas partie de l'inventionExample not part of the invention
Ces résultats montrent que les compositions 1 et 3 conformes a l'invention, c'est à dire contenant l'association d'un dérive de paraphénylènediamine de formule (I) et d'un coupleur de formule (II) conduisent a des colorations résistant beaucoup mieux a la transpiration que les colorations obtenues avec les comDositions 2 et Λ qui ne font pas partie de l'invention car elles contiennent l'association d'un dérive de paraphénylènediamine de formule (I) conforme a l'invention et d'un coupleur ne répondant pas a la formule (II) de l'invention Ces compositions 2 et 4 de l'art antérieur sont par exemple αecπtes dans la demande de brevet FR-A-2 364These results show that the compositions 1 and 3 in accordance with the invention, that is to say containing the association of a paraphenylenediamine derivative of formula (I) and of a coupler of formula (II) lead to resistant coloring. much better at transpiration than the colorings obtained with comDositions 2 and Λ which are not part of the invention because they contain the association of a paraphenylenediamine derivative of formula (I) in accordance with the invention and of a coupler which does not correspond to the formula (II) of the invention These compositions 2 and 4 of the prior art are, for example, approved in patent application FR-A-2 364
EXEMPLES 5 à 12 DE TEINTUREEXAMPLES 5 to 12 OF DYEING
On a prépare les compositions tinctoriales conformes a l'invention, suivantes (teneurs en grammes) The following dye compositions were prepared in accordance with the invention (contents in grams)
55
--
- -
ιo -ιo -
--
- -
- 15 -- 15 -
--
--
--
- 20 - - 20 -
- Parfum, conservateur q.s- Perfume, preservative q.s
- Ammoniaque à 20 % de NH3 10,0 g - Ammonia at 20% NH 3 10.0 g
Les mèches de cheveux ont été teintes dans les nuances figurant dans le tableau ci-dessousThe locks of hair were dyed in the shades shown in the table below

Claims

REVENDICATIONS
1 Composition pour la teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisée par le fait qu'elle comprend, dans un milieu approprié pour la teinture • 1 Composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a suitable medium for dyeing •
- au moins une base d'oxydation choisie parmi les dérivés de paraphénylènediamine de formule (I) suivante et leurs sels d'addition avec un acideat least one oxidation base chosen from the para-phenylenediamine derivatives of formula (I) below and their addition salts with an acid
dans laquelle in which
- R, représente un atome d'hydrogène, un radical mésyle, carbamoyle ou acétyle,- R, represents a hydrogen atom, a mesyl, carbamoyl or acetyl radical,
- n est un nombre entier compris entre 1 et 4 inclusivement ,- n is an integer between 1 and 4 inclusive,
- au moins un coupleur choisi parmi les composés de formule (II) suivante et leurs sels d'addition avec un acide- at least one coupler chosen from the compounds of formula (II) below and their addition salts with an acid
dans laquelle in which
- R, représente un radical hydroxyle ou un groupement NHR4 ou R désigne un atome d'hydrogène, un radical alkyle en C,-C4 l monohydroxyalkyle en C.-C . ou polyhydroxyalkyle en C,-C4 - R3 représente un atome d'hydrogène, un radical alkyle en C1-C4, alcoxy en C,-C ou un atome d'halogène choisi parmi le chlore, le brome et le fluor , étant entendu que lorsque n = 2, que R, représente un radical mésyle, que R3 représente un radical méthyle en position 6, et que R2 représente un groupement NHR4, alors R. est différent d'un atome d'hydrogène- R, represents a hydroxyl radical or an NHR 4 group or R denotes a hydrogen atom, a C 1 -C 4 alkyl radical, monohydroxyalkyl C 1 -C 4 . or C, -C 4 polyhydroxyalkyl - R 3 represents a hydrogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 alkoxy or a halogen atom chosen from chlorine, bromine and fluorine, it being understood that when n = 2 , that R represents a mesyl radical, that R 3 represents a methyl radical in position 6, and that R 2 represents an NHR 4 group, then R. is different from a hydrogen atom
2. Composition selon la revendication 1 , caractérisée par le fait les dérivés de paraphénylènediamine de formule (I) sont choisis parmi la 2-β-mésylamιnoéthyloxy paraphénylènediamine, la 2-β-uréιdoéthyloxy paraphénylènediamine, la 2-β-acétylamιnoéthyloxy paraphénylènediamine et la 2-β-amιnoethyloxy paraphénylènediamine, et leurs sels d'addition avec un acide2. Composition according to Claim 1, characterized in that the paraphenylenediamine derivatives of formula (I) are chosen from 2-β-mesylamιnoethyloxy paraphenylenediamine, 2-β-ureιdoethyloxy paraphenylenediamine, 2-β-acetylamιnoethyloxy paraphenylenediamine and -β-amιnoethyloxy paraphenylenediamine, and their addition salts with an acid
3 Composition selon la revendication 1 ou 2, caractérisée par le fait que les coupleurs de formule (II) sont choisis parmi le méta-aminophénol, le 5-amιno 2-méthoxy phénol, le 5-amιno 2-(β-hydroxyéthyloxy) phénol, le 5-amιno 2-methyl phénol, le 5-N-(β-hydroxyéthyl)amιno 2-méthyl phénol, le 5-N-(-,'-hydroxypropylamιno) 2-méthyl phénol, le 1 ,3-dιhydroxy benzène, le 2-mεthyl 1 ,3-dιhydroxy benzène, le 4-chloro 1 ,3-dιhydroxy benzène, et leurs sels d'addition avec un acide3 Composition according to claim 1 or 2, characterized in that the couplers of formula (II) are chosen from meta-aminophenol, 5-amιno 2-methoxy phenol, 5-amιno 2- (β-hydroxyethyloxy) phenol , 5-amιno 2-methyl phenol, 5-N- (β-hydroxyethyl) amιno 2-methyl phenol, 5-N - (-, '- hydroxypropylamιno) 2-methyl phenol, 1, 3-dιhydroxy benzene , 2-methyl 1, 3-dιhydroxy benzene, 4-chloro 1, 3-dιhydroxy benzene, and their addition salts with an acid
4 Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que les sels d'addition avec un acide sont choisis parmi les chlorhydrates, les bromhydrates, les sulfates et les tartrates4 Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulfates and tartrates
5 Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que le ou les dérives de paraphénylènediamine de formule (I) et/ou leur(s) sels d'addition avec un acide représentent de 0 0005 à 10 % en Doids du poids total de la composition tinctoriale 6 Composition selon la revendication 5, caractérisée par le fait que le ou les dérives de paraphénylènediamine de formule (I) et/ou leur(s) sels d'addition avec un acide représentent de 0,05 a 7 % en poids du poids total de la composition tinctoriale5 Composition according to any one of the preceding claims, characterized in that the paraphenylenediamine derivative (s) of formula (I) and / or their addition salt (s) with an acid represent from 0 0005 to 10% in Weight of the total weight of the dye composition 6 Composition according to Claim 5, characterized in that the paraphenylenediamine derivative (s) of formula (I) and / or their addition salt (s) with an acid represent from 0.05 to 7% by weight of the total weight of the dye composition
7 Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que le ou les coupleurs de formule (II) et/ou leur(s) sels d'addition avec un acide représentent de 0,0001 a 5 % en poids du poids total de la composition tinctoriale7 Composition according to any one of the preceding claims, characterized in that the coupler (s) of formula (II) and / or their addition salt (s) with an acid represent from 0.0001 to 5% by weight of the total weight of the dye composition
1010
8 Composition selon la revendication 7 caractérisée par le fait le ou les coupleurs de formule (II) et/ou leur(s) sels d'addition avec un acide représentent de 0 005 a 3 % en poids du poids total de la composition tinctoriale8 Composition according to Claim 7, characterized in that the coupler (s) of formula (II) and / or their addition salt (s) with an acid represent from 0 005 to 3% by weight of the total weight of the dye composition
b 9 Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait que ledit milieu approprie pour la teinture est constitue par de l'eau ou par un mélange d'eau et d'au moins un solvant organique choisi parmi les alcanols inférieurs en C-1 -C4 le glycerol les glycols et ethers de glycols les alcools aromatiques les produits analogues et leurs mélanges 0b 9 Composition according to any one of the preceding claims, characterized in that the said medium suitable for dyeing is constituted by water or by a mixture of water and at least one organic solvent chosen from lower alkanols in C-1 -C4 glycerol glycols and glycol ethers aromatic alcohols analogues and their mixtures 0
10 Composition selon l'une quelconque des revendications précédentes caractérisée par le fait qu'elle présente un pH compris entre 5 et 1210 Composition according to any one of the preceding claims, characterized in that it has a pH of between 5 and 12
1 1 Composition selon l'une quelconque des revendications précédentes ^ caractérisée par le fait qu'elle contient en outre d autres bases d oxydation différentes αes dérives de paraphénylènediamine de formule (I) et de leurs sels d addition avec un acide et/ou d'autres coupleurs différents des coupleurs de formule (I I) et de leurs sels d addition avec un acide et/ou des colorants directs1 1 Composition according to any one of the preceding claims ^ characterized in that it also contains other oxidation bases different αes derivatives of paraphenylenediamine of formula (I) and their addition salts with an acid and / or d other couplers other than the couplers of formula (II) and their addition salts with an acid and / or direct dyes
i 12 Drocede de teinture des fibres keratiniαues et en particulier des tiores kératiniques humaines telles que les cneveux caractérise par le tait αue I on applique sur ces fibres une composition tinctoriale telle que définie a l'une quelconque des revendications 1 à 1 1 et que l'on révèle la couleur à pH acide, neutre ou alcalin à l'aide d'un agent oxydant qui est ajoute juste au moment de l'emoloι à la composition tinctoriale ou qui est présent dans une composition 5 oxydante appliquée simultanément ou séquentiellement de façon séparéei 12 D rocede keratiniαues for dyeing fibers and in particular human keratin tiores such as cneveux was characterized by αue I is apply to these fibers a dye composition as defined in any one of claims 1 to 1 1 and that the color is revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just to the moment of emoloι to the dye composition or which is present in an oxidizing composition 5 applied simultaneously or sequentially separately
13 Procédé selon la revendication 12, caractérisé par le fait que l'agent oxydant présent dans la composition oxydante est choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels tels que les13 The method of claim 12, characterized in that the oxidizing agent present in the oxidizing composition is chosen from hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as
I O perborates et persulfatesI O perborates and persulfates
14 Dispositif a plusieurs compartiments ou "kit" de teinture a plusieurs compartiments dont un premier compartiment renferme une composition tinctoriale telle que définie à l'une quelconque des revendications 1 a 1 1 et un14 Multi-compartment device or multi-compartment dyeing "kit", a first compartment of which contains a dye composition as defined in any one of claims 1 to 1 1 and a
I 5 second compartiment renferme une composition oxydante comprenant un agent oxydant I 5 second compartment contains an oxidizing composition comprising an oxidizing agent
EP97912242A 1996-11-07 1997-10-23 Composition de teinture d'oxydation des fibres keratiniques comprenant un derive de paraphenylenediamine et procede de teinture mettant en oeuvre cette composition Withdrawn EP0954275A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9613600A FR2755365B1 (en) 1996-11-07 1996-11-07 KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
FR9613600 1996-11-07
PCT/FR1997/001901 WO1998019662A1 (en) 1996-11-07 1997-10-23 Oxidation dyeing composition for keratinous fibers containing a paraphenylenediamine derivative and dyeing method using same

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EP0954275A1 true EP0954275A1 (en) 1999-11-10

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EP97912242A Withdrawn EP0954275A1 (en) 1996-11-07 1997-10-23 Composition de teinture d'oxydation des fibres keratiniques comprenant un derive de paraphenylenediamine et procede de teinture mettant en oeuvre cette composition

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EP (1) EP0954275A1 (en)
JP (1) JP3293634B2 (en)
AR (1) AR009405A1 (en)
AU (1) AU4950697A (en)
CA (1) CA2270576A1 (en)
FR (1) FR2755365B1 (en)
WO (1) WO1998019662A1 (en)

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US6040482A (en) * 1999-03-05 2000-03-21 Milliken & Company Oxyalkylene-substituted aminophenol intermediate
WO2022203601A1 (en) * 2021-03-24 2022-09-29 National University Of Singapore Compounds useful as hair dyes

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FR2364888A1 (en) 1976-09-17 1978-04-14 Oreal NEW PARAPHENYLENEDIAMINES SUBSTITUTED ON THE CORE IN POSITION 2 AND THEIR APPLICATION IN THE DYING OF KERATINIC FIBERS
CH661501A5 (en) 1982-01-26 1987-07-31 Oreal COMPOUNDS DERIVATIVE FROM AMINO-3 PROPANOL-2 FOR USE IN DYEING HAIR, PREPARATION METHOD THEREOF, DYE COMPOSITION CONTAINING THE SAME, AND HAIR DYEING METHOD THEREOF.
FR2586913B1 (en) 1985-09-10 1990-08-03 Oreal PROCESS FOR FORMING IN SITU A COMPOSITION CONSISTING OF TWO SEPARATELY PACKED PARTS AND DISPENSING ASSEMBLY FOR THE IMPLEMENTATION OF THIS PROCESS
FR2707488B1 (en) 1993-07-13 1995-09-22 Oreal Keratin fiber oxidation dye composition comprising a para-aminophenol, a meta-aminophenol and a paraphenylenediamine and / or a bis-phenylalkylenediamine.
FR2707489B1 (en) 1993-07-13 1995-09-22 Oreal Keratin fiber oxidation dye composition comprising a para-aminophenol, 2-methyl 5-aminophenol and a paraphenylenediamine and / or a bis-phenylalkylenediamine.
FR2715297B1 (en) 1994-01-24 1996-02-23 Oreal A keratin fiber oxidation dye composition comprising a paraphenylenediamine derivative and a metaaminophenol derivative, and a dyeing process using such a composition.
FR2715296B1 (en) 1994-01-24 1996-04-12 Oreal Keratin fiber oxidation dyeing composition comprising a paraphenylenediamine, a metalphenylenediamine and a para-aminophenol or a meta-aminophenol, and dyeing process using such a composition.
FR2715295B1 (en) 1994-01-24 1996-04-12 Oreal A keratin fiber oxidation dye composition comprising a paraphenylenediamine derivative and a metaphenylenediamine derivative, and dyeing process using such a composition.
FR2715298B1 (en) 1994-01-24 1996-02-23 Oreal Composition for dyeing oxidation of keratin fibers comprising a derivative of paraphenylenediamine and 5-amino 2-methyl phenol, and dyeing process using such a composition.

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Title
See references of WO9819662A1 *

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AR009405A1 (en) 2000-04-12
JP2000504345A (en) 2000-04-11
CA2270576A1 (en) 1998-05-14
AU4950697A (en) 1998-05-29
FR2755365B1 (en) 1999-08-06
JP3293634B2 (en) 2002-06-17
US6440176B2 (en) 2002-08-27
US20020013969A1 (en) 2002-02-07
FR2755365A1 (en) 1998-05-07

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