DYE COMPOSITION COMPRISING A PARA-PHENYLENEDIAMINE OXIDATION BASE AND AN AMPHOTERIC OR CATIONIC POLYMER IN A MEDIUM RICH IN FATTY SUBSTANCES

Abstract

The present invention relates to a composition for dyeing keratin fibres, in particular keratin fibres such as the hair, comprising: a) at least one oxidation base 3-(2,5-diaminophenyl)-1-propanol and/or acid salts thereof and/or solvates thereof such as hydrates; b) at least one coupler; c) at least one polymer chosen from cationic polymers and amphoteric polymers, and mixtures thereof; d) at least one fatty substance; the total amount of fatty substances being at least 10%, e) optionally at least one basifying agent; and f) optionally at least one chemical oxidizing agent. The invention also relates to a process for dyeing keratin fibres such as the hair using the composition of the invention, and to a multi-compartment device for using the composition of the invention.

Claims

1. Composition comprising: a) at least one oxidation base 3-(2,5-diaminophenyl)-1-propanol and/or acid salts thereof and/or solvates thereof such as hydrates; b) at least one coupler; c) at least one polymer chosen from cationic polymers and amphoteric polymers, and mixtures thereof; d) at least one fatty substance; the total amount of fatty substances being at least 10% by weight relative to the total weight of the composition, e) optionally at least one basifying agent; and f) optionally at least one chemical oxidizing agent.

2. Composition according to the preceding claim, in which the oxidation base(s) chosen from 3-(2,5-diaminophenyl)-1-propanol, acid salts thereof or solvates thereof are present in an amount ranging from 0.0001% to 20% by weight, preferably from 0.005% to 10% by weight and in particular from 0.01% to 10% by weight relative to the total weight of the composition.

3. Composition according to either of the preceding claims, in which the coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

4. Composition according to any one of the preceding claims, characterized in that the cationic polymers are chosen from polymers whose cationic charge is greater than or equal to 4 meq/g and preferably chosen from the following families: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulae (I) to (III) below: ##STR00017## in which: R.sub.3, which may be identical or different, denote a hydrogen atom or a CH.sub.3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R.sub.4, R.sub.5 and R.sub.6, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical; R.sub.1 and R.sub.2, which may be identical or different, represent hydrogen or an alkyl group containing from 1 to 6 carbon atoms; X.sup.− denotes an anion derived from a mineral or organic acid, (2) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers comprising, as constituent of the chain, units corresponding to formula (V) or (VI): ##STR00018## in which formulae k and t are equal to 0 or 1, the sum k+t being equal to 1; R.sub.12 denotes a hydrogen atom or a methyl radical; R.sub.10 and R.sub.11, independently of each other, denote an alkyl group containing from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably contains 1 to 5 carbon atoms, or a lower (C.sub.1-C.sub.4) amidoalkyl group, or R.sub.10 and R.sub.11 may denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; Y.sup.− is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate, R.sub.10 and R.sub.11, independently of each other, preferably denote an alkyl group containing from 1 to 4 carbon atoms, (3) quaternary polymers of vinylpyrrolidone and of vinylimidazole, (4) the quaternary diammonium polymer containing repeating units corresponding to the formula: ##STR00019## in which formula (VII): R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms, or C1-C6 lower hydroxyalkyl aliphatic radicals, or else R13, R14, R15 and R16, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second heteroatom other than the nitrogen, or else R13, R14, R15 and R16 represent a linear or branched C.sub.1-C.sub.6 alkyl radical which is substituted with a nitrile, ester, acyl, amide or —CO—O—R17-D or —CO—NH—R17-D group in which R17 is an alkylene and D is a quaternary ammonium group; A.sub.1 and B.sub.1 represent polymethylene groups containing from 2 to 20 carbon atoms, which groups may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X.sup.− denotes an anion derived from a mineral or organic acid; A.sub.1, R13 and R15 may form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A.sub.1 denotes a saturated or unsaturated, linear or branched alkylene or hydroxyalkylene radical, B.sub.1 may also denote a group (CH2)n-CO-D-OC—(CH2)p- in which: n and p, which may be identical or different, are integers ranging from 2 to 20 approximately, D denotes: a) a glycol residue of formula: —O-Z-O—, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae:
—(CH.sub.2—CH.sub.2—O).sub.x—CH.sub.2—CH.sub.2—
—[CH.sub.2—CH(CH.sub.3)—O].sub.y—CH.sub.2—CH(CH.sub.3)— where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue, such as a piperazine derivative; c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the divalent radical
—CH.sub.2—CH.sub.2—S—S—CH.sub.2—CH.sub.2—; d) a ureylene group of formula: —NH—CO—NH—, (5) polyquaternary ammonium polymers formed from units of formula (VIII): ##STR00020## in which formula: R22, R23, R24 and R25, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or —CH2CH2(OCH2CH2)pOH radical, in which p is equal to 0 or to an integer between 1 and 6, with the proviso that R22, R23, R24 and R25 do not simultaneously represent a hydrogen atom, t and u, which may be identical or different, are integers between 1 and 6, v is equal to 0 or to an integer between 1 and 34, X.sup.− denotes an anion such as a halide, A denotes a radical of a dihalide or represents preferably —CH2-CH2-O—CH2-CH2-, (6) polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives, and mixtures thereof.

5. Composition according to claim 4, in which the cationic polymer(s), preferably with a charge density of greater than or equal to 4 meq/g, are chosen from families (2) and (4), in particular cationic cyclopolymers, polymers containing units of formula (VII), and mixtures thereof, preferably from dimethyldiallylammonium chloride homopolymers and hexadimethrine chloride.

6. Composition according to one of the preceding claims, characterized in that the amphoteric polymer(s) are chosen from the following compounds: (1) polymers comprising as monomers at least one monomer derived from a vinyl compound carrying a carboxyl group, preferably acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and at least one basic monomer derived from a substituted vinyl compound containing at least one basic atom, chosen from the following: a) dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylates, dialkylaminoalkylmethacrylamides and dialkylaminoalkylacrylamides, b) trialkylaminoalkyl methacrylate salts and trialkylaminoalkyl acrylate salts, and salts of trialkylaminoalkylmethacrylamide and of trialkylaminoalkylacrylamide, (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides and methacrylamides substituted on the nitrogen with an alkyl radical preferably containing from 2 to 12 carbon atoms, b) at least one acidic comonomer containing one or more reactive carboxylic groups, preferably chosen from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, containing 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides, c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate, (3) copolymers comprising as monomers at least one monomer derived from a vinyl compound bearing a carboxylic group, such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and at least one monomer of diallyldialkylammonium salt type, the alkyl groups containing from 1 to 6 carbon atoms; (4) crosslinked and alkylated polyamino amides partially or totally derived from polyamino amides of general formula: ##STR00021## in which R10 represents a divalent radical derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol containing 1 to 6 carbon atoms of these acids, or a radical derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine, and Z denotes a radical derived from a bis(primary), mono- or bis(secondary) polyalkylene-polyamine and preferably represents: a) in proportions of from 60 to 100 mol %, the radical: ##STR00022## where x=2 and p=2 or 3, or else x=3 and p=2, this radical being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine; b) in proportions of from 0 to 40 mol %, the radical (X) above in which x=2 and p=1 and which is derived from ethylenediamine, or the radical derived from piperazine: ##STR00023## c) in proportions of 0 to 20 mol %, the radical —NH—(CH2)6-NH— derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a difunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, and being alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or salts thereof, (5) polymers comprising zwitterionic units of formula: ##STR00024## in which R11 denotes a polymerizable unsaturated group, such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R12 and R13 represent a hydrogen atom, methyl, ethyl or propyl, and R14 and R15 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R14 and R15 does not exceed 10, (6) polymers derived from chitosan comprising monomer units corresponding to the following formulae: ##STR00025## unit D being present in proportions of between 0 and 30%, unit E in proportions of between 5% and 50% and unit F in proportions of between 30% and 90%, it being understood that, in this unit F, R16 represents a radical of formula: ##STR00026## in which, if q=0, R17, R18 and R19, which may be identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue that are optionally interrupted with one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the radicals R17, R18 and R19 being, in this case, a hydrogen atom; or, if q=1, R17, R18 and R19 each represent a hydrogen atom, and also the salts formed by these compounds with bases or acids; (7) polymers derived from the N-carboxyalkylation of chitosan; (8) polymers containing units corresponding to the general formula (XII): ##STR00027## in which R20 represents a hydrogen atom, a CH3O, CH3CH2O or phenyl group, R21 denotes a hydrogen atom or a lower alkyl radical such as methyl or ethyl, R22 denotes a hydrogen atom or a lower alkyl radical such as methyl or ethyl, R23 denotes a lower alkyl radical such as methyl or ethyl or a radical corresponding to the formula: —R24-N(R22)2, R24 representing a —CH2-CH2-, —CH2-CH2-CH2- or —CH2-CH(CH3)- group, R22 having the meanings mentioned above, and also the higher homologues of these radicals, containing up to 6 carbon atoms; (9) amphoteric polymers of the -D-X-D-X— type chosen from: a) polymers obtained by reaction of chloroacetic acid or sodium chloroacetate with compounds comprising at least one unit of formula:
-D-X-D-X-D-   (XIII) where D denotes a radical ##STR00028## and X denotes the symbol E or E′, E or E′, which may be identical or different, denote a divalent radical that is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can comprise, in addition to the oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups, b) polymers of formula:
-D-X-D-X—  (XIV) where D denotes a radical ##STR00029## and X denotes the symbol E or E′ and at least once E′; E having the meaning given above and E′ is a divalent radical that is an alkylene radical bearing a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl radicals and comprising one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain that is optionally interrupted with an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate, (10) (C1-C5)alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an N,N-dialkylaminoalkylamine or by semiesterification with an N,N-dialkanolamine; and mixtures thereof.

7. Composition according to any one of the preceding claims, characterized in that the amphoteric polymer(s) are chosen from acrylic acid/acrylamidopropyltrimethylammonium chloride copolymers, acrylic acid/acrylamidopropyltrimethylammonium chloride/acrylamide copolymers, copolymers comprising dimethyldiallylammonium chloride and acrylic acid as monomers optionally combined with acrylamide, and mixtures thereof, preferably from acrylic acid/acrylamidopropyltrimethylammonium chloride copolymers.

8. Composition according to any one of the preceding claims, in which the polymer(s) chosen from cationic polymers and amphoteric polymers represent from 0.01% to 10%, better still from 0.05% to 7% and even more preferentially from 0.1% to 5% by weight relative to the total weight of the composition.

9. Composition according to one of the preceding claims, characterized in that the fatty substance(s) are chosen from C.sub.6-C.sub.16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides and plant waxes, non-silicone waxes and silicones, and mixtures thereof.

10. Composition according to any one of the preceding claims, characterized in that the fatty substance(s) are liquid at room temperature and at atmospheric pressure, and are preferably non-silicone-based.

11. Composition according to any one of the preceding claims, characterized in that the fatty substances are chosen from C.sub.6-C.sub.16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, triglycerides, fatty alcohols, esters of fatty acids and/or of fatty alcohols other than triglycerides, or mixtures thereof, and preferably from liquid petroleum jelly, polydecenes, liquid fatty alcohols, liquid esters of fatty acids and/or of fatty alcohols, or mixtures thereof.

12. Composition according to any one of the preceding claims, characterized in that the content of fatty substances ranges from 15% to 80% by weight, preferably from 25% to 75% by weight, in particular from 30% to 70% by weight and advantageously from 30% to 60% by weight relative to the total weight of the composition.

13. Composition according to any one of the preceding claims, which comprises at least one basifying agent chosen from ammonia, alkali metal carbonates or bicarbonates, sodium hydroxide or potassium hydroxide, organic amines chosen from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (II), or mixtures thereof: ##STR00030## in which formula (II) W is a divalent C.sub.1-C.sub.6 alkylene radical optionally substituted with one or more hydroxyl groups or a C.sub.1-C.sub.6 alkyl radical, and/or optionally interrupted with one or more heteroatoms such as O, or NR.sub.u; R.sub.x, R.sub.y, R.sub.z, R.sub.t and R.sub.u, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 hydroxyalkyl or C.sub.1-C.sub.6 aminoalkyl radical.

14. Composition according to any one of the preceding claims, in which the basifying agent is chosen from ammonia or alkanolamines, preferably monoethanolamine, and neutral or ionic amino acids.

15. Composition according to any one of the preceding claims, which comprises a chemical oxidizing agent, preferably hydrogen peroxide.

16. Process for dyeing keratin fibres, in particular the hair, comprising the application to the keratin fibres of the composition as defined according to any one of the preceding claims.

17. Process according to the preceding claim, in which the composition as described according to any one of claims 1 to 15 is obtained by mixing at least two compositions, a first composition (A) which comprises the oxidation base 3-(2,5-diaminophenyl)-1-propanol and/or acid salts thereof or solvates thereof, and a second composition (B) which comprises at least one chemical oxidizing agent, it being understood that: at least one of the compositions (A) or (B) comprises the polymer chosen from cationic polymers, amphoteric polymers and mixtures thereof, and at least one fatty substance, such that the fatty substance content of the composition resulting from the mixing of compositions (A) and (B) is at least 10%, preferably greater than 25%, preferably greater than 30% by weight, relative to the weight of the composition derived from the mixing of (A) and (B).

18. Process according to claim 17, in which the composition applied to the fibres is obtained from composition (A), from composition (B) and from a third composition at least partly comprising the fatty substance(s), this third composition preferably being anhydrous.

19. Multi-compartment device comprising a first compartment containing composition (A) which comprises the oxidation base 3-(2,5-diaminophenyl)-1-propanol and/or an acid salt or solvate thereof, and a second compartment containing composition (B) which comprises at least one chemical oxidizing agent, it being understood that at least one of the compositions (A) or (B) comprises the polymer(s) chosen from cationic polymers, amphoteric polymers and mixtures thereof, and at least one fatty substance, such that the fatty substance content of the composition resulting from the mixing of compositions (A) and (B) is at least 10%, preferably greater than 25%, preferably greater than 30% by weight, relative to the weight of the composition derived from the mixing of (A) and (B).

Description

EXAMPLE

Example 1

[0277] The following compositions have been prepared in which the amounts are expressed in grams of active materials.

[0278] Dye Compositions (g %)

TABLE-US-00001 Chemical name A B Sodium metabisulfite 0.45 0.45 Monoethanolamine 5.83 5 Ethylenediaminetetraacetic acid 0.2 0.2 1-Methyl-2-hydroxy-4-β- 0.22 hydroxyethylaminobenzene 1-β-Hydroxyethyloxy-2,4-diaminobenzene 0.031 dihydrochloride 2-Methyl-1,3-dihydroxybenzene (2- 0.3 methylresorcinol) 1-3-Dihydroxybenzene (resorcinol) 0.96 1-Hydroxy-3-aminobenzene 0.15 Purified 5-amino-6-chloro-o-cresol 0.25 2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2- 1.2 a]pyrazol-1-one dimethanesulfonate 2-[(3-Aminopyrazolo[1,5-a]pyridin-2- 0.13 yl)oxy]ethanol hydrochloride 3-(2,5-Diaminophenyl)propan-1-ol hydrochloride 2.5 0.2 Mineral oil (petroleum jelly)° 60 60 Polyquaternium-67 (Softcat Polymer SL-100 from 0.19 0.19 Amerchol) Deionized water 17.069 19.47 Oxyethylenated stearyl alcohol (2 OE) 1.13 1.13 Oxyethylenated stearyl alcohol (20 OE) 3.88 3.88 (50/50 C.sub.8/C.sub.10) Alkyl (2)-polyglucoside as a 60% 2.4 2.4 aqueous solution (Oramix CG 110 from SEPPIC) Oxyethylenated sorbitan monolaurate (4 OE) 2.4 2.4 Vitamin C 0.25 0.25

[0279] Oxidizing Composition C (g %)

TABLE-US-00002 C Pentasodium pentetate 0.06 Hydrogen peroxide 6 Sodium stannate 0.04 Phosphoric acid qs pH = 2.2 Tetrasodium pyrophosphate 0.03 Mineral oil (petroleum jelly) 20 Hexadimethrine chloride (Mexomere PO from 0.15 Chimex) Polyquaternium-6 (Merquat-100 from Nalco) 0.2 Water qs 100 Glycerol 0.5 Cetearyl alcohol 6 Steareth-20 5 PEG-4 Rapeseedamide 1.2 Tocopherol 0.1

[0280] At the time of use, each of the compositions A and B is mixed with one time its own weight of oxidizing composition C.

[0281] The mixtures thus obtained are applied to natural hair containing 90% white hairs.

[0282] After a leave-on time of 35 minutes at room temperature, the hair is rinsed and washed with a standard shampoo.

[0283] After drying, a beautiful light-chestnut shade is obtained on the hair with formula A and a natural coppery-red dark blond shade is obtained with formula B.

Example 2

[0284] The following compositions have been prepared in which the amounts are expressed in grams of active materials.

TABLE-US-00003 B′ B″ invention comparative Sodium metabisulfite 0.45 0.45 Monoethanolamine 4 4 Ethylenediaminetetraacetic acid 0.2 0.2 6 HYDROXY BENZOMORPHOLINE 0.04 0.04 1-BETA-HYDROXYETHYLOXY-2,4- 0.16 0.16 DIAMINOBENZENE 2 Hcl 2-METHYL-1,3-DIHYDROXYBENZENE 0.17 0.17 (2-METHYL RESORCINOL) Para aminophenol 0.13 0.13 1,3-DIHYDROXYBENZENE 0.21 0.21 (RESORCINOL) 1-HYDROXY-3-AMINO-BENZENE 0.16 0.16 3-(2,5-DIAMINOPHENYL)PROPAN- 4.18 × 10.sup.−3 — 1-OL HCl mol 2-2 hydroxyethyl para phenylenediamine — 4.18 × 10.sup.−3 mol MINERAL OIL 60 60 PERFUME 0.72 0.72 Cationic Hydroxyethylcellulose 0.19 am* 0.19 am (Polyquaternium-67) SOFTCAT SL-100 WATER qs qs Oxyethylenated stearyl alcohol 1.13 1.13 (2 OE) Oxyethylenated stearyl alcohol 3.88 3.88 (20 OE) (50/50 C.sub.8/C.sub.10) Alkyl (2)-polyglucoside 2.4 am  2.4 am as a 60% aqueous solution (Oramix CG 110 from SEPPIC) Oxyethylenated sorbitan monolaurate 2.4 2.4 (4 OE) Vitamin C 0.25 0.25 *Active material

[0285] At the time of use, each composition B′ and B″ is mixed with the oxidizing composition C of example 1 at a weight ratio of 1/1.

[0286] The resulting mixture are each applied on natural hair locks (BN), which represents the hair root, and permed hair locks (BP), which represents the hair tips, in an amount of 10 g of composition per 1 g of hair, and left for 35 minutes at room temperature (25° C.).

[0287] Then the hair was rinsed with water, washed with the “Pro Classics concentrated” shampoo (L'Oréal Professionnel), diluted at 10%, and dried.

[0288] Selectivity Evaluation

[0289] The color of the hair was determined using the CIE L*a*b* system with a Minolta CM2006D spectrophotometer (illuminant D65, angle 10°, specular component included) in the CIELab system.

[0290] According to this system, L* indicates the lightness of the color of the hair.

[0291] The chromaticity coordinates are expressed by the parameters a* and b*, a* indicating the axis of red/green shades and b* the axis of yellow/blue shades.

[0292] The selectivity of the dyeing is measured by calculating the variation of ΔE according to the formula:

ΔE=√{square root over ((L*−L.sub.0*).sup.2+(a*−a.sub.0*).sup.2+(b*−b.sub.0*).sup.2)}

[0293] In which L, a* and b* represent the values measured on medium sensibilized hair and L0*, a0* and b0* represent the values measured on highly sensibilized hair.

[0294] The selectivity is represented by the difference of color between the colored natural hair and sensibilized hair: the more is the ΔE value, the more the difference of color between natural and sensibized hair is important, which is representative of the homogeneity of the coloration between the raw and the tips along the lock of hair.

[0295] The following results are obtained:

TABLE-US-00004 Hair type L* a* b* ΔE B′ + C BN 22.14 1.16 0.36 3.85 (invention) BP 18.39 0.54 −0.24 B″ + C BN 26.24 2.18 2.04 5.94 (comparative) BP 20.64 1.28 0.28

[0296] The mixtures B′+C according to the invention provide less selective colorations (lower ΔE value) than the mixture of compositions B″+C (comparative): the difference between the raw and the tips is lower with B′+C than with B″+C: the coloration along the lock of hair is more homogenous with B′+C.

Example 3

[0297] The following compositions have been prepared in which the amounts are expressed in grams of active materials.

TABLE-US-00005 D D′ (inv) (comp) Ethanolamine 4 4 SODIUM LAURYL ETHER 2.5 2.5 SULFATE (2.2 OE) 28% in aqueous solution HYDROXYETHYL CELLULOSE 2.5 2.5 (PM: 1.300.000) Vitamine C 0.5 0.5 1-METHYL-2-HYDROXY-4- 0.5 0.5 BETA HYDROXYETHYL- AMINOBENZENE 1-METHYL-2-HYDROXY-4- 0.5 0.5 AMINO-BENZENE 1,3-DIHYDROXYBENZENE 0.2 0.2 (RESORCINOL) 2,3-DIAMINO-6,7-DIHYDRO- 4.04 .Math. 10.sup.−3 4.04 .Math. 10.sup.−3 1H,5H- PYRAZOLO[1,2- mol mol A]PYRAZOL-1-ONE DIMETHANESULFONATE 3-(2,5-DIAMINOPHE- 3.43 × 10.sup.−3 — NYL)PROPAN-1-OL- mol HYDROCHLORIDE 2-2 hydroxyethyl para 3.43 × 10.sup.−3 phenylenediamine mol SEQUESTRANT 2 2 Coco-betaine 3 am 3 am REDUCING AGENT 0.5 0.5 Oxyethylenated stearyl 0.1 0.1 alcohol (2 OE) Oxyethylenated stearyl 0.1 0.1 alcohol (20 OE) Mineral oil 60 60 PEG-40 hydrogenated 1 1 castor oil Water Qsp 100 Qsp 100

[0298] Oxidizing Composition E (g %)

TABLE-US-00006 E Hydrogen peroxide 6 Etidronic acid teratrasodic salt in aqueous solution 0.2 (30%) Tetrasodium pyrophosphate 0.04 Sodium salicylate 0.035 DIMETHYL DIALLYL AMMONIUM CHLORIDE/ 0.74 ACRYLIC ACID COPOLYMER (80/20) as a 60% aqueous solution in water (Merquat 280) Caprylyl/capryl polyglucoside as a 60% aqueous 3 solution Water qs 100 Glycerol 4

[0299] At the time of use, each composition D and D′ is mixed with the oxidizing composition E of example 1 at a weight ratio of 1/1.

[0300] The resulting mixture are each applied on natural hair locks (BN), which represents the hair root, and permed hair locks (BP), which represents the hair tips, in an amount of 10 g of composition per 1 g of hair, and left for 35 minutes at room temperature (25° C.).

[0301] Then the hair was rinsed with water, washed with the “Pro Classics concentrated” shampoo (L'Oréal Professionnel), diluted at 10%, and dried.

[0302] The selectivity is evaluated according to the protocole of example 2.

[0303] The following results are obtained:

TABLE-US-00007 Hair type L* a* b* ΔE D + E BN 26.87 15.16 10.56 9.32 (inv) BP 20.95 10.57 5.02 D′ + E BN 29.58 18.40 13.71 12 (comp) BP 21.81 12.78 6.49

[0304] The mixtures D+E according to the invention provide less selective colorations (lower ΔE value) than the mixture of compositions D′+E (comparative): the difference between the raw and the tips is lower with D+E than with D′+E: the coloration along the lock of hair is more homogenous with D+E.