Hair dyeing method employing at least one ortho-diphenol, one titanium derivative and one carboxylic acid

Abstract

The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers, such as the hair, in which the said fibers are treated starting from one or more cosmetic compositions comprising a) one or more ortho-diphenol(s), b) one or more inorganic titanium salt(s) or alkoxytitanium(s), c) one or more acid(s) and d) optionally one or more chemical oxidizing agent(s), such as hydrogen peroxide or one or more hydrogen peroxide generating system(s).

Claims

1. A method for dyeing keratinous fibers, the method comprising: applying to the fibers: a) a first composition comprising at least one ortho-diphenol; b) a second composition comprising at least one inorganic titanium salt or alkoxytitanium; c) a third composition comprising at least one carboxylic acid chosen from those of formula (I) below or salts thereof: ##STR00012## wherein: A is chosen from a saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon group, monovalent when n is zero or polyvalent when n is greater than or equal to 1, comprising from 1 to 50 carbon atoms which is optionally interrupted with at least one heteroatom and/or optionally substituted; or a monovalent (C.sub.1-C.sub.6)alkyl group or a polyvalent (C.sub.1-C.sub.6)alkylene group optionally substituted with at least one hydroxyl group; and n is an integer ranging from 0 to 10; and d) optionally, a fourth composition comprising at least one chemical oxidizing agent; wherein at least one composition chosen from the first composition, the second composition, the third composition, or the fourth composition has an acidic pH.

2. The method according to claim 1, wherein the at least one ortho-diphenol comprises an aromatic ring chosen from benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochroman, chromene, isochromene, quinoline, tetrahydroquinoline, or isoquinoline, wherein the aromatic ring comprises at least two hydroxyl groups carried by two contiguous adjacent atoms of the aromatic ring.

3. The method according to claim 1, wherein the at least one ortho-diphenol chosen from those of formula (II) below, or oligomers, tautomers, optical isomers, geometrical isomers, salts, solvates, or hydrates thereof: ##STR00013## wherein: R.sup.1 to R.sup.4, which are identical or different, are chosen from: i) hydrogen, ii) halogen atoms, iii) hydroxyl groups, iv) carboxyl groups, v) (C.sub.1-C.sub.20)alkyl carboxylate or (C.sub.1-C.sub.20)alkoxycarbonyl groups, vi) optionally substituted amino groups, vii) optionally substituted linear or branched (C.sub.1-C.sub.20)alkyl groups, viii) optionally substituted linear or branched (C.sub.2-C.sub.20)alkeny groups, ix) optionally substituted cycloalkyl groups, x) (C.sub.1-C.sub.20)alkoxy groups, xi) (C.sub.1-C.sub.20)alkoxy(C.sub.1-C.sub.20)alkyl groups, xii) (C.sub.1-C.sub.20)alkoxyaryl groups, xiii) aryl groups which can optionally be substituted, xiv) aryl groups, xv) substituted aryl groups, xvi) heterocyclic groups which are saturated or unsaturated, optionally bearing a cationic or anionic charge and which are optionally substituted and/or optionally condensed with an aromatic ring, the aromatic ring optionally substituted, or xvii) radical groups comprising at least one silicon atom; or or, optionally: two of the substituents carried by two adjacent carbon atoms R.sup.1-R.sup.2, R.sup.2-R.sup.3 or R.sup.3-R.sup.4 optionally form, together with the carbon atoms carrying them, a saturated or unsaturated, aromatic or non-aromatic ring optionally comprising at least one heteroatom and optionally fused with at least one saturated or unsaturated ring optionally comprising at least one heteroatom; or R.sup.1 to R.sup.4 together form from one to four rings; or R.sup.2 and R.sup.3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring carrying the two hydroxyls.

4. The method according to claim 1, wherein the at least one ortho-diphenol derivative is chosen from: flavanols, catechin, epicatechin gallate, or quercetin; anthocyanidins, cyanidin, delphinidin, or petunidin; anthocyanins, anthocyans, or myrtillin; ortho-hydroxybenzoates or gallic acid salts; flavones or luteolin; hydroxystilbenes or 3,3,4,5-tetrahydroxystilbene, optionally oxylated (for example glucosylated); 3,4-dihydroxyphenylalanine or derivatives thereof; 2,3-dihydroxyphenylalanine or derivatives thereof; 4,5-dihydroxyphenylalanine or derivatives; dihydroxycinnamates, caffeic acid, or chlorogenic acid; ortho-polyhydroxycoumarins; ortho-polyhydroxyisocoumarins; ortho-polyhydroxycoumarones; ortho-polyhydroxyisocoumarones; ortho-polyhydroxychalcones; ortho-polyhydroxychromones; quinones; hydroxyxanthones; 1,2-dihydroxybenzene or derivatives thereof; 1,2,4-trihydroxybenzene or derivatives thereof; 1,2,3-trihydroxybenzene or derivatives thereof; 2,4,5-trihydroxytoluene or derivatives thereof; proanthocyanidins, proanthocyanidins A1, A2, B1, B2, B3, or C1, chroman or chromene; proanthocyanins; tannic acid; ellagic acid; haematein; brazilin; brazilein; gallic acid; tannic acid; haematoxylin; or mixtures thereof.

5. The method according to claim 1, wherein the at least one ortho-diphenol derivative is chosen from extracts of animals, bacteria, fungi, algae, plants, or fruit.

6. The method according to claim 1, wherein the at least one ortho-diphenol derivative is chosen from haematoxylin, brazilin, gallic acid, tannic acid, haematein, or brazilein.

7. The method according to claim 1, wherein the at least one carboxylic acid is chosen from compounds of formula (I) wherein A is chosen from a monovalent (C.sub.1-C.sub.6)alkyl or polyvalent (C.sub.1-C.sub.6)alkylene group optionally substituted with at least one hydroxyl group, and n is an integer ranging from 0 to 5; citric acid, lactic acid, tartaric acid; or glycolic acid.

8. The method according to claim 1, in which the at least one carboxylic acid is present in an amount ranging from about 0.1% to about 20% by weight, relative to the total weight of the composition.

9. The method according to claim 1, wherein the at least one inorganic titanium salt or alkoxytitanium is chosen from inorganic salts, titanium halides, titanium sulfates, and/or titanium phosphates.

10. The method according to claim 1, wherein the at least one inorganic titanium salt or alkoxytitanium has an oxidation state of 2 or Ti(II), 3 or Ti(III) or 4 or Ti(IV).

11. The method according to claim 1, wherein the at least one inorganic titanium salt or alkoxytitanium is chosen from alkoxytitaniums, wherein the alkoxytitaniums may correspond to the formula Ti(OR).sub.n, wherein n is equal to 2, 3 or 4, and R is chosen from a linear or branched (C.sub.1-C.sub.10)alkyl or (C.sub.2-C.sub.10)alkenyl group optionally substituted with at least one atom or group chosen from halo, hydroxyl, or (di)(C.sub.1-C.sub.4)(alkyl)amino.

12. The method according to claim 1, further comprising applying a composition comprising at least one chemical oxidizing agent chosen from hydrogen peroxide, at least one hydrogen peroxide generating system, or urea hydrogen peroxide.

13. The method according to claim 1, further comprising applying at least one basifying agent chosen from i) (bi)carbonates, ii) aqueous ammonia, iii) alkanolamines, monoethanolamine, diethanolamine, triethanolamine, or derivatives thereof, iv) oxyethylenated and/or oxypropylenated ethylenediamines, v) inorganic or organic hydroxides, vi) alkali metal silicates or sodium metasilicates, vii) amino acids, basic amino acids, arginine, lysine, ornithine, citrulline, or histidine; viii) the compounds of formula (V) below: ##STR00014## wherein: W is chosen from a divalent (C.sub.1-C.sub.8)alkylene radical optionally substituted with at least one hydroxyl group, or at least one (C.sub.1-C.sub.4)alkyl radical optionally interrupted with at least one heteroatom, oxygen, sulfur, or N(R.sub.e) group; and R.sub.a, R.sub.b, R.sub.c, R.sub.d and R.sub.e, which may be identical or different, are chosen from a hydrogen atom, (C.sub.1-C.sub.4)alkyl radicals, hydroxy(C.sub.1-C.sub.4)alkyl radicals, propylene radicals, or mixtures thereof.

14. The method according to claim 1, wherein the at least one of the first composition, the second composition, the third composition, and/or the fourth composition further comprise at least one organic solvent chosen from lower C.sub.1-C.sub.4 alkanols, ethanol, isopropanol, polyols, polyol ethers, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol, aromatic alcohols, benzyl alcohol, phenoxyethanol, aromatic alcohols, benzyl alcohol, or mixtures thereof.

15. The method according to claim 1, comprising: applying to the keratin fibers the first composition, the second composition, and the third composition to form treated keratin fibers; and applying to the treated keratin fibers an alkaline composition, comprising: at least one basifying agent, and; optionally, at least one chemical oxidizing agent chosen from hydrogen peroxide or at least one hydrogen peroxide generating system.

16. The method according to claim 15, wherein: the at least one ortho-diphenol derivative is chosen from haematein, brazilein, gallic acid or tannic acid, when the method does not comprise applying a chemical oxidizing agent; or haematoxylin or brazilin, when the method does comprise applying a chemical oxidizing agent; the at least one inorganic titanium salt or alkoxytitanium is chosen from Ti(III) or Ti(IV) salts or compounds; the at least one carboxylic acid is chosen from compounds corresponding to formula (I) wherein A is chosen from a monovalent (C.sub.1-C.sub.6)alkyl or polyvalent (C.sub.1-C.sub.6)alkylene group optionally substituted with at least one hydroxyl group, and n is an integer ranging from 0 to 5, citric acid, or lactic acid; the at least one chemical oxidizing agent is chosen from hydrogen peroxide or at least one hydrogen peroxide generating system; the at least one basifying agent is chosen from alkanolamines, (bi)carbonates, alkali metal, or alkaline earth metal (bi)carbonates; the composition comprising the at least one carboxylic acid has an acidic pH; and the composition comprising the at least one basifying agent has an alkaline pH.

17. A cosmetic composition for dyeing keratinous fibers, comprising: a) at least one ortho-diphenol; b) at least one inorganic titanium salt or alkoxytitanium; c) at least one carboxylic acid represented by formula (I) below or salts thereof: ##STR00015## wherein: A is chosen from a saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon group, monovalent when n is zero or polyvalent when n is greater than or equal to 1, comprising from 1 to 50 carbon atoms which is optionally interrupted with at least one heteroatom and/or optionally substituted; or a monovalent (C.sub.1-C.sub.6)alkyl group or a polyvalent (C.sub.1-C.sub.6)alkylene group optionally substituted with at least one hydroxyl group; and n is an integer ranging from 0 to 10; d) optionally, a fourth composition comprising at least one chemical oxidizing agent; e) optionally, a fifth composition comprising at least one basifying agent chosen from alkanolamines, (bi)carbonates, alkali metal, or alkaline earth metal (bi)carbonates; and f) optionally, at least one organic solvent chosen from lower C.sub.1-C.sub.4 alkanols, ethanol, isopropanol, polyols, polyol ethers, 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hexylene glycol, aromatic alcohols, benzyl alcohol, phenoxyethanol, aromatic alcohols, benzyl alcohol, or mixtures thereof; wherein at least one composition chosen from the first composition, the second composition, the third composition, the fourth composition, and/or the fifth composition has an acidic pH.

18. A multicompartment device comprising from 2 to 5 compartments containing from 2 to 5 compositions, the device comprising: a) a first composition comprising at least one ortho-diphenol; b) a second composition comprising at least one inorganic titanium salt or alkoxytitanium; c) a third composition comprising at least one carboxylic acid chosen from those of formula (I) below, or salts thereof: ##STR00016## wherein: A is chosen from a saturated or unsaturated, cyclic or non-cyclic and aromatic or non-aromatic hydrocarbon group, monovalent when n is zero or polyvalent when n is greater than or equal to 1, comprising from 1 to 50 carbon atoms which is optionally interrupted with at least one heteroatom and/or optionally substituted; or a monovalent (C.sub.1-C.sub.6)alkyl group or a polyvalent (C.sub.1-C.sub.6)alkylene group optionally substituted with at least one hydroxyl group; and n is an integer ranging from 0 to 10; and d) optionally, a fourth composition comprising at least one chemical oxidizing agent; and e) optionally, a fifth composition comprising at least one basifying agent chosen from alkanolamines, (bi)carbonates, alkali metal, or alkaline earth metal (bi)carbonates; wherein at least one composition chosen from the first composition, the second composition, the third composition, the fourth composition, and/or the fifth composition has an acidic pH; and wherein the first composition, the second composition, the third composition, the fourth composition, and/or the fifth composition are aqueous or pulverulent.

Description

DYEING EXAMPLES

Example 1

(1) The following compositions are prepared from the following ingredients in the following proportions, indicated in grams:

(2) Dyeing Compositions:

(3) TABLE-US-00001 Ingredients CAS Composition 1 Composition 2 Pure 517-28-2 4 g 4 g haematoxylin Ethanol 15 g 15 g Citrate/sodium 7647,-01- 46.8 g 58.3 g hydroxide/ Trimethyl-1H- hydrogen indol-4-amine chloride, buffer hydrochloride pH = 2 (20 C.) 7732-18-5 Certipur ref. (water) 109433 (Merck) Titanium(III) 7705-07-9 34.2 g chloride in solution ref. 14010 (Sigma) Titanium(III) 19495-50-8 22.7 g sulfate ref. 495182 (Aldrich) Water q.s. for 100 g q.s. for 100 g

(4) Alkaline Composition B:

(5) TABLE-US-00002 Ingredients Amount Sodium bicarbonate 5 g L-Arginine 7 g Aqueous hydrogen peroxide solution (50%) 2.4 g Water q.s. 100 g pH agent pH 9.2
Procedure

(6) Each composition 1 or 2 is applied to locks of natural or permanent-waved Caucasian hair comprising 90% white hairs and locks of natural Chinese hair comprising 100% white hairs, in a proportion of 2 grams of composition per 1 gram of hair. The compositions are subsequently left to stand on the locks for 45 minutes at a temperature of 40 C.

(7) Composition B is subsequently applied to each of the locks in a proportion of 2 grams of composition per one gram of locks. The pH of composition B is 9.2. The leave-in time is 15 minutes at a temperature of 45 C. The locks are subsequently washed with Elseve Multivitamin shampoo, rinsed and then dried under a hood.

(8) The colourations obtained are measured using a Minolta CM-3600D spectrocolorimeter in comparison with undyed hair.

(9) The persistences are also measured using the same spectrocolorimeter in comparison with hair which has not been subjected to a persistence test.

(10) Dyeing Results

(11) The colour of the locks was evaluated in the CIE L* a* b* system using a Minolta Spectrophotometer CM3600D colorimeter. In this L* a* b* system, the three parameters respectively denote the intensity of the colour (L*), the green/red colour axis (a*) and the blue/yellow colour axis (b*).

(12) Buildup of the Colour:

(13) The variation in colouration between the locks of permanent-waved grey hair comprising 90% white hairs (90 PW) or the locks comprising 100% white hairs which are untreated (control) and after treatment or dyeing are defined by (E*) according to the following equation:
E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.o*).sup.2+(b*b.sub.o*).sup.2)}

(14) In this equation, L*, a* and b* represent the values measured on locks of hair after dyeing and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured on locks of undyed virgin hair. The higher the E* value, the better is the buildup of the colour.

(15) TABLE-US-00003 Untreated hair L* a* b* Natural Caucasian, 90% 68.76 0.72 15.5 white hairs Permanent-waved Caucasian, 67.38 0.76 15.03 90% white hairs Natural Chinese, 100% 74.92 2.4 23.92 white hairs

(16) Black locks are obtained which are very intensely coloured, as is shown by the following colorimetric measurements.

(17) TABLE-US-00004 E* Hair after dyeing Colour L* a* b* buildup Composition 1 + B Natural Caucasian, 90% black 20.76 1.42 1.16 50.1 white hairs Permanent-waved Caucasian, black 20.16 1.37 0.78 49.33 90% white hairs Natural Chinese, 100% black 20.91 1.66 1.3 58.55 white hairs Composition 2 + B Natural Caucasian, 90% black 21.99 0.79 1.58 48.8 white hairs Permanent-waved Caucasian, black 20.1 0.59 1.32 49.23 90% white hairs Natural Chinese, 100% grey/black 26.41 1.7 4.06 52.42 white hairs
Persistence of the Colour

(18) The hair is then subjected to tests of persistence towards light (Xenotest Alpha).

(19) The hair dyed by composition 1+B is subjected in addition to tests of persistence:

(20) towards sweat by immersion at 37 C. in an oven for 48 hours in artificial sweat having composition C.

(21) TABLE-US-00005 Ingredients Amount Sodium chloride 10 g Disodium phosphate 1 g Histidine 0.25 g Water q.s. 100 g Lactic acid q.s. for pH 3.2

(22) and towards shampoos (Elseve Multivitamin shampoo).

(23) The locks dyed starting from the compositions described above were exposed to light.

(24) The colour of the locks was evaluated, before and after exposure to light, before and after treatment with sweat or before and after successive shampooing operations, in the L* a* b* system, by means of a spectrophotometer as defined above.

(25) The variation in the colouring of the locks, before and after exposure to light, before and after treatment with sweat or before and after successive shampooing operations, is measured by E according to the following equation:
E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.o*).sup.2+(b*b.sub.o*).sup.2)}

(26) In this equation, L*, a* and b* represent the values measured after external treatment of the locks (exposure to light, sweat or successive shampooing operations) and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured before exposure.

(27) The greater the E value, the greater the difference in colour of the lock before and after external treatment, which shows a reduced persistence towards light.

(28) The results in terms of persistence are collated in the following table:

(29) TABLE-US-00006 Light Artificial exposure sweat After 10 (40 h (48 h, shampooing Xenotest) 37 C.) operations % loss/ % loss/ % loss/ unexposed unexposed unwashed Hair hair hair hair Composition 1 + B Natural Caucasian, 90% 3.61 1.92 white hairs Permanent-waved Caucasian, 3.47 9.12 2.06 90% white hairs Natural Chinese, 100% 5.19 3.85 white hairs Composition 2 + B Natural Caucasian, 90% 7.30 white hairs Permanent-waved Caucasian, 3.55 90% white hairs Natural Chinese, 100% 7.31 white hairs

(30) It is seen that the hair dyed according to the invention exhibits a very good level of persistence which is confirmed by the colorimetric values (very low percentages of losses in E* with respect to hair which has not been subjected to the persistence test).

Example 2

(31) The following compositions are prepared from the following ingredients in the following proportions, indicated in grams:

(32) Dyeing Composition:

(33) TABLE-US-00007 Composition 3 Composition 4 Ingredients Invention Comparative Logwood extract comprising 76% of 4 g 4 g haematoxylin Ethanol 15 g 15 g Benzyl alcohol 5 g 5 g Titanium(IV) sulfate as a 15% solution, 28 g 28 g sold under the name 10326250 by Fisher Chemical (CAS 13693-11-3) Sodium glycolate 13 g Water q.s. 100 g q.s. 100 g pH agent q.s. for pH = q.s. for pH = 2.8 0.2 2.8 0.2

(34) Developing Composition:

(35) TABLE-US-00008 Ingredients Composition B Sodium bicarbonate 5 g L-Arginine 7 g Aqueous hydrogen peroxide solution (50%) 1.7 g Thickener q.s. for Water q.s. 100 g pH agent pH 9.9

(36) Locks of natural and permanent-waved Caucasian hair comprising 90% white hairs and locks of natural Chinese hair comprising 100% white hairs are successively treated with composition 3 or 4, which is left to stand at 40 C. for 45 minutes and then wrung out, and with composition B, which is then left to stand at 40 C. for 15 minutes, in a proportion of 2 grams of each of the compositions per gram of hair.

(37) On conclusion of these leave-in times, the locks are washed with Elseve Multivitamin shampoo, rinsed and then dried under a hood.

(38) It is found visually that locks which are intensely coloured black are obtained with composition 3 according to the invention whereas the locks are very weakly coloured with comparative composition 4. This is corroborated with the colorimetric results below:

(39) TABLE-US-00009 Untreated hair L* a* b* Natural Caucasian, 90% 66.48 0.5 15.14 white hairs Permanent-waved Caucasian, 66.3 0.53 14.31 90% white hairs Natural Chinese, 100% 77.4 2.12 23.99 white hairs

(40) TABLE-US-00010 E* Hair after dyeing Colour L* a* b* buildup Composition 3 + B Natural Caucasian, 90% black 22.96 0.99 0.26 46 white hairs Permanent-waved Caucasian, black 20.03 0.65 0.65 48.25 90% white hairs Natural Chinese, 100% black 23.55 0.8 0.04 58.95 white hairs Composition 4 + B Natural Caucasian, 90% white 53.99 3.24 8.97 14.2 white hairs Permanent-waved Caucasian, grey 41.39 4.36 9.75 25.61 90% white hairs Natural Chinese, 100% white 59.67 3.17 11.69 21.6 white hairs