Cosmetic treatment processes and kit

Abstract

The present invention relates to a cosmetic process for treating keratin materials, which can give them, especially in a long-lasting and reversible manner, interesting cosmetic properties; this process comprising the application to said materials: in a first stage, of a cosmetic composition comprising at least one graftable species, comprising at least one unit of formula (Ia): and in a second stage, of a cosmetic composition comprising at least one cosmetic active agent bearing at least one unit of formula (Ia): ##STR00001## The invention also relates to a kit comprising said compositions.

Claims

1. A cosmetic process for treating keratin materials, comprising applying to said materials a cosmetic composition comprising, as a mixture: at least one compound bearing at least one unit of formula (Ia): ##STR00168## at least one cosmetic active agent bearing at least one unit of formula (Ia): ##STR00169## and at least one polymer which comprises: (a) a polymer backbone -POL-, and (b) at least one junction group of formula (I) linked to said polymer backbone, bearing at least one unit (Ia), wherein formula (I) ##STR00170## in which: R1 represent a divalent carbon-based radical chosen from (i) a linear or branched C.sub.1-C.sub.32 alkyl group, (ii) a C.sub.4-C.sub.16 cycloalkyl group and (iii) a C.sub.4-C.sub.16 aryl group; optionally comprising 1 to 8 heteroatoms chosen from O, N, S, F, Si and P; and/or optionally substituted with an ester or amide function or with a C.sub.1-C.sub.12 alkyl radical; R2 represents a methyl group.

2. The cosmetic process according to claim 1 wherein the polymer having a backbone is obtained by polymerization of a monomer selected from the group consisting of: a) (meth)acrylates of formula CH.sub.2CHCOOR.sup.4 or CH.sub.2C(CH.sub.3)COOR.sup.4 in which R.sup.4 represents: a hydrogen, a linear, cyclic or branched C1-C30 alkyl group, into which are optionally inserted one or more heteroatoms selected from the group consisting of O, N, S and P; substituted with one or more substituents selected from the group consisting of OH, halogens, and groups Si (R.sub.7)(R.sub.8), in which R.sub.7 and R.sub.8, which may be identical or different, represent a C1-C6 alkyl group or a phenyl group; a C.sub.3 to C.sub.20 aryl group; a C.sub.4 to C.sub.30 aralkyl or alkylaryl group, wherein the alkyl group is a C.sub.1 to C.sub.8 alkyl group; a C4-C12 heterocycloalkyl group containing one or more heteroatoms selected from the group consisting of O, N, P and S, the ring being aromatic or non-aromatic; a C4-C30 alkylheterocycloalkyl group, wherein the alkyl group is a C.sub.1 to C.sub.8 alkyl group; said aryl and aralkyl groups optionally comprising, intercalated, one or more heteroatoms selected from the group consisting of O, N, S and P, and/or optionally being substituted with one or more substituents selected from the group consisting of hydroxyl groups, halogen atoms and linear or branched C.sub.1-C.sub.4 alkyl groups, which may themselves comprise, intercalated, one or more heteroatoms selected from the group consisting of O, N, S and P and/or which may be substituted with one or more substituents selected from the group consisting of hydroxyl groups, halogen atoms , and groups Si (R.sub.7)(R.sub.8), in which R.sub.7 and R.sub.8, which may be identical or different, represent a C.sub.1 to C.sub.6 alkyl group, or a phenyl group; b) (meth)acrylamides of formula CH.sub.2CHCONR.sup.6R.sup.5 or CH.sub.2C(CH.sub.3)CONR.sup.6R.sup.5 in which R.sup.5 and R.sup.6, which may be identical or different, have the same meanings as for the groups R.sup.4 above; c) vinyl monomers of formula: CH.sub.2CHR.sup.9, CH.sub.2CHCH.sub.2R.sup.9 or CH.sub.2C(CH.sub.3)CH.sub.2R.sup.9 in which R.sup.9 is a selected from the group consisting of hydroxyl, Cl, F, NH.sub.2, acetamide (NHCOCH.sub.3) and OR.sub.10 in which R.sub.10 represents a phenyl group or a C1-C12 alkyl group; OCOR.sub.11 in which R.sub.11 represents: (i) a linear or branched C.sub.2 to C.sub.12 alkyl group, (ii) a C.sub.3 to C.sub.12 cycloalkyl group, (iii) a C.sub.3-C.sub.20 aryl group, (iv) a C.sub.4 to C.sub.30 aralkyl group wherein the alkyl group is a C.sub.1 to C.sub.8 alkyl group, (v) a saturated or unsaturated, aromatic or non-aromatic, 4- to 12-membered heterocycloalkyl group containing one or more heteroatoms selected from the group consisting of O, N and S, (vi) a C.sub.1 to C.sub.4 alkylheterocycloalkyl group,; said alkyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl or alkylheterocycloalkyl groups optionally being substituted with one or more substituents selected from the group consisting of hydroxyl groups, halogen atoms and linear or branched C.sub.1-C.sub.4 alkyl groups in which are optionally intercalated one or more heteroatoms selected from the group consisting of O, N, S and P, said alkyl groups also optionally being substituted with one or more substituents optionally hydroxyl groups, halogen atoms, and groups Si(R.sub.7)(R.sub.8), in which R.sub.7 and R.sub.8, which may be identical or different, represent a C.sub.1 to C.sub.6 alkyl group, or a phenyl group. d) ethylenically unsaturated monomers comprising at least one carboxylic acid (COOH), phosphonic acid (PO.sub.3H.sub.2) or sulfonic acid (SO.sub.3H) function, and e) ethylenically unsaturated monomers comprising at least one primary, secondary or tertiary amine function.

3. The cosmetic process according to claim 2, wherein the monomer a) is selected from the group consisting of selected from the group consisting of methyl (meth)acrylate and ethyl (meth)acrylate; the monomer d is represented by the formula CH.sub.2C(R.sub.19)(Z1).sub.z1-(Z2).sub.z2Y in which: R.sub.19 is a hydrogen atom or a methyl radical; Z1 is a divalent group selected from the group consisting of COO, CONH, CONCH.sub.3, OCO and O, z.sub.1 is 0 or 1; Z2 is a linear, branched or cyclic, saturated or unsaturated, optionally aromatic divalent carbon-based radical, of 1 to 30 carbon atoms, which optionally comprises 1 to 30 heteroatoms selected from the group consisting of O, N, S and P; z.sub.2 is 0 or 1; and Y is a selected from the group consisting of COOH, SO.sub.3H, OSO.sub.3H, PO(OH).sub.2 and OPO(OH).sub.2; and the monomer e) is represented by the formula:
CH.sub.2C(R.sub.19)(Z1).sub.z1(Z2).sub.z2X in which: R.sub.19, Z1, Z2, z.sub.1 and z.sub.2 have the same meanings as in the formula for monomer d); and either X is a group of formula NR.sub.17R.sub.18 with R.sub.17 and R.sub.18 representing, independently of each other, i) a hydrogen atom; (ii) a linear, branched or cyclic, saturated or unsaturated, optionally aromatic C1-C30 alkyl group, which may comprise 1-10 heteroatoms selected from the group consisting of O, N, S and P; (iii) an alkylene oxide group of formula (R.sub.20O).sub.yR.sub.21 with R.sub.20 representing a linear or branched C.sub.2-C.sub.4 alkyl, R.sub.21 is hydrogen or a linear or branched C.sub.2-C.sub.30 alkyl radical and y is between 1 and 250 inclusive; R.sub.17 and R.sub.18 may form, together with the nitrogen atom, a saturated or unsaturated, optionally aromatic ring comprising in total 5 to 8 atoms; said ring also optionally being fused with one or more other saturated or unsaturated, optionally aromatic rings, each comprising 5 to 7 atoms; or X represents a group R.sub.15NR.sub.16-in which R.sub.15 and R.sub.16 form, with the nitrogen atom, a saturated or unsaturated, optionally aromatic ring comprising in total 5, 6, 7 or 8 atoms; said ring optionally being fused with one or more other saturated or unsaturated, optionally aromatic rings, each comprising 5, 6 or 7 atoms.

4. The cosmetic process according to claim 1 wherein the polymer having a backbone is selected from the group consisting of polydienes, polyesters, polycarbonates, polyacetals, polyoxyalkylenes, polythioethers, perfluoropolyethers, polyolefins, polyorganosiloxanes, vinyl polymers, poly(meth)acrylics, cellulose derivatives and polysaccharide derivatives.

5. The cosmetic process according to claim 4 wherein the cellulose derivatives and polysaccharide derivatives are selected from the group consisting of ethers and esters.

6. The cosmetic process according to claim 1 wherein the polymer is obtained from the reaction: of at least one monomer (a) which comprises at least two identical or different polymerizable groups, selected from the group consisting of NCO and NCS, or the activated or blocked form thereof; of at least one monomer (b) comprising at least two identical or different polymerizable groups bearing labile hydrogen, selected from the group consisting of OH, SH, NH.sub.2 and NHR, with R representing a C.sub.1-C.sub.6 alkyl group; and at least one of the monomers (a) and/or (b) comprising at least one junction group, which is capable of forming at least 3 H bonds.

7. The cosmetic process according to claim 6 wherein at least one of the monomers (a) and/or (b) comprising at least one junction group, which is capable of forming at least 4 H bonds.

8. The cosmetic process according to claim 6 wherein at least one of the monomers (a) and/or (b) comprising at least one junction group, which is capable of forming at least 5 H bonds.

9. The cosmetic process according to claim 1 wherein the polymer is obtained from the reaction of at least one polyalkene polymer functionalized with at least one reactive group, with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group(s) of the functionalized polyalkene polymer, said junction group being capable of forming at least 3 H (hydrogen) bonds.

10. The cosmetic process according to claim 9 wherein the reaction is a condensation reaction and the junction group is capable of forming at least 4 H (hydrogen) bonds.

11. The cosmetic process according to claim 1 wherein the polymer has a number-average molecular mass (Mn) between 1,000 and 3,000,000.

12. The cosmetic process according to claim 1, wherein the compound bearing the unit (Ia) is selected from the compounds of formula (II), and salts and hydrates and tautomeric forms thereof: ##STR00171## in which: X represents a linear or branched, saturated or unsaturated, divalent C1-C30 hydrocarbon-based chain, optionally interrupted with and/or bearing, at one or both of its ends, one or more divalent groups chosen from N(R), N.sup.+(R)(R), O, S, C(O), SO.sub.2, and an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused divalent C3-C7 (hetero)cyclic radical, optionally comprising one or more identical or different heteroatoms chosen from N, S and O, optionally substituted with OH or NRR; with R and R, which may be identical or different, chosen from a hydrogen, a linear or branched, saturated or unsaturated C1-C4 alkyl radical, optionally substituted with OH and/or NRR, with R and R, which may be identical or different, chosen from H or a linear or branched, saturated or unsaturated C1-C4 alkyl radical; p is equal to 0 or 1; q is equal to 0 or 1; Y represents a linear, branched and/or cyclic, saturated or unsaturated divalent C 1-C 18 hydrocarbon-based chain, optionally substituted with OH and/or NRR, W represents a unit for grafting onto keratin materials and is selected from the group consisting of W represents: (i) a thiol, (ii) a protected thiol of formula SPr with Pr representing: a) a protecting group such as a saturated or unsaturated, fused or non-fused, aromatic or non-aromatic C5-C6 heterocycle, optionally comprising N, O, S and/or P heteroatoms; b) an sp.sup.2 carbon protecting group; c) an sp.sup.3 carbon protecting group; d) a metal protecting group; e) a substituted sulfur atom protecting group; f) a photosensitive protecting group such as nitrobenzyl or benzylsulfonyl aromatic groups; iii) a nucleofugal group; and (iv) a group containing one or more siloxanes.

13. The cosmetic process as claimed in claim 1, in which the compound bearing the unit (Ia) is selected from the group consisting of the following compounds: ##STR00172## ##STR00173##

14. The cosmetic process as claimed in claim 1, in which the compound bearing the unit (Ia) is in an amount of from 0.1% to 10% by weight in the composition comprising it.

15. The cosmetic process as claimed in claim 1, in which the cosmetic active agent bearing at least one unit of formula (Ia) is a at least one member selected from the group consisting of keratin fiber caring agents; dyeing active agents; compounds containing active hydrophilic chains; compounds containing silicone chains; fatty substances; UV-screening agents; hyaluronic acid; and derivatives of hyaluronic acid.

16. The process as claimed in claim 1, in which the cosmetic active agent is a cosmetic active agent for caring for keratin fibers of formula (III), and also the salts, addition salts, isomers, hydrates, and tautomeric forms thereof: ##STR00174## in which: R1 H and R2 methyl; and Z represents a monovalent radical chosen from: (i) a linear or branched C9 to C32 (saturated) alkyl radical; (ii) a linear or branched C9 to C32 (unsaturated) alkene radical; said radicals optionally being substituted with 1 to 8 groups chosen from OH, OR, SO.sub.3H, SO.sub.3R, SO.sub.2NRR, COOH, NRR and N.sup.+RRR, with R, R and R H or C1-C6 alkyl; and/or said radicals optionally comprising 1 to 8 divalent groups chosen, alone or as a mixture, from NH (or NH), O, C(O), C(NH), N.sup.+(CH.sub.3).sub.2-An.sup.-(Ad.sup.-: anion); or alternatively N(trivalent).

17. The process as claimed in claim 1, in which the cosmetic active agent is a supramolecular oil, which is obtainable by reaction between: on the one hand, at least one oil bearing at least one nucleophilic and/or electrophilic reactive function, and on the other hand, at least one junction group capable of establishing hydrogen bonds with one or more partner junction groups, each junction group pairing involving at least 3 hydrogen bonds, said junction group bearing at least one reactive function capable of reacting with the reactive function borne by the oil, said junction group comprising at least one unit of formula (I) or (II): ##STR00175## in which: R1 and R3, which may be identical or different, represent a divalent carbon-based radical chosen from (i) a linear or branched C.sub.1-C.sub.32 alkyl group, (ii) a C.sub.4-C.sub.16 cycloalkyl group and (iii) a C.sub.4-C.sub.16 aryl group; optionally comprising 1 to 8 heteroatoms chosen from O, N, S, F, Si and P; and/or optionally substituted with an ester or amide function or with a C.sub.1-C.sub.12 alkyl radical; or a mixture of these groups; R2 represents CH.sub.3.

18. The process as claimed in claim 1, in which the cosmetic active agent is a supramolecular wax, which is obtainable by reaction between: at least one wax bearing at least one reactive function chosen from OH and COOH, or even anhydride, and at least one junction group capable of establishing hydrogen bonds with one or more partner junction groups, each junction group pairing involving at least 4 hydrogen bonds, said junction group bearing at least one complementary reactive function capable of reacting with the reactive function borne by the wax, said junction group comprising at least one unit of formula (I) or (II): ##STR00176## in which: R1 and R3, which may be identical or different, represent a divalent carbon-based radical chosen from (i) a linear or branched C.sub.1-C.sub.32 alkyl group, (ii) a C.sub.4-C.sub.16 cycloalkyl group and (iii) a C.sub.4-C.sub.16 aryl group; optionally comprising 1 to 8 heteroatoms chosen from O, N, S, F, Si and P; and/or optionally substituted with an ester or amide function or with a C.sub.1-C.sub.12 alkyl radical; or a mixture of these groups; R2 represents CH.sub.3.

19. The process as claimed in claim 1, in which the cosmetic active agent bearing at least one unit of formula (Ia), or the mixture of such active agents, is present in the composition in an amount of from 0.01% to 50% by weight relative to the total weight of the composition.

20. The process as claimed in claim 2, in which the compound bearing the unit (Ia) is chosen from the following compounds: ##STR00177## ##STR00178##

21. The process as claimed in claim 3, in which the compound bearing the unit (Ia) is chosen from the following compounds: ##STR00179## ##STR00180##

22. The process as claimed in claim 4, in which the compound bearing the unit (Ia) is chosen from the following compounds: ##STR00181## ##STR00182##

Description

EXAMPLE 1

Graftable Species A

Preparation of 4-[(4-{[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)carbamoyl]amino}butyl)amino]-4-oxobutyl imidothiocarbamate hydrochloride

(1) ##STR00156##

1/ Preparation of tert-butyl [4-({[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)butyl]carbamate (compound 2) from N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)-1H-imidazole-1-carboxamide (compound 1)

(2) ##STR00157##

(3) To a solution of 1.72 g of tert-butyl(4-aminobutyl)carbamate (9.1 mmol) in 50 ml of dichloromethane were added 2 g of N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)-1H-imidazole-1-carboxamide (compound 1) (9.1 mmol) prepared according to the procedure described by E. W. Meijer et al., J. Am. Chem. Soc., 2003, 125, p. 6860. The solution was stirred at reflux for 4 hours. The final product was obtained by precipitation from acetone. After filtering off and washing with acetone, the final product was dried under reduced pressure to give 4.02 g (11.8 mmol) of pure hygroscopic product in the form of a white powder, in a yield of greater than 99% (compound 2).

(4) 1H and 13C NMR spectra compliant (DMSO)

2/ Preparation of N-(4-aminobutyl)-N-(6-methyl-4-oxo-1,4-dihydropyvrimidin-2-yl)urea hydrochloride (compound 3) from tert-butyl [4-({[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)butyl]carbamate

(5) ##STR00158##

(6) To a solution of 3.02 g of tert-butyl[4-({[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)butyl]carbamate (8.9 mmol) in 10 ml of ethyl acetate were added 9.28 g of 35% hydrochloric acid (89.5 mmol). The solution was stirred at 5 C. for 1 hour. The final product was obtained by precipitation from acetone. After filtering off and washing with acetone, the final product was dried under reduced pressure to give 2.28 g (9.5 mmol) of pure product (compound 3) in the form of a white powder, in a yield of greater than 99% (hygroscopic product). 1H and 13C NMR spectra compliant (DMSO)

3/ Preparation of 4-chloro-N-(4-{[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)carbamoyl]amino}butyl)butanamide (compound 4) from N-(4-aminobutyl)-N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea hydrochloride

(7) ##STR00159##

(8) To a solution of 20 g of N-(4-aminobutyl)-N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea hydrochloride (70 mmol) in 200 ml of water cooled to 0 C. were added alternately 11.6 g of sodium hydroxide (0.29 mol) and 24.4 ml of chlorobutyl chloride (0.22 mol). The solution was stirred for 18 hours at room temperature. The product was obtained by filtration. The final product was dried under reduced pressure to give 14.2 g (41.4 mmol) of pure product (compound 4) in the form of a white powder, in a yield of 54%.

(9) 1H and 13C NMR spectra compliant (DMSO)

4/ Preparation of 4-[(4-{[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)carbamoyl]amino}butyl)amino]-4-oxobutyl imidothiocarbamate hydrochloride from 4-chloro-N-(4-{[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)carbamoyl]amino}butyl)butanamide

(10) ##STR00160##

(11) To a solution of 10.7 g of 4-chloro-N-(4-{[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)carbamoyl]amino}butyl)butanamide (3 mmol) in 100 ml of 2-propanol were added 2.84 g of thiourea (4 mmol). The solution was stirred for 17 hours at reflux. The product was obtained by filtration. The final product was dried under reduced pressure to give 10.7 g (25.5 mmol) of pure desired product in the form of a yellow powder, in a yield of 82%.

(12) 1H and 13C NMR spectra compliant (DMSO)

EXAMPLE 2

Dye A

(13) The functionalized ureidopyrimidone dye used is a mixture consisting essentially of 2-({4-[bis(2-hydroxyethyl)amino]-2-nitrophenyl}amino)ethyl[6-({[(6-isopropyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)hexyl]carbamate.

(14) ##STR00161##

(15) 4 g of 2,2-[4-(2-hydroxyethylamino)-3-nitrophenylimino]diethanol were dissolved in 75 ml of anhydrous tetrahydrofuran. 4.51 g of N-(5-isocyanatopentyl)-N-(6-isopropyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea were added portionwise, under an argon atmosphere and with stirring, followed by addition of 3 drops of dibutyltin dilaurate (DBTDL). The reaction medium was then stirred at this temperature for 3 hours; the disappearance of the isocyanate function was monitored by infrared. After total disappearance of the isocyanate function, the reaction medium was filtered through Celite and then concentrated to half its volume. The reaction medium was then poured into 800 ml of ethyl ether with vigorous stirring and the precipitate obtained was filtered off on a sinter funnel. The product was then dried under vacuum to give 7 g of a violet powder, in a yield of about 80%.

(16) Analysis by HPLC coupled to a mass spectrometer shows the predominant formation of the desired product [M+H]+=607 and also a remaining amount of starting material and of double-reaction product of mass M=928.

(17) 15 mg of dye thus prepared are placed in a 25 ml flask, and 100 l of benzyl alcohol and 400 l of ethyl alcohol are added. The mixture is heated slightly to 40 C. in order to dissolve the dye (ultrasonication if necessary). Finally, 1000 l of water are added. An opaque violet solution is obtained.

EXAMPLE 3

Dye B

(18) Preparation of the dye of formula:

(19) ##STR00162##

(20) This dye is prepared according to the procedure described in EP 1 310 533 B1, example 22 (dye 21).

(21) 15 mg of this dye were placed in a 25 ml flask, and 100 l of benzyl alcohol and 500 l of ethyl alcohol were added. The mixture was then heated slightly to 40 C. in order to dissolve the dye, with ultrasonication to complete the dissolution. 900 l of water were then added to obtain an opaque orange solution.

EXAMPLE 4

(22) 150 mg locks of hair were first moistened with water and then shampooed with 0.2 g of shampoo containing 15% of sodium lauryl sulfate in water, and then rinsed with water.

(23) The test solution was applied to the entire lock placed on a suitable drip tray, for 30 minutes at 60 C. After wringing dry and rinsing with water, the treated lock was observed to see whether or not there was coloration.

(24) The control was a lock of hair which did not undergo the grafting treatment (no treatment with a graftable species).

(25) Test 1 (Control)

(26) 1.5 ml of dye solution A at 0.8% (0.025 mol/I) were applied to the locks, for 30 minutes at 60 C.

(27) Observation: very very pale coloration

(28) Test 2 (Control)

(29) 1.5 ml of dye solution B at 1% (0.025 mol/I) were applied to the locks, for 30 minutes at 60 C.

(30) Observation: no coloration

(31) Test 3 (Invention)

(32) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at room temperature (25 C.). The lock was then wrung dry, and 1.5 ml of solution of dye A at 0.8%, as prepared in example 2, were then applied for 15 minutes at 60 C. The lock was then rinsed with tap water for 10 seconds between the fingers, and was then dried between two absorbent towels.

(33) Observation: a slight coloration was thus obtained.

(34) Test 4 (Invention)

(35) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at 60 C. The lock was then wrung dry, and 1.5 ml of solution of dye A at 0.8%, as prepared in example 2, were then applied for 15 minutes at 60 C. The lock was then wrung dry, washed with water and dried.

(36) Observation: a slight coloration was thus obtained.

(37) Test 5 (Invention)

(38) 1.5 ml of a 1% solution of graftable species A (solution of spontaneous pH) were applied to a 150 mg lock of hair, for 15 minutes at 25 C. The lock was then wrung dry, and 1.5 ml of solution of dye A at 0.8%, as prepared in example 2, were then applied for 15 minutes at 60 C. The lock was then wrung dry, washed with water and dried.

(39) Observation: a moderate coloration was thus obtained.

(40) Test 6 (Invention)

(41) 1.5 ml of a 5% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at 25 C. The lock was then wrung dry, and 1.5 ml of solution of dye A at 0.8%, as prepared in example 2, were then applied for 15 minutes at 60 C. The lock was then wrung dry, washed with water and dried.

(42) Observation: a strong coloration was thus obtained.

(43) Increasing the concentration of graftable species makes it possible to increase the coloration.

EXAMPLE 5

Screening Agent C

Dibutyl 4,4-[(6-{[4-({[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)butyl]amino}-1,3,5-triazine-2,4-diyl)diimino]dibenzoate

Preparation of dibutyl 4,4-[(6-{[4-({[(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)amino]carbonyl}amino)butyl]amino}-1,3,5-triazine-2,4-diyl)diimino]dibenzoate 9 from N-(4-aminobutyl)-N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea hydrochloride 1

(44) ##STR00163##

(45) To a suspension of 100 mg of butyl 4-[(4-{[4-(butoxycarbonyl)phenyl]amino}-6-chloro-1,3,5-triazin-2-yl)amino]benzoate 9A (0.2 mmol) in 4 ml of acetonitrile were added 4.8 mg of N-(4-aminobutyl)-N-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea hydrochloride 1 (0.2 mmol) and 66 l of diisopropylethylamine (0.4 mmol). The solution was stirred for 6 hours at reflux. The final product was obtained by precipitation from water and then dried under reduced pressure to give 0.06 g (0.09 mmol) of pure product 9 in the form of a white powder, in a yield of 40%. .sup.1H NMR (DMSO): 0.9-0.94 ppm (t, 6H); 1.43-1.72 ppm (m, 12H); 2.38 ppm (s, 3H); 3.17 ppm (t, 2H); 3.40 ppm (t, 2H); 4.38-4.4 ppm (t, 4H); 5.66 ppm (s, 1H); 7.74-7.76 ppm (d, 4H); 7.99-8.01 ppm (d, 4H)

(46) UV (CHCl.sub.3) lambda max: 310 nm Emax: 79940, E1%=1140

EXAMPLE 6

(47) An antisun cream having the following composition is prepared:

(48) Phase A:

(49) Screening agent C of Example 5: 3% butylmethoxydibenzoylmethane (Parsol 1789) 2% Bis(ethylhexyloxyphenol)methoxyphenyltriazine (Tinosorb S) 3% C12-15 Alkyl benzoate 15% Cetyl alcohol 0.5% Stearic acid 1.5% Mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols 2% Dimethicone 0.5% Triethanolamine 0.45% Preserving agent 1%
Phase B: Glycerol 5% Complexing agent 0.1% Monocetyl phosphate 1%
Phase C: Xanthan gum 0.2% Acrylic acid/stearyl methacrylate copolymer 0.2% Isohexadecane 1%
Phase D:

(50) Triethanolamine qs pH 7

(51) The fatty phase (A) is heated to 70 C. The aqueous phase (B) is heated in the final container. Phase (C) is prepared: dispersion of the powders in the oil with rotorstator stirring, and the fatty phase is then emulsified in the aqueous phase. Phase (C) is then introduced with faster stirring, and the mixture is then stirred slowly until it has cooled to room temperature. The mixture is neutralized (D).

(52) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) are applied to a 150 mg lock of hair, for 15 minutes at room temperature (25 C.). The lock is then wrung dry, and the antisun cream is then applied.

(53) The hair thus treated has good protection against sunlight.

EXAMPLE 7

Haircare Active Agent D

1-(6-Methyl-4-oxo-1,4-dihydropyrimidin-2-yl)-3-octadec-9-enylurea (6)

Preparation of 1-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)-3-octadec-9-enylurea 6 from isocytosine bearing a carbamic function activated with carbonyldiimidazole 1A

(54) ##STR00164##

(55) To a solution of 6.43 ml of 70% technical-grade oleylamine (0.027 mol) in 100 ml of dichloromethane were added 6 g of 2-(1-imidazolylcarbonylamino)-6-methyl-4[1H]-pyrimidinone 1A (0.027 mol). The reaction mixture was refluxed for 6 hours, and then evaporated under reduced pressure to give a white paste. This paste was then taken up in 200 ml of acetone, and the precipitate obtained was filtered off on a sinter funnel. The product was dried under vacuum and then recrystallized from a minimum amount of hot ethanol. 10.3 g of a white powder were thus obtained in a yield of 90%.

(56) 1H and 13C NMR spectra compliant.

EXAMPLE 8

(57) The following hair composition is prepared: Compound D of example 7: 0.5% Cetylstearyl alcohol (50/50 C16-C18): 15% Cetyl esters: 2% Water qs 100%

(58) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at room temperature (25 C.). The lock was then wrung dry, and the hair composition was then applied.

(59) The hair thus treated shows good disentangling in wet medium and also has a soft, silky feel after drying.

EXAMPLE 9

Compound Bearing a Hydrophilic Chain E

1-(2,5,8,11,14,17,20-heptaoxadocosan-22-yl)-3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea

(60) ##STR00165##

(61) To a suspension of 4.38 g of 2-(1-imidazolylcarbonylamino)-6-methyl-4[1H]-pyrimidinone 1A (0.02 mol) in 200 ml of ethyl acetate were added 7.4 g of 2,5,8,11,14,17,20 heptaoxadocosan-22-amine (0.0218 mol). The reaction mixture was refluxed for 12 hours. The mixture was then allowed to return to room temperature, and was evaporated under reduced pressure. The residue was taken up in acetone (50 ml) and then filtered to remove the imidazole. The filtrate was evaporated under reduced pressure and then taken up again in 50 ml of acetone and filtered. The filtrate was evaporated under reduced pressure. 5.9 g of the expected product were thus obtained in the form of a pasty oil, in a yield of 60%.

(62) 1H and 13C NMR spectra compliant.

EXAMPLE 10

(63) The following hair composition is prepared: Compound E of example 9 1% Cetylstearyl alcohol (50/50 C16-C18): 3% behenyltrimethylammonium chloride cationic surfactant: 1.5% Water qs 100%

(64) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at room temperature (25 C.). The lock was then wrung dry, and the hair composition was applied.

(65) The hair thus treated shows good disentangling properties in wet and dry medium and also has a soft, silky feel in a humid atmosphere.

EXAMPLE 11

Silicone Compound F

(66) ##STR00166##

(67) To a suspension of 5 g of aminopropyl polydimethylsiloxane (n being 8- 8.5) (DMS-A11 sold by the company Gelest) (0.0056 mol) in 20 ml of ethyl acetate were added 3.12 g of 2-(1-imidazolylcarbonylamino)-6-isopropyl-4[1H]-pyrimidinone (0.0126 mol). The reaction mixture was then maintained at 60 C. for 3 hours and then allowed to return to room temperature. It was then evaporated under reduced pressure, and the residue was taken up in 100 ml of ethyl ether. The organic phase was washed with 1N hydrochloric acid solution and then washed with saturated ammonium chloride solution, dried over sodium sulfate, filtered and then evaporated under reduced pressure. 7.8 g of a white powder were thus obtained, in a yield of 90%.

(68) 1H and 13C NMR spectra compliant.

EXAMPLE 12

(69) The following hair composition is prepared:

(70) TABLE-US-00002 Silicone compound F of example 11 4.2 g Dimethoxyethane 47.66 g Ethanol 42.90 g Isododecane 4.76 g Solution of 2M HCl/water qs 100 g

(71) The silicone compound F is dissolved in the dimethoxyethane and the solution is then diluted by addition of ethanol and isododecane. The HCl solution is then added to neutralize the final solution, and water is added to make up to 100 g.

(72) 1.5 ml of a 1% solution of graftable species A (solution of pH 9, adjusted with 32% aqueous ammonia) were applied to a 150 mg lock of hair, for 15 minutes at room temperature (25 C.). The lock was then wrung dry, and the hair composition was applied.

(73) The hair thus treated shows good hairstyle hold and good hair sheen.

EXAMPLE 13

Dye G

(74) ##STR00167##

(75) 5 g of Disperse Red 1 (n=0.0159; 1 eq.) were placed in 94 ml of tetrahydrofuran in a 250 ml three-necked flask. 5.62 g of SPM2A ureidopyrimidine isocyanate derivative (n=0.0175 mol; 1.1 eq.) dissolved in 20 ml of tetrahydrofuran were then added dropwise via an addition funnel. 20 L of DBTL (cat.) were then added, and the reaction mixture was maintained overnight at room temperature under argon. A red precipitate gradually formed. It was then filtered off on a sinter funnel, washed with ethyl acetate and dried under vacuum to give 8.674 g (n=0.014 mol) of a red powder, in a yield of 86%.

EXAMPLE 14

(76) Reversibility Study: Violet to Red Coloration

(77) Preparation of the Violet Dye A Solution (1.2510.sup.2 mol/l)

(78) 38 mg of dye A of Example 2 were placed in a 25 ml flask, and 200 l of benzyl alcohol and 800 l of ethyl alcohol were added. The mixture was heated slightly to 40 C. with a hairdryer in order to dissolve the dye (ultrasonication if necessary). Finally, 4000 l of water were added. An opaque violet solution was thus obtained.

(79) Preparation of the Red Dye G Solution (1.2510.sup.2 mol/l)

(80) 70 mg of dye G of Example 13 were placed in a 25 ml flask, and 500 l of benzyl alcohol and 500 l of ethyl alcohol were added. The mixture was heated slightly to 40 C. with a hairdryer in order to dissolve the dye (ultrasonication if necessary). 2 ml of ethyl alcohol and 2 ml of water were then added. A red solution was thus obtained.

(81) Change of Dye: In 4 Steps

(82) 1) Fixing of the Graftable Species A

(83) 5 mL of aqueous solution of the graftable species A of example 1 at 6% by weight and of spontaneous pH were applied for 15 minutes with heating to 60 C. to a 500 mg lock of hair SA20. The lock was then wrung dry, followed by application of

(84) 2) Fixing of the Violet Dye A

(85) 5 mL of solution of violet dye A were applied with heating at 60 C. for 15 minutes. A lock dyed a dark violet color was thus obtained.

(86) 3) Shampooing

(87) The lock was then shampooed with 0.2 mL of a sodium lauryl sulfate solution at 2% by weight (strong decrease in coloration) and was wrung dry.

(88) 4) Fixing of the Red Dye G

(89) 5 mL of the solution of red dye G were applied with heating at 60 C. for 15 minutes. The lock was wrung dry and then dried to obtain a lock dyed red.