PROCESS FOR TREATING KERATIN FIBERS EMPLOYING AN ANHYDRIDE ACRYLIC POLYMER IN OILY DISPERSION AND AN AMINE COMPOUND

Abstract

The disclosure relates to a process for treating keratin fibers comprising, in a first stage, the application to said fibers of an oily dispersion (A) comprising i) particles of copolymers of alkyl acrylates and anhydride acrylics, ii) stabilizers, and iii) one or more hydrocarbon-based oils, and then, in a second stage, the application to said fibers of a composition (B) comprising iv) one or more amine compounds; or the application to said fibers of an oily dispersion (D) comprising said ingredients i), ii), iii) and iv), wherein v) one or more dye(s) and/or pigment(s) may be in the dispersion (A) or (D), in a composition (B), and/or in another composition (C). The disclosure further relates to a multi-compartment kit comprising the ingredients i) to v), and an oily dispersion (A) comprising v) the one or more dyes and/or pigments.

Claims

1.-26. (canceled)

27. A process for treating keratin fibers, comprising: 1a) applying to the keratin fibers an oily dispersion (A), wherein the oily dispersion (A) comprises: i) at least one particle comprising at least one ethylenic copolymer of: a) C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, and b) ethylenically unsaturated anhydride compound; ii) at least one stabilizer comprising at least one ethylenic polymer chosen from: c) polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers, d) copolymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate and (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, or a combination thereof; and iii) at least one hydrocarbon-based oil; and 1b) subsequently applying to the keratin fibers a composition (B), wherein the composition (B) comprises: iv) at least one amine compound chosen from: e) polyamine compounds bearing several primary amine and/or secondary amine groups, f) amino alkoxysilanes, or a combination thereof; or 2) applying to the keratin fibers an oily dispersion (D), wherein the oily dispersion (D) comprises: i) at least one particle comprising at least one ethylenic copolymer of: a) C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, and b) ethylenically unsaturated anhydride compound; ii) at least one stabilizer comprising at least one ethylenic polymer chosen from: c) polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers, d) copolymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate and (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, or a combination thereof; iii) at least one hydrocarbon-based oil; and iv) at least one amine compound chosen from: e) polyamine compounds bearing several primary amine and/or secondary amine groups, f) amino alkoxysilanes, or a combination thereof; and 3) optionally, applying to the keratin fibers a composition (C) comprising v) at least one dye and/or at least one pigment; wherein dispersion (A), dispersion (D), and/or composition (B) optionally further comprises v) at least one dye and/or pigment.

28. The process of claim 27, wherein the a) (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate is chosen from those of formula: ##STR00012## wherein R is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and R is chosen from a (C.sub.1-C.sub.4)alkyl group.

29. The process of claim 27, wherein the b) ethylenically unsaturated anhydride compound is chosen from derivatives of the maleic anhydride of formula (Ib) and the itaconic anhydride of formula (IIb): ##STR00013## wherein in formulae (Ib) and (IIb), R.sub.a, R.sub.b and R.sub.c, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group.

30. The process of claim 27, wherein the i) at least one particle of the dispersion (A) or (D) comprises from 80% to 99.99% by weight of the a) C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, and from 0.01% to 20% by weight of the b) ethylenically unsaturated anhydride compound, relative to the total weight of the at least one particle.

31. The process of claim 27, wherein the at least one particle i) is present in dispersion (A) or (D) in an amount ranging from 20% to 60% by weight, relative to the total weight of the dispersion (A) or (D).

32. The process of claim 27, wherein the ii) at least one stabilizer of dispersion (A) or (D) comprises at least one ethylenic polymer chosen from: c) polymers of monomers of formula H.sub.2C?C(R)C(O)OR, wherein R is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and R is chosen from a (C.sub.5-C.sub.10)cycloalkyl group; d) copolymers of H.sub.2C?C(R)C(O)OR and H.sub.2C?C(R)C(O)OR, wherein R is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, R is chosen from a (C.sub.1-C.sub.4)alkyl group, and R is chosen from a (C.sub.5-C.sub.10)cycloalkyl group; or mixtures thereof.

33. The process of claim 27, wherein the dispersion (A) or (D) comprises from 10% to 50% by weight of at least one ethylenic polymer chosen from copolymers d), and from 50 to 90% by weight of at least one ethylenic polymer chosen from polymers c), relative to the total weight of the sum of the i) at least one particle and the ii) at least one stabilizer.

34. The process of claim 27, wherein the iii) at least one hydrocarbon-based oil is chosen from volatile apolar oils, and consists of carbon and hydrogen atoms.

35. The process of claim 27, wherein the dispersion (A) or (D) is in inverse emulsion of water-in-oil (W/O) type, and further comprises at least one surfactant.

36. The process of claim 27, wherein the at least one amine compound of composition (B) or of dispersion (D) is chosen from the amino alkoxysilanes f) of formula (IVa): ##STR00014## wherein in formula (IVa): R.sub.1 is a linear or branched, saturated or unsaturated, cyclic or acyclic C.sub.1-C.sub.10 hydrocarbon-based chain substituted with a group chosen from: primary amine NH.sub.2 or secondary amine N(H)R, wherein R is chosen from a (C.sub.1-C.sub.4)alkyl group, and an aryl or aryloxy group substituted with an amino or (C.sub.1-C.sub.4)alkylamino group or with a C.sub.1-C.sub.4 aminoalkyl group; or wherein R.sub.1 is optionally interrupted in its chain with a heteroatom or a carbonyl group (CO), and R.sub.1 being linked to a silicon atom directly via a carbon atom; R.sub.2 and R.sub.3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms; z denotes an integer ranging from 1 to 3; and x denotes an integer ranging from 0 to 2; wherein z+x=3.

37. The process of claim 36, wherein the amino alkoxysilanes of formula (IVa) are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane, or N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane.

38. The process of claim 27, wherein the at least one amine compound of composition (B) or of dispersion (D) chosen from the e) polyamine compounds bearing several primary amine and/or secondary amine groups is chosen from: poly((C.sub.2-C.sub.5)alkyleneimines); poly(allylamines); polyvinylamines and copolymers thereof; polyamino acids containing NH.sub.2 groups; aminodextran; amino polyvinyl alcohol; copolymers based on acrylamidopropylamine; chitosans; polydi(C.sub.1-C.sub.4)alkylsiloxanes comprising amine groups at the chain end or on side chains; or mixtures thereof.

39. The process of claim 38, wherein the polydi(C.sub.1-C.sub.4)alkylsiloxanes comprising amine groups at the chain end or on side chains are chosen from: polyamine compounds comprising end or side amino(C.sub.1-C.sub.6)alkyl groups of formula (IVb), (IVc), or (IVd): ##STR00015## wherein in formula (IVb): R.sup.a and R.sup.b, which may be identical or different, are chosen from a (C.sub.1-C.sub.4)alkyl group, (C.sub.1-C.sub.4)alkoxy, aryl, aryloxy, aryl(C.sub.1-C.sub.4)alkyl, or an aryl(C.sub.1-C.sub.4)alkoxy; R.sup.c and R.sup.c, which may be identical or different, are chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, an amino(C.sub.1-C.sub.4)alkyl, or (C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl group; X represents a covalent bond or an oxygen atom; ALK and ALK, which may be identical or different, represent a (C.sub.1-C.sub.6)alkylene group; and n represents an integer greater than 2; ##STR00016## wherein in formula (IVc): R.sup.a, R.sup.b, and R.sup.d, which may be identical or different, are chosen from a (C.sub.1-C.sub.4)alkyl group, (C.sub.1-C.sub.4)alkoxy, aryl, aryloxy, aryl(C.sub.1-C.sub.4)alkyl, or aryl(C.sub.1-C.sub.4)alkoxy, wherein R.sup.d may also represent a (C.sub.1-C.sub.6)alkyl group substituted with a (C.sub.1-C.sub.4)alkylamino or an amino group; R.sup.c is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; ALK represents a (C.sub.1-C.sub.6)alkyl group; and n and m, which may be identical or different, represent an integer greater than 2; ##STR00017## wherein in formula (IVd): R.sup.a and R.sup.b, which may be identical or different, are chosen from a (C.sub.1-C.sub.4)alkyl groups, (C.sub.1-C.sub.4)alkoxy, aryl, aryloxy, aryl(C.sub.1-C.sub.4)alkyl, or aryl(C.sub.1-C.sub.4)alkoxy; R.sup.d is chosen from a (C.sub.1-C.sub.6)alkyl group optionally substituted with a (C.sub.1-C.sub.4)alkylamino or amino group; R.sup.c is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; ALK represents a (C.sub.1-C.sub.6)alkylene group; and n represents an integer greater than 2; and amodimethicones of formula (IVe): ##STR00018## wherein in formula (IVe) R.sup.a and R.sup.b, which may be identical or different, are chosen from a (C.sub.1-C.sub.4)alkyl group, (C.sub.1-C.sub.4)alkoxy, aryl, aryloxy, aryl(C.sub.1-C.sub.4)alkyl, or aryl(C.sub.1-C.sub.4)alkoxy; R.sup.c is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; R.sup.e is chosen from a hydroxyl, (C.sub.1-C.sub.4)alkoxy, amino or (C.sub.1-C.sub.4)alkylamino group; R.sup.f is chosen from a (C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)alkoxy group, a hydroxyl or O(SiR.sub.2).sub.xR group, wherein R represents a (C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.4)alkoxy group and R represents a (C.sub.1-C.sub.4)alkoxy or hydroxyl group; R.sup.g is chosen from a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; ALK and ALK, which may be identical or different, represent a (C.sub.1-C.sub.6)alkylene group; n and m, which may be identical or different, represent an integer greater than 2, and p and x are integers greater than or equal to 0.

40. The process of claim 39, wherein: the polydi(C.sub.1-C.sub.4)alkylsiloxanes of formula (IVb) are chosen from compounds of formula (IVb) and (IVb) below: ##STR00019## wherein in formula (IVb), the value of n is such that the weight-average molecular weight of the compound is between 500 and 55 000; and wherein in formula (IVb), R.sup.c, R.sup.c, ALK, ALK, and n are as defined previously for those in formula (IVb); the polydi(C.sub.1-C.sub.4)alkylsiloxanes of formula (IVc) are chosen from compounds of the following formula (IVc) ##STR00020## wherein in formula (IVc), the values of n and m are such that the weight-average molecular weight of the compound is between 1000 and 55 000; the polydi(C.sub.1-C.sub.4)alkylsiloxanes of formula (IVd) are chosen from compounds of the following formula (IVd): ##STR00021## wherein in formula (Ivd), the value of n is such that the weight-average molecular weight of the compound is between 500 and 3000; the amodimethicones of formula (IVe) are chosen from compounds of formula (IVe) and formula (IVe) below: ##STR00022## wherein in formula (IVe): ALK represents a (C.sub.1-C.sub.6)alkylene group; ALK represents a (C.sub.1-C.sub.6)alkylene group; and m, n and p, which may be identical or different, represent an integer greater than 2, wherein the values of m, n and p are such that the weight-average molecular weight of the compound is between approximately 5000 and 500 000; ##STR00023## wherein in formula (IVe): R.sup.a and R.sup.b, which may be identical or different, are chosen from a (C.sub.1-C.sub.4)alkyl group or a (C.sub.1-C.sub.4)alkoxy group; R.sup.c is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; R.sup.f is chosen from a (C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)alkoxy group, or O(SiR.sub.2).sub.xR, wherein R represents a (C.sub.1-C.sub.4)alkyl group and R represents a hydroxyl or (C.sub.1-C.sub.4)alkoxy group; R.sup.g is chosen from a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; ALK represents a (C.sub.1-C.sub.6)alkylene group; ALK represents a (C.sub.1-C.sub.6)alkylene group; n and m, which may be identical or different, represent an integer greater than 2; and x is an integer greater than or equal to 0; wherein the values of m, n and x are such that the weight-average molecular weight of the compound is between 2000 and 700,000.

41. The process of claim 27, wherein composition (B) further comprises the iii) at least one hydrocarbon-based oil.

42. The process of claim 27, wherein composition (B) is aqueous and further comprises at least one chitosan and/or at least one polyamino acid.

43. The process of claim 27, wherein composition (B) is anhydrous.

44. The process of claim 27, wherein: the at least one dye is chosen from: oxidation dyes including at least one oxidation bases, optionally combined with one or more coupling agents; direct dyes chosen from azo direct dyes, (poly)methine dyes, carbonyl dyes, azine dyes, nitro(hetero)aryl dyes, tri(hetero)arylmethane dyes, porphyrin dyes, phthalocyanine dyes, natural direct dyes; natural dyes chosen from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orcein, or extracts or decoctions containing these natural dyes; or a combination thereof; and the at least one pigment is chosen from: organic nitroso pigment, nitro pigment, azo pigment, xanthene pigment, quinoline pigment, anthraquinone pigment, phthalocyanin pigment, metal complex type pigment, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, or quinophthalone; mineral or inorganic pigments chosen from iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue, or titanium oxide, or a combination thereof.

45. The process of claim 27, wherein the at least one pigment is chosen from organic pigments, mineral or inorganic pigments, fluorescent pigments, thermochromic pigments, photochromic pigments, coated or uncoated nacres in the form of pigment powder or paste, lakes, glitter flakes, or mixtures thereof; wherein the at least one pigment is dispersed in the disperse (A), composition (B), and/or disperse (D); and wherein the at least one pigment is surface-treated with an organic agent.

46. The process of claim 27, wherein composition (C) is applied to the keratin fibers after the oily dispersion (A) is applied to the keratin fibers and before composition (B) is applied to the keratin fibers.

47. The process of claim 27, wherein the oily dispersion (A) is applied to the keratin fibers after composition (C) is applied to the keratin fibers and before composition (B) is applied to the keratin fibers.

48. The process of claim 27, wherein after applying to the keratin fibers the oily dispersion (A) and before applying to the keratin fibers composition (B), without rinsing, the keratin fibers are dried in the air or by using a drying device.

49. The process of claim 27, wherein composition (C) is applied to the keratin fibers before the oily dispersion (D) is applied to the keratin fibers.

50. A kit comprising: a first compartment comprising a dispersion (A), wherein the dispersion (A) comprises: i) at least one particle comprising at least one ethylenic copolymer of: a) C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, and b) ethylenically unsaturated anhydride compound; ii) at least one stabilizer comprising at least one ethylenic polymer chosen from: c) polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers, d) copolymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate and (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, or a combination thereof; and iii) at least one hydrocarbon-based oil; a second compartment comprising a composition (B), wherein the composition (B) comprises: iv) at least one amine compound chosen from: e) polyamine compounds bearing several primary amine and/or secondary amine groups, f) amino alkoxysilanes, or a combination thereof; and optionally a third compartment comprising a composition (C), wherein the composition (C) comprises at least one dye and/or at least one pigment.

51. An oily dispersion (A) comprising: i) at least one particle comprising at least one ethylenic copolymer of: a) C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, and b) ethylenically unsaturated anhydride compound; ii) at least one stabilizer comprising at least one ethylenic polymer chosen from: c) polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers, d) copolymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate and (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate, or a combination thereof; iii) at least one hydrocarbon-based oil; and v) optionally at least one dye and/or at least one pigment, wherein when the at least one pigment is present, the oily dispersion (A) is anhydrous and does not comprise any polyamine compound bearing primary amine and/or secondary amine groups, and does not comprise any amino alkoxysilanes.

52. The oily dispersion (A) of claim 51, wherein the oily dispersion (A) is in emulsion of water-in-oil (W/O) type, and further comprises at least one surfactant.

Description

EXAMPLES

Example 1

[0430] The oily dispersions (A) are formed as a whole [particles i)+stabilizer ii)] containing: [0431] 70% by weight of (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)(alkyl)acrylate a) (such as ethyl acrylate), [0432] 10% by weight of ethylenically unsaturated anhydride compound b) (such as maleic anhydride), and [0433] 20% by weight of polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers c) (such as isobornyl acrylate).

[0434] The preparation of these oily dispersions was performed in a 1 liter pilot reactor. The synthesis is performed in two steps:

[0435] In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60140) in the presence of a small amount of ethyl acrylate and of a radical initiator (T21S). In the first step, the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.

[0436] In the second step, the rest of the ethyl acrylate and the maleic anhydride are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator Trigonox 21S (T21S).

[0437] After stripping, the polymer is at a solids content of 52% in the isododecane. The ratios employed to obtain the stabilizer and the particulate core are summarized in the table below:

TABLE-US-00001 Mass percentage Mass percentage in Stabilizer - the stabilizer and Particulate core Monomer the particulate core Stabilizer ii) 22 Isobornyl acrylate 92 Ethyl acrylate 8 Particulate 78 Ethyl acrylate 87 core i) Maleic anhydride 13

Amount of Reagents:

Step 1:

[0438]

TABLE-US-00002 Reagents: Mass (g) Isobornyl acrylate 50 Ethyl acrylate 4 T21S 0.54 Isododecane/EtOAc (60/40) 96

[0439] Isododecane added between the two steps:

TABLE-US-00003 Reagent Mass (g) Isododecane/EtOAc (60/40) 80

Step 2:

[0440]

TABLE-US-00004 Mass added to the beaker Reagents: Mass (g) for the addition (g) Ethyl acrylate 171 196.65 Maleic anhydride 25 28.7 T21S 1.96 2.25 Isododecane/EtOAc 196 225.4 (60/40)

Experimental Protocol:

[0441] Isododecane/ethyl acetate (60/40), isobornyl acrylate, ethyl acrylate and T21S are introduced as feedstock into a reactor. The medium is heated to 90? C. under argon and with stirring. The solids content during this first step is 35.9%.

[0442] After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 97% (ethyl acrylate consumption: 97%).

[0443] After 2 hours of reaction, isododecane/ethyl acetate (60/40) are introduced into the feedstock. The medium is heated to 90? C.

[0444] Once the medium is at 90? C., ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky. The solids content is 40%.

[0445] After 7 hours of synthesis, traces of the starting monomers remain.

[0446] 1 L of isododecane and of ethyl acetate are then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is about 52%.

Example 2

[0447] The combination of particles i)+stabilizer ii) was prepared in the following manner: [0448] 75% by weight of (C.sub.1-C.sub.4)alkyl (C.sub.1-C.sub.4)alkyl)acrylate a) (such as ethyl acrylate), [0449] 5% by weight of ethylenically unsaturated anhydride compound b) (such as maleic anhydride), and [0450] 20% by weight of polymers of (C.sub.3-C.sub.12)cycloalkyl (C.sub.1-C.sub.6)(alkyl)acrylate monomers c) (such as isobornyl acrylate).

[0451] The synthesis was performed in a 1 liter pilot reactor in two steps:

[0452] In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of ethyl acrylate and of a radical Initiator (T21S). In the first step, the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.

[0453] In the second step, the rest of the ethyl acrylate and the maleic anhydride are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator (T21S).

[0454] After stripping, the polymer is at a solids content of 49% in the isododecane.

[0455] The ratios employed to obtain the stabilizer and the particulate core are summarized in the table below:

TABLE-US-00005 Mass percentage Mass percentage in Stabilizer - the stabilizer and Particulate core Monomer the particulate core Stabilizer ii) 22 Isobornyl acrylate 92 Ethyl acrylate 8 Particulate 78 Ethyl acrylate 94 core i) Maleic anhydride 6

Amount of Reagents:

Step 1:

[0456]

TABLE-US-00006 Reagents: Mass (g) Isobornyl acrylate 50 Ethyl acrylate 4 T21S 0.52 Isododecane/EtOAc (60/40) 96

Isododecane Added Between the Two Steps:

[0457]

TABLE-US-00007 Reagent Mass (g) Isododecane/EtOAc (60/40) 80

Step 2:

[0458]

TABLE-US-00008 Mass added to the beaker Reagents: Mass (g) for the addition (g) Ethyl acrylate 183.5 211.03 Maleic anhydride 12.5 14.38 T21S 1.96 2.25 Isododecane/EtOAc 196 225.4 (60/40)

Experimental Protocol:

[0459] Isododecane/ethyl acetate (60/40), isobornyl acrylate, ethyl acrylate and T21S are introduced as feedstock into the reactor. The medium is heated to 90? C. (nominal medium temperature) under argon and with stirring. The solids content during this first step is 35.9%.

[0460] After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 98% (ethyl acrylate consumption: 97%).

[0461] After 2 hours of reaction, isododecane/ethyl acetate (60/40) are introduced into the feedstock. The medium is heated to 90? C.

[0462] Once the medium is at 90? C., ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by addition. At the end of the introduction by addition, the medium is milky. The solids content is 40%.

[0463] After 7 hours of synthesis, traces of the starting monomers remain.

[0464] 1 L of isododecane and of ethyl acetate are then stripped (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is about 49%.

[0465] Amine compounds used:

TABLE-US-00009 Amine compound 1 Amine compound 2 Poly(dimethylsiloxane), Bis-cetearyl amodimethicone, bis(3-aminopropyl) 2-[(2-aminoethyl)amino]propyl Me, di-Me, terminated (PDMS-diNH.sub.2) [(C.sub.14-.sub.20-alkyldimethylsilyl)oxy]-terminated (CAS Number: (CAS Number: 1126942-72-0) 106214-84-0) (Mn = 50 000 g/mol)

[0466] The various combinations were evaluated in terms of the hair strand makeup or coating of keratin fibers, i.e. the coating of the keratin fibers with dyes/pigments. A comparison of the resistance to shampoo washing of the coatings was performed with the comparative composition below.

2-Step Process:

[0467] The following compositions and dispersions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Dispersiin (A1):

[0468]

TABLE-US-00010 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 10 (active material - a.m.) D&C Black 2 (carbon black) dispersed in isododecane, 3 polyglyceryl-3 diisostearate, propylene carbonate and quaternary amine/mineral clay complex, ingredient v), Isododecane, ingredient iii) qs 100

Composition (B1)

[0469]

TABLE-US-00011 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0470] The various steps of the protocol for applying to keratin fibers (natural hair containing 90% white hairs, also known as 90% NW): [0471] Application to the keratin fibers (dry hair) of dispersion (Ax) in a bath ratio of 0.5 g of dispersion or composition/g of hair; [0472] The lock is dried with a hairdryer; [0473] 3 hours after application of dispersion (Ax), application of composition (Bx) in a bath ratio of 0.5 g of composition (Bx)/g of hair; and then [0474] The lock is dried with a hairdryer.

[0475] The evaluations in terms of resistance to shampoo washing are thus performed 24 hours after the application.

Example 3: Application in 2 StepsDispersion (A1) Comprising Example 1+Carbon Black, Followed by Application of Composition (B1) Comprising the Amine Compound 2

[0476] A test was performed by applying only dispersion (A1). The tests of resistance to shampoo washing were observed after application of dispersion (A1) alone and for the process according to the invention, i.e. after application of dispersion (A1) and of composition (B1) or (B2).

[0477] The evaluation results are summarized in the tables below:

[0478] After application of dispersion (A1) before and after two shampoo washes: it is seen visually that the black coloring obtained after application of dispersion (A1) has almost completely disappeared after two shampoo washes.

[0479] These observations were corroborated with the L*, a* and b* colorimetric measurement results.

[0480] The colorimetric data for each of the locks are measured with a Minolta CM-3610d spectrophotometer. In this L*a*b* system, L represents the lightness, a* indicates the green/red color axis and b* indicates the blue/yellow color axis. The higher the value of L, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.

Colorimetric Measurements:

[0481]

TABLE-US-00012 Number of shampoo washes L 0 shampoo washes 28.92 2 shampoo washes 62.23

[0482] After application of dispersion (A1) before and after two shampoo washes: It is seen that the intense black coloring (L=28.92) obtained after application of dispersion (A1) has almost completely disappeared after two shampoo washes (L=62.23).

[0483] After application of dispersion (A1) and then of composition (B1) at 0, then 1 and then 5 shampoo washes:

[0484] Visually, the intense black coloring appears unchanged between the coloring obtained Just after having performed the process of the invention and after 1 and 5 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after 5 shampoo washes. The feel is very pleasant.

[0485] The colorimetric results were corroborated with the L*, a* and b* colorimetric measurement and color build-up results.

[0486] The color build-up on hair thus corresponds to the variation in coloring between the locks of dyed NW hair (natural gray hair containing 90% white hairs) and the non-dyed (i.e. untreated) NW hair, which is measured by (?E) according to the following equation:

[00001]$?E=\sqrt{{\left(L^{?}-L_0^{?}\right)}^2+{\left(a^{?}-a_o^{?}\right)}^2+{\left(b^{?}-b_o^{?}\right)}^2}$

[0487] In this equation, L*, a* and b* represent the values measured after dyeing of the NW hair, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured before dyeing of the NW hair. The higher the DE value, the better the build-up of the coloring.

TABLE-US-00013 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 28.92 ?0.16 2.73 32.21 1 shampoo wash 30.03 ?0.31 3.17 31.02 5 shampoo washes 29.82 ?0.12 3.08 31.24

[0488] It is seen from the above table that the values of L, a and b do not change significantly, after 1 shampoo wash and 5 shampoo washes.

Example Application in 2 StepsDispersion (A2) Comprising Example 1+Pigment: Nacre Followed by Application of Composition (Bi) Comprising Amine Compound 2

[0489] The following compositions and dispersions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Dispersion A2

[0490]

TABLE-US-00014 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 15 (a.m.) Nacre (Mica coated with brown iron oxide), CI 77491 - 6 ingredient v) Isododecane, ingredient iii) qs 100

Compostion B2

[0491]

TABLE-US-00015 Ingredients Amount (g) Amine compound 2, ingredient iv) 8 (a.m.) Isododecane, ingredient iii) qs 100

[0492] The intense chromatic coloring appears unchanged between the coloring obtained just after having performed the process of the invention, and this is found even after 20 successive shampoo washes:

TABLE-US-00016 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 34.88 ?14.19 ?11.39 40.63 20 shampoo washes 36.34 ?14.45 ?10.63 39.31

Example 5: Application in 2 StepsDispersion (A2) Comprising Example 1+Pigment: Nacre Followed by Application of Composition (B1) Comprising Amine Compound 2

Dispersion A2

[0493]

TABLE-US-00017 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 15 (a.m.) Nacre (mica coated with brown iron oxide) - ingredient v) 6 Isododecane, ingredient iii) qs 100

Composition (B1)

[0494]

TABLE-US-00018 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0495] Visually, the chromatic coppery coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 10 or even 20 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after more than 10 shampoo washes. The feel Is very pleasant. These color results were corroborated with the colorimetric measurements.

Colorimetric Measurements:

[0496]

TABLE-US-00019 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 35.43 ?16.78 ?10.45 40.73 10 shampoo washes 34.89 ?15.9 ?11.22 41.20 20 shampoo washes 35.37 ?15.95 ?12.35 41.68

[0497] It is seen from the above table that the values of L, a and b and ?E do not change significantly, after 10 or even 20 successive shampoo washes.

Example 6: Application in 2 StepsDispersion (A3) Comprising Example 2+Pigment: Nacre Followed by Application of Composition (B1) Comprising Amine Compound 2

Dispersion A3

[0498]

TABLE-US-00020 Ingredients Amount (g) Combination of particle example 2, ingredients i), ii) 15 (a.m.) Red 7, isopropyl titanium triisostearate, triethoxysilylethyl 6 polydimethylsiloxyethyl dimethicone, ingredient v) Isododecane, ingredient iii) qs 100

Composition (B1)

[0499]

TABLE-US-00021 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0500] Visually, the chromatic coppery coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 10 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after 10 shampoo washes. The feel is very pleasant. The color results on keratin fibers were corroborated with the L, a, b colorimetric measurements.

TABLE-US-00022 Number of shampoo washes L a b 0 shampoo washes 42.79 27.4 4.97 10 shampoo washes 44.62 28.62 4.68

[0501] It is seen from the above table that the values of L, a and b do not change significantly, after 10 successive shampoo washes.

Example 7: Application in 2 StepsDispersion (A4) Comprising Example 1+Pigment: Black Iron Oxide Followed by Application of Composition (B1) Comprising Amine Compound 2

Dispersion (A4)

[0502]

TABLE-US-00023 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 15 (a.m.) Black iron oxide (CI: 77499), ingredient v) 6 Isododecane, ingredient iii) qs 100

Composition (B1)

[0503]

TABLE-US-00024 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0504] Visually, the intense and deep black coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 10 successive shampoo washes. In addition, the hair strands appear Individualized after treatment, with a respected volume, and this is found even after 10 shampoo washes. The feel is very pleasant.

Example 8: Application in 2 StepsDispersion (A5) Comprising Example 1+Pigment: Lake Blue 1 Followed by Application of Composition (81) Comprising Amine Compound 2

Dispersion (A5)

[0505]

TABLE-US-00025 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 15 (a.m.) Blue 1 lake CI 42090 (&) triethoxycaprylylsilane, 6 ingredient v) Isododecane, ingredient iii) qs 100

Composition (B1)

[0506]

TABLE-US-00026 Ingredients Amount (g) Amine compound 2, ingredient iv) 8 (a.m.) Isododecane, ingredient iii) 95

[0507] Visually, the intense and chromatic blue coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 10 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after 10 shampoo washes. The feel is very pleasant.

Example 9: Application in 2 StepsDispersion (A6) Comprising Example 1+Pigment: Red 7 Followed by Application of Composition (81) Comprising Amine Compound 2

Dispersion A9

[0508]

TABLE-US-00027 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 15 (a.m.) D&C Red 7 calcium salt of lithol red B, CI 15850, 6 ingredient v) Isododecane, ingredient iii) qs 100

Composition (B1)

[0509]

TABLE-US-00028 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0510] Visually, the intense and chromatic red coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 10 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after 10 shampoo washes. The feel is very pleasant.

Example 10: Application in 3 StepsComposition (C1) Comprising the Pigment Black 2, Followed by Application of Dispersion (A7) Comprising Example 1, and then Application of Composition (B1) Comprising the Amine Compound 2

Application Protocol: 3-Step Protocol

[0511] The various steps of the protocol for application to 90% NW hair: [0512] 1. Application to dry hair of the pigment alone conveyed in a cosmetic solvent (water, isododecane), application of composition (C) [0513] 2. The lock is dried with a hairdryer [0514] 3. Dispersion (A7) is applied directly after drying, in a bath ratio of 0.5 g of formula/g of hair [0515] 4. The lock is dried with a hairdryer [0516] 5. 3 hours after application of (A7), application of composition (B1), in a bath ratio of 0.5 g of formula/g of hair [0517] 6. The lock is dried with a hairdryer [0518] 7. The evaluations in terms of resistance to shampoo washing are thus performed 24 hours after the application of (B1).

Composition (C)

[0519]

TABLE-US-00029 Ingredients Amount (g) D&C Black 2 (carbon black - CI 77266) & Laureth-21, 3 (a.m.) ingredient v) Water qs 100

Dispersion (A7)

[0520]

TABLE-US-00030 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 10 (a.m.) Isododecane, ingredient iii) qs 100

Composition (B1)

[0521]

TABLE-US-00031 Ingredients Amount (g) Amine compound 2, ingredient iv) 5 (a.m.) Isododecane, ingredient iii) 95

[0522] Visually, the intense and deep black coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 1 and 5 successive shampoo washes. In addition, the hair strands appear Individualized after treatment, with a respected volume, and this is found even after 10 shampoo washes. The feel is very pleasant. The color results on keratin fibers are corroborated with the L, a, b colorimetric measurements.

Colorimetric Measurements:

[0523]

TABLE-US-00032 Number of shampoo ?E color washes L a b build-up 5 shampoo washes 25.42 0.1 2.32 4.9 10 shampoo washes 25.53 0.05 1.32 4.6

[0524] It is seen from the above table that the values of L, a and b and ?E do not change significantly, after 5 or even 10 successive shampoo washes.

Examples 11 to 13

[0525] In examples 11 to 13 below, the following dispersions and compositions were prepared.

[0526] The amounts are given in g per 100 g of dispersion or composition.

[0527] The various steps of the protocol for applying to keratin fibers (natural hair containing 90% white hairs, also known as 90% NW): [0528] Application to the keratin fibers (dry hair) of composition (Cx), in a bath ratio of 0.5 g of dispersion or composition/g of hair; [0529] The lock is dried with a hairdryer; [0530] 1 hour after application of dispersion (Cx), application of composition (D), in a bath ratio of 0.5 g of composition (D)/g of hair; and then [0531] The lock is dried with a hairdryer.

[0532] The evaluations in terms of resistance to shampoo washing are thus performed 24 hours after the application.

Example 11

Composition (C1)

[0533]

TABLE-US-00033 Ingredients Amount (g) Red iron oxide (CI: 77491), ingredient v) 6 (a.m.) Isododecane qs 100

Dispersion D

[0534]

TABLE-US-00034 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 6 (a.m.) Amine compound 2, ingredient iv) 14 Isododecane, ingredient iii) qs 100

[0535] The colorimetric data for each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Colorimetric Measurements:

[0536]

TABLE-US-00035 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 40.09 24.39 20.2 32.78 5 shampoo washes 46.34 18.05 19.21 23.84

[0537] Visually, the intense red coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 5 successive shampoo washes. In addition, the hair strands appear Individualized after treatment, with a respected volume, and this is found even after 5 shampoo washes. The feel is very pleasant.

Example 12

Composition (C2)

[0538]

TABLE-US-00036 Ingredients Amount (g) Red iron oxide treated with 2% of isopropyl titanium 6 (a.m.) triisostearate, ingredient v) Isododecane qs 100

Dispersion D

[0539]

TABLE-US-00037 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 6 (a.m.) Amine compound 2, ingredient iv) 14 Isododecane, ingredient iii) qs 100

[0540] The colorimetric data for each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Colorimetric Measurements:

[0541]

TABLE-US-00038 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 38.9 23.73 20.39 33.23 5 shampoo washes 49.57 17.6 19.23 21.26

[0542] Visually, the intense red coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 1 and 5 successive shampoo washes. In addition, the hair strands appear Individualized after treatment, with a respected volume, and this is found even after 5 shampoo washes. The feel is very pleasant.

Example 13

Composition (C2)

[0543]

TABLE-US-00039 Ingredients Amount (g) Red iron oxide 8% treated with isopropyl titanium 6 (a.m.) triisostearate and triethoxysilylethyl polydimethylsiloxyethyl dimethicone, ingredient v) Isododecane qs 100

Dispersion D

[0544]

TABLE-US-00040 Ingredients Amount (g) Combination of particle example 1, ingredients i), ii) 6 (a.m.) Amine compound 2, ingredient iv) 14 Isododecane, ingredient iii) qs 100

[0545] The colorimetric data for each of the locks are then measured with a Minolta CM-3810d spectrophotometer.

Colormetric Measurements:

[0546]

TABLE-US-00041 Number of shampoo ?E color washes L a b build-up 0 shampoo washes 40.87 19.96 18.72 29.18 5 shampoo washes 48.58 15.5 18.85 20.44

[0547] Visually, the intense red coloring appears unchanged between the coloring obtained just after having performed the process of the invention and after 1 and 5 successive shampoo washes. In addition, the hair strands appear individualized after treatment, with a respected volume, and this is found even after 5 shampoo washes. The feel is very pleasant.