Hair dyeing process comprising a block polymer bearing phosphonic acid groups and a pigment

Abstract

The invention relates to a hair dyeing process comprising at least one pigment, at least one additional component selected from cross linking agents and/or plasticizers and at least one block polymer comprising: a first block with a glass transition temperature (Tg) of greater than or equal to 40 C. derived from a monomer CH.sub.2C(R.sub.1)COOR2 in which R.sub.1=H or methyl, R.sub.2=C.sub.4 to C.sub.12 cycloalkyl group; and a second block with a glass transition temperature (Tg) of less than or equal to 20 C. derived from a vinylphosphonic acid and from a monomer CH2=C(R.sub.1)COOR.sub.3 in which R.sub.1=H or methyl, R.sub.3=linear or branched C.sub.1 to C.sub.6 unsubstituted alkyl group, with the exception of a tert-butyl group or a methoxyethyl group.

Claims

1. A hair dyeing process comprising the application on hair of (i) at least one pigment, (ii) at least one block polymer comprising: at least one first block with a glass transition temperature (Tg) of greater than or equal to 40 C. and obtained from at least one (meth)acrylate monomer of formula CH.sub.2C(R.sub.1)COOR.sub.2 in which R.sub.1 represents H or a methyl radical and R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group; and at least one second block with a glass transition temperature (Tg) of less than or equal to 20 C. and is obtained from at least one vinylphosphonic acid monomer of formula (I) and from at least one (meth)acrylate monomer of formula CH.sub.2C(R.sub.1)COOR.sub.3 in which R.sub.1 represents H or a methyl radical and R.sub.3 represents either a linear or branched C.sub.1 to C.sub.6 unsubstituted alkyl group, with the exception of a tert-butyl group or a methoxyethyl group; said vinylphosphonic acid monomer of formula (I) being: ##STR00007## in which: R1 denotes H or CH.sub.3; X denotes a covalent bond and n denotes an integer ranging from 0 to 14; or X denotes a COO group and n denotes an integer ranging from 2 to 6, and (iii) at least one additional compound selected from plasticizers and/or crosslinking agents.

2. The process according to claim 1, wherein the first block is obtained from at least one acrylate monomer of formula CH.sub.2CHCOOR.sub.2 in which R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group, and from at least one methacrylate monomer of formula CH.sub.2C(CH.sub.3)COOR.sub.2 in which R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group; and optionally an additional monomer chosen from linear or branched C.sub.8-C.sub.22 alkyl (meth)acrylates.

3. The process according to claim 2, wherein, for the first block, said acrylate monomer and said methacrylate monomer are in acrylate/methacrylate mass proportions of between 30/70 and 70/30.

4. The process according to claim 3, wherein the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

5. The process according to claim 1, wherein the proportion of the first block ranges from 60% to 80% by weight of the polymer.

6. The process according to claim 1, wherein, for the monomer of formula (I): X denotes a covalent bond and n is an integer ranging from 0 to 6 or X denotes a COO group and n is an integer ranging from 2 to 4.

7. The process according to claim 1, wherein, for monomer of formula (I), R1=H and X denotes a covalent bond and n is an integer ranging from 0 to 4.

8. The process according to claim 1, wherein monomer of formula (I) is selected from the group consisting of: vinylphosphonic acid; 3-butenylphosphonic acid; 4-pentenylphosphonic acid; 10-undecenylphosphonic acid; 11-dodecenylphosphonic acid; 2-phosphonoethyl ester of 2-methyl-2-propenoic acid; and 2-phosphonoethyl ester of 2-propenoic acid.

9. The process according to claim 1, wherein the second block comprises a monomer selected from the group consisting of isobutyl acrylate, ethyl acrylate, n-butyl acrylate and methoxyethyl acrylate, and mixtures thereof.

10. The process according to claim 1, wherein, for the second block, the vinylphosphonic acid monomer of formula (I) and said (meth)acrylate monomer are in (meth)acrylate/vinylphosphonic acid monomer of formula (I) mass proportions ranging from 1 to 10.

11. The process according to claim 1, wherein the proportion of the second block ranges from 20% to 40% by weight of the polymer.

12. The process according to claim 1, wherein the at least one block polymer comprises an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

13. The process according to claim 1, wherein the at least one block polymer has a polydispersity index of greater than 2.

14. The process according to claim 1 in which a composition comprising the at least one pigment, the at least one block polymer, and the at least one additional compound is applied to the hair and the amount of pigment in the composition applied to the hair is between 0.5% and 40% by weight relative to the total weight of the composition.

15. The process according to claim 1, wherein a composition comprising the at least one pigment, the at least one block polymer, and the at least one additional compound is applied to the hair and the additional compound is a crosslinking agent is an amine compound chosen from polyamine compounds bearing several primary amine groups and/or secondary amine groups and amino alkoxysilanes, the composition being anhydrous when the crosslinking agent is an amino alkoxysilane.

16. The process according to claim 15, wherein the amine compound comprises from 2 to 20 carbon atoms.

17. The process according to claim 15, wherein the amine compound is selected from the group consisting of N-methyl-1,3-diaminopropane, N-propyl-1,3-diaminopropane, N-isopropyl-1,3-diaminopropane, N-cyclohexyl-1,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methylbis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylenetriamine, 1,2-bis(3-aminopropylamino)ethane, N,N-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylenediamine, tris(2-aminoethyl)amine and spermidine.

18. The process according to claim 15, wherein the crosslinking agent is an amino alkoxysilane and the amino alkoxysilane is of formula (III):
R.sub.1Si(OR.sub.2).sub.z(R.sub.3).sub.x(III) in which: R.sub.1 is a linear or branched, saturated or unsaturated, cyclic or acyclic C.sub.1-C.sub.6 hydrocarbon-based chain substituted with a group selected from the group consisting of the following groups: amine NH.sub.2 or NHR with R=C.sub.1-C.sub.4 alkyl, an aryl or aryloxy group substituted with an amino group or with a C.sub.1-C.sub.4 aminoalkyl group, R.sub.1 possibly being interrupted in its chain with a heteroatom or a carbonyl group, R.sub.1 being linked to the 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, with z+x=3.

19. The process according to claim 15, wherein the amine compound is an amine-based polymer, having a weight-average molecular weight ranging from 500 to 1 000 000.

20. The process according to claim 19, wherein the amine compound is an amine-based polymer selected from the group consisting of: poly((C.sub.2-C.sub.5)alkyleneimines) and copolymers thereof; polydimethylsiloxanes comprising primary amine groups at the chain end or on side chains of formula (A) or (B) or (C): ##STR00008## wherein: in formula (A): the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55 000; in formula (B), the values of n and m are such that the weight-average molecular weight of the silicone is between 1000 and 55 000; in formula (C), the value of n is such that the weight-average molecular weight of the silicone is between 500 and 3000; amodimethicones of formula (D): ##STR00009## in which R, R and R, which may be identical or different, each represent a C.sub.1-C.sub.4 alkyl or hydroxyl group, A represents a C.sub.3 alkylene group and m and n are such that the weight-average molecular weight of the compound is between approximately 5000 and 500 000, polyether diamines; polytetrahydrofuran ,-diamines, polytetramethylene glycol ,-diamines, or polybutadiene ,-diamines; polyamidoamine dendrimers bearing amine end functions; and poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary amine side functions.

21. The process according to claim 18, wherein the crosslinking agent is an amine compound selected from the group consisting of polydimethylsiloxanes comprising primary amine groups at the chain end or on side chains and 3-aminopropyltriethoxysilane.

22. The process according to claim 15, wherein the amine compound is used in a mole ratio of amine group of the amine compound/phosphonic acid of the polymer ranging from 0.01 to 10.

23. The process according to claim 18, wherein when the composition contains an amino alkoxysilane, it comprises a C.sub.2-C.sub.5 monoalcohol in a content ranging from 0.1% to 5% by weight relative to the total weight of the composition.

24. The process according to claim 15, wherein the additional compound is a plasticizer and the plasticizer is selected from the group consisting of tri-n-butyl citrate, tripropylene glycol monomethyl ether (INCI name: PPG-3 methyl ether) and trimethyl pentaphenyl trisiloxane and non volatile oil.

25. The process according to claim 1 wherein a clay selected from clays of the smectite family, of the kaolinite family, optionally modified clays of the halloysite, dombassite, antigorite, benthierine, pyrophyllite, montmorillonite, beidellite, vermiculite, talc, stevensite, hectorite, bentonite, saponite, chlorite, sepiolite and illite family is further applied to the hair.

26. The process according to claim 1 wherein a salt of divalent or trivalent metal ions selected from salts of ions derived from Al(III), Ca(II), Cu(II), Fe(II), Fe(III), Mg(II), Mn(II), Zn(II) and mixtures thereof is further applied to the hair.

27. The process according to claim 1 wherein a metal oxide selected from titanium dioxide, iron oxides, zirconium oxides, zinc oxides, cerium oxides and chromium oxides is further applied to the hair.

28. The process according to claim 18, wherein the composition is formed by mixing two different compositions between 1 minute and 24 hours before application to keratin materials.

29. The process according to claim 18, wherein the composition further comprises an oil.

30. A composition comprising (i) at least one pigment, (ii) at least one block polymer comprising: at least one first block with a glass transition temperature (Tg) of greater than or equal to 40 C. and obtained from at least one (meth)acrylate monomer of formula CH.sub.2C(R.sub.1)COOR.sub.2 in which R.sub.1 represents H or a methyl radical and R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group; and at least one second block with a glass transition temperature (Tg) of less than or equal to 20 C. and is obtained from at least one vinylphosphonic acid monomer of formula (I) and from at least one (meth)acrylate monomer of formula CH.sub.2C(R.sub.1)COOR.sub.3 in which R.sub.1 represents H or a methyl radical and R.sub.3 represents either a linear or branched C.sub.1 to C.sub.6 unsubstituted alkyl group, with the exception of a tert-butyl group or a methoxyethyl group; said vinylphosphonic acid monomer of formula (I) being: ##STR00010## in which: R1 denotes H or CH.sub.3; X denotes a covalent bond and n denotes an integer ranging from 0 to 14; or X denotes a COO group and n denotes an integer ranging from 2 to 6, and (iii) at least one additional compound selected from plasticizers and/or crosslinking agents.

31. The composition according to claim 30, wherein the block polymer is present in a content ranging from 0.1% to 40% by weight and the pigment is present in a content ranging from 0.5% and 40% by weight, all weights relative to the total weight of the composition.

Description

EXAMPLE 1: ISOBORNYL METHACRYLATE/ISOBORNYL ACRYLATE (35/35)-CO-ISOBUTYL ACRYLATE/VINYLPHOSPHONIC ACID (25/5) COPOLYMER (COPOLYMER 1)

(1) 150 g of isododecane were placed in a 1 litre reactor and the solvent was then heated, increasing the temperature from 25 C. to 90 C. over 1 hour.

(2) 105 g of isobornyl methacrylate, 105 g of isobornyl acrylate and 1.8 g of initiator 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 from AkzoNobel) were then added over 1 hour, while maintaining the temperature at 90 C. The mixture was maintained at 90 C. for 1 hour 30 minutes.

(3) 75 g of isobutyl acrylate, 15 g of vinylphosphonic acid, 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane and 20 g of ethanol were then added over 30 minutes, still at 90 C.

(4) The mixture was maintained at 90 C. for 3 hours and was then diluted with 150 g of isododecane, and then concentrated by distillation to remove the unreacted monomers.

(5) A solution containing 50% by weight of the polymer in isododecane was finally obtained.

(6) The polymer obtained has a number-average molecular weight (Mn) of 20 800 and a weight-average molecular weight (Mw) of 3 122 000; with an Ip=15.

(7) Preparation of the Dyeing Compositions

(8) Comparison 1:

(9) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (15% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES) and qs to 100% with isododecane.

(10) Invention 1:

(11) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (15% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 3% of tributylcitrate (plasticizer) and qs to 100% with isododecane.

(12) Invention 2:

(13) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (15% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 3% of isohexadecane (plasticizing non volatile oil) and qs to 100% with isododecane.

(14) Invention 3:

(15) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (15% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 3% of isononyle isonanoate (plasticizing non volatile oil) and qs to 100% with isododecane.

(16) Invention 4:

(17) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (7.5% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 7.5% of (3-aminopropyl)triethoxysilane APTES (crosslinking agent) and qs to 100% with isododecane.

(18) Invention 5:

(19) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (15% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 3% of poly(dimethylsiloxane), bis(3-aminopropyl) terminated with Mn 25000 g/mol (PDMS-diNH2) and qs to 100% with isododecane.

(20) Invention 6:

(21) A dyeing composition was prepared from the solution of example 1 containing the copolymer 1 as above described (7.5% active material in isododecane), 6% of pigment (MICA (and) IRON OXIDES), 7.5% of APTES, 3% of Tributylcitrate and qs to 100% with isododecane.

(22) Comparison 2:

(23) A comparative composition was prepared from a solution of a pseudo block ACRYLIC ACID/ISOBUTYL ACRYLATE/ISOBORNYL ACRYLATE COPOLYMER 50% in isododecane (15% active material), 6% of pigment (MICA (and) IRON OXIDES) and qs 100% isododecane.

(24) Evaluation of the Color Resistance

(25) These dyeing compositions were applied on locks of natural hair with 90% of white hair. The compositions were applied on dried hair and on wet hair. 0.5 g of the dyeing composition was applied on 1 g of hair lock. After 24 h hours, the locks were washed and dried. Then, the locks were evaluated on dried hair after 1 shampoo, after 3 shampoos and then after 5 shampoos.

(26) The color resistance was visually evaluated on dried hair after 1 shampoo, 3 shampoos and 5 shampoos according to a resistance evaluation scale ranging from 5 (high color resistance) to 1 (no color resistance).

(27) After water rinsing and after 1, 3 and 5 shampoos, the color resistance was visually evaluated according to a color resistance evaluation scale ranging from 5 (high color resistance) to 1 (no color resistance).

(28) TABLE-US-00001 Application Water After 1 After 3 After 5 on resistance shampoo shampoo shampoo Comparison 1 Dried hair 5 1 1 1 Comparison 2 Dried hair 5 1 1 1 Invention 1 Dried hair 5 2 1 1 (tributyl citrate) Invention 2 Dried hair 5 2 1 1 (isohexa- decane) Invention 3 Dried hair 5 4 1 1 (isononyl isonanoate ) Invention 4 Dried hair 5 4 1 1 (APTES) Invention 5 Dried hair 5 2 1 1 ((PDMS diNH2) Invention 6 Dried Hair 5 5 3 1 (APTES + Tributyl citrate)

(29) These examples show that the composition of the invention provides an improvement of the color resistance to shampoos. After 5 shampoos, the color is still acceptable.