Blue polymeric hair dyes

1. Cationic polymeric dye with a hue value of h=210° to 330°, comprising

(a) a polymer backbone,

(b) a residue of an organic dye, and

(c) optionally colorless organic groups,

wherein (b) and (c) are covalently bound to the polymer backbone (a), the cationic charges can independently be part of the dye or the colorless organic groups and the residues of the organic dyes (b) are selected from the group consisting of 1,4-diamino-anthraquinone, thiazolazo, benzothiazolazo, thiadiazolazo and imidazolazo dyes.

2. Polymeric dye according to claim 1 , wherein 1 to 3 different residues of an organic dye (b) are bound to the polymer backbone (a).

3. Polymeric dye according to claim 1 , wherein the polymer backbone (a) is selected from polyethyleneimine, polypropyleneimine, polyvinylamine; polyvinylimine; polysiloxane; polystyrene, polyvinylimidazol, polyvinylpyridine, poly-DADMAC, polyvinylalcohol, polyacrylate, polymethacrylate; polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof; polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams; polysaccharide, starch, cellulose, lignin; and copolymers and blends of the mentioned polymers.

4. Polymeric dye according to claim 1 which corresponds to the formula

wherein

A and B, independently from each other represent a polymer backbone (a);

X 1 and X 2 , independently from each other are a linkage group selected from —C 1 -C 30 alkylene-, —C 2 -C 12 alkenylene-, —C 5 -C 10 arylene, —C 5 -C 10 cycloalkylene or —C 1 -C 10 alkylene(C 5 -C 10 arylene) which may be interrupted and/or terminated at one or both ends by one or more than one —O—, —S—, —N═, —N(R 1 )—, S(O)—, —SO 2 —, —(CH 2 CH 2 —O) 1-5 —, —(CH 2 CH 2 CH 2 —O) 1-5 —, —C(O)—, —C(O)O—, —OC(O)—,

—CON(R 1 )—, —C(NR 1 R 2 ) 2 —, —(R 1 )NC(O)—, —C(S)R 1 — or an optionally substituted, saturated or unsaturated, fused or non-fused aromatic or nonaromatic (hetero)cyclic bivalent radical optionally comprising at least one heteroatom; —O—; —S—; —N(R 1 )—; —S(O)—; SO 2 —; —(CH 2 CH 2 —O) 1-5 —; —C(O)—; —C(O)O—, —OC(O)—;

—C(O)N(R 1 )—; S(O) 2 N(R 1 )—; —C(NR 1 R 2 ) 2 —; —(R 1 )NC(O)—; —C(S)R 1 —;

saturated or unsaturated, fused or non-fused aromatic or nonaromatic bivalent radical optionally comprising at least one heteroatom, which is optionally substituted by C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 2 -C 12 alkenyl, C 5 -C 10 aryl, C 5 -C 10 cycloalkyl, C 1 -C 10 alkyl(C 5 -C 10 arylene), halogen, hydroxy; or the direct bond;

R 1 and R 2 independently from each other hydrogen; unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C 1 -C 14 alkyl; C 1 -C 14 hydroxyalkyl; C 1 -C 14 -aminoalkyl; C 2 -C 14 alkenyl; C 6 -C 10 aryl; C 6 -C 10 aryl-C 1 -C 10 alkyl; or C 5 -C 10 alkyl(C 5 -C 10 aryl);

Y 1 and Y 2 independently from each other are a residue of an organic dye (b), hydrogen, halogen or C 1 -C 6 alkyl; C 1 -C 6 alkoxy; C 1 -C 6 alkylamino; C 6 -C 10 aryloxy; C 6 -C 10 arylamino; SO 2 R 1 ; wherein at least one of Y 1 and Y 2 is a residue of an organic dye;

An 1 and An 2 independently from each other are an anion;

a and b independently from each other are a number from 1 to 3;

m is a number from 0 to 5000;

n is a number from 0 to 5000; and

p is a number from 1 to 5000;

wherein the sum of m+n+p≧3.

5. Polymeric dye according to claim 4 , wherein

X 1 and X 2 , independently from each other are a bivalent radical of formula (2a) -(T) t (Z) z —, wherein

T is a radical selected from saturated or unsaturated, linear or branched —C 1 -C 12 alkylene, —C(O)—, —(CH 2 CH 2 —O) 1-5 —, —(CH 2 CH 2 CH 2 —O) 1-5 —, —C(O)O—, —OC(O)—, —N(R 1 )—, —CON(R 1 )—, —(R 1 )NC(O)—, —O—, —S—, —S(O)—, —S(O) 2 —, —S(O) 2 —N(R 1 )—, and —N + (R 1 )(R 2 )—, which may be interrupted and/or terminated at one or both ends by one or more than one —O—, —S—, —SO 2 —, —N(R 5 )—, —C(O)—,

—CON(R 5 )—, —(R 5 )NC(O)— and which is optionally substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 6 aryl, halogen, hydroxy or Y + ; or is a direct bond;

Z is —(CH 2 ) 2 SO 2 —; —CH 2 CHRCO—NR 1 —; or a biradical of formula

R 1 and R 2 independently from each other are hydrogen; C 1 -C 6 alkyl; C 1 -C 6 alkoxy; C 1 -C 6 alkylamino; C 6 -C 10 aryloxy; or C 6 -C 10 arylamino;

R a is hydrogen; C 1 -C 6 alkyl; C 1 -C 6 -alkoxy; C 1 -C 6 -alkylamino; C 6 -C 10 -aryloxy; C 6 -C 10 -arylamino; SO 2 R 1 ; chlorine; or fluorine;

Y is R a ; Y 1 a+ ; or Y 2 b+ ;

Y 1 a+ and Y 2 b+ are halogen; hydrogen; CH 3 ; or a residue of an organic dye selected from the group consisting of 1,4-diamino-anthraquinone, thiazolazo, benzothiazolazo, thiadiazolazo and imidazolazo dyes, wherein at least one of the Y 1 a+ and Y 2 b+ is a residue of an organic dye; and

a and b independently from each other are 1, 2 or 3.

6. Dyes according to claim 5 , wherein

T is selected from —C 2 -C 3 alkylene-; C(O)—; —C(O)—CH 2 —; and —S(O) 2 —C 2-6 alkylene-;

Z is hydrogen or C 1 -C 6 alkyl; or a a biradical of formula

R 1 and R 2 independently from each other are hydrogen; C 1 -C 3 alkyl; C 1 -C 4 -alkoxy; C 1 -C 4 -alkylamino; C 6 aryloxy; or C 6 arylamino;

R a is chlorine, fluorine, methyl or SO 2 CH 3 ;

Y 1 a+ and Y 2 b+ are hydrogen; halogen; CH 3 ; or a residue of an organic dye selected from 1,4-diaminosubstituted anthraquinone, thiazolazo, benzothiazolazo, thiadiazolazo and imidazolazo dyes, wherein at least one of the Y 1 a+ and Y 2 b+ is a residue of an organic dye;

t and z, independently from each other are 0 or 1, with the proviso that at least one of t or z is 1.

7. Dye according to claim 1 , wherein the molecular weight of the polymeric dye is from 400 to 500000.

8. Dye according to claim 1 , wherein the polymer is a polyethyleneimine with a average molecular weight from 400-1800 g/mol, and the organic dye is bound via the primary secondary or tertiary amines of the polyethyleneimine.

9. Dye according to claim 1 , wherein the polymer is a homopolymer or a copolymer of 4-vinylpyridine or 2-vinylpyridine or vinylimidazole.

10. Dye according to claim 1 , which corresponds to formula

wherein

the poly-4-vinylpyridine has an average molecular weight of MW=1000 and 500000 g/mol,

Y 1 is a residue of an organic dye (b) as defined in claim 1 ,

X 1 is defined as a linkage group selected from —C 1 -C 30 alkylene-, —C 2 -C 12 alkenylene-, —C 5 -C 10 arylene, —C 5 -C 10 cycloalkylene or —C 1 -C 10 alkylene(C 5 -C 10 arylene) which may be interrupted and/or terminated at one or both ends by one or more than one —O—, —S—, —N═, —N(R 1 )—, S(O)—, —SO 2 —, —(CH 2 CH 2 —O) 1-5 —, —(CH 2 CH 2 CH 2 —O) 1-5 —, —C(O)—, —C(O)O—, —OC(O)—,

—CON(R 1 )—, —C(NR 1 R 2 ) 2 —, —(R 1 )NC(O)—, —C(S)R 1 — or an optionally substituted, saturated or unsaturated, fused or non-fused aromatic or nonaromatic (hetero)cyclic bivalent radical optionally comprising at least one heteroatom; —O—; —N(R 1 )—; —S(O)—; SO 2 —; —CH 2 CH 2 —O) 1-5 —; —C(O)—; —C(O)—, —OC(O)—;

—C(O)N(R 1 )—; S(O) 2 N(R 1 )—; —C(NR 1 R 2 ) 2 —; —(R 1 )NC(O)—; —C(S)R 1 —; saturated or unsaturated, fused or non-fused aromatic or nonaromatic bivalent radical optionally comprising at least one heteroatom, which is optionally substituted by C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 2 -C 12 alkenyl, C 5 -C 10 aryl, C 5 -C 10 cycloalkyl, C 1 -C 10 hydroxy(C 5 -C 10 arylene), halogen, hydroxy; or the direct bond;

R 1 and R 2 independently from each other hydrogen; unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C 1 -C 14 alkyl; C 1 -C 14 hydroxyalkyl; C 1 -C 14 -aminoalkyl; C 2 -C 14 alkenyl; C 6 -C 10 aryl; C 6 -C 10 aryl-C 1 -C 10 alkyl; or C 5 -C 10 alkyl(C 5 -C 10 aryl); and

the ratio of n:m is between 1:10 and 10:1.

11. Dye according to claim 4 , which corresponds to formula

wherein

R 3 is C 1 -C 5 alkyl.

12. Dye according to claim 4 , which corresponds to formula

wherein

R 3 is C 1 -C 5 alkyl.

13. Process for the preparation of the dyes according to claim 1 by using at least one of the following reactive dye building blocks

14. Dyes prepared by the reaction between polyethyleneimine and compounds of formula

15. A composition comprising at least one dye of formula (1a) or (1b) as defined in claim 4 .

16. A composition according to claim 15 comprising in addition at least one single further direct dye and/or an oxidative agent.

17. A composition according to claim 15 in form of a shampoo, a conditioner, a gel or an emulsion.

18. A method of dyeing organic material, which comprises treating the organic material with at least one dye of formula (1a), (1b) or (1c) according to claim 4 .

19. A method according to claim 18 , which comprises treating the organic material with at least one dye of formula (1a), (1b) or (1c) and an oxidative agent and, optionally, a further direct dye.

20. A method according to claim 18 , which comprises treating the organic material with at least one compound of formula (1a), (1b) or (1c) and at least one single oxidative dye, or treating the organic material with a dye of formula (1a), (1b) or (1c) and at least one single oxidative dye and an oxidative agent.

21. A method according to claim 18 wherein the organic material is selected from keratin-containing fibers.

22. A method according to claim 21 wherein the keratin-containing fiber is human hair.