Colored polymers from azo dye monomers containing olefinic groups

Claim 2

A coloured polymer obtained by the co-polymerisation of at least one uncoloured polymerisable olefin and at least one azo dye which is free from water-solubilising groups and contains at least one polymerisable olefinically unsaturated group and has the formula: A--N═N--E wherein: A represents the residue of a carbocyclic diazotisable amine containing at least one electron-withdrawing substituent; and E represents the residue of a heterocyclic coupling component of the aminopyrazole, 2,6-diaminopyridine, 2,6-dihydroxypyridine or aminopyrimidine series; or A represents the residue of a heterocyclic diazotisable amine containing at least one electron-withdrawing substituent; and E represents the residue of a heterocyclic coupling component of the aminopyrazole, 2,6-diaminopyridine, 2,6-dihydroxypyridine or aminopyrimidine series; or A represents the residue of a heterocyclic diazotisable amine containing at least one electron-withdrawing substituent; and E represents the residue of a carbocyclic coupling component, the or each polymerisable group being attached to a carbon atom forming part of residue A or E.

Claim 3

A coloured polymer according to claim 1 wherein the azo dye of the formula A--N═N--E is: 2-ethyl-4,6-bis(2-methacryloyloxyethylamino)-5-(4-nitrophenylazo)pyrimidine; N,N-bis(2-acryloyloxyethyl)amino-3-methyl-4-(4-cyano-3-methylisothiazol-5-ylazo)benzene; N,N-bis(2-acryloyloxyethyl)amino-3-methyl-4-[4-cyano-3-(cyanomethyl)-1-methylpyrazol-5-ylazo]benzene; N,N-bis(2-acryloyloxyethyl)amino-3-methyl-4-(3,5-dicyano-4-methylthiophene-2-ylazo)benzene; and N,N-bis(2-methacryloyloxyethyl)amino-3-methyl-4-(4,5-dicyano-1-methylimidazol-2-ylazo)benzene.

Claim 4

A coloured polymer according to claim 1 wherein: A represents 4-(1,1-bisacryloxymethylpropoxycarbonyl)aniline and E represents 1-ethyl-5-cyano-4-methyl-5-hydroxypyrid-2-one; A represents 2-chloro-4-nitroaniline and E represents 1-[2,3-bis(acryloyloxy) prop-1-yl)-3-cyano-2-hydroxy-4-methylpyrid-6-one; A represents 2-chloro-4-nitroaniline and E represents 2,4,6-tris (2-acryloyloxyethylamino)-2-chloropyrimidine; A represents 2-chloro-4-nitroaniline and E represents 4,6-bis(2-acryloyloxy ethylamino)-2-thiomethylpyrimidine; A represents 2-chloro-4-nitroaniline and E represents 4,6-bis(2-acryloyloxy ethylamino)-2-N,N-bis-ethylaminopyrimidine; A represents 2-chloro-4-nitroaniline and E represents 5-(2,3-bis-acryloyloxy) prop-1-ylamino-1,3-dimethylpyrazole; A represents 2-chloro-4-nitroaniline and E represents 2,6-bis(2-acryloyloxy ethylamino)-3-cyano-4-methylpyridine; A represents 4-nitroaniline and E represents 2,4-bis-(2-acryloyloxyethyl amino)-4-chloropyrimidine; A represents 4-nitroaniline and E represents 2,4,6-tris-(2-acryloyloxyethyl amino)-pyrimidine; A represents 4-nitroaniline and E represents 2,6-bis(2-acryloyloxyethyl amino)-3-cyano-4-methylpyridine; A represents 4-nitroaniline and E represents 1-[2,3-bis(acryloyloxy)propy-1-yl]-3-cyano-2-hydroxy-4-methylpyrid-6-one; A represents 4-aminostyrene and E represents 1-(3-acryloyloxy-n-propyl)-3-cyano-2-hydroxy-4-methylpyrid-6-one; A represents 4-acryloyloxyethylaminosulphonylaniline and E represents 1-(3-acryloyloxy-n-propyl)-3-cyano-2-hydroxy-4-methylpyrid-6-one; A represents 2-chloro-4-nitroaniline and E represent 4,6-bis-(2-methacryloyl oxyethylamino)-2-ethylpyrimidine; A represents 4-nitroaniline and E represents 4,6-bis-(2-acryloyloxyethyl amino)-2-ethylpyrimidine; A represents 4-nitroaniline and E represents 4,6-bis-(2-methacryloyloxyethyl amino)-2-ethylpyrimidine; A represents 4-nitroaniline and E represents 4,6-bis-[2-(1-bromoacryloyloxy) ethylamino]-2-ethylpyrimidine; A represents 4-nitroaniline and E represents 4,6-bis-(2-(1-methoxyacryloyl oxy)ethylamino]-2-ethylpyrimidine.

Claim 5

A coloured polymer according to claim 1 wherein the or each polymerisable olefinically unsaturated group has the formula: ##STR17## wherein X represents an atom or group linking the olefinic group to a carbon atom present in residue A or residue E, n has the value 0 or 1 and each of R 1 , R 2 and R 3 independently represents a hydrogen or halogen atom or a hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, cycloalkyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, nitro, cyano, acyloxy or alkoxycarbonyl group.

Claim 6

A coloured polymer according to claim 4 wherein each of R 2 and R 3 is hydrogen and R 1 is hydrogen, halogen, lower alkyl, cyano or alkoxycarbonyl.

Claim 7

A coloured polymer according to claim 5 wherein R 1 is methyl.

Claim 8

A coloured polymer according to claim 4 wherein the or each polymerisable group has the formula: --O--CO--CR.sup.5 =CH.sub.2 wherein R 5 is hydrogen or lower alkyl.

Claim 9

A coloured polymer according to claim 3 wherein R 5 is methyl.

Claim 10

A coloured polymer according to claim 1 wherein the azo dye contains two polymerisable olefinically unsaturated groups.

Claim 11

A coloured polymer according to claim 4 wherein the azo dye has the formula: ##STR18## wherein A 2 represents the residue of a carbocyclic diazotisable amine containing at least one electron-withdrawing substituent and optionally one or more non-ionic substituent not electron-withdrawing in character; E 2 represents the residue of a heterocyclic coupling component; m is an integer of at least 1; and R 1 , R 2 , R 3 , X, and n have the meanings given in claim 2, the dye being free from water-solubilising groups.

Claim 12

A coloured polymer according to claim 4 wherein the azo dye has the formula: ##STR19## wherein A 3 represents the residue of a heterocyclic diazotisable amine containing at least one electron-withdrawing substituent and optionally one or more non-ionic substituent not electron-withdrawing in character; E 2 represents the residue of a heterocyclic coupling component; m is an integer of at least 1, and R 1 , R 2 , R 3 , X, and n have the meanings given in claim 4, the dye being free from water-solubilising groups.

Claim 13

A coloured polymer according to claim 4 wherein the azo dye has the formula: ##STR20## wherein A 3 represents the residue of a heterocyclic diazotisable amine containing at least one electron-withdrawing substituent and optionally one or more non-ionic substituent not electron-withdrawing in character; E 1 represents the residue of a carbocyclic coupling component; m is an integer of at least 1, and R 1 , R 2 , R 3 , X, and n have the meanings given in claim 2, the dye being free from water-solubilising groups.

Claim 14

A coloured polymer according to claim 1 which contains repeat units derived from at least one azo dye as defined in claim 1 and from at least one uncoloured polymerisable olefin.

Claim 15

A coloured co-polymer according to claim 13 containing from 2 to 10% by weight of units derived from an azo dye.

Claim 16

A coloured co-polymer according to claim 12 wherein the uncoloured polymerisable olefin is methyl methacrylate.

Claim 17

An aqueous dispersion or latex containing from 20 to 50% by weight of the coloured polymer defined in claim 1.

Claim 18

An aqueous dispersion or latex according to claim 16 wherein the coloured polymer contains (a) from 2 to 10% by weight of units derived from at least one azo dye as defined in claim 1 having at least two methacryloyl groups, and (b) from 98 to 90% by weight of units derived from a mixture of co-monomers containing from 99.9 to 95% by weight of methyl methacrylate and from 0.1 to 5% by weight of an N-methylolacrylamide derivative.