GB2317184A - Bis-[(2-[(Indanylazo)-sulpho-naphthalenylamino]-triazin-4-yl)amino]- substituted derivatives, free of fibre-reactive groups, as colourants for ink jet inks - Google Patents

Abstract

Compounds of the Formula (1) and salts thereof are provided: B 1 and B 2 each independently is an optionally substituted indanyl group; each J independently is a group of the Formula (2): R 3 is H or optionally substituted alkyl; n is an integer from 0 to 3; R 1 and R 2 each independently is H; alkyl; cycloalkyl; alkenyl; aryl; or aralkyl, each of which is optionally substituted; L is a divalent organic linking group; or L, R 1 and/or R 2 together with the nitrogen atoms to which they are attached form a 5 or 6 membered ring; each X independently represents a group of the formula: wherein: ```W represents a group of the formula -OR 4 ; -SR 4 or -NR 4 R 5 ; ```R 4 and R 5 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or R 4 and R 5 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or optionally R 4 and/or R 5 is, or contains a flexibly spaced amine; ```the compounds of Formula (1) being free from fibre-reactive groups. Also claimed are inks containing a compound of Formula (1), a process of ink jet printing and a substrate printed with the inks.

Description

CHEMICAL COMPOUNDS This invention relates to chemical compounds and more particularly to coloured azo compounds and inks containing such compounds suitable for use in the coloration of substrates, especially sheet materials such as paper, and especially by a printing process such as ink jet printing.

According to a first aspect of the present invention, there is provided a compound of the Formula (1) and salts thereof:

wherein: B' and B2 each independently is an optionally substituted indanyl group; each J independently is a group of the Formula (2):

R3 is H or optionally substituted alkyl; n is an integer from 0 to 3; R' and R2 each independently is H; alkyl; cycloalkyl; alkenyl; aryl; or aralkyl, each of which is optionally substituted; L is a divalent organic linking group; or L, R' andlor R2 together with the nitrogen atoms to which they are attached form a 5 or 6 membered ring; each X independently represents a group of the formula:

W represents a group of the formula -OR4; -SR4 or-NR4R5; R4 and R5 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or R4 and R5 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or optionally R4 andlor R5 is or contains a flexibly spaced amine; the compound of Formula (1) being free from fibre-reactive groups.

In a first preferred embodiment of the present invention L, B1, B2, R1 R2, R3, R4 and R5 are free from flexibly spaced amines.

In a second preferred embodiment of the present invention at least one of the groups represented by L, R4 and R5 contain one or more flexibly spaced amine(s). More preferably L contains a flexibly spaced amine and I or at least one of R4 and R5 is or contain a flexibly spaced amine.

A flexibly spaced amine is an optionally substituted amino group which is spaced from the group to which it is attached by one or more optionally substituted alkylene groups attached to the nitrogen of the amino group. The flexibly spaced amine may be a terminal group or a divalent residue forming part of a larger group.

Where the flexibly spaced amine is a terminal group it is a group of the formula:

wherein: A is an optionally substituted alkylene linking group containing one or more carbon atoms; Z' and Z2 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or Zg and Z2 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or Z' and A together with the nitrogen to which they are attached form a 5 or 6 membered ring.

Examples of flexibly spaced amines which are terminal groups include:

,Alkyl ,CH3 --Alkylenee-NI CH N, NH , CH2$2NNH Where the flexibly spaced amine is a divalent residue forming part of a larger group, it is a group of the formula:

wherein: A and Z1 are as hereinbefore defined; or A and Z1 together with the nitrogen to which they are attached form a 5 or 6 membered ring.

Examples of flexibly spaced amines in the form of a divalent residue include:

-Alkylene-N- --(CH2)2-N-- s -(CH2)2-N-' Alkyl H

When any of R', R2, R3, R4, R5, Z1 or Z2 is optionally substituted alkyl, preferred groups include for example optionally substituted C1 10-alkyl, preferably C, 6-alkyl groups and more preferably optionally substituted C14-alkyl groups which may be straight or branched chained.

Preferred optionally substituted cycloalkyl groups which may be represented by R1, R2, R4, R5, Z1 or Z2 include for example, optionally substituted Cs12-cycloalkyl, preferably optionally substituted Cs-cycloalkyl and especially optionally substituted cyclohexyl.

When any of R', R2, R4, R5, Z1 or Z2 is optionally substituted alkenyl, preferred groups include for example, optionally substituted C2 6-alkenyl, preferably optionally substituted C26alkenyl groups.

Preferred optionally substituted aryl groups which may be represented by R', R2, R4, R5, Z1 or Z2 include for example, mono and bicyclic aryl groups for example, naphthyl and phenyl, preferably phenyl, each of which may be optionally substituted.

When any of Rr, R2, R4, R5, Z1 or Z2 represent optionally substituted aralkyl groups it is preferably optionally substituted aryl-C14 -alkylene, more preferably phenyl-C,4- alkylene and especially benzyl and phenylethyl.

Preferred optionally substituted alkylene linking groups represented by A include for example, optionally substituted C1.10-alkylene, preferably optionally substituted C1- alkylene more preferably C24-alkylene optionally substituted by -OH, -SO3H and -COOH, and especially methylene, ethylene and propylene.

Preferred heterocyclic groups which may be represented by R4, R5, Z1 or Z2 are 5 or 6 membered rings and include for example, thienyl; pyrrolyl; pyridyl; pyrimidyl; tetrahydrofuryl; furanone pyrrolidinyl; pyrrolidinone; piperidyl; piperazinyl and morpholinyl.

When R4 and R5; Z1 and Z2; or Z1 and A; together with the nitrogen atom to which those groups are attached form a 5 or 6 membered ring, it is preferably piperidino, morpholino or piperazinyl; Optional substituents which may be present on R', R2, R3, R4, R51 B', B2, A, Z1 and Z2 are preferably selected from H; C14-alkyl optionally substituted with -OH, -SO3H or COOH, more preferably C,4-alkyl, or hydroxyC24-alkyl and especially methyl and hydroxyethyl; C14-alkoxy especially methoxy and ethoxy; aryl, especially phenyl optionally substituted with, -NH2 -OH, -SO3H or -COOH ; aryl-C1.4-alkyl, more preferably phenyl-C14- alkyl, and especially benzyl; amido, especially C14-alkyl amido; halogen; hydroxy; nitro; -CF3; -CN; -SO3H; -COOR8, where R8 is H or C,4-alkyi; or a 5 or 6 membered heterocyclic group for example, tetrahydrofuryl, piperazinyl or morpholinyl.

When W is a group of the formula -OR4 or -SR4 it is preferred that R4 is H; optionally substituted C,4-alkyl, preferably C,4-alkyl optionally substituted by -OH, -SO3H or -COOH and especially methyl, ethyl, propyl, hydroxyethyl-, sulphoethyl-, sulphopropyl-, carboxyethyl- and carboxypropyl-; a flexibly spaced amine or a group containing a flexibly spaced amine as hereinbefore defined.

It is especially preferred that W is -OH.

When W is a group of the formula -NR4R5 it is preferred that R4 and R5 each independently is H; optionally substituted C,-alkyl, more preferably C,4-alkyl, C"-alkyl substituted by -OH, -COOH or -SO3H and especially methyl, ethyl carboxyethyl, carboxypropyl hydroxyethyl, hydroxypropyl, sulphoethyl and sulphopropyl; optionally substituted aryl, especially optionally substituted phenyl; optionally substituted aralkyl, especially optionally substituted benzyl; a flexibly spaced amine or a group containing a flexibly spaced amine.

It is especially preferred that each W independently is a group of the formula NHRs wherein Rs is H; optionally substituted C,4-alkyl, more preferably C,4-alkyl, C14-alkyl substituted by -OH, -COOH or -SO3H and especially methyl, ethyl carboxyethyl, carboxypropyl hydroxyethyl, hydroxypropyl, sulphoethyl and sulphopropyl; optionally substituted aryl, especially optionally substituted phenyl; optionally substituted aralkyl, especially optionally substituted benzyl; or a flexibly spaced amine or a group containing a flexibly spaced amine as hereinbefore defined.

When the group representing W is substituted, preferred substituents are ClA alkyl, especially methyl and ethyl; C14-alkoxy, especially methoxy; halo; -CN; -NO2; -COOH; -OH; and -SO3H.

Preferred divalent organic linking groups represented by L include for example: alkylene, more preferably C14-alkylene, and especially C24-alkylene each of which is optionally interrupted; alkenylene, more preferably C2 12-alkenylene; arylene, more preferably an arylene group containing up to ten carbon atoms, and especially, phenylene and naphthylene; aralkylene, more preferably C7.11-aralkylene and especially phenylene-C, -alkylene; two of the hereinbefore defined arylene groups joined together either directly or through a divalent link; or optionally, L may contain a flexibly spaced amine; each of the above divalent organic linking groups may be substituted or unsubstituted.

When L is an alkylene group it is preferably C24-alkylene optionally interrupted by -O-, -S-, phenylene, -NR6-, -SS-, -C(O)- or -CO(O)-, wherein R6 is H, C,4-alkyl, or hydroxy -C,4-alkyl.

Preferred alkylene and aralkylene groups represented by L include, for example: ethylene 1,2- and 1,3-propylene 2-hydroxy-1 ,3-propylene 1- and 2-phenyl-1 3-propylene 2-(4'-sulphophenyl)-1 3-propylene 1,4-, 2,3- and 2,4-butylene 2methyl1 ,3-propylene 2-methyl-2 ,4-pentylene 2,2-dimethyl-1 ,3-propylene 1 -phenylethylene 1 -chloro-2,3-propylene 1,6- and 1,5-hexylene 2,3-diphenyl-1 ,4-butylene 1 -(methoxycarbonyl)-1 ,5-pentylene 1 -carboxy-1 ,5-pentylene 2,7-heptylene 3-methyl-1 6-hexylene m-, o- or p- xylylene 4-phenylsulphonyl -CH=CH -CH2CH=CHCH2 -CH2CH20CH2CH2 -CH2CH2SCH2CH2 -CH2CH2SSCH2CH2 -CH2NHCH2 Preferred arylene groups represented by L include for example 1,2-, 1,3- and 1,4phenylene and 1,4-naphthylene which are optionally substituted.

When L is two arylene groups joined together directly it is preferably a biphenylene group, for example optionally substituted 4,4'-biphenylene.

When L represents two arylene groups joined by a divalent linking group, the linking group is preferably -0-; -S-; -NR6-; -C(O)-; C2-C6-alkenylene; or C1.6-alkylene optionally interrupted by -O-, -S-, -NR6-, -SS-, -OC(O)- or -C(O); wherein R6 is as hereinbefore defined.

Preferred arylene groups joined by a divalent linking group include for example, diphen4,4'-ylene-methane;

When L, R' and/or R2 together with the nitrogen atoms to which they are attached for a 5 or 6 membered ring it is preferably a piperazine residue of the formula:

in which each of R7 and R8 independently is H or C, 6-alkyl optionally substituted by -OH, preferably methyl, ethyl, propyl or hydroxyethyl.

Where the divalent organic linking group L is substituted, the substituents is/are selected from H; alkyl, preferably C,4-alkyl and especially methyl; alkoxy, preferably CIA- alkoxy and especially methoxy; halo; -SO3H; -COOH; -OH; -CN; or -NO2.

When any of the indanyl groups represented by B' and B2 is substituted it is preferably substituted by at least one, more preferably 1 to 3 sulpho group(s).

It is especially preferred that B' and B2 each independently is an indan-5-yl group of the Formula (3):

wherein m is an integer from 0 to 3.

In the group of the Formula (3) it is preferred that m is 0 or 1. When m is 1 it is preferred that the sulpho group is attached at the 6-position in the indanyl group.

In the group of Formula (2), it is preferred that n is 1. When n is 1, it is preferred that the sulpho group is attached at the 3 position on the naphthalene nucleus.

Preferably the group of the formula:

is attached at the 1 position in the group of Formula (2).

A particularly preferred group which may be represented by J is of the Formula (4):

wherein R3 is as hereinbefore defined.

In view of the foregoing preferences, especially preferred compounds according to the present invention are of the Formula (5) and salts thereof:

wherein L and each W, R' and R3 independently is as hereinbefore defined.

It is preferred that the sulpho group is attached at the 6- position on the indanyl group in Formula (5).

First Preferred Embodiment As hereinbefore mentioned in the first preferred embodiment of the present invention L, B', B2, R1, R2, R3, R4 and R5 are free from flexibly spaced amines.

Accordingly, in the first preferred embodiment, preferred groups of the formula NR4Rs include for example, -N H2; 4-alkyl-NH-, especially methylamino, ethylamino and N-methylethyl amino; (C,4-alkanol)amino, especially (ethanol)amino; (carboxy-C,,- alkyl)amino, especially (carboxyethyl)amino and (carboxypropyl)amino; (sulpho-C,.4- alkyl)amino, especially (sulphoethyl)amino and (sulphopropyl)amino; hydroxy-C2.4- alkylamino, especially hydroxyethylamino; heterocyclic groups such as piperidino, morpholino, 1-pyrrolidinyl, 2-pyrrolidinone, 3-amino4, 5-dihydro-2-furanone and tetrahydrofuryl groups of the formula:

anilino; phenyl-C,,-alkylene-NH-, optionally substituted by -OH, -SO3H or -COOH especially phenyl-ethylamino and benzylamino.

Preferred groups of the formula -OR4 or -SR4 in the first preferred embodiment include for example,-OH, -SH, -S-C1.6-alkyl and -O-C, 6-alkyl optionally substituted by -OH, -SO3H or -COOH. It is especially preferred that W is -OH.

Second Preferred Embodiment As hereinbefore mentioned in the second preferred embodiment of the present invention at least one of the groups represented by L, R4 and R5 is, or contains, one or more flexibly spaced amine(s).

Accordingly, in the second preferred embodiment of the present invention, preferred groups represented by R4 and R5 which are flexibly spaced amines are of the hereinbefore defined formula:

for example, aminoethyl; 3-(dimethylamino)propyl;

and N, N-dimethylaminoethyl.

Preferred groups represented by R4 and R5 which contain one or more flexibly spaced amine(s) include for example, an alkyl or a phenyl group substituted by a group of the hereinbefore defined formula:

or an alkyl group interrupted by a group of the hereinbefore defined formula -A-N(Zt)-; for example: -(C H2)2NH(CH2)2N H2; -(CH2)3N (CH3)(CH2)3NH2;

In the second preferred embodiment it is preferred that one, or more preferably, each W independently is a group of the formula -NHR5, wherein R5 is a flexibly spaced amine or a group containing a flexibly spaced amine, especially a terminal group of the formula -A-NZ'Z2 wherein A, Z' and Z2 are as hereinbefore defined.

Preferred groups of the formula -NHRs represented by W in the second preferred embodiment include for example, a residue of an optionally substituted C28-alkylene diamine, especially ethylene diamine, propylene diamine and N,Ndimethylethylenediamine; triamines, for example H2N(CH2)3N(CH3)(CH2)3NH2 an amine or diamine containing a piperazinyl group for example, 1,4-bis(3-aminopropyl)piperazine or 1 -(2-aminoethyl)piperazine.

In the second preferred embodiment of the present invention it is preferred that the divalent linking group represented by L contains one or more flexibly spaced amine(s).

Preferred divalent organic linking groups which contain one or more flexibly spaced amine(s) include one of the hereinbefore mentioned divalent organic linking groups interrupted by a group of the formula:

wherein A and Z' are as hereinbefore defined. Examples of groups represented by L which contain a flexibly spaced amine include:

-(CH2)3N(CH3)(CH2)3 It is especially preferred that L contains a residue of the formula:

in which each of A, R7 and R8 independently is as hereinbefore defined.

Accordingly, an especially preferred group represented by the group -NR'-L-NR2is of the formula

wherein Al and A2 each independently is Ct4-alkylene and R', R2, R7 and R8 are as hereinbefore defined.

In the second embodiment of the present invention it is especially preferred that L, R4 and/or R5 each is or contain one or more flexibly spaced amine(s). It is especially preferred that the flexibly spaced amine(s) contains a piperazine ring.

when in the second preferred embodiment of the present invention any of the groups L, R4 and R5 is not, or does not contain, a flexibly spaced amine, that group is preferably one of the hereinbefore defined preferred groups of the first preferred embodiment. For example, if the divalent linking group contains a flexibly spaced amine and the groups represented by W do not, it is preferred that each W is, for example, -OH, -NH2, or a hydroxyalkylamine group.

The compounds of Formula (1) are free from fibre reactive groups. The term fibre reactive group is well known in the art and is described for example in our EP 0 356 014 Al. Such fibre reactive groups are capable, under suitable conditions, of reacting with the hydroxyl groups present in cellulosic fibres or with the amino groups present in natural fibres to form a covalent linkage between the fibre and the dye. As examples of fibre reactive groups excluded from the compounds of Formula (1) there may be mentioned aliphatic sulphonyl groups which contain a sulphate ester group in beta-position to the sulphur atom, e.g. beta-sulphato-ethylsulphonyl groups, alpha, beta- unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, alpha-chloro-acrylic acid, alpha-bromoacrylic acid, propiolic acid, maleic acid and mono-and dichloro maleic acids; also the acyl radicals of acids which contain a substituent which reacts with cellulose in the presence of an alkali, e.g. the radical of a halogenated aliphatic acid such as chloroacetic acid, beta-chloro and beta-bromopropionic acids and alpha, beta-dichloroand dibromopropionic acids or radicals of vinylsulphonyl- or beta-chloroethylsulphonyl- or beta-sulphatoethyl-sulphonyl-endo- methylene cyclohexane carboxylic acids. Other examples of cellulose reactive groups are tetrafluorocvclobutyl carbonyl, trifluoro cvclobutenyl carbonyl, tetrafluorocvclobutylethenyl carbonyl, trifluoro-cvclobutenylethenyl carbonyl; activated halogenated I, 3-dicyanobenzene radicals; and heterocyclic radicals which contain 1, 2 or 3 nitrogen atoms in the heterocyclic ring and at least one cellulose reactive substituent on a carbon atom of the ring.

It is to be understood that the compounds of the present invention include not only compounds in their free acid form shown in Formula (1), but also to the salts thereof and to mixtures of compounds of Formula (1).

Preferred salts are those with an alkali metal, particularly Na+, Li+ or K+ or a substituted ammonium cation.

The substituted ammonium cation may be a quaternary ammonium group of the formula +NQ4 in which each Q independently is an organic radical, or two or three Qs together with the nitrogen atom to which they are attached form a heterocyclic ring and all remaining Qs are selected from C,4-alkyl or C,4-alkyl substituted by -OH. Preferred organic radicals represented by Q are C14-alkyl radicals, especially methyl. Preferred heterocyclic rings formed by +NQ4 are 5 or 6 membered heterocyclic rings.

As examples of quaternary ammonium groups of formula +NQ4 there may be mentioned N+(CH3)4, N+(CH2CH3)4, N+(C2H5)3CH3, N+(C3H7)3CH3, N+(C2H5)2(C2H4OH)2, N+(C2H4OH)3C2H5, N+(CH3)3C2H4OH, N+(C2H4OH)3CH3, N-methyl pyridinium, N,N-dimethyl piperidinium and N,N-dimethyl morpholinium.

Alternatively, the substituted ammonium cation may be a group of formula +NHT3 wherein each T independently is H or C,,-alkyl, C,-alkyl substituted by -OH, or two or three groups represented by T together with the nitrogen atom to which they are attached form a 5 or 6 membered ring, especially a pyridine, piperidine or morpholine ring.

As examples of groups of formula +NHT3 there may be mentioned (CH3)3N+H, (CH3)2N+H21 H2N+(CH3)(CH2CH3), CH3N+H3, CH3CH2N+H3, H2N+(CH2CH3)2, CH3CH2CH2N+H3, +NH4, (CH3)2CHN+H3, N+H(C2H4OH)3, N+H2(C2H4OH)(CH3), N+H(C2H4OH)2(C2H5), pyridinium, piperidinium and morpholinium.

According to a further feature of the present invention there is provided a process for the manufacture of compounds of Formula (1) comprising condensing the disazo compound of the Formula (6) with a compound of the formula WH, preferably in the presence of a base:

Wherein: B', B2, L, R1, R2 and each J are as hereinbefore defined; and each Q independently is a labile atom or group.

Preferred labile atoms are halogens, especially Cl and Br and a preferred labile group is -OSO3H. It is especially preferred that Q is Cl.

The base may be any inorganic base such as an alkali metal or alkali earth metal hydroxide, carbonate or bicarbonate or an organic base. Preferred organic bases are tertiary amines such as N-alkylated heterocycles, for example N-(C,,-alkyl)morpholine, N-(C,-alkyl)piperidine, N, N1-di(C,,-alkyl)piperazine; tri(C,-alkyl)amines, for example triethylamine; and optionally substituted pyridines, especially pyridine.

The amount of base used may be varied between wide limits but it is preferred to use less than 40, more preferably less than 10 and especially from 3 to 5 moles for each mole of the compound of Formula (6).

The condensation is preferably performed in a liquid medium, preferably an aqueous medium and especially water. Ambient temperatures may be employed in conjunction with a reaction time of, for example, 5-24 hours, or elevated temperatures can be used for a shorter period.

After the condensation the product may be isolated by precipitating the product as a salt from the reaction mixture, for example by the addition of a suitable alkali metal salt, especially sodium chloride. Alternatively, the product may be isolated in its free acid form by acidifying the reaction mixture, preferably using a mineral acid, especially hydrochloric acid. Where the product precipitates as a solid it may be separated from the mixture by filtration.

If desired unwanted anions may be removed from the product of the above process by dialysis, osmosis, ultrafiltration or a combination thereof.

The product of the above process may be converted, where necessary, to the alkali metals NH4+, quaternary ammonium or organic amine salt by the addition of ammonia, ammonium hydroxide, primary, secondary, tertiary or quaternary amine or alkali metal salt. When the base used in the condensation process is an organic amine an excess may be used so that the sulpho groups in the compound of Formula (1) automatically result as their organic amine salt.

Where W is a group of the formula -OH, the compounds of Formula (1) may be prepared by hydrolysis of the compound of Formula (6). The hydrolysis is preferably performed using an aqueous solution of a suitable base, for example NaOH or sodium carbonate.

Where the compound of Formula (1) has different groups represented by W, the compound of Formula (6) may be condensed first with a 1 molar equivalent of a compound of formula W'H, where W' is as hereinbefore defined for W, followed by a further condensation with a compound of formula WH, or hydrolysis of the resulting compound, to give the compound of Formula (1).

The compounds of Formula (6) may be prepared by methods analogous to those described in the prior art for other disazo compounds. Thus, for example, a suitable method comprises: (i) diazotising an optionally substituted amino indan compounds of Formula (7): B-NH2 (7) wherein B is as hereinbefore defined for B' and B2; to form the corresponding diazonium salt; (ii) condensing a compound of the Formula (8) with a triazine compound of the Formula (9) preferably in the presence of a base:

wherein R3, n and each Q independently is as herein before defined; (iii) coupling the resultant triazinylamino compound with the diazonium salt to form the azo compound of Formula (10):

wherein: J and each Q independently is as hereinbefore defined; and B represents B' and/or B2 as herein before defined; (iv) condensing the azo compound of Formula (10) with a diamine of the formula NHR1LNR2H to give the compound of Formula (6).

Diazotisation of the optional, substituted amino indan may be carried out using any suitable diazotisation agent. Conveniently the diazotisation agent is formed in-situ, for example by dissolving an alkali metal nitrite, preferably sodium nitrite, in a molar excess of mineral acid, preferably HCI.

Normally at least 1 mole of diazotisation agent per mole of the optionally substituted amino indan will be used, preferably from 1 to 1.25 moles.

The temperature of the diazotisation is not critical and may conveniently be carried out at from -50C to 20"C, preferably from 0 to 10"C and especially from to 0 to 5 C.

It is preferred that the condensation of the compound of Formula (8) with the compound of Formula (9) is carried out in the presence of a dispersant. Any convenient dispersant may be utilised, for example Calsolene oil.

It is also possible to prepare the compounds of Formula (1) by condensing the compound of formula WH with the compound of Formula (10) preferably in the presence of a base. The resultant monochlorotriazinyl azo dye is then condensed with a diamine of the formula NHR'LNHR2 preferably at pH > 7 to give the bis azo dye of Formula (1).

As examples of aminoindan compounds of Formula (7) which are suitable there may be mentioned 5-aminoindan and 5 aminoindan-6-sulphonic acid.

The compound of Formula (8) is preferably 8-amino-1-naphthol-3,6-disulphonic acid.

It is preferred that the compound of Formula (9) is cyanuric chloride.

As examples of suitable diamines of formula NHR'LNR2H, there may be mentioned piperazine, 2,5-dimethylpiperazine, 2-, 3- and 4-aminobenzylamines, o-, mand p-xylylene diamines and phenylene diamines, 1-(2-aminoethyl)piperazine, 1,4-bis(3aminopropyl)piperazine and 1,4-Bis[3-(4-aminophenyl- sulphonamido)propyl] piperazine.

As examples of suitable compounds of formula WH, there may be mentioned alcohols, for example phenols, and alkanols, preferably methanol and ethanol; primary and secondary aliphatic, cycloaliphatic and aromatic amines and diamines for example, ammonia, 2-hydroxyethylamine, 1 -2-(aminoethyl)piperazine, 1,4-bis(3aminopropyl)piperazine, ethylenediamine, N, N-dimethylethylenediamine, 4-aminosalicylic acid, tetrahydrofurfurylamine, morpholine, piperazine and piperidine.

The compounds of the invention may be isolated by known methods, for example spray drying or precipitation and filtration.

The compounds of Formula (1) are useful as colorants for inks, especially ink jet printing inks. The compounds exhibit high solubility in water and aqueous media and provide prints which have a good water with a strong magenta shade on plain paper.

According to a second aspect of the present invention there is provided an ink comprising a compound of Formula (1) and a liquid medium, preferably an aqueous medium. It is preferred dimethylacetamide; ketones or ketone-alcohols, preferably acetone, diacetone alcohol, methyl ether ketone and cyclohexanone; ethers for example, tetrahydrofuran or dioxane; oligo- or poly-alkylene glycols for example, diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol; alkenyleneglycols or thioglycols containing a C2-C6-alkylene group for example, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol or hexylene glycol, thioglycol and thiodiglycol; polyols for example, glycerol or 1,2,6-hexanetriol; C1 -alkyl-ethers of polyhydric alcohols for example, 2methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol; heterocyclic ketones, for example, 2-pyrrolidone and N-methyl-2-pyrrolidone, N-ethyl-2pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclic esters, for example caprolactone; or mixtures containing two or more, especially from 2 to 8 of the aforementioned water-soluble organic solvents for example thiodiglycol and a second glycol or diethylene glycol and 2-pyrrolidone.

Preferred water-soluble organic solvents are 2-pyrrolidone; N-methylpyrrolidone; alkylene glycols, oligo-alkylene glycols and diols, for example ethylene glycol, diethylene glycol, triethylene glycol, thiodiglycol and pentane-1,5-diol; C,4-alkyl ethers of polyhydric alcohols, for example 2-methoxy-2-ethoxy-2-ethoxy-ethanol; and polyethylene glycols with a molecular weight of up to 500;. A preferred specific solvent mixture is a binary or temary mixture of water and diethylene glycol and/or, 2-pyrrolidone or Nmethylpyrrolidone in weight ratios 75-95:25-5 and 60-80:0-20:0-20 respectively. An especially preferred specific solvent mixture is a binary or tertiary mixture of water and thiodiglycol and/or 2-pyrrolidone or N-methylpyrrolidone in weight ratios 75-98:25-2 and 60-90:0-10:0-10 respectively.

It is preferred that the inks further comprise one or more surfactants to aid the penetration of the dye into a paper substrate. Suitable surfactants include anionic surfactants for example, fatty acid salts and alkylbenzenesulphonates; cationic surfactants for example, aliphatic amine salts and quaternary ammonium salts; and non ionic surfactants for example, ethylene oxide adducts of higher alcohols, of alkylphenols, of higher alcohol fatty acid esters, of fatty acid amides, of polypropylene glycol, of acetylene, fatty acid esters of polyhydric alcohols and amino acid and betaine type amphoteric surfactants. It is preferred that the surfactant is a non-ionic surfactant, more preferably poly(ethylene oxide) adducts of acetylene, for example SURFYNOL 465 TM (available from Air Products Ltd). Where a surfactant is used in an ink it is preferably present at a concentration in the range of from 0.01 to 10%, more preferably from 0.05 to 5% and especially from 0.1 to 2% based upon the total weight of the ink.

Examples of suitable ink media are given in US 4,963,189, US 4,703,113, US 4,626,284 and EP-A-0425150.

According to a third aspect of the present invention there is provided a process for printing a substrate with an ink using an ink jet printer, characterised in that the ink contains at least one compound of Formula (1).

Preferred inks for use in the process are those defined in the second aspect of the present invention.

A suitable process for the application of an ink as hereinbefore defined comprises forming the ink into small droplets by ejection from a reservoir through a small orifice so that the droplets of ink are directed at a substrate. This process is commonly referred to as ink jet printing, and preferred ink jet printing processes for the present inks are piezoelectric ink jet printing and thermal ink jet printing. In thermal ink jet printing, programmed pulses of heat are applied to the ink in the reservoir by means of a resistor adjacent to the orifice, during relative movement between the substrate and the reservoir.

Preferred substrates for ink jet printing include for example, plastic, textile, metal, glass, overhead projector slides, or paper.

Preferred papers are plain and treated papers, which may have an acid, alkaline or neutral character; plastic.

When the substrate is a textile material, it is preferably a natural, semi-synthetic or synthetic material. Examples of natural textile materials include wool, silk, hair and cellulosic materials, particularly cotton, jute, hemp, flax and linen. Examples of synthetic and semi-synthetic materials include polyamides, polyesters, polyacrylonitriles and polyurethanes.

According to a fourth aspect of the present invention, there is provided a paper, an overhead projector slide or a textile printed with an ink according to the second aspect of the present invention or by means of the process according to the third aspect of the present invention.

The invention is further illustrated but not limited by the following Examples in which all parts and percentages are by weight unless stated otherwise.

Svnthesis A: Preparation of 5-aminoindanSsulPhonic Acid 5-Aminoindan (48.59) was finely ground and added with vigorous stirring to concentrated sulphuric acid (200ml). The mixture was heated at 95"C for 20 hours then cooled to ambient temperature and drowned out into ice (8009). The title product was filtered off, washed with acetone and dried under vacuum at ambient temperature.

Svnthesis B: Preparation of 1.4-Bisf3-(4-aminoPhenvlsulphonamido)propyllpiperazine

Stage (i) N-Acetylsuphanilyl chloride (18.709) was dissolved in a mixture of tetrahydrofuran (400ml) and water (400ml). 1 ,4-Bis(3-aminopropyl)piperazine (8.029) was dissolved in tetrahydrofuran (100ml) and added dropwise to the sulphonyl chloride solution. After adjusting to pH 8.5 with 2N sodium carbonate, the solution was stirred at 30"C for 2 hours. The precipitate which formed was, filtered off, washed with water then acetone and dried under vacuum at ambient temperature to give a fine white powder (21.92g).

Staae (ii) The product from stage (i) (20.509) and potassium hydroxide (30g) were refluxed in ethanol (1500ml) for 3 days. The solution was allowed to cool to room temperature, and the precipitate which formed was filtered off. After drying under vacuum at ambient temperature, this afforded the title compound as its dipotassium salt (14.519).

Example 1 Preparation of:

Staae (i) To a solution of 5-aminoindan-6-sulphonic acid (5.339) in water (100ml) at pH6 was added 2N sodium nitrite solution (I I ml). The reaction mixture was added to a mixture of ice and concentrated HCI (5ml) whilst maintaining the temperature below 5"C.

After stirring for 11/2 hours any excess nitrous acid was destroyed by the addition of 10% (w/w) aqueous sulphamic acid.

Staae (ii) To a suspension of cyanuric chloride (4.619) in acetone (70ml) and ice/water (100ml) containing a few drops of Calsolene oil was added a solution of 1-amino-8naphthol-3,6-disulphonic acid (8.009) in water (100ml) at pH6, whilst maintaining the temperature at 0-5"C. The reaction mixture was then stirred for 30 minutes at 0-50C.

Staae (iii) The solution containing the dichlorotriazinyl compound from stage (ii) was adjusted to pH2 using 2N Na2CO3 solution and was stirred for 30 minutes. To this solution was added the diazonium salt from stage (i). The pH of the reaction mixture was adjusted to 6 using 2N Na2CO3 solution and the reaction mixture was stirred for 2 hours at a temperature of 0-5"C.

Stave (iv) To the solution of the dichlorotriazinyl azo dye solution from stage (iii) was added a solution of 1,4-bis(3-aminopropyl)piperazine (2.509) in water (25ml). The reaction mixture was then stirred at ambient temperature for 3 hours whilst maintaining the pH in the range 8-9. The pH of the reaction mixture was then adjusted to pH 7 with 2N hydrochloric acid and stirred for a further 12 hours. The precipitated bis(monochlorotriazinyl azo) dye was isolated by filtration and was dried under vacuum at ambient temperature.

Stave (v) To a solution of the bis(monochlorotriazinyl azo) dye (2.469) from stage (iv) in water (100ml) was added 1,4-bis(3-aminopropyl)piperazine (I .80g). The reaction mixture was heated to 75"C and was held at this temperature for 3 hours. Sodium chloride (10g) was added to the reaction mixture and, after cooling to room temperature, the final product was isolated by filtration. The product was dialysed and was then dried at a temperature of 60"C for 12 hours.

Ink Jet Printing To an ink base comprising 88 parts water, 5 parts 2-pyrrolidone, 5 parts thiodiglycol and 2 parts SURFYNOL 465TM (available from Air Products Limited) was added the title dye to give a 4% solution of the title dye in the ink base. The solution was then adjusted to pH 10 using NH3 and filtered through a 0.45m membrane.

When this ink was applied to plain XEROX TM acid paper using an ink jet printer bright magenta prints were obtained with excellent wet fastness.

The wet fastness of the prints was measured using a wet fastness test in which the reflected optical density (ROD) of each of four squares of a test print is measured using a previously calibrated X-RiteTM densitometer and the correct filter for the colour under test. The average ROD for the four squares is calculated. The print is then immersed in de-ionised water (pH 5.5+1.0, temp. 22+2"C) and stirred slowly for 5 minutes using a magnetic stirrer. The print is removed from the water, placed on absorbent paper and allowed to dry (room temperature, approx. 2h). When dry, the ROD for each of the four squares is again measured and the average value calculated.

The wet fastness is expressed as follows: % wet fastness = Average ROD after immersion x 100 Average ROD before immersion The prints had an excellent fastness of 80%.

Examples 2 to 8 in Table 1 are bisazo compounds of the Formula (11)

Formula(l 1) The compounds were prepared using a method analogous to that of Example 1 by coupling diazotised 5-aminoindan-6-sulphonic acid with 8-(4,6-dichlorotriazin-2-ylamino) I-naphthol-3,6-disulphonic acid followed by condensation first with a diamine of the formula H2NLNH2 followed by condensation with a compound of the formula WH.

The dyes of Examples 2 to 8 were formulated into inks by dissolving the dyes in an ink base of the same composition as that used in Example 1, to give a 4% solution of the dye in the ink base. The resultant inks were then applied to plain XEROX TM acid paper using an ink jet printer.

The wet fastness of the prints was then measured using the same test as Example 1.

Table 1

Example H2NLNH2 WH Wet No. Fastness (%) 2 1,4-Bis(3-aminopropyl)piperazine 2-aminoethanol 42% 3 1,4Bis(3-aminopropyl)piperazine I -(2-aminoethyl)piperazine 51 % 4 1 ,4-Bis(3-aminopropyl)piperazine N, Ndimethylethylene 41 % diamine 5 1,4-Bis(3-aminopropyl)piperazine ammonia 44% 6 1,4-Bis[3-(4-aminophenyl- 2-aminoethanol 58% sulphonamido)propyll piperazine 7 1 ,4-Bis[3-(4-aminophenyl- morpholine 34% sulphonamido)propyl]piperazine 8 H2N(CH2)3N(CH3)(CH2)3NH2 H2N(CH2)3N(CH3)(CH2)3NH2 62% Example 9 PreParation of:

Staae (i) To a solution of 5-aminoindan-6-sulphonic acid (16.409) in water (300ml) at pH6 was added 2N sodium nitrite solution (80ml). The reaction mixture was added a mixture of ice and concentrated HCI (20ml) whilst maintaining the temperature below 5 C. After stirring for I IA hours any excess nitrous acid was destroyed by the addition of 10% (w/w) aqueous sulphamic acid solution.

Stage (ii) To a suspension of cyanuric chloride (13.839) in acetone (200ml) and ice/water (300ml) containing a few drops of Calsolene oil was added a solution of 8-amino-1- naphthol-3,6-disulphonic acid (24.009) in water (300ml) at pH6, whilst maintaining the temperature at 0-50C. The reaction mixture was stirred for 30 minutes at 0-5"C, adjusted to pH2 with 2N sodium carbonate and stirred for a further 30 minutes.

Staae (iii) The solution of diazonium salt from stage (i) was added to the solution containing the dichlorotriazinyl compound from stage (ii). The reaction mixture was raised to pH6 with 2N sodium carbonate and stirred for 2 hours at 0-5"C then 16 hours at room temperature. The product was precipitated by salting to 5% w/v with sodium chloride, filtered, washed with 10% w/v sodium chloride solution and acetone and finally dried under vacuum at ambient temperature.

Stage (iv) 4-Aminosalicylic acid (2.299) was dissolved in water (75ml) at pH6, and added to a solution of the dichlorotriazinyl azo dye (11.299) from stage (iii) in 200ml water. The solution was adjusted to pH5 with 2N sodium carbonate and stirred for an hour. The solution was then diluted to 600ml with water and salted to 10% w/v with sodium chloride.

The resultant precipitate was filtered off, washed with 15% aqueous sodium chloride solution and acetone, and finally dried under vacuum at ambient temperature.

Staae (v) The monochlorotriazinyl azo dye from stage (iv) (2.629) and 1,4-bis(3aminopropyl)piperazine (0.309) were heated in water (100ml) at 60"C, maintaining the solution at pH10 with 2N sodium hydroxide. After 4 hours a further 0.59g of the product from stage (iv) was added and the mixture heated for a further 3 hours at 60"C/pH10.

The solution was then salted to 10% w/v with sodium chloride, cooled and the precipitate formed was filtered off. The product was dialysed then dried at 60"C.

Ink Jet Printing The title dye was added to an ink base with the same composition as that of Example 1, to give a 4% solution of the dye in the ink base. When this ink was applied to plain XEROX TM acid paper using an ink jet printer bright magenta prints were obtained.

The prints had a wet fastness of 42% when measured using the same wet fastness test as Example 1.

Examples 1 to 9 illustrate compounds according to the second preferred embodiment of the present invention.

Example 11: Preparation of

Staae (i) To a solution of 5-aminoindan-6-sulphonic acid (16.40g) in water (300ml) at pH6 was added 2N sodium nitrite solution (80ml). The reaction mixture was added to a mixture of ice and concentrated HCI (20ml) whilst maintaining the temperature below 5"C.

After stirring for 1Y2 hours any excess nitrous acid was destroyed by the addition of 10% (w/w) aqueous sulphamic acid solution.

Stave (ii) To a suspension of cyanuric chloride (13.839) in acetone (200ml) and ice/water (300ml) containing a few drops of Calsolene oil was added a solution of 8-amino-1- naphthol-3,6-disulphonic acid (24.009) in water (300ml) at pH6, whilst maintaining the temperature at 0-5"C. The reaction mixture was stirred for 30 minutes at 0-5"C, adjusted to pH2 with 2N sodium carbonate and stirred for a further 30 minutes.

Stave (iii) The solution of diazonium salt from stage (i) was added to the solution containing the dichlorotriazinyl compound from stage (ii). The reaction mixture was raised to pH6 with 2N sodium carbonate and stirred for 2 hours at 0-5"C then 16 hours at room temperature. The product was precipitated by salting to 5% w/v with sodium chloride, filtered, washed with 10% w/v sodium chloride solution and acetone and finally dried under vacuum at ambient temperature.

Stage (iv) Trans-2,5-dimethylpiperazine (0.579) was dissolved in water (100ml) at 0-5"C.

The dichlorotriazinyl dye from stage (iii) (9.09g) was added, and the mixture stirred at pH10, whilst warming to room temperature for a total of 6 hours. The product was precipitated by acidifying to pH 6.5 with concentrated HCI followed by salting to 4% w/v with sodium chloride. The product was filtered off, washed with 10% brine solution followed by acetone and finally dried under vacuum at ambient temperature.

Staae (v) The bis-monochlorotriazinyl azo dye from stage (iv) (2.339) and ethanolamine (0.55g) were heated in water (100ml) at 75"C for 3 hours. The solution was salted to 8% w/v with sodium chloride and cooled. The product was filtered off, dialysed and dried at 60"C.

Ink Jet Printing To an ink base comprising 88 parts water, 5 parts 2-pyrrolidone, 5 parts thiodiglycol and 2 parts Surfynol 465 TM was added the title dye to give a 4% solution of the dye in the ink base. The solution was adjusted to pH 10 using NH3 and filtered through a 0.45pm membrane.

When the ink was applied to plain Xerox TM acid paper using an ink jet printer, strong bright magenta prints were obtained with good water and light fastness. After 48 hours exposure in an Atlas Xenon Weatherometer Ci35A the prints exhibited a light fastness of AE = 24.99.

The wet fastness of the prints was measured using the same method described in Example 1. The prints had a wet fastness of 39%.

Example 12: Preparation of:

The bis-monochlorotriazinyl dye from stage (iv) of Example 1 (2.339) was dissolved in water (100ml) and the solution was adjusted to pH 11 with 2N sodium hydroxide. The mixture was heated at 750C for a total of 11 hours. The solution was allowed to cool to room temperature, acidified to pH6 with 2N HCI and salted to 2% w/v with sodium chloride. The product was filtered off, dialysed and dried at 60"C.

Ink Jet Printing To an ink base comprising 88 parts water, 5 parts 2-pyrrolidone, 5 parts thiodiglycol and 2 parts Surfynol 465 was added the title dye to give a 4% solution of the dye in the ink base. The solution was adjusted to pH 10 using NH3 and filtered through a 0.45pm membrane.

When the ink was applied to plain Xerox acid paper using an ink jet printer, strong bright magenta prints were obtained with good water and light fastness. After 48 hours exposure in an Atlas Xenon Weatherometer Ci35A the prints had a light fastness AE value of 15.65.

The wet fastness of the prints was measured using the same test described in Example 1 using the same wet fastness test as Example 1. The prints exhibited a wet fastness of 38%.

Examples 10 to 12 illustrate compounds according to the first preferred embodiment of the present invention.

Further compounds according to the first embodiment of the present invention are of the Formula (11). The compounds may be prepared as described in Example 2 by coupling diazotised 5-aminoindan-6-sulphonic acid with 8-(4,6-dichlorotriazin-2-ylamino) l-naphthol-3,6-disulphonic acid followed by condensation first with a diamine of the formula H2NLNH2 followed by condensation with a compound of the formula WH shown in Table 2.

Table 2

Example H2NLNH2 WH No.

13 2,5-dimethyl-piperazine 2-aminoethanol 14 2,5-dimethyl-piperazine NH3 15 2,5-dimethyl-piperazine H2O 16 2,5-dimethyl-piperazine 3-mercapto-1 propanesulphonic acid 17 2,5-di methyl-pi pe razine aminoacetic acid 18 1 4-phenylenediamine 2-aminoethanol 19 4,4'4iamino-2,2'-stilbene NH3 20 p-xylylenediamine 2-aminoethanol

Claims (24)

1. CLAIMS 1. A compound of the Formula (1) and salts thereof:

   wherein: B1 and B2 each independently is an optionally substituted indanyl group; each J independently is a group of the Formula (2):

   R3 is H or optionally substituted alkyl; n is an integer from 0 to 3; R1 and R2 each independently is H; alkyl; cycloalkyl; alkenyl; aryl; or aralkyl, each of which is optionally substituted; L is a divalent organic linking group; or L, R' and/or R2 together with the nitrogen atoms to which they are attached form a 5 or 6 membered ring; each X independently represents a group of the formula:

   W represents a group of the formula -OR4; -SR4 or-NR4R5; R4 and R5 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or R4 and R5 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or optionally R4 and/or R5 is or contains a flexibly spaced amine; the compound of Formula (1) being free from fibre-reactive groups.
2. 2. A compound according to claim 1 wherein L, B', B2, R1, R2, R3, R4 and R5 are free from flexibly spaced amines.
3. 3. A compound according to claim 1 wherein at least one of the groups represented by L, R4 and R5 contain one or more flexibly spaced amine(s).
4. 4. A compound according to claim 3 wherein L contains a flexibly spaced amine and / or at least one of R4 and R5 is or contains a flexibly spaced amine.
5. 5. A compound according to claim 1 wherein at least one W is a group of the formula -OR4 or -SR4 wherein R4 is H, optionally substituted C,4-alkyl, a flexibly spaced amine or a group containing a flexibly spaced amine.
6. 6. A compound according to claim 1 wherein each W independently is a group of the formula -NR4R5 wherein R4 and R5 each independently is H, optionally substituted C16- alkyl, optionally substituted aryl, optionally substituted aralkyl, a flexibly spaced amine or a group containing a flexibly spaced amine.
7. 7. A compound according to claim 6 wherein R4 is H.
8. 8. A compound according to any one of the previous claims wherein L, R' and/or R2 together with the nitrogen atoms to which they are attached form a piperazine residue of the formula:

   in which each of R7 and R8, independently is H or C,4-alkyl optionally substituted by -OH.
9. 9. A compound according to claim 4 wherein R4 and / or R5 is a flexibly spaced amine of the formula:

   wherein: A is an optionally substituted alkylene linking group containing one or more carbon atoms; Z' and Z2 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or Z' and Z2 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or Z' and A together with the nitrogen to which they are attached form a 5 or 6 membered ring.
10. 10. A compound according to either claim 3 or claim 4 wherein L, R4 and/or R5 each is or contain one or more flexibly spaced amine(s).
11. 11. A compound according to either claim 3 or claim 4, wherein L contains a residue of the formula:

    wherein: A and Z' are as defined in claim 8; or A and Z1 together with the nitrogen to which they are attached form a 5 or 6 membered ring.
12. 12. A compound according to either claim 3 or claim 4 wherein the flexibly spaced amine(s) contains a piperazine ring.
13. 13. A compound according to any either claim 3 or claim 4 wherein L contains a residue of the formula:

    in which each of R7 and R8 independently is as defined in claim 8; and A is an optionally substituted alkylene linking group containing one or more carbon atoms.
14. 14. A compound according to claim 13 wherein R7 and R8 are H.
15. 15. A compound according to either claim 3 or claim 4 wherein each W independently is a group of the formula -NHRS, wherein R5 is a flexibly spaced amine or a group containing a flexibly spaced amine.
16. 16. A compound according to any one of claims 1 to 15 wherein B' and B2 each independently is of the Formula (3):

    wherein m is an integer from 0 to 3.
17. 17. A compound according to any one of claims 1 to 16 wherein each J independently is of the Formula (4):
18. 18. A compound of the Formula (5) and salts thereof:

    wherein L and each W, R' and R3 independently is defined in claim 1.
19. 19. An ink comprising a compound according to any one of claims 1 to 18 and a liquid medium.
20. 20. An ink according to claim 19 wherein the liquid medium comprises water and one or more water soluble organic solvent(s) in a weight ratio of 99:1 to 1:99.
21. 21. A process for printing a substrate with an ink using an ink jet printer, characterised in that the ink contains a compound according to any one of claims 1 to 18.
22. 22. A paper, an overhead projector slide or a textile printed with an ink according to either claim 19 or claim 20, or by means of the process according to claim 21.
23. 23. A dye substantially as hereinbefore described in any one of the examples.
24. 24. An ink substantially as hereinbefore described in any one of the examples.