GB2317183A - (Indanyl-azo)-(triazinylamino)-naphthol-sulphonic acids, free of fibre-reactive groups, as colourants for ink jet inks - Google Patents

Abstract

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

R1 is H or optionally substituted alkyl; n is an integer from 0 to 3; L' and L2 each independently is a group of the formula -OR2; -SR2 or NR2R3; wherein R2 and R3 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or R2 and R3 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or optionally R2 and/or R3 each independently 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 B, R1, R2 and R3 are free from flexibly spaced amines.

In a second preferred embodiment at least one of the groups represented by R2 and/or R3 contain one or more a flexibly spaced amine(s), more preferably R2 and / or R3 is or contain a flexibly spaced amine group.

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 which forms 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 group containing one or more carbon atoms; Z1 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.

Examples of flexibly spaced amines which are terminal groups include:

,Alkyl CH3 ---Alkylenee-N\ CH2- H X H NH , tcH2$2Nm/'mNH 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 Z' are as hereinbefore defined; or A and Z' 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:

-AlkyIene-N- --(CH2)2-N s -(CH2)2-N-' Alkyl H and ~Fm N- -N N and -(C H2)2 N N my 'my When any of R1, R2, R3, Z1 or Z2 represent an optionally substituted alkyl group it is preferably optionally substituted C"O-alkyl, more preferably optionally substituted C1- alkyl and more especially optionally substituted C,4-alkyl.

Preferred optionally substituted cycloalkyl groups which may be represented by R2, R3, Z1 or Z2 include for example, optionally substituted CS,2-cycloalkyl, preferably optionally substituted C,-cycloalkyl and especially optionally substituted cyclohexyl.

When any of R2, R3, Z1 or Z2 represent an optionally substituted alkenyl group it is preferably optionally substituted C24-alkenyl more preferably optionally substituted C2A alkenyl.

Preferred optionally substituted aryl groups which may be represented by R2, R3, 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 R2, R3 Z1 or Z2 represent an optionally substituted aralkyl group it is preferably optionally substituted aryl-C,4-alkylene, more preferably phenyl-C24-alkylene and especially benzyl and phenylethyl-.

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

Preferred heterocyclic groups which may be represented by R2, R3, Z1 or Z2 are 5 or 6 membered rings, for example thienyl; pyrrolyl; pyridyl; pyrimidyl; tetrahydrofuryl; furanone; pyrrolidinyl; pyrrolidinonyl; piperidino; piperazinyl and morpholinyl groups.

When R2 and R3; Z1 and Z2; or Z' 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.

Preferred optional substituents which may be present on R', R2, R3, B, Z1 and Z2 include, for example H; C,4-alkyl, more preferably C,4-alkyl and especially methyl and ethyl; hydroxyC24-alkyl, especially hydroxyethyl; C,,-alkoxy, especially methoxy and ethoxy; aryl, preferably phenyl; aralkyl, preferably aryl-C, -alkyl, more preferably benzyl; amido, especially C,4-alkyl amido; halogen; hydroxy; nitro;-CN; -CF3 -SO3H; -COOR, where R is H or C,4-alkyl; or a 5 or 6 membered heterocyclic group, for example tetrahydrofuryl, piperazinyl or morpholinyl.

when L1 and/or L2 is a group of the formula -OR2 or -SR2 it is preferred that R2 is H; optionally substituted C,4-alkyl, preferably C,-alkyl optionally substituted by -OH, SO3H or -COOH and especially methyl, ethyl, propyl, hydroxyethyl-, sulphoethyl-, sulphopropyl-, carboxyethyl- and carboxypropyl-; or a flexibly spaced amine or a group containing a flexibly spaced amine. It is especially preferred that L' and/or L2 are -OH.

Where L' and/or L2 is a group of the formula -NR2R3 it is preferred that R2 and R3 are each independently H; optionally substituted C,-alkyl, more preferably C,4-alkyl, C1- alkyl substituted by OH, COOH or SO3H and especially methyl, ethyl, carboxyethyl, carboxypropyl, hydroxyethyl, hydroxypropyl, sulphoethyl and sulphopropyl; optionally substituted CS12-cycloalkyl, especially optionally substituted cyclohexyl; optionally substituted aryl, especially optionally substituted phenyl; optionally substituted aralkyl, especially optionally substituted benzyl; a 5 or 6 membered heterocyclic group, especially pyrimidyl, furanone, pyrrolidinyl, pyrrolidinone, piperazino and tetrahydrofuryl; or a flexibly spaced amine or a group containing a flexibly spaced amine; or R2 and R3 together with the nitrogen to which they are attached form a 5 or 6 membered ring, especially piperidino and morpholino.

It is preferred that L' and L2 are groups of the formula -NHR3 wherein R3 is H; optionally substituted C,-alkyl, more preferably C,4-alkyl or C,4-alkyl substituted by -OH, -COOH or -SO3H and especially methyl, ethyl carboxyethyl, carboxypropyl hydroxyethyl, hydroxypropyl, sulphoethyl and sulphopropyl; optionally substituted CS,2-cycloalkyl, especially optionally substituted cyclohexyl; optionally substituted aryl, especially optionally substituted phenyl; optionally substituted aralkyl, especially optionally substituted benzyl; a 5 or 6 membered heterocyclic group, especially tetrahydrofuryl or furanone.

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

It is especially preferred that B is an indan-5-yl group of the Formula (3):

wherein m is an integer from 0 to 3.

It is preferred that m is O 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 in the group of Formula (2), it is preferred that the sulpho group is attached at the 3 position on the naphthalene nucleus.

Preferably the group of the formula:

wherein R' is as hereinbefore defined, 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 R' 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 L2 are 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 In the first preferred embodiment of the present invention preferred groups of the formula -NR2R3 represented by L' and L2 include for example -N H2; C,-alkylamino, especially ethylamino, propylamino and N-ethylpropylamino; cyclohexylamino; (C1- alkanol)amino groups, especially (ethanol)amino and N-methyl(ethanol)amino; (carboxy C,4-alkyl)amino, especially (carboxyethyl)amino and (carboxypropyl)amino; (sulpho-C14- alkyl)amino, especially (sulphoethyl)amino and (sulphopropyl)amino; optionally substituted arylamino, preferably phenylamino optionally substituted by one or more group(s) selected from -COOH, -SO3H, and -OH; N-ethylanilino; diphenylanilino; naphthylamino; aralkylamino groups containing up to il carbon atoms especially benzylamino; and heterocyclic groups, for example piperidino, morpholine, 1-pyrrolidinyl, 2-pyrrolidinone, 3-amino-4,5-dihydro-2-furanone, pyrazolyl and tetrahydrofuryl-C,4- alkylamino for example, tetrahydrofuryl-methylamino-.

It is especially preferred that in the first preferred embodiment of the present invention each of L1 and L2 independently is amino; hydroxyethylamino; hydroxypropylamino; 2-carboxy4-sulphoanilino; 2-carboxy-5-sulpho anilino; 4-carboxy-3hydroxy anilino; 4-methyl-2-sulphoanilino; or a tetrahydrofuryl group of the formula:

Second Preferred Embodiment As herein before stated in the second preferred embodiment of the present invention at least one of the groups represented by R2 andlor R3 is a flexibly spaced amine or contain a flexibly spaced amine group. When R2 or R3 is a flexibly spaced amine it is preferably a group of the hereinbefore defined formula

for example, aminoethyl-; 3-(dimethylamino)propyl-; N,N-dimethylaminoethyl; -(CH2)3NH2;

Preferred groups which contain a flexibly spaced amine which may be represented by R2 and/or R3 include for example, an alkyl or phenyl group substituted by a hereinbefore defined group of the formula:

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

It is especially preferred that the flexibly spaced amine(s) contain a piperazine ring.

In the second preferred embodiment of the present invention when L1 and/or L2 represent a group of the formula -NR2R3, a preferred flexibly spaced amine represented by least one of the groups R2 and R3 in the compound of Formula (1) is of the formula -A NZ1Z2 wherein A, Z1 and Z2 are as hereinbefore defined, especially a piperazine residue of the formula:

wherein: A is as hereinbefore defined; and R4, R5 and R6 each independently are H or optionally substituted C, 6 alkyl.

It is preferred that each R4, R5 and R6 independently is H; hydroxy-C24-alkyl, amino-C24-alkyl, methyl, ethyl or propyl.

It is especially preferred that in the second embodiment of the present invention L' and L2 are groups of the formula -NHR3 wherein R3 is as hereinbefore defined provided at least one of the groups represented by R3 is a flexibly spaced amine.

Preferred groups of the formula -NHR3 represented by at least one of L' andlor L2 in the second preferred embodiment include for example, a residue of an optionally substituted C24-alkylene diamine, especially ethylene diamine, propylene diamine and N,N-dimethylethylenediamine; an amine or diamine containing a piperazinyl group for example, 1 ,4-bis(3-aminopropyl) piperazine and 1 -(2-aminoethyl)piperazine.

As will be realised in the second embodiment of the present invention one or both groups represented by L1 and L2 may contain a flexibly spaced amine. Preferably one of L1 or L2 contains a flexibly spaced amine and the other group is free from flexibly spaced amines. When one of the groups represented by L' and L2 is free from flexibly spaced amines, that group is preferably one of the hereinbefore described preferred groups of the first preferred embodiment of the present invention, for example amino; hydroxyethylamino; hydroxypropylamino; 2-carboxy4-sulphoanilino; 2-carboxy-5-sulpho anilino; 4-carboxy-3-hydroxy anilino; 4-methyl-2-sulphoanilino; and tetrahydrofuryl groups of the formula:

The compounds of the present invention 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 O 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 betaposition to the sulphur atom, e.g. beta-sulphato-ethylsulphonyl groups, alpha, betaunsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, alphachloro-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 for example, chloroacetic acid, beta-chloro and beta-bromopropionic acids and alpha, beta-dichloro- and 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 tetrafluorocyclobutyl carbonyl, trifluoro-cvclobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl, trifluorocvclobutenylethenyl carbonyl; activated halogenated 1,3-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 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 C14-alkyl substituted by -OH. Preferred organic radicals represented by Q are C,.4-alkyl radicals, especially methyl. Preferred heterocyclic rings formed by +NQ4 are 5 or 6 membered heterocyclic rings.

As examples of quatemary 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+(C2H40H)3C2H5, N+(CH3)3C2H40H, N+(C2H40H)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, C14-alkyI 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+H2, H2N+(CH3)(CH2CH3), CH3N+H3, CH3CH2N+H3, H2N+(CH2CH3)2, CH3CH2CH2N+H3, +NH4, (CH3)2CHN+H3, N+H(C2H40H)3, N+H2(C2H40H)(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 a compound of the Formula (1) comprising condensing the disazo compound of the Formula (6) with a compound of the formula L2H, preferably in the presence of a base:

wherein: Q is a labile atom or group; and B, J, L' and L2 are as hereinbefore defined.

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 for example, an alkali metal or alkali earth metal hydroxide, carbonate or bicarbonate or an organic base. Preferred organic bases are tertiary amines for example, N-alkylated heterocycles, for example N-(C,,- alkyl)morpholine, N-(C,,-alkyl)piperidine, N,N'cli(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, more 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 NH4+, quaternary ammonium or organic amine salt by the addition of ammonia, ammonium hydroxide, primary, secondary, tertiary or quaternary amine. 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.

When L1 and/or L2 is a group of the formula -OH, the compounds of Formula (1) may be prepared by hydrolysis of the compound of Formula (6). The comopund of Formula (6) is preferably hydrolysed by heating the compound in an aqueous solution containing a suitable base, for example NaOH or sodium carbonate.

The compounds of Formula (6) may be prepared by methods analogous to those described in the prior art for other azo compounds. Thus, for example, a suitable method comprises: (i) diazotising optionally substituted amino indan compounds of Formula (7): B-NH2 (7) wherein B is as hereinbefore defined; 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 R', n and each Q independently is as hereinbefore defined; (iii) coupling the resultant triazinylamino compound with the diazonium salt to form the azo compound of Formula (10):

wherein: B, J and each Q independently is as hereinbefore defined; (iv) condensing the azo compound of Formula (10) with a compound of the formula L1H to give the compounds of Formula (6).

Diazotisation of the optionally 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 -5 C to 20"C, preferably from 0 to 10"C and especially from 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.

Altematively, the compounds of Formula (1) may be prepared as follows: 1. condensing the triazine compound of Formula (9) with a compound of the formula L'H followed by condensation with a compound of the formula L2H, where L' and L2 are as hereinbefore defined; 2. condensing the resulting triazine derivative with a compound of the formula H-J-H, where J is as hereinbefore defined; and 3. coupling the resultant compound with a compound of Formula (7) which has been diazotised.

As examples of suitable aminoindan compounds of Formula (8) there may be mentioned 5-aminoindan and 5 aminoindan-6-sulphonic acid.

The compound of formula H-J-H is preferably 8-amino-I -naphthol-3,6-disulphonic acid.

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

Preferred compounds of the formula L'H and L2H suitable for use in the first preferred embodiment of the present invention include for example, phenols; alcohols, for example methanol and ethanol and especially primary and secondary aliphatic and aromatic amines for example ammonia, ethanolamine, tris(hydroxymethyl)aminomethane, 2-pyrrolidinone, 3-amino4,5-dihydro-2-furanone, furfurylamine, 2-amino-5-sulphobenzoic acid, 4-amino salicyclic acid, 2-amino-5-methyl benzene sulphonic acid and heterocyclic bases, for example piperidine and morpholine In the second preferred embodiment of the present invention examples of suitable compounds of the formula L1H and L2H preferably include at least one compound selected from for example, 2-(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, ethylenediamine, N,N-dimethylethylenediamine, 2-aminomethyltetrohydrofuran, 2-, 3- and 4- aminobenzylamines, o-, m- and p- xylene diamines, phenylene diamines, and heterocyclic bases, for example piperazine and 2,5-dimethylpiperazine; and one group selected from one of the above mentioned compounds suitable for use in the first preferred embodiment of the present invention.

The reactions leading to the formation of the compounds of the invention may be performed using conditions that have been fully described in the prior art for such reactions. Similarly, the compounds may be isolated by known methods, for example spray drying or precipitation and filtration.

According to a second aspect of the present invention, there is provided a colorant for an ink, characterised in that the colorant is a compound of Formula (1). The compounds of Formula (1) exhibit high solubility in water and aqueous media, have good water and light fastness and give a print with a strong magenta shade on plain paper when used as a colorant for an ink.

According to a third 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 that the compound of Formula (1) is completely dissolved in the liquid medium to form a solution.

The ink preferably contains from 0.5% to 20%, more preferably from 1% to 15%, and especially from 1% to 5%, by weight of the compound of Formula (1) based on the total weight of the ink. Although many inks contain less than 5% by weight of colorant, it is desirable that the compound has a water solubility of around 10% or more to allow the preparation of concentrates from which more dilute inks can be prepared and to minimise the chance of precipitation of colorant if evaporation of solvent occurs during use of the ink.

The liquid medium is preferably water or a mixture of water and one or more water-soluble organic solvent(s). The weight ratio of water to organic solvent(s) is preferably from 99:1 to 1:99, more preferably from 95:1 to 50:50 and especially from 90:10 to 60:40.

The water-soluble organic solvent is preferably selected from C, 6-alkanols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol n-pentanol, cyclopentanol and cyclohexanol; diols, preferably diols having from 2 to 12 carbon atoms, for example pentane-1 ,5-diol; amides, for example dimethylformamide or 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; C,-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; C14-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 ternary mixture of water and diethylene glycol and/or, 2-pyrrolidone or N methylpyrrolidone 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 quatemary 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 am ides, 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 and semi-synthetic materials include polyamides, polyesters, polyacrylonitriles and polyurethanes.

The preferred ink used in the process according to the fourth aspect of the present invention is as hereinbefore described for the third aspect of the present invention.

According to a fifth aspect of the present invention, there is provided a paper, an overhead projector slide or a textile printed with an ink according to the third aspect of the present invention or by means of the process according to the fourth 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: Prenaration of 5-Aminoindan-6-sulphonic 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.

Example 1 Preparation of:

Staae 1: Diazotisation A solution of 5-aminoindan-6-sulphonic acid (10.679) in water (250ml) and 2N sodium nitrite solution (25ml) at pH6 was added to a mixture of ice and concentrated hydrochloric acid (13ml) at a temperature of 0-5"C. After stirring for 2 hours at 0-5"C excess nitrous acid was destroyed by the addition of 10% sulphamic acid.

Staae 2: Condensation A solution of cyanuric chloride (9.22g) in acetone (120ml) was added to a mixture of ice and water (200ml) containing a few drops of Calsolene oil as a dispersant. A solution of 8-amino-1-naphthol-3,6-disulphonic acid (16.009) in water (200ml) at pH6 was added to the cyanuric chloride suspension whilst maintaining the temperature of the reaction mixture at 0-5"C. After stirring for 30 minutes the pH was adjusted to pH2 using 2N sodium carbonate solution and was stirred for a further hour. The reaction mixture was then screened to remove any insoluble material.

Stage 3: Coupling The diazonium salt from stage 1 was added to the reaction mixture from stage 2 whilst maintaining the temperature at 0-5"C. The reaction mixture was adjusted to pH6 using 2N sodium carbonate solution and was stirred at ambient temperature for 2 hours.

Stage 4: Condensation with 2-Aminobenzoic Aåd-5 Sul Dhonic Acid A solution of 2-aminobenzoic acid -5-sulphonic acid (11.009) in water (100ml) at pH6 was added to the dichlorotriazine dye solution from stage 3. The reaction mixture was stirred at 30"C for 1 hour and then at ambient temperature for 12 hours at pH 5.5.

The monochlorotriazinyl dye was precipitated out of solution by the addition of sodium chloride to the reaction mixture to give 9% w/v sodium chloride in the reaction mixture.

The monochloro triazine dye was isolated by filtration, washed with 15% sodium chloride solution, followed by acetone. The product was then dried under vacuum at ambient temperature.

Stage 5: Condensation with Ammonia Solution The monochlorotriazine dye (2.589) from stage 4 was dissolved in water (100ml) and adjusted to pH 9.5 with 0.88 (specific gravity) ammonia solution. The reaction mixture was heated at 60"C for 4 hours whilst maintaining the pH in the range of pH 9-9.5 by the addition of further 0.88 (s.g.) ammonia solution. Sodium chloride was added to the reaction mixture to give a 15% (w/v) sodium chloride solution. The reaction mixture was cooled to ambient temperature and the precipitated product was isolated by filtration. The dye was 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 465To (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 Th acid paper using an ink jet printer, strong, bright magenta prints were obtained with excellent light fastness. After an exposure of 48 hours using an Atlas Xenon Weatherometer Ci35A, the prints exhibited a AE of 13.5.

Examples 2-6 in Table 1 are azo compounds of the formula:

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)1-naphthol-3,6-disulphonic acid followed by condensation, first with an amine of the formula L1H, followed by condensation with an amine of the formula L2H. The dyes of Examples 2 to 6 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 resulting ink was then applied to plain Xerox acid paper using an ink jet printer and the light fastness of the prints was measured as in Example 1.

Table 1

Example L'H LZH Light fastness No. (aE) 3 S03H 3 NH2 OH 13.7 CO2H H2N4CO2H SO3H 4 NH2 H2N(CH2)2OH 12.8 5 NH2 (HOCH2)3CNH2 11.9 Y2HOH 6 iy2OH H2N 19.1 CO2H Examples 1 to 6 illustrate compounds according to the first preferred embodiment of the present invention.

Example 7 Preparation of a mixture of the formula:

wherein X and X' each independently is a group of the formula: -NHCH2CH(CH3)NH2, or NH2CH2CH(CH3)NH Staae (i) A solution of 1,2-diaminopropane (2.979) in ice/water (75ml) was adjusted to pH 3.5 with concentrated hydrochloric acid. To this solution was added a solution of cyanuric chloride (3.699) in acetone (30ml) whilst maintaining the temperature at less than 5"C.

The reaction mixture was then allowed to warm to ambient temperature and was stirred for 12 hours at a pH of 5.5.

Staae (ii) A solution of 8amino-l -naphthol-3,6-disulphonic acid (6.409) in water 100ml at pH6 was added to the suspension of the monochlorotriazine derivative from Stage (i).

The reaction mixture was then adjusted to pH 2.2 with 2N hydrochloric acid and was warmed to 800C and held at this temperature for 1.5 hours. The reaction mixture was cooled to ambient temperature and sodium chloride was added to give a 20% (wiz) sodium chloride solution. The pH of the reaction mixture was adjusted to pH9 and the sodium salt of 8-(4 ,6-bis(2-aminopropyl-1 -amino)triazin-2-yl-am ino)-1 -naphthol-3,6- disulphonic acid was collected by filtration and was dried at ambient temperature.

Stage (iii) To a solution of 5-aminoindan-6-sulphonic acid (0.859) in water (40ml) at pH6 was added 2N sodium nitrite solution (2.2ml). The reaction mixture was then added to a mixture of ice and concentrated hydrochloric acid (1.5ml). The reaction mixture was stirred at 0-5 C for 1 hour and excess nitrous acid was destroyed by the addition of 10% aqueous sulphonic acid solution.

Stage (iv) To a solution of the substituted triazine compound from Stage (ii) (3.309) in water (75ml) at pH7 was added the diazotised 5-aminoindan-6-sulphonic acid from stage (iii) whilst maintaining the temperature in the range 0-5"C. The reaction mixture was stirred at 0-5"C for 1 hour and was then allowed to warm to ambient temperature. Methanol (50ml) was then added to the reaction mixture and the pH of the solution was adjusted to pH3 by the addition of 2N HCI.

The product was isolated by filtration, dialysed and dried at 600C.

Ink Jet Printing To an ink base comprising 87.5 parts water, 5 parts 2-pyrrolidone, 5 parts thiodiglycol and 2.5 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 Th acid paper using an ink jet printer, strong, bright magenta prints were obtained with excellent light fastness. After an exposure of 48 hours using an Atlas Xenon Weatherometer Ci35A, the prints exhibited a AE of 13.5.

The wet fastness of the prints obtained 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-RiteN 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 a wet fastness of 38%.

Example 8 Preparation of:

Stage (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 to a mixture of ice and concentrated HCI (20ml) whilst maintaining the temperature below 5"C.

After stirring for 1W 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 0-5"C. The reaction mixture was stirred for 30 minutes at 0-50C, 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% wtv with sodium chloride, filtered, washed with 10% wiv 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% wlv 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) (2.189) and N,Ndimethylethylenediamine (0.889) were heated in water (100ml) at 60"C for 1 hour. The solution was cooled, and sufficient isopropanol (approx. 300ml) was added to cause precipitation. The title product was filtered off and dialysed and finally dried at 60"C.

Ink Jet Printina A 4% solution of the dye in an ink base was prepared as in Example 1. When applied to Xerox acid paper using an ink jet printer, the dye gave strong Magenta prints with good water and light fastness. The print had wet fastness of 37% when measured using the same wet fastness test as Example 7. After 48 hours exposure using an Atlas Xenon Weatherometer Ci35A, the print had bE = 11.9.

Example 9 Preparation of a compound of the formula:

The compound was prepared in an analogous manner to the compound of Example 8 by condensing an amine of the formula L'H with the dichlorotriazinyl azo dye from stage (iii) of Example 8, followed by condensation with an amine of the formula L2H to give the title product.

The title product was formulated into an ink as in Example 1 and applied to plain Xerox acid paper using an ink jet printer. The wet-fastness and light-fastness of the prints was measured as in Example 7.

Table 2 shows the amine of the formulae L1H, L2H and the light and wet fastness of the prints obtained.

Table 2

L'H L2H Water Fastness Light Fastness (%) (AE) NH2 (a) 44 15.2 NH2 OH HN N(CH2)2NH2 my CO2H Notes : (a) The 1-aminoethylpiperazine may bond to the triazine ring via the nitrogen at the 4-position in the piperazine ring or with the nitrogen in the amino group.

Examples 7 to 9 illustrate compounds according to the second preferred embodiment of the present invention.

Claims (21)

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

wherein: B is an optionally substituted indanyl group; J is a group of the Formula (2):

R1 is H or optionally substituted alkyl; n is an integer from 0 to 3; L1 and L2 each independently is a group of the formula -OR2; -SR2 or -NR2R3; wherein R2 and R3 each independently is H; optionally substituted alkyl; optionally substituted cycloalkyl; optionally substituted alkenyl; optionally substituted aryl; optionally substituted aralkyl; a heterocyclic group; or R2 and R3 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or optionally R2 and/or R3 each independently is or contains a flexibly spaced amine; the compound of Formula (1) being free from fibre-reactive groups.

2. A compound according to claim 1 wherein B, R1, R2 and R3 are free from flexibly spaced amines.

3. A compound according to claim 1 wherein at least one of the groups represented by R2 and/or R3 contain one or more flexibly spaced amine(s).

4. A compound according to claim 3 wherein R2 and / or R3 is or contain a flexibly spaced amine group.

5. A compound according to claim 1 wherein at least one of L' and/or L2 independently is a group of the formula -OR2 wherein R2 is H; optionally substituted C,4alkyl; or a flexibly spaced amine or a group containing a flexibly spaced amine.

6. A compound according to claim 1 wherein at least one of L1 and/or L2 independently is a group of the formula -SR2 wherein R2 is H; optionally substituted C 6alkyl; or a flexibly spaced amine or a group containing a flexibly spaced amine.

7. A compound according to claim 1 wherein at least one of L1 and/or L2 independently is a group of the formula -NR2R3 wherein R2 and R3 are each independently H; optionally substituted C,6-alkyl; optionally substituted CS,2-cycloalkyl; optionally substituted aryl; optionally substituted aralkyl; a 5 or 6 membered heterocyclic group; a flexibly spaced amine or a group containing a flexibly spaced amine; or R2 and R3 together with the nitrogen to which they are attached form a 5 or 6 membered ring.

8. A compound according to either claim 3 or claim 4 wherein the flexibly spaced amine is a group of the formula:

wherein: A is an optionally substituted alkylene 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 Z1 and Z2 together with the nitrogen to which they are attached form a 5 or 6 membered ring; or Z1 and A together with the nitrogen to which they are attached form a 5 or 6 membered ring.

9. A compound according to either claim 3 or claim 4 wherein the flexibly spaced amine contains a piperazine ring.

10. A compound according to either claim 3 or claim 4 wherein the flexibly spaced amine is a piperazine residue of the formula:

wherein: A is as defined in claim 8; and R4, R5 and R6 each independently is H or optionally substituted C,4 alkyl.

11. A compound according to either claim 3 or claim 4 wherein one of L1 and/or L2 contains a flexibly spaced amine and the other group is free from flexibly spaced amines.

12. A compound according to any one of the previous claims wherein B is of the Formula (3):

wherein m is an integer from 0 to 3.

13. A compound according to any one of the previous claims wherein J is of the Formula (4):

wherein: R' is H or optionally substituted alkyl.

14. A compound of the Formula (5) and salts thereof:

wherein L1 and L2 are as defined in claim 1.

15. A colorant for an ink, characterised in that the colorant is a compound according to any one of the preceding claims.

16. An ink comprising a compound according to any one of claims 1 to 14 and a liquid medium.

17. An ink according to claim 16 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.

18. 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 14.

19. A paper, an overhead projector slide or a textile printed with an ink according to either claim 16 or claim 17, or by means of the process according to claim 18.

20. A dye substantially as hereinbefore described in any one of the examples.

21. An ink substantially as hereinbefore described in any one of the examples.