GB2337053A - Azo dyes for ink jet printing having at least two (carboxy/sulpho/phosphono)-substituted (2-hydroxy-6-oxo-5-(1-pyridyl)-3-pyridyl)azophenyl units - Google Patents

Abstract

Compounds of Formula (1) and salts and tautomers thereof: wherein: n is 2 or 3; L is a direct link or a di- or tri-valent linking group; each Q independently is of the formula: each R<SP>1</SP> and R<SP>2</SP> independently is H, optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl; each W and X independently is -COOH, -SO 3 H, -PO 3 H 2 or alkyl substituted by one or more groups selected from -COOH, -SO 3 H and -PO 3 H 2 ; each Y and Z independently is a substituent other than those defined for W and X; a is 1-5; b is 0-4; C is 0-3; d is 1-4; (a+b) in each Q is 5 or less; and (c+d) in each Q is 4 or less, are useful as colorants in inks. Also claimed are inks containing a compound of the Formula (1), an ink jet printing process using the inks, a substrate printed with the inks, an ink jet printer cartridge containing the inks and an ink jet printer containing the ink jet printer cartridge.

Description

2337053 1 COMPOUNDS This invention relates to dyes, to inks and to their

use in inkjet printing (%P"). UP is a non-impact printing technique in which droplets of ink are ejected through a fine nozzle onto a substrate without bringing the nozzle into contact with the substrate.

There are many demanding performance requirements for dyes and inks used in UP. For example they desirably provide sharp, non-feathered images having good waterfastness, light-fastness and optical density. The inks are often required to dry quickly when applied to a substrate to prevent smudging, but they should not form a crust over the tip of an ink jet nozzle because this will stop the printer from working. The inks should also be stable to storage over time without decomposing or forming a precipitate which could block the fine nozzle.

According to the present invention there is provided a compound of Formula (1) or a salt or tautomer thereof:

each R' and R 2 each W and X each Y and Z each a each b each c each d wherein:

L Q] n Formula (1) is 2 or 3; is a direct link or a di- or tri-valent linking group; n L each Q independently is of the formula:

(VV)d R 2 N N (Y Mb J), HO N 0 11 R R 2 1 independently is H, optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl; independently is -COOH, -SO,H, - P03H2or alkyl substituted by one or more groups selected from -COOH, - S03H and -P03H2; independently is a substituent other than those defined for W and X; independently is 1 to 5; independently is 0 to 4; independently is 0 to 3; independently is 1 to 4; 2 each d independently is 1 to 4; (a + b) in each Q independently has a value of 5 or less; and (c + d) in each Q independently has a value of 4 or less.

Preferably each b and c independently is 0, 1 or 2, more preferably 0 or 1.

Preferably each a and d independently is 1, 2 or. 3, more preferably 1 or 2.

Preferably (a+b) in each group Q independently has a value of 1, 2 or 3, more preferably 1 or 2. Preferably (c+d) in each group Q independently has a value of 1, 2 or 3, more preferably 1 or 2.

Preferably each W and X independently is -COOH, -S03H, -P03H2 or C,10alkyl (more preferably C,,,,-alkyl) substituted by one, two or three (more preferably one) groups selected from -COOH, -S03H, and -P03H2.

More preferably each W and X independently is -COOH, -S03H or C,_.4kyl substituted by -COOH or _S03H. It is especially preferred that each X is COOH. It is especially preferred that each W independently is -COOH or _S03H, more especially -S03H.

Preferably at least one W is ortho to the azo group (-N=W) in each Q.

Preferably each Y and Z independently is alkyl optionally substituted by a group other than -S03H, -COOH or -P03H2; optionally substituted aryl; optionally substituted araikyi; halo (especially F and Cl); nitro; cyano; -CIF3; -OR 3; -NR'R'; -SRC>; -C(O)R 7; -C(O)OR'1; -S02R9; or -SOR"; wherein:

R 3 and R' each independently is H, optionally substituted alkyl or optionally substituted ary]; R 7, R8, R9 and W0 each independently is optionally substituted alkyl; R 4 and R 5 each independently is H, optionally substituted alkyl, optionally substituted aryl, -C(O)(C1-6-alkyi), -C(O)NH2, or R and R5 together with the nitrogen to which they are attached form a 5- or 6 membered ring.

When any of Y and Z is optionally substituted alkyl it is preferably Cl-1. -alky], more preferably C,,B-alkyl optionally substituted by -OH, nitro, cyano, halo (especially F or Cl), amino, -NH(C,,-hydroxyalkyi) or -NH(C1,-alkyl).

3 4 6 7 When any of W, R2, R, R' Rs, R, R, R', R9 and R is optionally substituted alkyl it is preferably optionally substituted C,.10-alkyl, more preferably optionally substituted Cl.,, alkyl. Preferred optional substituents on the alkyl group are -OH, -COOH, _S03H, -P03H2, nitro, amino, halo (preferably F or Cl). Especially preferred optional substituents are selected from -OH, -COOH and -SO,H.

3 When any of R', R', R', R 4, R' and R' is optionally substituted aryl it is preferably optionally substituted phenyl or optionally substituted naphthyl, especially optionally substituted phenyl. Preferred optional substituents on the aryl group are C,4-alkoxy, (C,,-hydroxyalkyi)-C,,-alkoxy-, -OH, -COOH, -SO,H, -CF3, amino, -NH(C,-4alkyl), -NH(C,-,-hydroxyalkyi), -NH(-C(O)(C,,-alkyl)), halo (especially F or Cl), nitro, -C(O)(Cl,aikyi), -S02(C,-,aikyi) and C,_44kyl optionally substituted by - OH, -COOH and -S03H.

2 When any of W, R ' Y or Z is aralkyl it is preferably optionally substituted phenyl-(alkylene)- or optionally substituted naphthyl-(aikylene)-, more preferably optionally substituted phenyl-(C,-6-alkyiene)- or optionally substituted naphthyi-(C,-,,aikylene)- and especially optionally substituted benzyi. Preferred optional substituents on the aralkyl groups are those listed above for the aryl groups, more preferably Cl,-alkyi, Cl,-alkoxy, -S03H, -COOH, amino, nitro, F or Cl.

When R 4 and R5 together with the nitrogen to which they are attached form a 5- or 6- membered ring they preferably form an optionally substituted morphoiine or optionally substituted piperazine ring.

Preferred optional substituents on the 5- or 6- membered rings which may be formed by R 4 and R 5 together with the nitrogen to which they are attached are selected from -OH, -COOH, _S03H, Cl-4-alkoxy and Cl,-alkyl optionally substituted by -OH, 0 -COOH or -S03H.

R 7, R', R9 and R10 are preferably each independently optionally substituted Cl-4-alky], more preferably Cl-4-alkyi and especially methyl or ethyl.

Preferably R' is H, optionally substituted Cl-10-alky], optionally substituted phenyl or optionally substituted phenyl-(C1-6-alkylene), more preferably H, phenyl, benzyl or Cl,B.alkyl optionally substituted by -OH, _S03H or -COOH, especially H or Cl-4-alkyl, and more especially H.

Preferably R' is optionally substituted Cl-10-alkyl, optionally substituted phenyl or optionally substituted benzyl, more preferably phenyl, benzyi or Cl-6- alkyl optionally substituted by -OH, -COOH or -S03H, especially Cl-4-alkyl. It is especially preferred that R' is methyl or ethyl.

Preferably each Y independently is Cl-4-alkyl.

It is especially preferred that each b is 0 and each a is 1 or 2.

When a is 1 it is preferred that the group represented by X is at the 3position.

Preferably each Z independently is optionally substituted phenyl, halo (especially F and Cl), nitro, cyano, -CF3, -OR 3, -NR 4 Rs, -SR 6, -C(O)R 7, -C(O)OR8, - S02R', -SOR') or alkyl (especially Cl_.-alkyl) optionally substituted by a group other than -COOH, _S03H or P03H2. More preferably each Z is Cl,-alkyl optionally substituted by -OH.

It is especially preferred that each c is 0 and each d is 1.

4 For ease of synthesis of the compounds of Formula (1) it is preferred that each Q is the same.

When L is a direct link, the term 'Urect HW refers to a covalent bond between the phenyl groups of two groups represented by 0.

When L is a divalent linking group it preferably comprises less than 30 carbon atoms, more preferably less than 20 carbon atoms, especially less than 10 carbon atoms.

Preferred divalent linking groups are selected from -0-, -S-, -S02-, optionally substituted, optionally interrupted alkylene, optionally substituted optionally interrupted alkyenylene, -NIR11-, -S02INIR 12_, -C(O)NR 13_, -NR 14C(O)NR 15_, -NR"C(O)-(alkylene)- C(O)NR,7 - and a group of the Formula (2):

T N A -\ A N N-- A- Formula (2) wherein:

each A independently is S or NR"; C, R 12, R 13, R 14 7 R15, R16, R 17 and W' each independently is H or optionally substituted alkyl, more preferably H or Cl-, -alkyl optionally substituted by -OH, -S03H, -COOH or -NH2, especially H or Cl-4-alkyl and more especially H; T is -OR19, -SIR 20, -NIR 21R22 or halo (preferably -F or -Cl); 0 R and R 21 each independently is H, optionally substituted aryl or optionally substituted alkyl; and each independently is H, optionally substituted ary], optionally substituted alkyl, -C(O)(C,-6-alkyl) or -C(O)NH2 or R 21 and R22 together with the nitrogen to which they are attached form an optionally substituted morpholine or piperazine ring, Preferably W' and R each independently is H, optionally substituted phenyl or optionally substituted Cl-6-alkyl.

Preferably R 21 and R 22 each independently is H, optionally substituted phenyl, optionally substituted Cl-6alky], -C(O)(C,-6-alkyl) or -C(O)N1H12 or R 2' and R 22 together with the nitrogen to which they are attached form an optionally substituted morpholine or piperazine ring.

Preferably each A independently is NC, more preferably NH or N(C,-4alkyl), and especially NH.

R'and R 22 C Preferably T is -OR", -SR 20, -NR 21R 22, more preferably -OH, -O(C1,- alkyl), -SH, -S(C1,-alkyl), -NH2, -NH(C1,-alkyl), -N(C,,-alkyl)2, -NH(C,,- hydroxyaikyi), -N(C,,-hydroxyalkyi)2 or morpholine.

When L is an alkylene group it is preferably an optionally substituted C21,-alkylene group which is optionally interrupted by -0-, -S-, -NR 21, -C(O)- or - C(O)0-, wherein R 21 is H, Cl-4-alkyl, or C,-hydroxyalkyl.

When L is alkenylene, it is preferably optionally substituted -C2-6alkenylene-, more preferably -CH=CH-.

When any of the divalent linking group L, W9, R20, R 21 or R 22 is substituted, the substituents are preferably selected from amino, nitro, halo (preferably F or Cl), -S03H, COOH, -OH, -CN, -N02, C,-hydroxyalkyl, carboxy-C,,-alkyl, sulpho-C,-alkyl, Cl-4-alkoXY (especially methoxy) and phenyl optionally substituted by Cl,-alkyl, - COOH, -OH or - S03H.

Examples of preferred optionally interrupted alkylene and alkenylene groups represented by L include: ethylene; 1,2- & 1,3-propylene; 2-hydroxy-1,3- propylene; 1,4-, 2,3- and 2,4-butylene; 2-methyl-1,3-propylene; 2-methy]-2,4-pentylene; 2, 2-dim ethyl- 1, 3 propylene; 1 -chloro-2,3-propylene; 1,6- & 1,5-hexylene; -CH2NHCH2-; 1carboxy-1,5 pentylene; 2,7-heptylene; 3-methyi-1,6-hexylene; -CH2CH=CHCH2_; - CH2CH2OCH2CH2-, and -CH2CH2SCH2CH2_.

0 When L is -NR"C(O)-(alkylene)-C(O)NR"-, it is preferably -NR'6C(O)-(C1-6-alkyiene)-C(O)NR"-, more preferably -NHC(O)-(C2-5alkylene)-C(O)NH-.

When L is a trivalent linking group it is preferably a group of the Formula (3):

A' N = A'-\ __ N A 1 Formula (3) wherein:

each A' independently is S or NW8; and each R" independently is as hereinbefore defined.

Each A' is preferably NC, more preferably NH or N(C1-4-alkyl) and especially NK Preferably n is 2.

When n is 2, L is preferably a direct link; -0-; -S-; -S02_; -NR"-; S02NR 12_; -C(O)NR 13_; -NR 14C(O)NW5-; -NR"C(O)-(C,-,-alkylene)-C(O)NR 17_; a group of the hereinbefore defined Formula (2); -CH=CH- or optionally substituted C2-10-alkylene optionally interrupted by -0-; -S-; -NR 23_; _C(O)_; or -C(O)O-; wherein R", R12, R 13, R 14, R15 23 W' W' and R are as hereinbefore defined.

6 In view of the forgoing preferences, a first preferred embodiment of the present invention comprises a compound of the Formula (4) or a salt or tautomer thereof:

L I- -- - - - 0 W),)q R 25 -tL N N (4, HO N 0 24 R 1 2 Formula (4) wherein:

each X'and W' independently is -COOH, -S03H or C,-6-alkyl substituted by COOH or -S03H; R 24 is H or C,-alkyl optionally substituted by -OH, -S03H or -COOH; R 25 is C,_,-alkyl; each Z' independently is optionally substituted phenyl, halo (especially F and Cl), nitro, cyano, -CF3, -OR 3, -NR 4 R5, -SRr', -C(O)R 7, -C(O)ORB, -S02R', -SOW' or alkyl optionally substituted by a group other than -COOH, -S03Hor -P03H2; 12_ 13_ is a direct link, -0-, -S-, -S02-, -NR'1-, -S02INIR, -C(O)NR ' -INIR 14C(O)NR 15_' -NR"C(O)-(C1.6-alkylene)-C(O)NR"-, a group of the hereinbefore defined Formula (2), -CH=CH- or optionally 13_ substituted C2-M-alkylene optionally interrupted by -0-, -S-, -NR -C(O)- or -C(0)0--, q is 1 or 2; t is 1 or 2; p is 0, 1 or 2; and R 3 R 4 R5, R6, R 7 R 8 R9, R10, R", R 12, R 13, R 14, R15, R16 R 17 and R 23 are as hereinbefore defined.

Preferably each X' is -COOH.

Preferably each W' is independently -COOH or -S03H, more preferably -S03H. It is especially preferred that each W is attached ortho to the azo group (-N=N-).

Preferably each Z' independently is Cl, F, nitro, cyano, hydroxy, C,-6alkoxy, -C(O)(C1-6-alkyl), -C(O)(C,-6-hydroxyalkyl), -C(O)O(C1-4-alkyl), NR 26R 17 or Cl-6-alkyl 2 17 17 optionally substituted by -OH, F, Cl or -NR 6R, wherein R and R each independently is H, Cl,-hydroxyalky], -C(O)NH2, -C(O)(C,-alkyl), Cl,-alkyl optionally substituted by 7 -OH, -S03H, -COOH or -NH2, or R and R 21 together with the nitrogen to which they are attached form a morpholine or piperazine ring. It is especially preferred that each Z, independently is Cl,-alkyl optionally substituted by -OH, more especially methyl or ethyl.

R is preferably H or C,-4-alkyl, more preferably H.

R15 is preferably methyl or ethyl, more preferably methyl.

It is especially preferred that q is 1 and X' is -COOH and is at the 3position on the pyridinium drig.

Preferably L' is a direct link, -CH=CH-, C2-10-alkylene, -NHC(O)NH-, -NHC(O)-(C,-,-alkylene)-C(O)NH-, -NH-, -S02NH- or a group of the hereinbefore defined Formula (2).

A second preferred embodiment of the present invention comprises a compound of the Formula (4) or a salt or tautomer thereof wherein X' is COOH; q is 1; p is 0; t is 1 or 2; W'S -S031-1; L' is a direct link, CH=CH-, C2-1ralkylene, -NHC(O)NH-, -NHC(O)-(C1-6-alkylene)-C(O)NH-, -NH-, -S02NW or a group of the hereinbefore defined Formula (2); and R 2' and R Mare as hereinbefore defined.

A third preferred embodiment of the present invention comprises a compound of the Formula (4) or a salt or tautomer thereof wherein q is 1; X' is -COOH and is at the 3 position on the pyridinium ring; P'S 0; t iS 1; W' iS S03H; Uis a direct link, -CH=Cl-1-,C2-1._ alkylene or -NI-IC(O)NW; R is H; and R is methyl or ethyl.

In another preferred embodiment the dyes of the invention contain at least as many -COOH groups as -S031-1 groups. For example the dyes may contain two -COOH groups andtWO -S031-1 groups.

The compounds of Formula (1) may be prepared by coupling the diazonium salt of an amine of the Formula (5) with approximately n molar equivalents of a compound of the Formula (6), wherein n is as hereinbefore defined:

Wd - IF N112 MC, Formula (5) R 2 - n (X).

-N'r, HO N 0 Mb 1 R Formula (6) wherein R', R 2, L, W, X, Y. Z, a, b, c, d and n are as hereinbefore defined.

The coupling reaction is preferably performed at a pH in the range 5 to 8, more preferably 5.5 to 6.0 Preferably the coupling reaction is performed at a temperature of from OOC to 400C.

8 The diazotisation of the amine of the Formula (5) is preferably performed in an aqueous medium at a pH below 7 in the presence of a suitable diazotising agent. Preferably the diazotising agent is formed in situ, for example by dissolving an alkali metal nitrite (preferably sodium nitrite) in a molar excess of a mineral acid (preferably HCI), The compound of the Formula (6) may be prepared by condensing a compound of the Formula (7) with a compound of the Formula (8):

(X).

N (Y)t, +N 0 1 11 1 - CH2CMR. cl R2C(O)CH2C(O)OCH2CH3 Formula (7) Formula (8) 2 wherein W, R ' X, Y, a and b are as hereinbefore defined.

The condensation is preferably performed under alkaline conditions.

Preferably the condensation is performed at a temperature of from 80 to 100,1C.

The compound of Formula (7) is preferably prepared by condensing the compound of the Formula (9) with a compound of the Formula Cl-CH2CONHIRI wherein R' is as hereinbefore defined:

(X) (Y)'::nN" 0 Formula (9) wherein X, Y, a and b are as hereinbefore defined.

When L is of the Formula (2) or (3) the compounds of Formula (1) are preferably prepared by condensing cyanuric chloride with approximately 2 molar equivalents of a compound of the formula Q-AH, wherein Q and A are as hereinbefore defined; followed by a further condensation with an approximately molar equivalent of a compound of the Formula TH when n = 2, or Q-AH when n = 3.

When L is -NW'C(O)NIR'- the compound of Formula (5) is preferably prepared by condensing approximately 2 molar equivalents of a compound of the Formula (10) with phosgene. The resulting compound is then converted to a compound of Formula (5) by acid hydrolysis of the acetyl amino groups using a suitable acid such as H2SO4:

9 H \ N NHC(O)CH3 R 14 " (Z), Formula (10) wherein W, Z, c and d are as hereinbefore defined.

The compounds of the present invention may be in the free acid or salt form. Preferred salts are water-soluble, for example alkali metal salts, especially lithium, sodium and potassium salts, ammonium and substituted ammonium salts and mixed salts thereof. Especially preferred salts are salts with sodium, lithium, ammonia and volatile amines, more especially sodium salts.

The compounds of the present invention are conveniently synthesised in the form of an alkali metal salt, for example the Na salt. This may be converted into a different salt using known techniques. For example, an alkali metal salt of a dye may be converted wholly or partially into a salt with ammonia or an amine by dissolving an alkali metal salt of the dye in water, acidifying with a mineral acid and adjusting the pH of the solution to pH 9 to 9.5 with ammonia or the amine and removing the alkali metal cations by dialysis.

Alternatively the alkali metal ion may be partially or wholly exchanged for an optionally substituted ammonium ion by a conventional ion exchange method.

The present invention covers all tautomeric forms of the compounds of Formulae (1) and (4). For example the hydrazo tautomers of the compounds of Formulae (1) and (4).

0 The present invention covers compounds of the Formula (1), compositions comprising two or more compounds of the Formula (1), and compositions comphsing one or more compounds of the Formula (1) and one or more other dyes other than a compound of the Formula (1). Preferred compositions comprise a compound of the Formula (1) and a black andlor a yellow dye.

A first preferred composition comprises a compound of the Formula (1) and one or more yellow dyes other than a compound of Formula (1). Preferred yellow dyes are selected from Cl Direct Yellow 86, Cl Direct Yellow 132, Cl Direct Yellow 142, Cl Acid Yellow 23 and the dye described in Example 10 of EP 468 747.

A second preferred composition comprises a compound of the Formula (1) and one or more black dyes. Preferred black dyes are selected from Cl Direct Black 19, Cl Direct Black 168, Cl Reactive Black 31 and the dye described in Example 2 of EP 356 080.

The. compounds according to the present invention are useful as a colorant in inks, especially inks used in ink jet printing processes. The compounds (especially in the form of a salt with an alkali metal, ammonia or a volatile amine) exhibit a high solubility in aqueous media and provide bright yellow prints having high water-fastness and high light fastness.

According to a second aspect of the present invention there is provided an ink comprising a medium and a compound or a composition according to the first aspect of the present invention.

Preferably the ink comprises:

(a) from 0.01 to 30 parts of a compound of the Formula (1) or (4) or a salt or tautomer thereof; and (b) from 70 to 99.99 parts of a liquid medium or a low melting point solid medium; wherein all parts are by weight and the number of parts of (a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, more preferably from 0.5 to 15, and especially from 1 to 5 parts. The number of parts of component (b) is preferably from 99.9 to 80, more preferably from 99.5 to 85, especially from 99 to 95 parts.

When the medium is a liquid, preferably component (a) is completely dissolved in component (b). Preferably component (a) has a solubility in component (b) at 200C of at least 10%. This allows the preparation of concentrates which may be used to prepare more dilute inks and reduces the chance of the dye precipitating if evaporation of part of the liquid medium occurs during storage.

Preferred liquid media include water, a mixture of water and an organic solvent 0 and an organic solvent free from water.

When the medium comprises a mixture of water and an organic solvent, the weight ratio of water to organic solvent is preferably from 99:1 to 1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to 80:20.

It is preferred that the organic solvent present in the mixture of water and organic solvent is a water-miscible organic solvent or a mixture of such solvents. Preferred water miscible organic solvents include Cl-6-alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanoi; linear amides, preferably dimethylformamide or dimethylacetamide; ketones and ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscible ethers, preferably tetrahydrofuran and dioxane; diols, preferably diols having from 2 to 12 carbon atoms, for example pentane-1, 5-diol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferably diethylene glycol, thethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol; mono-C,_ralkyl ethers of diols, preferably mono-C,,- alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxyethanol, 2-(2- methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2ethoxyethoxy) ethoxy]-ethanol and ethyleneglycol monoallylether; cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethy]-2-pyrrolidone, caprolactam and 1,3- dimethylimidazolidone; cyclic esters, preferably caprolactone; sulphoxides, preferably dimethyl sulphoxide and suipholane. Preferably the liquid medium comprises water and 2 or more, especially from 2 to 8, water-soluble organic solvents.

Especially preferred water-soluble organic solvents are cyclic amides, especially 2pyrrolidone, N-methyl-pyrrolidone and N-ethyi-pyrroiidone; diols, especially 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyieneglycol and tdethyleneglycol; and mono- Cl,-alkyl and Cl-4-alkyl ethers of diols, more preferably mono- C1.4-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxy-2-ethoxy-2-ethoxyethanol.

A preferred liquid medium comprises: (a) from 75 to 95 parts water; and (b) from 25 to 5 parts in total of one or more solvents selected from diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol; wherein the parts are by weight and the sum of the parts (a) and (b) = 100.

Another preferred liquid medium compriises:

from 60 to 80 parts water; from 2 to 20 parts diethyiene glycol; and from 0.5 to 20 parts in total of one or more solvents selected from 2pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam, pentane-1,5- diol and thiodiglycol; wherein the parts are by weight and the sum of the parts (a), (b) and (c) = 100.

Examples of further suitable ink media comprising a mixture of water and one or more organic solvents are descdbed in US 4,963,189, US 4,703,113, US 4, 626,284 and EP 4,251,50A.

When the liquid medium comprises an organic solvent free from water, (i.e. less than 1% water by weight) the solvent preferably has a boiling point of from 30C, to 2000C, more preferably of from 400 to 1500C, especially from 50 to 1250C. The organic solvent may be water-im miscible, water-miscible or a mixture of such solvents. Preferred water miscible organic. solvents are any of the hereinbefore described water- miscible organic solvents and mixtures thereof. Preferred water-immiscible solvents include, for example, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH2C12; and ethers, preferably diethyl ether; and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent, preferably a polar solvent is included because this enhances solubility of the dye in the liquid medium. Examples of polar solvents include C,-alcohols. In view of the foregoing preferences it is especially preferred that where the liquid medium is an organic solvent 0 12 free from water it comprises a ketone (especially methyl ethyl ketone) Wor an alcohol (especially a Cl-4-alkanol, more especially ethanol or propanoi).

The organic solvent free from water may be a single organic solvent or a mixture of two or more organic solvents. It is preferred that when the medium is an organic solvent free from water it is a mixture of 2 to 5 different organic solvents. This allows a medium to be selected which gives good control over the drying characteristics and storage stability of the ink.

Ink media comprising an organic solvent free from water are particularly useful where fast drying times are required and particularly when printing onto hydrophobic and non-absorbent substrates, for example plastics, metal and glass.

Preferred low melting solid media have a melting point in the range from 600C to 1250C. Suitable low melting point solids include long chain fatty acids or alcohols, preferably those withCl.-24 chains, and sulphonamides. The dye of Formula (1) or (4) may be dissolved in the low melting point solid or may be finely dispersed in it.

The ink may also contain additional components conventionally used in ink jet printing inks, for example viscosity and surface tension modifiers, pH buffers, corrosion inhibitors, biocides, kogation reducing additives and surfactants which may be ionic or non-ionic.

Preferably the pH of the ink according to the second aspect of the present 0 invention is from 2 to 8, more preferably from 3 to 6 and especially from 4 to 6.

The compounds according to the first aspect of the present invention exhibit a high solubility in water. Accordingly it is preferred that the ink medium is water or a mixture of water and one or more water-miscible organic solvent. An especially preferred ink comprises:

(a) from 0.01 to 30, more preferably 1 to 5 parts of a compound of Formula (1) or (4) or a salt or tautomer thereof; (b) from 75 to 98, preferably 80 to 97 parts water; and (c) from 2 to 25, preferably 2 to 20 parts of water-miscible organic solvent; wherein all parts are by weight and the sum of the parts (a) + (b) + (c) = 100.

A third aspect of the invention provides a process for printing an image on a substrate comprising applying an ink containing a compound of the Formula (1) or (4) to the substrate by means of an ink jet printer.

The ink used in this process is preferably an ink according to the second aspect of the present invention.

The ink jet printer preferably applies the ink to the substrate in the form of droplets which are ejected through a small orifice onto the substrate. Preferred ink jet printers are piezoelectric ink jet printers and thermal ink jet printers. In thermal ink jet printers, programmed pulses of heat are applied to the ink in a reservoir by means of a resistor 13 adjacent to the orifice, thereby causing the ink to be ejected in the fomi of small droplets directed towards the substrate during relative movement between the substrate and the orifice. In piezoelectric ink jet printers the oscillation of a small crystal causes ejection of the ink from the orifice.

The substrate is preferably paper, plastic, a textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, especially paper.

Preferred papers are plain or treated papers which may have an acid, alkaline or neutral character. Examples of commercially available treated papers include HP(R11,1) Premium Coated Paper (available from Hewlett Packard Inc), HP Photopaper (available from Hewlett Packard Inc), Stylus Pro 720 dpi Coated Paper, Epsonfhoto Quality Glossy Film (available fromSeiko Epspn,.Corp.), Epson Photo Quality Glossy Paper (available from Seiko Epson Corp.), Canon/HR 101 High Resolution Paper (available from Canon), Canon GP 201 Glossy Paper (available from Canon), and Canon HG 101 High Gloss Film (available from Canon).

A fourth aspect of the present invention provides a paper, an overhead projector slide or a textile material printed with an ink according to the second aspect of the present invention or by means of a process according to the third aspect of the present invention.

According to a fifth aspect of the present invention there is provided an ink jet printer cartridge comprising a chamber and an ink, the ink being present in the chamber and 0 wherein the ink contains a compound of the Formula (1) as hereinbefore defined in relation to the first aspect of the invention. Preferably the ink is an ink according to the second aspect of the present invention.

Preferably the ink jet printer cartridge comprises of at least three chambers, a yellow ink containing a compound of the Formula (1) as hereinbefore defined in relation to the first aspect of the invention, a cyan ink and a magenta ink, the yellow, cyan and magenta inks being present in different chambers of the cartridge.

According to a sixth aspect of the present invention there is provided an ink jet printer containing an ink jet printer cartridge, wherein the ink jet printer cartridge is as defined in the sixth aspect of the present invention.

The invention is further illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.

14 Example 1 Dye (1) 0 OH S03 H H C-N CH3 C C H 0 N/ N HOS H OH 0 U C H 3C N-JIMOH N 0 11 \N HO H Dye (1) Dye (1) was prepared in the form of its sodium salt as follows:

Stage 1 (a): Preparation of Intermediate (A) HOOC n±CH2CONH2.ci ≥_ 1 Intermediate (A) Chloroacetamide (339.4g at 98% strength) was added to N,N- dimethyiformamide (DIVIF) (21). To the resulting solution was added nicotinic acid (466.4g at 98% strength) followed by further DIVIF (800mi) whilst warming the mixture to 900C. The mixture was stirred at this temperature for 2 1/2 hours and allowed to self cool to room temperature. The resulting precipitate was filtered off, washed with acetone and dried under vacuum at 500C to give Intermediate (A). (Yield = 478g).

0 Stage 1 (b): Preparation of Intermediate (B):

COOH CH3 N 1 A HO N 0 1 H Intermediate (B) Intermediate (A) (450g) was added to ethylacetoacetate (277.2g) and methylated spirit 740 P (1.251). To this was added sodium hydroxide pellets (188.5g in total dissolved in methylated spirit 740 P (800mi) and water (840mi)). The mixture was then heated to reflux for total of 17 hours and then cooled to room temperature. The resulting solid was filtered off, washed with methylated spirit 740 P and dried under vacuum 4011C to give Intermediate (B). (Yield = 102.2g at 33% Strength).

Stage 1(c):Diazotisation and Coupling 4A-Diaminostillbene, 2-2' disulphonic acid ( 0.02 mole, 7.8g @ 95% strength) was added to water (100mi) followed by conc. HCI ( 30mi). The mixture was cooled to 0 to 50C and NaN02 aq. (2N, 21 mi) was added portionwise over 1.5 hours. The mixture was stirred for a further 0.5 hours at 0 to 51C. Excess HN02 was then destroyed with sulphamic acid.

Intermediate (B) ( 0.04 mole 9.88g @ 100% strength) was dissolved in water (1 00mi) and added to the above mixture. The pH was raised to 5.5-6 by addition of solid NaHC03and the mixture stirred for approximately 12 hours whilst allowing it to self-warm to room temperature. Sodium chloride ( 50g, approximately 20% w/v) was added to the mixture and the resulting precipitate filtered, washed with 20% NaCI (aq) and pulled dry on a filter.

Stage 1(d):Purification The product of stage 1 (c) was re-dissolved in distilled water (approx. 41) at pH 9.5 and desaiinated by reverse osmosis. The solution was then screened and the water evaporated to leave the title product in the form of its sodium salt. (Yield = 13.3g).

Example 2

0 Dye (2) 0 OH N 0 OH H 3c--_ N1H S03H N N CH 11 OH 0= ---3 N N N / H HO 3s OH Dye (2) Dye (2) was prepared in the form of its sodium salt using the process deschbed in Example 1 except that in stage 1(c) there was used 4,4'- diamino-2,2'biphenyidisulphonic acid ( 0.02 mole, 6.89g @ 100% strength.) in place of 4,4-diaminostiiibene2,2'-disulphonic acid.

Yield = 11.2g.

16 Inks Dye (2) (0.30g) was added too "xture consisting of water (8.50g), 2- Pyrrolidone (0.5g), ( TM thiodiglycol (0.5g) and Surfynol/465 (0.20g) (a surfactant commercially available from Air Products Inc.) and dissolved by sonicating in a sonic bath. The pH was adjusted to pH9.5 with ammonia using a pH meter. The ink was filtered through a 0.45gm filter and put into one chamber of a Canon trichamber ink jet cartridge.

Ink Jet Printin-g Tpe cartridge was placed in a Canon 4300 printer and the ink was applied to XeroxOcid 4024 paper, SEC 720 dpi coated paper, SEC glossy paper and SEC glossy film.

The resulting prints were a bright yellow shade with a high chroma. The prints exhibited good water-fastness and a high optical density.

Example 3

0 0 OH 0 CH3 H1 N HO 0 O-SO3H H3C N OH 0 O=Z NH IN : \ N N N H H HO H03s Dye (3) Dye(3) was prepared in the form of its sodium salt as follows: Sta-ge 2(a) Preparation of N,N'bis(4-amino-2-sulphophenvi)urea 5-acetylamino-2-aminobenzenes'uiphonic acid ( 1.0 mole, 230g) was added to water (900mi) and the pH adjusted to 7.0 by addition of caustic liquor whilst maintaining temperature at approximately 150C by addition of ice. Phosgene (0.9 mole, 89.1 g) was added to the mixture whilst maintaining the pH at 6 to 6.5 by addition of caustic liquor allowing the temperature of the mixture to rise to 40 to 451C. Sulphuric acid ( 78% strength. 2.90 mole, 364g) was added and the resulting mixture heated to 700C for 6 hours. The mixture was then cooled to room temperature by addition of ice and the resulting precipitate filtered off, washed and dried.

Yield 273.4 g @ 100% strength.

17 Sta-ge 2( The product of stage 2(a) was diazotized and coupled to Intermediate B using the process described in stage 1 (c) of Example 1, except the in place of 4,4'-diaminostilibene2,2'-disulphonic acid there was used N, Mbis(4-am ino-2-sulphophenyl) urea.

0 The resulting product was purified as described in stage 1(d) of Example 1 to give the title product in the form of its sodium salt.

Example 4 - Inks Inks according to the formulations shown in Tables 1, 2 and 3 may be prepared. In Tables 1 to 3 the Dye described in the first column is the Dye made in the above examples of the same number. Numbers quoted in the second column onwards refer to the number of parts of the relevant ingredient and all parts are by weight. The inks may be applied to paper by thermal or piezo inkjet printing. The following abbreviations are used in Table 1, 2 and 3:

PG = propylene glycol NIVIP = N-methyl pyrrolidone P12 = propane- 1, 2diol CET= cetyl ammonium bromide TBT = tertiary butanol GLY = glycerol H 1,6 = Hexane 1,6-diol CAP-L = a-caprolactam EA = ethanolamine DEA = diethanolamine PEG 200 = Polyethylene glycol (average molecular weight of 200) DEG-MBE = diethylene glycol monobutyl ether DEG = diethylene glycol 2P 2-pyrrolidone UR Urea PHO = Na2HPO, and TDG = thiodiglycol P-1,5 = Pentane-1,5-diol CAP =c-caprolactone TEA = triethanolomine BUT = V-butyrolactone 1 TABLE 1

Ink Dye Dye Water PG DEG NMP P-1,5 TEA DEA BUT CAP EA CAP-L Content 1 1 2.0 80 5 6 4 5 2 3 3.0 90 5 4.8 0.2 3 2 10,0 85 3 3 3 5 1 4 2 2.1 91 8 1 1 3.1 86 5 0.2 3.8 5 6 1 1.1 81 9 0.5 0.5 9 7 3 2.5 60 4 15 3 3 6 10 8 1 5 65 20 10 5 9 1 2.4 75 5 4 5 6 5 2 4.1 80 3 5 2 9.7 0.3 11 2 3.2 65 5 4 6 5 4 6 5 12 1 5,1 96 4 13 2 10.8 90 5 5 14 3 10.0 80 2 6 2 5 1 4 2 1.8 80 5 15 16 3 2.6 84 11 5 17 2 3.3 80 2 10 2 6 18 1 12.0 90 7 0.3 2.7 19 1 5.4 69 2 20 2 1 3 3 1 6.0 91 4 5 co TABLE 2

Ink Dye Dye Water PEG DEG- NIVIP H-1,6 TEA DEA BUT CAP EA CAP-L Content 200 MBE 21 1 2.0 80 5 6 4 5 22 2 3.0 90 5 4.8 0.2 23 2 10.0 85 3 3 3 5 1 24 3 2.1 91 8 1 3 3.1 86 5 0.2 3.8 5 26 2 1.1 81 9 0.5 0.5 9 27 1 2.5 60 4 15 3 3 6 5 4 28 3 5 65 20 10 5 29 1 2.4 75 5 4 5 6 5 1 4.1 80 3 5 2 9.7 0.3 31 2 3.2 65 5 4 6 5 4 6 5 32 3 5.1 96 4 33 3 10.8 90 5 5 34 1 10.0 80 2 6 2 5 1 4 1 1.8 80 5 15 36 1 2.6 84 11 5 37 2 3.3 80 2 10 2 6 38 2 12.0 90 7 0.3 2.7 39 3 5.4 69 2 20 2 1 3 3 1 6.0 91 4 5 m ill TABLE 3

1 Ink Dye Dye Water PG DEG NIVIP CET TBT MG UR PHO 2P P12 Content 41 1 3.0 80 15 0.2 4.8 42 2 9.0 90 3.8 1.2 5 43 2 1.5 85 5 5 0.15 4.65 0.2 44 2 2.5 90 6 3.88 0.12 2 3.1 82 4 8 0.3 5.7 46 3 0.9 85 9.8 5 0.2 47 2 8.0 90 4.7 5 0.3 48 3 4.0 70 10 4 1 4 11 49 2 2.2 75 4 10 3 2 6 3 10.0 91 6 3 51 1 9.0 76 9 7 2.05 0.95 5 52 1 5.0 78 5 11 6 53 3 5.4 86 7 7 54 2 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 9.5 2 2.0 90 10 56 1 2 88 10 2 57 3 5 78 5 12 5 58 1 8 70 2 8 15 5 59 1 10 80 8 12 2 10 80 10 bi (D wherein- n L each Q 21

Claims (19)

1. A compound of Formula (1) or a salt or tautomer thereof:

L __4 ()] n Formula (1) is 2 or 3; is a direct link or a di- or tri-valent linking group; independently is of the formula:

(W)d R 2 N 45, N (Z), HO N 0 A 1 each R' and R 2 each W and X each Y and Z independently is H, optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl; independently is -COOH, -S03H, P03H2 or alkyl substituted by one or more groups selected from -COOH, _S03H and -P03H2; independently is a substituent other than those defined for W and X; each a independently is 1 to 5; each b independently is 0 to 4; each c independently is. 0 to 3; each d independently is 1 to 4; (a + b) in each Q independently has. a value of 5 or less; and (c + d) in each Q independently has a value of 4 or less.

2. A compound according to claim 1 wherein:

each Y and each Z independently is alkyl optionally substituted by a group other than -S03H, -COOH or -P03H2; optionally substituted ary]; optionally substituted aralkyl; halo; nitro; cyano; -CF3; -OR 3; -NR 4 W; -S R' '; C(O)R 7; -C(O)OW; -S02R9; or -SOR10; R 3 and R' each independently is H, optionally substituted alkyl or optionally substituted aryl; 22 0 R', R8, R' and R each independently is optionally substituted alkyl; R' and R' each independently is H, optionally substituted alkyl, optionally substituted aryl, -C(O)(C1-6-alkyl), -C(O)N1-12, or R' and R' together with the nitrogen to which they are attached form a 5- or 6membered ring.

3. A compound according to either claim 1 or claim 2 wherein: L is a direct link or a divalent linking group selected from -0-, -S-, -S02-, optionally substituted optionally interrupted alkylene, optionally substituted optionally interrupted alkyenylene, -NR"-, -S02NR 12_, C(O)NIR13-, -NR 14C(O)NW-5-, -NR 16C (0)-(alkylene)CONR 17_, and a group of the Formula (2):

T N -- A A N N-- A- Formula (2) each A independently is S or NW; 12 13 14 R", R, R, R, R15, R16, R"and W' are each independently H or optionally substituted alkyl; is -OR'9, -SIR 20, -NR"R' or halo; each independently is H, optionally substituted aryi or optionally substituted alkyl; and each independently is H, optionally substituted aryl, optionally substituted alkyl, -C(O)(C,,-alkyl) or -C(O)N1-12 or R 21 and R' together with the nitrogen to which they are attached form an optionally substituted morpholine or piperazine ring.

T R19 and R 20 R 2'and R 22

4. A compound according to any one of the preceding claims wherein (a+b) in each group Q independently has a value of 1, 2 or 3.

5. A compound according to any one of the preceding claims wherein (c+d) in each group 0 independently has a value of 1, 2 or 3.

23

6. A compound according to claim 1 of the Formula (4) or a salt or tautomer thereof:

W), R -3D._ N (4, HO N 0 24 R Formula (4) 2 wherein:

each X'and W' independently is -COOH, _S03H or C,6-alkyl substituted by COOH or -S03H; R 24 is H or C,-6-alkyl optionally substituted by -OH, -S03H or -COOH; R 25 is C,_,-alkyl; each Z1 independently is optionally substituted phenyl, halo, nitro, cyano, -CF3, -OR 3, -NR 4 Rs, -SR 6, -C(O)R 7, -C(O)OR8, -S02R9, -SOW0 or alkyl optionally substituted by a group other than -COOH, _S03H or -P03H2; 12 13_ L' is a direct link, -0-, -S-, -S02-, -NC-, -S02NR, -C(O)NR -NR MC(O)NW-5-, -NR"C(O)-(C1-6-alkylene)-C(O)NR"-, a group of the Formula (2), -CH=CH- or optionally substituted C2-10-alkylene optionally interrupted by -0-, -S-, -NR M_' -C(O)- or -C(O)O-:

T N A N /A N A- 0 Formula (2) each A independently is S or W'; R", R 12, R 13, R 14 R15, R16, R 17 and W' are each independently H or optionally substituted alkyl; is H, C,-4- alkyl, or C,-4-hydroxyalkyl; is 1 or 2; is 1 or 2; p is 0, 1 or 2; and R3, R 4, R5, RG, R

7 Re, R9 and R10 are as defined in claim 2.

R 23 q t 24 7. A compound according to claim 6 wherein:

xl is -COOH; q is 1; p is 0; t is 1 or 2; W1 'S -S03IHI; and L' is a direct link, -CH=CH-, C2-10-alkylene, -NHC(O)NW, -NHC(O)-(C,,,- alkylene) C(O)NW, -NH-, -S02INIH- or a group of the Formula (2) as defined in claim 6.

8. A compound according to claim 6 wherein:

q is 1; xl is -COOH and is at the 3-position on the pyridinium ring; p is 0; t is 11; WI is S03H; L' is a direct link, -CH=CH-, C2-10-alkylene or -NHC(O)NH--, R 24 is H; and R 25 is methyl or ethyl.

9. A compound according to any one of the preceding claims wherein the compound is in the form of a lithium, sodium, potassium, ammonium or substituted ammonium salt, or a mixed salt thereof.

10. A composition comprising a compound according to any one of claims 1 to 9 and a black andlor a yellow dye.

11. An ink comprising a medium and a compound according to any one of claims 1 to 9 or a composition according to claim 10.

12. An ink according to claim 11 comphsing: (a) from 0.01 to 30 parts of a compound according to any one of claims 1 to 9; and (b) from 70 to 99. 99 parts of a liquid medium or a low melting point solid medium; wherein all parts are by weight and the number of parts of (a)+(b)=100.

13.

(a) (b) from 75 to 98 parts water; and (c) from 2 to 25 parts of water-miscible organic solvent; wherein all parts are by weight and the sum of the parts (a) + (b) + (c) = 100.

An ink according to either claim 11 or claim 12 comprising: from 0.01 to 30 parts of a compound according to any one of claims 1 to 9;

14. A process for printing an image on a substrate comprising applying an ink containing a compound according to any one of claims 1 to 9 to the substrate by means of an ink jet printer.

15. A paper, an overhead projector slide or a textile material printed with an ink according to any one of claims 11 to 13, or by means of a process according to claim 14.

16. An ink jet printer cartridge comprising a chamber and an ink, the ink being present in the chamber and wherein the ink contains a compound according to any one of claims 1 to 9.

17. A ink jet printer containing an ink jet printer cartridge according to claim 16.

0

18. A compound substantially as hereinbefore defined in relation to any one of the examples.

19. An ink substantially as hereinbefore defined in relation to any one of the examples.