GB2332439A

GB2332439A - Dye mixtures & ink jet inks based on 2-amino-4,6-bis[4-(sulphophenylazo)anilino]-1,3,5-triazines in combination with a black bis-, tris- or tetrakis-azo dye

Info

Publication number: GB2332439A
Application number: GB9826467A
Authority: GB
Inventors: Aidan Joseph Lavery; John Edward Presgrave
Original assignee: Zeneca Ltd
Current assignee: Syngenta Ltd
Priority date: 1997-12-18
Filing date: 1998-12-03
Publication date: 1999-06-23
Anticipated expiration: 2018-12-03
Also published as: GB2332439B; GB9826467D0

Abstract

Compositions are disclosed which comprise a dye of the formula (A) or salt thereof: [wherein: R<SP>1</SP> is C 1-4 -alkoxy or C 1-4 -alkyl; R<SP>2</SP> is H or C 1-4 -alkyl; and R<SP>3</SP> and R<SP>4</SP> are each independently H, C 1-4 -alkyl or C 1-4 -hydroxyalkyl] and a black dye of the Formula (1), (2), (3), (4), (5), (6), (7) or (8); and optionally a water-soluble cyan dye. (57) continued overleaf (57) cont [wherein R<SP>5</SP> is -COOH or -PO(OH 2 ); B is 1,4-phenylene carrying two groups selected from C 1-4 -alkyl and C 1-4 -alkoxy; m is 1 or 2; and R<SP>6</SP> is vinyl sulphonyl (or a group convertible thereto when treated with aqueous alkali) or hydroxyethyl sulphonyl.] Such compositions may be formulated as inks by the addition of a liquid or low-melting-point-solid medium and used in ink jet printing.

Description

WC 60269 1 COMPOSITION 2332439 This invention relates to a composition

comprising two or more dyes, to inks containing such compositions and to processes using said inks in printing and imaging technologies, especially inkjet printing.

Ink jet printing is a non-impact printing technique which involves ejecting, thermally or by action of an oscillating piezo crystal, droplets of ink continuously or on demand from a fine nozzle directly onto a substrate. The inks used in an ink jet printer are required to meet a number of criteria. For example they desirably provide sharp, nonfeathered images which have good waterfastness, lightfastness and optical density. Furthermore, the inks are required to dry quickly when applied to a substrate, however, they must not dry or crust over in the ink jet head as this can result in clogging of the ink jet nozzle. The inks are also required to be storage stable for long periods of time without deterioration in the properties of the ink.

We have found that mixtures of certain dyes are valuable as colorants for ink jet printing inks.

According to a first aspect of the present invention there is provided a composition comprising a black dye and a dye of Formula (A) or salt thereof:

2 3 -NR 2 N= NR 2 1 1 -Q- P±Q 7 p- 1 N N 1 SO3H R 't R S03H N R4 Formula (A) 2 3 wherein:

R' is C,-4-alkoxy or C,-4-alkyl; R 2 is H or C,,-alkyl; and R 3 and R 4 are each independently H, C,-4-alkyl or C,-4-hydroxyalkyl; wherein the black dye is selected from dyes of Formula (1), (2), (3), (4), (5), (6), (7) or (8) and salts thereof:

OH N=N-B-N=W- NH2 HOS 3 Formula (1) 03MC 60269 2 OH NH2 H03S H k S03 S03H Formula (2) H2N-C NHZ N=W-O-N=N NH 1 2 OH N=N---'N=N-b--NH2 HO 3S SO3H Formula (3) H2N OH 03H OH 1 "- N=N- CH=C- NH S03H HO H03,5 Formula (4) H2N OH -- S03H e N=W-J/ \c OH NH 1 CH=C H03S SO3H 035"4=03 H H S S03H Formula (5) NH2 OH so 3H OH N=N- CH=CH- N=N - NH2 HO,S S03H H03 H03S 3 Formula (6) SMC 60269 3 n ".-,"Cu HOOC N=N-[a 'Qz: N=N-- R N, N OH S03H S03H OCH3 Formula (7) H2N N= NH, 1 OH N=N--0 H03S S03H Formula (8) wherein R' is -COOH or -PO(O1-1)2; B is 1,4-phenylene carrying two groups selected from Cl-4-alkyl and Cl-4-alkoxy; m is 1 or 2; and R6 is vinyl sulphonyl, hydroxyethyl sulphonyl or a group which is convertible to vinyl sulphonyl when treated with aqueous alkali.

The-S03H group in the left hand phenyl group in Formula (A) is preferably at the 3-position.

R' is preferably meta to the azo group.

The group represented by R' is preferably methyl, ethyl, methoxy or ethoxy, especially methoxy.

The group represented by R 2 is preferably H or methyl, especially H. The group represented by R 3 and R 4 are preferably each independently H, methyl, ethyl or -CH2CH20H. It is preferred that one of R 3 and R 4 is H and the other is - CH2CH20H.

An especially preferred dye of the Formula (A) is of the formula below or a salt thereof:

SIVIC 60269 4 'N NH___ rNH-- S03H OCH3 NyN OCH3 NHCH 2 CH 2 OH SO H The above dye is available commercially as C.I.Direct Yellow 142. The composition may contain a single dye selected from the dyes of Formulae (1) to (8), or a mixture of two or more of the dyes of Formulae (1) to (8). The composition preferably comprises:

(a) from to 99 to 50 parts, more preferably 95 to 60 parts, especially 90 to 65 parts of one or more of the black dye(s); and from 1 to 50 parts, more preferably 5 to 40 parts, especially 10 to 35 parts of a dye of Formula (A); wherein the parts are by weight and the sum of the parts (a) and (b) = 100. A preferred mixture of dyes of Formulae (1) to (8) comprises a mixture of two or three different dyes of Formula (1). Such mixtures are described in EP 761,771 A and EP 771,860A. A preferred black dye of Formula (1) is of the Formula (9) or a salt thereof:

X OH -N=N- N= NH2 y HO S Formula (9) wherein:

R 5 is as hereinbefore defined; one of X and Y is Cl,-alkoxy and the other is C,4-alkyl or Cl-,-alkoxy; and m is 1 or 2.

When R6 in the dye of Formula (7) is a group which is convertible to a vinyl sulphonyl group when treated with aqueous alkali it is preferably of the formula:

-S02CH2CH20SO3H, -S02CH2CH2SS03H, -S02CH2CH2C1 or -S02CH2CH20COCI-13. It 'S preferred that R 6 'S -S02CH2CH20H or, more preferably, -S02CH2CH20S031-1. R' is preferably attached in the para position relative to the azo group in the dye of Formula (7).

Dyes of Formula (A) may be prepared by reacting an amine of formula HNR 3 R 4 with a chlorotriazine analogue of the compound of Formula (A) in which there is a Cl atom in place of the -NR 3 R group. The chlorotriazine analogue may be prepared by condensing 2 moles of a compound of Formula (B) with one mole of cyanuric chloride:

SIVIC 60269 1 N=N- NR2H 1 S03H Formula (B) The compounds of Formula (B) may be prepared by diazotising a sulphoaniline and coupling onto benzene carrying an R' and NR'H group.

Certain dyes of Formula (A) are commercially available, for example C.I. Direct Yellow 142.

The dyes of Formula (1) may be prepared using methods known in the art for the preparation of azo compounds. For example, suitable methods for the preparation of the dyes of Formula (1) are described in European patent applications No. EP 761,771A, EP 771,860A and EP 356 080A. The dyes of Formula (1) may be converted into the free acid form or into a salt with a counter ion other than sodium by using well known techniques. For example, the alkali metal salts of the dye of Formula (1) may be converted into a salt with ammonia or an amine by dissolving the dye in the form of a salt with an alkali metal, 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.

An example of a suitable process for converting the sodium salt of the dye of Formula (1) to the ammonium salt is analogous to that described in Example 21 of EP 356, 080A.

The dye of Formula (2) is Food Slack 2 and is commercially available from Bayer.

The dye of Formula (3) is commercially available from various manufacturers as C.I.Direct Black 19. The dye of Formula (3) may be prepared using conventional techniques for the preparation of azo dyes. For example a suitable method comprises:

(1) diazotising 1,4-phenylenediamine using, for example, sodium nitrite in a mineral acid at 0 to WC; (2) coupling 8-amino-l-naphthol-3,6-disulphonic acid with an approximately equimolar quantity of the diazotised 11,4-phenylene diamine from stage (1) under slightly acidic conditions; (3) adjusting the pH of the solution resulting from stage (2) so that it is alkaline, preferably in the range pH 8 to 9, and adding a further equimolar quantity of diazotised 1,4-phenylenediamine from stage (1); and (4) coupling the diazotised disazo dye formed in stage (3) with approximately 2 molar equivalents of 1,3-phenylenediamine to give the dye of Formula (3).

The dyes of Formulae (4) to (6) may be prepared using methods analogous to those used for the preparation of similar azo dyes. A suitable method comprises:

(1) diazotising 4,4'-diamino-stilbene-2,2'-disulphonic acid using, for example, sodium nitrite in a mineral acid at 0 to 50C; and SIVIC 60269 6 (2) coupling the diazonium salt from stage (1) with approximately 2 molar equivalents of a compound XH, preferably under mildly alkaline conditions. For the dye of formula (4) the compound XH is 2-amino-8-naphthol-6sulphonic acid. For the dye of formula (5) the compound XH is 8-amino-lnaphthol-3,6-disulphonic acid. For the dye of Formula (6) the compound XH is an approximately equimolar mixture of 8-aminol-naphthol-3,6disulphonic acid and 2-amino-8-naphthol-6-sulphonic acid.

The dye of Formula (7) wherein R' is -S02CH2CH2OS031-1, is commercially available from various manufacturers as C.I.Reactive Black 31. The dye of Formula (7) may be prepared using conventional methods for the preparation of azo dyes. For example, a suitable method comprises:

(1) diazotising 2-amino-8-naphthol-6-sulphonic acid and coupling the resultant diazonium salt with the pyrazolone compound of the formula:

1 COOH e HO-- ( lN (2) diazotising the compound of the formula:

OCH3 H2N 'I 1 R6 OCH3 wherein R' is as hereinbefore defined; (3) coupling the diazonium salt from stage (2) with the product of stage (1), preferably under alkaline conditions; and (4) heating the azo dye formed in stage (3) in the presence of cuprammonium sulphate and a suitable alkanolamine, such as dihydroxyethylamine, to give the dye of Formula (7).

When R' is hydroxyethyisulphonyi, it is preferred that the dye is prepared by hydrolysing a dye of the Formula (7) wherein R6 is -S02CH2CH2OS031-1.

The dye of Formula (8) is commercially available as C.I.Direct Black 168.

Dyes of the Formula (10) are described in EP 356 OBOA.

We have found that the addition of a cyan dye to a composition according to the first aspect of the present invention results in further improvements in print quality when -3MC 60269 7 the composition is incorporated into an ink. Accordingly, a second aspect of the present invention provides a composition comprising:

(i) a composition according to the first aspect of the present invention', and (ii) a water-soluble cyan dye.

The water-soluble cyan dye is preferably a water-soluble phthalocyanine dye, more preferably C.I. Direct Blue 199, C.I. Acid Blue 9, C.I. Direct Blue 307 or C.I. Reactive Blue 71.

The composition according to the second aspect of the present invention preferably comprises:

(i) up to 30, more preferably from 1 to 20 parts of one or more of the water- soluble cyan dye(s); (ii) from 0.5 to 30 parts, more preferably 1 to 20 parts of a dye of Formula (A); and (iii) from to 0.5 to 98 parts, more preferably 80 to 95 parts in total of one or more of the dyes according to Formulae (1), (2), (3), (4), (5), (6), (7) and (8); wherein all parts are by weight and the sum of the parts (i) + (ii) + (iii) = 100.

A preferred composition according to the second aspect of the present invention is where component (iii) is C.I.Direct Black 195 or C.I.Direct Black 168 (especially C.I.Direct Black 195), component (ii) is C.I.Direct Yellow 142 and component (i), is a cyan dye selected from C.I.Acid Blue 9, C.I.Direct Blue 199, C.I.Direct Blue 307, C.I.Reactive Blue 71 and C.I.Direct Blue 85.

The compositions according to the second aspect of the present invention are particularly useful when incorporated into inks for use in ink jet printers because they provide high quality prints with a good optical density and a particularly desirable neutral black shade.

The dyes present in the compositions according to the first and second aspects of the present invention may be in free acid form but are preferably in the form of water soluble salt. Preferred salts are alkali metal salts, especially lithium, sodium and potassium salts or ammonium and substituted ammonium salts. Especially preferred salts are those formed with ammonia and volatile amines. The dyes may be converted to the desired salt form using conventional techniques. For example, the dye may be precipitated in its free acid form by adding an appropriate acid to an aqueous solution of the dye. The acid form of the dye may then be treated with a suitable base such as to yield the desired salt. Alternatively, ion exchange techniques can be used to convert the dyes to the desired salt forms.

The dyes in the compositions according to the first and second aspects of the present invention may be, and preferably are, purified to remove undesirable impurities before they are incorporated into inks for ink jet printing. Conventional techniques may be employed for purifying the dyes, for example ultrafiltration, reverse osmosis andlor dialysis.

SIVIC 60269 8 According to a third aspect of the present invention there is provided an ink comprising:

W 0.01 to 40 parts of a composition according to the first or second aspect of the present invention; and (ii) 99.99 to 60 parts a liquid medium or a low melting point solid medium; wherein all parts are by weight and the number of parts (i) + (ii) = 100.

The number of parts of component (i) is preferably from 0.1 to 30, more preferably 1 to 25 and especially from 2 to 15.

It is preferred that when the medium is liquid, that the components present in the composition according to the first or second aspect of the present invention are dissolved completely in the medium to form a solution. Preferably the compositions have a solubility of 10% or more in the medium because this allows the preparation of concentrates which may be used to prepare more dilute inks and to minimise the chance of precipitation of colorant if evaporation of the liquid medium occurs during storage of the ink.

When the medium is a liquid it preferably comprises water, a mixture of water and one or more organic solvent(s), or an organic solvent.

When the medium comprises a mixture of water and one or more organic solvent(s), the weight ratio of water to organic solvent(s) 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(s) present in the mixture of water and organic solvent(s) are water-soluble organic solvent(s). Preferred water-soluble organic soivent(s) are selected from CI-6-alkanols, for example methanol, ethanol, n- propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol and n-pentanol; cyclic alkanols, for example cyclohexanol and cyclopentanol; diols, preferably diols with 2 to 12 carbon atoms, for example pentane-1,5-diol-, amides, for example dimethyfformamide or dimethylacetamide; ketones or ketone-alcohols, for example acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; ethers, for example tetrahydrofuran or dioxane; oligo- or poly-alkylene glycols, for example diethylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol and polypropylene glycol; alkyleneglycols or thioglycols containing a C2-6-alkylene group, for example ethylene glycol, propylene glycol, butylene glycol, pentylene glycol hexylene glycol and thiodiglycol; polyols, for example glycerol, pentan-1, 5-diol and 1,2,6-hexanetdol; Cl,-alkyl-ethers of polyhydric alcohols, for example 2- methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2- methoxyethoxy)ethoxy] ethanol, 2-[2-(2-ethoxyethoxy)-ethoxyl-ethanol, 2-(2-butoxyethoxy)ethanol and ethylene glycol-monoallylether; cyclic amides, for example 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclic esters, for example caprolactone; sulphoxides, for example dimethyl sulphoxide and sulpholane or mixtures containing two or more, especially from 2 to 8, of the aforementioned water- SIVIC 60269 9 soluble organic solvents, for example thiodiglycol and a second glycol or diethylene glycol and 2-pyrrolidone.

Especially preferred water-soluble organic solvents are 2-pyrrolidone; Nmethylpyrrolidone; alkylene- and oligo-alkylene-glycols, for example ethyleneglycol, diethyleneglycol, triethyleneglycol; and lower alkyl ethers of polyhydric alcohols, for example 2-methoxy-2-ethoxy-2ethoxyethanol; and polyethyleneglycols with a molecular weight of up to 500.

A preferred mixture of water and water-soluble organic solvents comprises:

(a) from 60 to 80 parts water; and (b) from 0.5 to 25 parts in total of one or more solvents selected from diethylene glycol 2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolcatone, caprolactam, pentane-1,5-diol, 2-(2-butoxyethoxy)ethanol and thiodiglycol; wherein the parts are by weight and the sum of the parts (a) and (b) = 100.

Examples of further suitable ink media comprising a mixture of water and one or more organic solvent(s) are given in US 4,963,189, US 4,703,113, US 4,626, 284 and EP 4,251,50A which are incorporated herein by reference thereto.

It is preferred to prepare the inks in a high purity form as is conventional for thermal ink jet printers. A combination of ultrafiftration, reverse osmosis and ion exchange may be used to render the total concentration of undesirable ions (e.g. halide, nitrite, nitrate, peroxide, divalent metal, trivalent metal and silicon) to less than 10 parts per million by weight relative to the weight of ink.

When the medium comprises an organic solvent it preferably has a boiling point of from 0 to 3000C, more preferably of from 50 to 2001C. The organic solvent may be water-immiscible or water-soluble. Preferred water-soluble organic solvents are any of the hereinbefore mentioned water-soluble organic solvents Preferred water- immiscible solvents include, for example, aliphatic hydrocarbons, esters, such as ethyl acetate, chlorinated hydrocarbons, such as CH2Cl2 and ethers, such as diethyl ether.

When the medium comprises a water-immiscible organic solvent a polar solvent such as an alcohol, ester, ether or amide is preferably added to enhance the solubility of the dyes in the medium. It is especially preferred that where the medium comprises an organic solvent, this is a ketones, especially methyl ethyl ketone or an alkanol especially ethanol and/or and n-propanol.

When the medium is/or contains organic solvent, it may comprise a single organic solvent or a mixture of two or more organic solvents. It is preferred that the medium comprises a mixture of 2 to 5 different organic solvents because this allows control to be exerted over the characteristics of the ink.

Inks in which the medium is wholly or mainly an organic solvent are used where fast drying times are required and particularly when printing onto hydrophobic and non absorbent substrates such as plastics, metal or glass.

SIVIC 60269 When the medium for the ink comprises a low melting point solid, the melting point of the solid is preferably in the range from 60"C to 1250C. Suitable low melting point solids include long chain fatty acids or alcohols, preferably those with C,8_24 chains and sulphonamides. The composition according to the first aspect of the present invention may be dissolved or finely dispersed in the low melting point solid.

The compositions according to the first and second aspects of the present invention are particularly useful as colorants; for aqueous inks because they exhibit high solubility in water and aqueous media and have high humidity fastness on substrates, often surface treated papers, used for the preparation of photorealistic prints.

Accordingly, it is preferred that the ink medium is water or, more preferably, a mixture of water and one or more water-soluble organic solvent(s).

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

According to a fourth 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 is as defined for the third 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 having a small orifice by means of a resistor adjacent to the orifice, thereby causing the ink to be ejected through the orifice in the form of small droplets directed towards the substrate during relative movement between the substrate and the orifice.

The substrate used in the ink jet printing process is preferably paper, plastic, textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, and especially paper.

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

According to a fifth aspect of the present invention, there is provided a paper an overhead projector slide or a textile material printed with an ink composition as hereinbefore defined for the third aspect of the present invention, or by means of the process according to the fourth aspect of the present invention.

A sixth feature of the present invention provides an ink jet printer cartridge, optionally refillable, containing an ink according to the third aspect of the present invention.

The invention is illustrated by the following examples.

SIVIC 60269 11 Examples 1 to 15 Dye compositions may be prepared having the following ingredients and amounts shown in Table A. The amounts quoted in Table A refer to the number of parts by weight of each component. Dyes 1, 2, 3 and 4 are the ammonium salts of the dyes shown below.

HOOC HOOC OH =,-!7 N=11NH2 H03S A Dye 1 OCH2CH3 OH -N=N- N=N- NH2 03PH2 CH3CH,0 O,S, H 3S Dye 2 OCH,CH, OH N=N N=N NH2 HO,S CO,H CHCH,0 Dye 3 OCH3 OH HOOC-0-N=N-0-_NH 2 CH30 HO.S' 3 Dye 4 Component Example No. (parts by weight given below) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 C. I. Direct Yellow 142 16.7 10 10 5 25 20 10 12 16.7 12.4 16 24 16.7 10 10 Dye of Formula (2) 85 Dye of Formula (3) 84 Dye of Formula (4) 87 Dye of Formula (5) 85 Dye of Formula (6) 76 Dye of Formula (7) 81 Dye of Formula (8) 83.3 Dye 1 80.3 80 25 70 Dye 2 3 45 47.5 25 Dye 3 45 47.5 25 84.1 Dye 4 10 5 83.3 C.I. Direct Blue 199 5 3.5 3 C.I. Direct Blue 307 5 5 C. I. Acid Blue 9 4 3 1 Component Example No. (parts by weight given below) 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 C.I. Direct Yellow 142 5 10 25 15 4.5 12.4 14.5 9.4 27.5 14,3 10 4 6 13.8 30 Dye of Formula (2) 40 54.2 31 Dye of Formula (3) 50 25 25 Dye of Formula (4) 24.5 20 Dye of Formula (5) 21 20 Dye of Formula (6) 50 30 Dye of Formula (7) 25 75 Dye of Formula (8) 42.4 60 Dye 1 85 50 40 42 55.5 60 15 Dye 2 40 25 42.5 Dye 3 5 25 42.5 Dye 4 26.4 10 86.2 C.I. Direct Blue 199 5 3.2 10.7 5 C. I. Direct Blue 307 5 5 5 4 C. I. Acid Blue 9 10 2.5 U) 9 0 0) 0 N cr) W Component Example No. (parts by weight given below) 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 C.I. Direct Yellow 142 7 9 4 10.2 9.1 2.5 10 15 4.6 10 1.5 9.5 20 31 3.8 Dye of Formula (2) 78 31 30 Dye of Formula (3) 55 45 Dye of Formula (4) 20 Dye of Formula (5) 20 80 Dye of Formula (6) 40 69 Dye of Formula (7) 80 98.5 45.5 Dye of Formula (8) 29.8 40 Dye 1 35 65.9 62 Dye 2 31 25 Dye 3 20 25 Dye 4 87 25 90 62 C.I. Direct Blue 199 15 4 5 4.2 C.I. Direct Blue 307 5 17.5 C. I. Acid Blue 9 --ti -01 2.4 - C$) 9 0 0) 0 N) G) to SIVIC 60269 Example 31

In place of C.I.Direct Yellow 142 in each of Examples 1 to 15 there may be used a dye having exactly the same formula except that (i) the sulpho groups are at the 4positions instead of the 3-positions; or in place of methoxy groups there are ethoxy groups; or in place of an -NHCH2CH20H group there is an -NI-ICH3 group.

Example 32

Inks 1 to 41 may be prepared having compositions described in Tables 1 and 11 wherein the second column identifies the relevant dye composition from the Examples in Table A. The third column shows the amount of dye composition in the ink. All amounts are parts by weight. Thus, by way of example, Ink 3 comprises:

(a) 3 parts of composition 2 in Table A (80 parts of Dye 1, 10 parts of Dye 4 and 10 parts C. 1. Direct Yellow 142); water; diethylene glycol; and N-methyl pyrollidone.

(b) 90 parts (C) 5 parts (d) 5 parts 25.

The following abbreviations are used in Table 1 and I L PG = propylene glycol DEG = Diethylene glycol NIVIP = N-methyl pyrollidone DIVIK = dimethyiketone IPA = isopropanol MEOH = methanol 2P = 2-pyrollidone M113K = methylisobutyl ketone P12 propane- 1, 2-diol BDL butane-2,3-diol CET cetyl ammonium bromide PHO Na2HP04 and TBT tertiary butanol TDG thiodiglycol The inks may be purified using standard UF, RO and ion exchange techniques to give very low (<5 p.p.m) concentrations of undesirable ions.

TABLE 1 ri) 9 0 (3) 0 N 0) (0 (3) Ink Composition Amount Water PG DEG NMP DMK NaOH Na Stearate IPA MEOH 2P MIBK 1 1 3 90 5 5 2 1 2.0 80 5 6 4 5 3 2 3.0 90 5 5 0.2 4 3 10.0 85 3 3 3 5 1 4 2.1 91 8 1 6 5 3.1 86 5 0.2 4 5 7 6 1.1 81 9 0.5 0.5 9 8 7 2.5 60 4 15 3 3 6 10 5 4 9 8 5 65 20 10 9 2.4 75 5 4 5 6 5 11 10 4.1 80 3 5 2 10 0.3 12 12 3.2 65 5 4 6 5 4 6 5 13 11 5.1 96 4 14 3 10.8 90 5 5 5 10.0 80 2 6 2 5 1 4 16 7 1.8 80 5 15 17 9 2.6 84 11 5 18 2 3.3 80 2 10 2 6 19 1 12.0 90 7 0.3 3 6 5.4 69 2 20 2 1 3 3 21 5 6.0 91 4 5 TABLE 11

Ink Composition Amount Water PG DEG NMP CET TBT TDG BDL PHO 2P P12 22 1 3.0 80 15 0.2 5 23 2 9.0 90 5 1.2 5 24 3 1.5 85 5 5 0.15 5.0 0.2 4 2.5 90 6 4 0.12 26 5 3.1 82 4 8 0.3 6 27 7 0.9 85 10 5 0.2 28 9 8.0 90 5 5 0.3 29 8 4.0 70 10 4 1 4 11 12 2.2 75 4 10 3 2 6 31 11 10.0 91 6 3 32 10 9.0 76 9 7 3.0 0.95 5 33 5 5.0 78 5 11 6 34 6 5.4 86 7 7 4 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 36 8 2.0 90 10 37 9 2 88 10 38 2 5 78 5 12 5 39 3 8 70 2 8 15 5 10 10 80 8 12 41 12 10 80 10 -L _i SIVIC 60269 18

Claims

UK CLAIMS

A composition comprising a black dye and a dye of Formula (A) or salt thereof:

2 3 2 3 N 2 2 of CI N= - / NR NR p 1 j N _N S03H R R' SO3H NR3R4 Formula (A) wherein:

R' is Cl-4-alkoxy or Cl-4-alkyl; R 2 is H or Cl-4-alkyl; and R 3 and R 4 are each independently H, Cl,-alkyl or C,-4-hydroxyalkyl; wherein the black dye is selected from dyes of the Formula (1), (2), (3), (4), (5), (6), (7) or (8) and salts thereof.

OH N=N-S-N=W- N112 H03S Formula (1) OH NH2 H03S-O- N=N--/ - \\ N=N-- HO.S H 3S S03 A S03H Formula (2) H2N-C N=It--0-N=N N=W--0-N= N1H2 H03S SO3H N112 OH Formula (3) SNIC 60269 19 OH 03H OH H2N N=t± CH NH2 =C 1:: S03H 1 SO3H H03S H03S' Formula (4) H2N OH N=N- /CH=CH N=N OH NH2 H03s SO H H 3 H03S H03S S03 Formula (5) NH2 OH S03H OH 1 N=N-. CH=CH N=N NH2 H03S S03H 1 H03S H03SJZj Formula (6) Cu 1-- 0 0 HOOC N=N R 6 N, OH N S03H 1 S03H OCH 3 Formula (7) H2N--0-N=N---NH- N= NH2 1 OH N=N-0 H03S S03H wherein Formula (8) R' is -COOH or -PO(OH)2; B is 1,4-phenylene carrying two groups selected from C,-alkyl and C,-alkoxy; 60269 m is 1 or 2; and R' is vinyl sulphonyl, hydroxyethyl sulphonyl or a group which is convertible to vinyl sulphonyl when treated with aqueous alkali.

2. A composition according to claim 1 wherein the dye of Formula (A) is of the Formula shown below or a salt thereof:

SO3H __ NZ i r N=N-P OCH N 1.,, N --p- NH NH 3 OCH3 SO H NHCH,CH20H 3. A composition according to either of the previous claims wherein the black dye is of the Formula (9) or a salt thereof:

X OH -N= NH2 Y HO S Formula (9) wherein:

R' is as hereinbefore defined; one of X and Y is Cl,-alkoxy and the other is C,,-alkyl or C,-alkoxy; and m is 1 or 2.

4. A composition according to any one of the previous claims comprising: (a) from to 99 to 50 parts of one or more of the black dye(s); and (b) from 1 to 50 parts of the dye of Formula (A); wherein the parts are by weight and the sum of the parts (a) and (b) = 100.

5. A composition comprising:

(i) a composition according to any one of claims 1 to 4; and (ii) a water-soluble cyan dye.

6. A composition according to claim 5 comprising:

(i) up to 30 parts of one or more of the water-soluble cyan dye(s); (ii) from 0.5 to 30 parts of the dye of Formula (A); and SIVIC 60269 21 (iii) from to 0.5 to 98 parts in total of one or more of the dyes according to Formulae (1), (2), (3), (4), (5), (6), (7) and (8) or salt thereof as defined in claim 1; wherein all parts are by weight and the sum of the parts (i) + (ii) + (iii) = 100.

7. An ink comprising: (i) 0.01 to 40 parts of a composition according to any one of claims 1 to 6; and (ii) 99.99 to 60 parts a liquid medium or a low melting point solid medium; wherein all parts are by weight and the number of parts (i) + (ii) = 100.

8. An ink according to claim 7 wherein the total concentration of undesirable ions is less than 10 parts per million by weight relative to the weight of ink.

9. A process for printing a substrate with an ink using an ink jet printer, characterised in that the ink is as defined in claim 7 or 8.

10. A paper an overhead projector slide or a textile material printed with an ink composition as defined in claim 7 or 8 or by means of the process according to claim 9.

11. An ink jet printer cartridge, optionally refillable, containing an ink according to claim 7 or 8.

12. An ink or a composition substantially as described in any one of the Examples herein.

25.