GB2341868A

GB2341868A - Sulpho and phenylaminosulphonyl substituted phthalocyanine derivatives and their use in ink jet inks

Info

Publication number: GB2341868A
Application number: GB9927927A
Authority: GB
Inventors: Mark Kenworthy
Original assignee: Avecia Ltd
Current assignee: Avecia Ltd
Priority date: 1999-11-26
Filing date: 1999-11-26
Publication date: 2000-03-29
Also published as: GB9927927D0

Abstract

Phthalocyanine compounds of Formula (1) have utility as colorants in inks for ink-jet printing and isotopic forms may be used in imaging devices (using X-rays, positron emission tomography or nuclear magnetic resonance or example), where Formula (1) represents: <EMI ID=1.1 HE=27 WI=68 LX=671 LY=613 TI=CF> <PC>which comprises any form of the compound: such as salt; stereoisomer, zwitterion, polymorph, complex, isotopic form, combinations thereof in the same species and mixtures thereof; where: <DL TSIZE=3> <DT>M<DD>represents H, metal, halometal, oxymetal and/or hydroxymetal; <DT>k<DD>is the inverse of half of the valency of M; <DT>Pc<DD>represents a phthalocyanine nucleus of Formula (2) : <EMI ID=1.2 HE=45 WI=42 LX=864 LY=1378 TI=CF> </DL> <DL TSIZE=4> <DT>L<DD>represents a linking group comprising a carbon-containing organic residue (especially -SO<SB>2</SB>-CH<SB>2</SB>CH<SB>2</SB>-); <DT>A<DD>represents -O-, -S- or -NR<SP>3</SP>-, where R<SP>3</SP> independently comprises H or a carbon-containing organic residue; <DT>R<SP>1</SP><DD>comprises at least one group independently selected from: an "optional substituent" (as defined in the description) and a carbon-containing organic residue; <DT>R<SP>2</SP> <DD>comprises a carbon-containing organic residue that preferably comprises at least one alkyl group substituted by at least one of: hydroxy, carboxy and sulpho; <DT>z<DD>represents an integer from 0 to 4; w represents an integer from 1 to 5; and the sum of w + z is from 1 to 5; and <DT>x<DD>and y each independently represent a non-zero number; and the mean of the sum of x + y is from about 1 to about 6; </DL> where the optional substituents include for example carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

Description

2341868 COMPOUND, COMPOSITION AND USE This invention relates to compounds,

to ink compositions comphsing them and to the use of such inks in ink jet phnting ("IJP"). 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 colorants and inks used in UP. For example they desirably provide sharp, non-feathered images having good water-fastness, 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.

The applicant has discovered that certain phthalocyanine compounds have particular utility as colorants for use in UP as they may produce prints with unexpectedly good optical density, light fastness andlor water fastness.

According to the present invention there is provided at least one compound of Formula (l):

m k Pc 1.1 (SO 3 H),, \ (SO 2 NH - {L-A-R 2 4) Y Formula (1) which comprises any form of the compound: such as salt; stereoisomer, zwitterion, polymorph, complex, isotopic form, combinations thereof in the same species and mixtures thereof; where: M represents H, metal, halometal, oxymetal andlor hydroxymetal; k is the inverse of half of the valency of M; 25 Pc comprises a phthalocyanine nucleus of Formula (2) 2 N N N N N N N Z_ Formula (2) L comprises a linking group comprising an optionally substituted Cl- 30carbyl; 3_ 3 A comprises -0-, -S- or -NR, where R independently comprises H or optionally substituted Cl-30carbyl; R' comprises at least one group independently selected from: an optional substituent and optionally substituted Cl-l.carbyl; R 2 comprises an optionally substituted C,30carbyl that comprises at least one alkyl group substituted by at least one group selected from: hydroxy, carboxy and sulpho; z comprises an integer from 0 to 4; w comprises an integer from 1 to 5; and the sum of w + z comprises from 1 to 5; and x and y each independently comprises a non-zero number; and the mean of the sum of x + y comprises from about 1 to about 6; where the optional substituents comprise at least one of: carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

The terms 'optional substituent' and/or 'optionally substituted' as used herein (unless followed by a list of other substituents) signifies the one or more of following groups (or substitution by these groups): carboxy, sulpho, formyl, hydroxy, amino, imino, nitrilo, mercapto, cyano, nitro, halo, methyl, methoxy and/or combinations thereof. These optional groups include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned groups (e.g. amino and sulphonyl combined represent a sulphamoyl radical). Preferred optional substituents comprise:

carboxy, sulpho, hydroxy, amino, mercapto, cyano, halo, methyl (optionally substituted by one or more halo) and/or methoxy (optionally substituted by one or more halo).

The term 'carbyl' as used herein denotes any organic radical moiety which comprises one or more carbon atoms and optionally one or more other heteroatoms preferably selected from: hydrogen, phosphorus, halo, nitrogen, oxygen and/or sulphur, more preferably from hydrogen, nitrogen, oxygen and/or sulphur. The term 'hydrocarbyl' as used herein denotes any radical moiety which comprises one or more hydrogen atoms and one or more carbon atoms. Most preferably 'carbyl' moieties comprise one or more of the following carbon containing moieties: alkyl, alkoxy, alkanoyl, carboxy, carbonyl, formyl and/or combinations thereof; optionally in combination with one or more of the following heteroatom containing moieties: oxy, thio, sulphinyl, sulphonyl, amino, imino, 3 nitrilo andlor combinations thereof. Carbyl moieties include all chemically possible combinations in the same moiety of a plurality (preferably two) of the aforementioned carbon containing andlor heteroatom moieties (e.g. alkoxy and carbonyl combined represent an alkoxycarbonyl radical):

Any radical group or moiety mentioned herein (e.g. as a substituent) refers to a monovalent radical unless otherwise stated or the context clearly indicates otherwise (e.g.

an alkylene moiety is bivalent and links two other moieties). A group which comprises a chain of three or more atoms signifies a group in which the chain wholly or in part may be linear, branched andlor form a ring (including spiro andlor fused rings). The total number of certain atoms is specified for certain substituents for example Cl, carbyl, signifies an carbyl moiety comprising from 1 to n carbon atoms.. In any of the formulae drawn herein if one or more ring substituents are not indicated as attached to any particular atom on the ring [for example the substituent R' in Formula (1)] the substituent may replace any H attached to an atom in the ring and may be located at any available position on the ring which is chemically suitable.

According to a further feature of the present invention there is provided an ink effective for use in ink jet printing (UP-effective) comprising a medium and a colorant comprising a UP-effective compound of Formula (1) as defined herein. Preferably in the ink of the present invention the compounds of Formula (1) comprise dyes, more preferably dyes comprising a predominately cyan colour.

The term 'WP effective' (for example with reference to the inks, compositions, ingredients, substituents andlor compounds described herein) will be understood to mean effective for use in ink-jet printing by for example: providing desirable properties to the ink, being compatible with any inert carriers andlor diluents suitable for formulating such inks, being compatible with ink jet printers andlor capable of being ink-jet printed. In relation to the processes described herein effective compounds are those which will undergo the specified reactions to form the compounds of the present invention. To be particularly acceptable for use in UP compounds of Formula (1) may be Ames negative.

In Formula (1) when M is a metal it may be selected from any UP-effective metal or mixture thereof in the same complex. The metal may exist in any suitable oxidation state and may be neutral or charged (i.e. an ion). M may also comprise a metal bonded to one or more oxygen atoms, halo atoms or hydroxy groups, for example at least one of:

AICI, MOH, RhCl, RhOH, InBr, InCI, 1n0H, GaCI, GaOH, ScCl and ScOH. Preferably M comprises a metal selected from U, Na, K, Mg, Ca, Ba, A], In, Ga, Zn, Si, Sn, Pb, Rh, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu; more preferably from Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu; and most preferably from Ni and Cu. Especially preferred compounds of Formula (1) are those in which M comprises Cu.

Preferred compounds of Formula (1) are those in which:

4 z is 0, 1 or 2; and when z is other than 0, R' represents an optionally substituted group independently selected from: carboxy, carboxyCl-6alkyl, sulpho, Cl-6alkyl, Cl-6alkoxy, halo, cyano, nitro, amino, Cl-6alkylamino, di(C1-6alkyl)amino, C,-12arylamido (e.g. benzamido), Cl-7alkanoylamino; Cl,alkylcarbamoyl and Cl-6alkylsulphamoyl; L represents a Cl-15carbyl group, which may be attached to the benzene ring at the position para to the sulphonylamino group attached to the Pc nucleus; A represents -S- or a protonable amino group comprising -NW- where R' represents H or an optionally substituted Cl-22carbyl that comprises at least one alkyl group substituted by hydroxy, carboxy andlor sulpho; R 2 independently represents an optionally substituted Cl-22carbyl that comprises at least one aikyl group substituted by hydroxy, carboxy and/or suipho; w is 1 and; x and y each represent from 1 to 3 and the sum of x + y is from 1 to 4.

More preferred compounds of Formula (1) are those preferred compounds in which:

M is Cu; L represents sulphonylC,-,5alkylene; A represents -S-; or -NR 3 where R 3 represents H or Cl_.alkyl optionally substituted by at least one of: hydroxy, sulpho or carboxy; R 2 represents C,ralkyl; C l.ary]; or Cl.,,a 1 kylene (YC -,a] kyle ne)n each optionally substituted by at least one group selected from: methyl, hydroxy, sulpho or carboxy; where n is 0, 1 or 2; and Y is independently, -0- or -N(C2H4)N-; z is 0 or 1; and the sumof x+yis4.

Most preferred compounds of Formula (1) are those more preferred compounds in which:

L represents sulphonylCl,aikylene attached to the benzene ring via the S atom and para to the -S02NH- group; A represents -S-; or -NR 3 where R 3 represents H or C,,alkyl optionally substituted by at least one of: hydroxy, sulpho andlor carboxy; R 2 represents Cl-1.alkyl; phenyl or Cl-4alkoxyCl-4alkyl; each optionally substituted by at least one group selected from: methyl, hydroxy, sulpho andlor carboxy; z is 0; and x and y are both 2; or x is 1 and y is 3 Specific compounds of Formula (1) comprise those compounds exemplified herein in their acid form(s); all UP-effective salts thereof, preferably their lithium, potassium, sodium andlor optionally substituted ammonium salt(s); and mixtures thereof, preferably UP-effective mixtures.

Compounds of Formula (1) may be in the form as shown in the structures herein (i.e. free acid form) but are preferably in the form of salts. Salts of Formula (1) may be formed from one or more organic and/or inorganic bases and/or acids and compounds of Formula (1) which are acidic and/or basic (for example acid and/or base addition salts).

Salts of Formula (1) comprise all UP-effective salts that may be formed from monovalent and/or multivalent acids and/or bases. Salts of Formula (1) also comprise all enantiomeric salts formed with UP-effective chiral acids and/or bases and/or any mixtures of enantiomers of such salts (for example racernic mixtures). The dyes may be converted into a salt using known techniques. The present invention comprises all lJP effective salts of Formula (1) and UP-effective mixtures thereof.

Preferred salts of Formulae (1) are alkali metal salts (especially lithium, sodium and potassium salts), and optionally substituted ammonium salts (especially salts with ammonia and volatile amines). More preferred salts are those with a cation of formula +NT, where each T is independently H or optionally substituted alkyl, or two groups represented by T are H or optionally substituted alkyl and the remaining two groups represented by T, together with the N atom to which they are attached, form a 5 or 6 membered ring (preferably a morpholine, pyridine or piperidine ring). Most preferably each T is independently H or C,-4alkyl, especially H, CH3 or CH3CH2, more especially H.

Examples of cations which are UP-effective comprise: 'NH4, morpholinium, piperidinium, pyridinium, (CH3)3NH, (CH3)2N4H2, H2N+(CH3)(CH2CHA CH3N4H3, CH3CH2N+H3, H2N+(CH2CH3)2, CH3CH2CH2N+H3, CH3CH2CH2N+H3, (CH3)2CHN+H3, N+(CH3)4, N+(CH2CH3)4, N-methyl pyridinium, N,N-dimethyl piperidinium and N,N- dimethyl morpholinium.

Certain compounds of Formula (1) may exist as one or more stereoisomers, for example, enantiomers, diastereoisomers, geometric isomers, tautomers, conformers and/or combinations thereof within the same moiety. The present invention comprises all UP-effective stereoisomers of compounds of Formula (1) and UP-effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more zwitterions, for example, moieties which comprise two or more centres of ionic charge. The present invention comprises all UP-effective zwitterions of Formula (1) and UP- effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more polymorphs, for example, phases, crystalline forms, amorphous forms, solid solutions, interstitial compounds and/or any mixtures thereof. The present invention comprises all lJP effective polymorphs of Formula (1) and UP-effective mixtures thereof.

Certain compounds of Formula (1) may exist in the form of one or more other complexes in addition to the metal complexes shown herein, for example, chelates, solvates, other organometallic complexes, and/or complexes with other UP- effective 6 ligands. Such complexes may be formed between an suitable substrate in which the compound of Formula (1) and/or the substrate may act as a ligand. The substrate may comprise one or more solvents to form solvates. The complexes may be non stoichiometric, for example if the complex is a hydrate it may comprise a hemihydrate, monohydrate and/or dihydrate. The present invention comprises all UPeffective complexes of Formula (1) and WIP-effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more isotopic forms in which one or more atoms in Formula (1) comprise one or more isotopes. The natural ratios of various isotopes may be altered by suitable means, for example certain 12C atoms in certain compounds of Formula (1) may be substantially replaced by the less common 14 C and/or 13C isotopes. Optionally certain isotopic forms of Formula (1) may be radio-active. Certain of the isotopic forms of Formula (1) may be used as means for selective imaging in imaging devices (for example devices using X-rays, positron emission tomography and/or nuclear magnetic resonance); and/or as tools to investigate the mode of action of compounds of Formula (1) in IJP. The present invention comprises all UP-effective, isotopic forms of Formula (1) and UP-effective mixtures thereof.

The present invention relates to all compounds of Formula (1) even those which may not be directly effective for use in UP because they exhibit undesirable properties.

Such compounds may nevertheless have utility in the field of the present invention for example as intermediates in the preparation and/or purification of UP- effective compounds of Formula (1) and/or as research tools and/or diagnostic aids in relation to lip.

Compounds of Formula (1) may be prepared the methods described below and by other suitable methods analogous to those described in the art for similar phthalocyanine compounds.

A preferred method for preparing compounds of Formula (1) in which L is S02C2H, comprises reacting compounds of Formula (3):

MkpC (S03H)x z (S02 NH {S02C 2 H4 OSO3H),)Y Formula (3) with compounds of formula R 2 AH where Pc, Mk, R1, w, x, y, z; and RI and A are as defined herein. Compounds of Formula (3) in which M is Cu, k is 0, z is 0 and w is 1 are available commercially.

The reactions leading to the formation of the present compounds may be performed under conditions that have been described in the art and compounds of 7 Formula (1) may be isolated by known methods such as spray drying or precipitation followed by filtration.

Preferably the ink of the present invention comprises:

(a) from 0.01 to 30 parts of an UP-effective compound of Formula (1); 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 colorant precipitating if evaporation of the liquid medium occurs during storage.

Preferred liquid media include water, a mixture of water and an organic solvent 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. Preferably the organic solvent comprising the mixture of water and organic solvent is a water-miscible organic solvent or a mixture of such solvents. The liquid medium may comprise water and preferably two or more, more preferably from 2 to 8, water-soluble organic solvents.

Preferred water-miscible organic solvents comprise:

Cl-6-alkanols, preferably methanol, ethanol, n-propanol, isopropanol, nbutanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and/or cyclohexanol; linear amides, preferably dimethyfformamide and/or dimethylacetamide; ketones and/or ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and/or diacetone alcohol; water-miscible ethers, preferably tetrahydrofuran and/or dioxane; diols, preferably C2-12diols (for example pentane-1,5-diol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and/or thiodiglycol) and/or oligo- and/or poly-alkyleneglycols (for example diethylene glycol, triethylene glycol, polyethylene glycol and/or polypropylene glycol); triols, preferably glycerol and/or 1,2,6-hexanetriol; C1,alkyl ethers of diols, preferably monoC,.4alkyl ethers Of C2-12diols: ffor example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy] -ethanol, 2-[2-(2-ethoxyethoxy)-ethoxy]ethanoI and/or ethyleneglycol monoallyl ether); 8 cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl- 2-pyrrolidone, caprolactam and/or 1,3-dimethylimidazolidone; cyclic esters, preferably caprolactone; sulphoxides, preferably dimethyl sulphoxide and/or sulpholane; and/or all IJP-effective mixtures thereof.

More preferred water-soluble organic solvents are selected from:

cyclic amides (e.g. 2-pyrrolidone, N-methyl-pyrrolidone and N-ethylpyrrolidone); diols, (e.g. 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyleneglycol and triethyleneglycol); C1,alkyl ethers of diols (e.g. 2-methoxy-2-ethoxy-2-ethoxyethanol); and all IJP-effective mixtures thereof.

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, caprolactarn and pentane-1,5-diol; where the parts are by weight and the sum of the parts (a) + (b) = 100.

Another preferred liquid medium comprises:

(a) from 60 to 80 parts water; (b) from 2 to 20 parts diethylene glycol; and (c) from 0.5 to 20 parts in total of one or more solvents selected from:

2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone, caprolactam, pentane-1,5 diol and thiodiglycol; where the parts are by weight and the sum of the parts (a) + (b) + (c) = 100.

Examples of further IJP-effective media for inks of the present invention comprise a mixture of water and one or more organic solvents are described in US 4, 963,189, US 4,703,113, US 4,626,284 and EP 0425150-A.

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 301 to 2001C, more preferably of from 400 to 1500C, especially from 50 to 1250C. The organic solvent may be water-immiscible, water-miscible or a mixture of such solvents. Preferred water miscible organic solvents comprise any of those described above and mixtures thereof.

Preferred water-immiscible solvents comprise aliphatic hydrocarbons; esters (for example ethyl acetate) chlorinated hydrocarbons (for example dichloromethane), ethers (for example diethyl ether) and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent, preferably it comprises a polar solvent (for example a C14alkanol) to enhance the solubility of the dye in the liquid medium. It is especially preferred that where the liquid medium is an 9 organic solvent free from water it comprises a ketone (especially methyl ethyl ketone) and/or an alcohol (especially a C1_4alkanol, more especially ethanol or propanol).

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 60"C to 1250C. Suitable low melting point solids include long chain fatty acids or alcohols, preferably those with C,8-24chains, and sulphonamides. The dye of Formula (1) 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 inks for UP, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, kogation reducing additives and surfactants which may be ionic or non- ionic.

A further aspect of the invention provides a process for printing an image on a substrate comprising applying to the substrate by means of an ink jet printer, an ink of the present invention as defined herein.

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 adjacent to the orifice, thereby causing the ink to be ejected in the form 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.

A further aspect of the present invention provides a paper, an overhead projector slide or a textile material printed with an ink and/or a colorant as defined herein and/or by means of a process as defined herein.

When the substrate is a textile material the ink according to the invention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer; and ii) heating the printed textile material at a suitable temperature, preferably from 50'C to 250"C, to fix the ink on the material.

Preferred textile materials are natural, synthetic and semi-synthetic materials.

Examples of preferred natural textile materials include wool, silk, hair and cellulosic materials, particularly cotton, jute, hemp, flax and linen. Examples of preferred synthetic and semi-synthetic materials include polyamides, polyesters, polyacrylonitriles and polyurethanes.

Preferably the textile matehal has been treated with an aqueous pretreatment composition comphsing a thickening agent and optionally a water-soluble base and a hydrotropic agent and dried phor to step i) above.

The pre-treatment composition preferably comprises a solution of the base and the hydrotropic agent in water containing the thickening agent. Particularly preferred pre treatment compositions are described more fully in EP 0534660-K The invention is further illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.

Example 1

Preparation of Cupc (SO 3_ Na 0 2 NH S OH)2 (SO 0 H a) Preparation of Cupc, (SO 3 H)2 (SO 2C1)2 Copper phthalocyanine (1 15g) was added in portions to stirred chlorosulphonic acid (310 mi) over 30 minutes keeping the temperature below 500C. The mixture was stirred for 30 minutes at 5WC before being heated gradually to 135-1400C over one hour, The temperature of the mixture was maintained at 1400C and it was stirred for 3 hours and then cooled to room temperature.

The mixture was heated to 450C and phosphorus trichlorlide (52.3g) was added dropwise over 1 hour 15 minutes, whilst the temperature was kept at 45- 501C. The temperature of the mixture was raised to 900C and was maintained at this for 3 hours and then cooled to room temperature.

The resulting solution was poured onto a stirred mixture of ice (1 kg), water (200 mi), concentrated hydrochloric acid (44 mi) and sodium chloride (40g) maintained at a temperature of OOC. The precipitated product was collected by filtration at reduced pressure and washed with ice-cold hydrochloric acid solution (0.5 M, 2 1) to obtain a paste which was dried under reduced pressure to obtain CUPC(SOMASO2C1)2 which was used directly in the next step.

b) Preparation of:

CUPC (SO 3 H)2 0 0 (so 2 N H -S O-S-OH)2 0 0 The sulphonyl chloride from step a) was added to a mixture of p-aminobenzenesulphatoethyisulphone (112.4 g) in water (500 mi) and ice (500 g). The mixture was stirred for 10-15 minutes and then the pH of the mixture was raised to between 6.5 to 7.0 with caustic liquor. The mixture was stirred at room temperature for 18 hours whilst maintaining the pH at 7.0 by adding 2N NaOH. Sodium chloride (10% w/v) was added to the mixture which was stirred for 20 minutes and the pH of the mixture was adjusted to 2.5 with concentrated hydrochloric acid. The mixture was stirred for a further minutes and the resultant precipitate was collected by filtration at reduced pressure and washed with ice cold brine (10%) and dried under reduced pressure to obtain 954.8 g of product.

c) Preparation of title sodium salt.

The compound from step b) above (318 g) was stirred in distilled water (700 g) and the pH of the solution was adjusted to 6.5 - 7.0 with 2N NaOH. Ethanolamine (16.07 g) was added to this solution and the mixture was heated to 80- 850C and maintained at this temperature for 18 hours. The mixture was cooled to room temperature and sodium chloride (20% w/v) was added and the pH of the mixture was adjusted to 7.0 with concentrated hydrochloric acid. The mixture was stirred and cooled to 1 OOC and stirred at this temperature for a further 30 minutes.

The resultant precipitate was collected by filtration at reduced pressure and washed with brine (20%) to obtain a paste. This was then dissolved in water (about 2 litres) and desalinated by reverse osmosis. The resultant solution was filtered and water was evaporated from the filtrate to give the title sodium salt (56.7 g).

Example 2

Preparation of Cupc (S03-Na 0 (SO NH -S OH)2 2 11 \/\N//0"'/ 0 H 12 This sodium salt (76.4 g) was prepared as described in Example 1 substituting 2aminoethoxyethanol (27.66 g) for the ethanolamine used in step 1 c.

Example 3

Preparation of CUPC (S03-Na+)2 0 OH (SO 2 N H SII 0 H) 2 11 N 0 This sodium salt (61.7 g) was prepared as described in Example 1 substituting diethanolamine (27.66 g) for the ethanolamine used in step 1 c. 10 Example 4 Preparation of Cupc (S03X +)2 0 OH 11 OH (SO 2 NH S)\,/)2 11 S 0 This potassium salt (70.43 g) was prepared as described in Example 1 substituting mercapto-1,2-propanediol (25.10 g) for the ethanolamine used in step 'I c and then, after the desalination in step lc, converting the sodium salt to the potassium salt as described below.

Example 5

Preparation of CUPC 1AS03- K +)2 0 SN H SII SO H 0 2)2 0 This potassium salt (79.15 g) was prepared as described in Example 1 substituting 3-mercaptopropanesulphonic acid (37.39 g) for the ethanolamine used in step lc and then, after the desalination in step 1 c, converting thesodium salt to the potassium salt as described below.

13 Example 6

Preparation of CUPC,,AS03Y)2 0 0 SNH--GSII,,/\ ^/kOH 02 11 S)2 0 This potassium salt (77.37 g) was prepared as described in Example 1 substituting 3-mercaptopropan ionic acid (28.03 g) for the ethanolamine used in step 1 c and then, after the desalination in step 1 c, converting the sodium salt to the potassium salt as described below.

Example 7

Preparation of Cupc (S03 X+)3 0 (SO NH S 0 H) 1 2 -G 111 0H a Preparation of (S03 H)3 CUPC \\ (S02 C1)l Copper phthalocyanine (1 15g) was added in portions to stirred chlorosulphonic acid (317 mi) and concentrated sulphuric acid (147 mi). The mixture was heated to 1400C for 3 hours and then cooled to room temperature. This mixture was then poured onto a stirred mixture of ice (1 kg), water (200 m[), concentrated hydrochloric acid (44 mi) and sodium chloride (40g). The precipitated product was collected by filtration at reduced pressure to obtain a paste Of CUPC(S031HIMSO2C01 (817.8 g) which was used directly in the next step.

b) Preparation of:

Cupc 1-AS03 H)3 0 SNH S O-S-OH), 02 11 11 0 0 The sulphonyl chloride from step a) was added to a mixture of p-a m i nobenzenesu lphatoethyisul phone (133 g) in water (700 mi) at pH 5.2 (adjusted by adding 15 % aqueous NaOH). The mixture was stirred at pH 5.2 and room temperature for 3 hours.. Sodium chloride (20% w/v) was added to the mixture which was stirred for 15 minutes and the pH of the mixture was adjusted to 1.0 with concentrated hydrochloric 14 acid. The resultant precipitate was collected by filtration at reduced pressure and washed with ice cold brine (10%) and dried under reduced pressure to obtain 688 g of product.

c) Preparation of title potassium salt.

The compound from step b) above (219 g) was stirred in distilled water (1 1) and ethanolamine (19.6 g) was added to this solution and the mixture was heated to 70-750C and maintained at this temperature for 3 hours. The mixture was cooled to room temperature and sodium chloride (20% w/v) was added. The pH of the mixture was then adjusted to 1.5 with concentrated hydrochloric acid and the mixture was stirred for 15 minutes.

The resultant precipitate was collected by filtration at reduced pressure and washed with brine (20%) to obtain a paste. This was then dissolved in water (about 2 litres) and desalinated by reverse osmosis. The resultant solution of the sodium salt was converted to a solution of the potassium salt as described below and water was evaporated from the solution to give the title potassium salt (53.0 g).

Example 8 Preparation of CUPC 1AS03- K +)3 0 (SO NH - S ^VO\/"OH), -G H\PN 2 11 0 H This potassium salt (60.6 g) was prepared as described in Example 7 substituting aminoethoxyethanol (33.7 g) for the ethanolamine used in step 7c.

Example 9

Preparation of CUPC 1.1 (SO 3- K +)3 0 OH -j (S02 N H - SII _^ /\,_, 0 H) 11 N 0 This potassium salt (61 g) was prepared as described in Example 7 substituting diethanolamine (34.3 g) for the ethanolamine used in step 7c.

Example 10 Preparation of Cupc (SO 3- K +)3 0 OH (S 0 N H -& SII)\\,, 0 H) 2 11 S 0 This potassium salt (54.0 g) was prepared as described in Example 7 substituting 3-mercapto-1,2-propanediol (30.11 g) for the ethanolamine used in step 7c.

Example 11 Preparation of CUPC (S03-K+)3 0 11 (S02NH Sl/ ^/'SO H), 0 This potassium salt (65.0 g) was prepared as described in Example 7 substituting 3-mercaptopropanesulphonic acid (44.80 g) for the ethanolamine used in step 7c.

Example 12 Preparation of CUPC.,AS03 X+)3 0 0 I\NI-1-&SIL,^ /\,LOH), S02 11 S 0 This potassium salt (55.5 g) was prepared as described in Example 7 substituting 3-mercaptopropionic acid (44.80 g) for the ethanolamine used in step 7c.

Examples 13 to 30 Additional examples of certain dyes represented generally by Formula (4) were prepared.

CUPC.AS03 H)x 0 (SO NH Sj" R) 2 11 Y 0 Formula (4) For each of the following Examples the specific R, x and y in Formula (4) is as set out in the table below. The following Examples with ratio x to y = 3 to 1 were made as described in Example 7 above, whereas those Examples with ratio x to y of 2 to 2 were prepared as described in Example 1 above. The acids of Formula (4) were converted into their sodium or potassium salts also as described in Examples 1 or 7 respectively.

16 Table of Examples 13 to 30 Example R X y

13 (-NHC16H33 3 1 14 4-NHClOH21 3 1 (-NHC12H25 3 1 16 (-NHC8H17 3 1 17 4-NHC6H13 3 1 18 <--NHC14H,9 3 1 19 3 1 H 3 1 H 21 4-SCOH21 3 1 22 '(-SC12H25 3 1 23 '(-SC121H125 2 2 24 -SC,,,H21 2 2 4-SC,,H17 3 1 26 (-SC,3H17 2 2 27 2 2 ----S 28 4-SC161-133 2 2 29 3 1 - S -C- 0 H ---S-C-OH 2 2 In the above Table the arrow indicates the point of attachment of the group R in the compound of Formula (4).

Salts The exemplified sodium salts (examples 1 to 3) prepared as described above, were converted to their purified potassium salts as follows. Each example was dissolved in distilled water. The solution was filtered and the volume of the filtrate adjusted to 4 17 litres. The solution was desalinated by reverse osmosis. The dissolved sodium salt was converted into the potassium salt by passing the solution through an ion- exchange column comprising Dowex HGRW resin staturated with potassium hydroxide solution (5% w/v). The solution of the potassium salt thus obtained was then filtered and water was evaporated form the filtrate to yield a purified potassium salt suitable for use directly in an ink as described below.

Inks The effectiveness in ink jet printing of compounds of Formula (1) was demonstrated as follows. Inks separately comprising each exemplified dye were prepared by dissolving 2 parts of the potassium salt, prepared as described above, in 98 parts of a mixture of water and 2-pyrrolidone (in a respective ratio of 90:10 by volume).

The inks were printed onto plain paper using a thermal ink-jet printer to give a bright cyan prints which had good optical density, water fastness and light fastness.

Further inks comprising the exemplified dyes may be may be prepared as described in the following tables in which the number in the first column (headed Ex. no.) denotes the example number of dye to be used in the ink. The dye may be in its free acid form andlor in the form of any UP-effective salt (e.g. potassium salt). 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 andlor piezo inkjet printing.

The following abbreviations are used in the tables:

PG = propylene glycol; DEG = diethylene glycol; NIVIP = N-methyl pyrollidone; DIVIK = dimethyiketone; NaST = Na stearate IPA = isopropanol; MEOH = methanol; 2P = 2-pyrollidone; M1131K methylisobutyl ketone; CET= cetyl ammonium bromide; TBT tertiary butanol; TDG thiodiglycol; BDL = butane-2,3-diol; PHO Na.HP04; P12 propane-11,2-diol.

CHL = cyclohexanol; and PIDIL pentan-11,5-diol.

18 TABLE 1

Ex. no. Dye Water PG DEG NMP DMK MEOH 2P MIBK 1 2.0 80 5 6 4 5 2 10.0 85 3 3 3 5 1 3 2.1 91 8 1 4 2.4 75 3 4 5 6 5 5.1 96 4 6 1.8 80 5 15 7 2.6 84 11 5 8 3.3 80 2 10 2 6 9 5.4 69 2 20 2 1 3 3 7.0 70 15 3 10 TABLE 11

Ex. No. Dye Water PG DEG NMP NaOH Na ST IPA 2P MIBK 11 2.0 70 7 6 3 2 12 4.0 65 4 6 0.7 5 13 1.0 50 4 5 1 14 3.1 86 5 2 0.2 4 5 1.1 81 2 9 0.5 0.5 9 TABLE Ill

Ex. No. Dye Water PG DEG NMP DMK IPA MEOH 2P MIBK 16 3.1 86 5 4 5 17 1.1 81 9 9 18 2.5 60 4 15 3 3 6 10 5 4 19 3.2 65 5 4 6 5 4 6 5 10.0 80 2 6 2 5 1 4 TABLE IV

Ex. no. Dye Water PG DEG NMP DMK NaOH Na ST IPA 21 3.0 90 5 5 0.2 22 5 65 5 20 10 23 4.1 80 5 2 10 0.3 24 10.8 90 5 12.0 90 7 0.3 3 19 TABLE V

Ex. no. Dye Water PG DEG NMP CET PHO 2P P12 26 3.0 80 15 0.2 5 27 9.0 90 5 1.2 5 28 2.5 90 6 4 0.12 29 3.1 82 4 8 0.3 6 10.0 91 6 3 1 5.0 78 5 11 6 2 6.0 63 3 4 2.0 3 3.0 72 15 0.8 3 4 5.4 86 5 7 3.0 7 2.0 90 10 10 TABLE V1

Ex. no. Dye Water PG DEG NMP CET TBT TDG 6 1.5 85 5 5 0.15 5.0 0.2 7 9.0 90 5 5 0.3 8 2.0 90 10 9 2.0 88 10 55 70 4 4 0.4 3 TABLE V11

Ex. no. Dye Water PG DEG NMP TBT TDG BDL PHO 2P 11 0.9 85 10 5 0.2 12 4.0 70 10 4 1 4 13 2.2 75 4 10 3 2 6 14 9.0 76 9 7 3.0 0.95 5 2.1 70 5 5 5 0.2 0.1 5 0.1 5 TABLE V11 I

Ex. no. Dye Water PG DEG NMP TBT TDG 2P 16 3.0 55 5 2.0 3 17 6.0 65 4 0.1 5 18 5.0 78 5 12 5 19 8.0 70 8 1 5 100 80 8 12 TABLE IX

Ex. no. Dye Water PG DEG NMP BDL PHO 2P P12 21 10.0 75 3 5 3 3 1 22 3.5 80 6 5 23 2.0 90 7 7 0.5 24 6.0 65 5 2 4.0 70 10 4 1 4 11 TABLE X

Ex. Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P No.

26 1.5 80 1 2 3 0.5 0.4 7 2 10 27 3.0 60 4 2.0 0.5 28 4.5 90 3 6 7.0 1 3 2 29 3.0 95 7 4 3 0.5 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 TABLE Xl

Ex. no. Dye Water PG DEG NMP CHL PHO 2P PDL 1 7.0 75 3 5 3 3 1 2 3.5 60 2 5 3 2.0 90 7 7 1.5 2 4 6.0 65 5 2 4.0 70 5 4 1 4 12 21

Claims

1. At least one compound of Formula (l):

MkPC 11/ (SO 3H). 1}1 (S02NH {L-A-R 2}W) Y Formula (1) which comprises any form of the compound: such as salt; stereoisomer, zwitterion, polymorph, complex, isotopic form, combinations thereof in the same species and mixtures thereof; where:

M represents H, metal, halometal, oxymetal andlor hydroxymetal; k is the inverse of half of the valency of M; Pc represents a phthalocyanine nucleus of Formula (2):

r, Nz: 1 N N= D N N N N N Formula (2) L represents a linking group comprising an optionally substitutedCl- 30carbyl; 3_ A represents -0-, -Sor -NR, where R3 independently comprises H or optionally substituted Cl-Mcarbyl; R' comprises at least one group independently selected from: an optional substituent and optionally substituted C,_1.carbyl; R

2 comprises optionally substituted Cl-30carbyl that comprises at least one alkyl group substituted by at least one of: hydroxy, carboxy and sulpho; z represents an integer from 0 to 4; w represents an integer from 1 to 5; and the sum of w + z is from 1 to 5; and x and y each independently represent a non-zero number; and the mean of the sum of x + y is from about 1 to about 6; where the optional substituents comprise at least one of: carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

22 2. At least one compound as claimed in claim 1, including salts thereof, in which: z is 0, 1 or 2; and when z is other than 0, R' represents an optionally substituted group independently selected from: carboxy, carboxyC,6alkyl, sulpho, Cl-ralkyl, Cl_.alkoxy, halo, cyano, nitro, amino, Cl,,alkylamino, di(C1_.alkyl)amino, C,-12arylamido, Cl,alkanoylarnino; C, .alkylcarbarnoyl and C,6alkylsulphamoyl; L represents a Cl-15carbyl group, which may be attached to the benzene ring at the position para to the sulphonylamino group attached to the Pc nucleus; A represents -S- or a protonable amino group comprising -NR'where R' represents H or an optionally substituted Cl-22carbyl that comprises at least one alkyl group substituted by hydroxy, carboxy andlor sulpho; R 2 independently represents an optionally substituted Cl-22carbyl that comprises at least one alkyl group substituted by hydroxy, carboxy andlor sulpho; w is 1 and; x and y each represent from 1 to

3 and the sum of x + y is from 1 to

4. 15 3. At least one compound as claimed in either preceding claim, including salts thereof, in which: M is Cu; L represents sulphonylCl-15alkylene; 20 A represents -S-; or -NR' where R' represents H or C,-6aikyl optionally substituted by at least one of: hydroxy, sulpho or carboxy; R 2 represents Cl-16alkyl; Cr,18aryl; or C1,.alkylene(YCl-6alkylene), each optionally substituted by at least one group selected from: methyl, hydroxy, sulpho and carboxy; where n is 0, 1 or 2-, and Y is independently, -0- or -N(C2H4)W; 25 z is 0 or 1; and the sum of x + y is 4. 4. At least one compound as claimed in any preceding claim, including salts thereof, in which: 30 L represents sulphonylClaikylene attached to the benzene ring via the S atom and para to the -S02NW group; A represents -S-; or -NR 3 where R 3 represents H or C,-4alkyl optionally substituted by at least one of: hydroxy, sulpho andlor carboxy; R 2 represents C1.1.alkyl; phenyl; or C,-4alkoxyCl-4alkyl; each substituted by at least one 35 group selected from: methyl, hydroxy, sulpho andlor carboxy; z is 0; and x and y are both 2; or x is 1 and y is 3.

23

5. At least one compound as exemplified herein, with reference to Examples 1 to 30 herein, including acid form(s); the lithium, potassium, sodium andlor optionally substituted ammonium salt(s) thereof; and any mixtures thereof.

6. An ink effective for use in ink jet printing, comprising a medium and a colorant comprising at least one compound as claimed in any preceding claim.

7. A process for printing a substrate with an ink as claimed in claim 6, using an ink-jet printer. 10

8. A substrate printed with an ink as claimed in claim 6, the substrate selected from one or more of: paper, an overhead projector slide and a textile material.

9. A process for the colouring a textile material with an ink as claimed in claim 6, the 15 process comprising the steps of. i) applying the ink to the textile material by ink-jet printing; and ii) heating the textile material at a suitable temperature to fix the ink on the material.

10. A textile material coloured with an ink as claimed in claim 6.

11. A process for preparing at least one compound of Formula (1) as claimed in any of claims 1 to 5, in which L is S02C21H14; the process comprising reacting at least one compound of Formula (3):

, (S03H), R 1} MkPC \ (S02NH -E(S02C2H40SO3H}w)y Formula (3) with at least one compound of formula R2AH where Pc, IVI,, R', w, x, y & z; and R 2 & A are as represented in claim 1.