GB2457256A

GB2457256A - Copper phthalocyanine dyes with sulpho, sulphamoyl and N-(2-carboxyethyl)sulphamoyl substituents for use in ink-jet printing

Info

Publication number: GB2457256A
Application number: GB0802254A
Authority: GB
Inventors: Prakash Patel
Original assignee: Fujifilm Imaging Colorants Ltd
Current assignee: Fujifilm Imaging Colorants Ltd
Priority date: 2008-02-07
Filing date: 2008-02-07
Publication date: 2009-08-12
Also published as: GB0802254D0

Abstract

A compound of formula (1) and salts thereof: <EMI ID=1.1 HE=33 WI=73 LX=657 LY=586 TI=CF> wherein: x, y, and z are all greater than 0 and less than 4; x+y+z is in the range of 2 to 4; Pc represents a phthalocyanine nucleus of formula: <EMI ID=1.2 HE=65 WI=67 LX=698 LY=1118 TI=CF> and the positions of the substituents on the phthalocyanine nucleus are such as would be obtained by chlorosulphonating copper phthalocyanine and condensing the product with ammonia and 3-aminopropionic acid. Such compounds have a strong cyan shade and may be formulated with a liquid medium to provide ink-jet inks. The latter may applied by an ink-jet printer to a substrate to form an image thereon.

Description

1 2457256 PhthalocvanifleS And Their Use In Ink-Jet Printflq This invention relates to compounds, compositions and inks, to printing processes, to printed substrates and to ink-jet printer cartridges.

Ink-jet printing 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. The set of inks used in this technique typically comprise yellow, magenta, cyan and black inks.

With the advent of high-resolution digital cameras and ink-jet printers it is becoming increasingly common for consumers to print off photographs using an ink-jet printer. This avoids the expense and inconvenience of conventional silver halide photography and provides a print quickly and conveniently.

While ink-jet printers have many advantages over other forms of printing and image development there are still technical challenges to be addressed. For example, there are the contradictory requirements of providing ink colorants that are soluble in the ink medium and yet display excellent wet-fastness (i.e. prints do not run or smudge when printed). The inks also need to dry quickly to avoid sheets sticking together after they have been printed, but they should not form a crust over the tiny nozzle used in the printer. Storage stability is also important to avoid particle formation that could block the tiny nozzles used in the printer especially since consumers can keep an ink-jet ink cartridge for several months. Furthermore, and especially important with photographic quality reproductions, the resultant images should not fade rapidly on exposure 10 light or common oxidising gases such as ozone. It is also important that the shade and chroma of the colorant are exactly right so that an image may be optimally reproduced. Another phenomenon which must be minimised is bronzing. Bronzing is a term used to describe a print defect where certain colours, particularly cyan, appear to have a bronze reflection when viewed in reflected light.

The problem of optimising the solubility of phthalocyaflifleS has been addressed in International Patent Application W099167334.

In International Patent Application W005/014725 it was shown that phthalocyanineS carrying defined substituents only in the 3-position display an enhanced light and ozone fastness.

However the problem of balancing all the conflicting and demanding properties outlined above remains.

The present invention provides a compound of Formula (1) and salts thereof: /(SO3H)x CUPC-(SO2NH2) (SO2NHCH2CH2CO2H) Formula (1) wherein: x, y and z are all greater than 0 and less than 4; x plus y plus z is in the range of 2 to 4; and Pc represents a phthalocyanifle nucleus of formula; 13 13 13 13 obtainab'e by means of a process which comprises: (i) chlorosulfonating copper phthalocyanifle pigment using a chlorosUlfOflatiflg agent; and (ii) condensing the product of step (i) with ammonia and 3aminoprOPiOniC acid, either at the same time or sequentially, to give a mixture of copper phthalocyanine dyes of Formula (1).

Preferably x is in the range of I to 3.

Preferably y is in the range of 1 to 3.

Preferably z is in the range of 0.1 to 3.

Preferably the sum of x plus y plus z is in the range of 3 to 4.

The chlorosulfonatiflg agent preferably compnses chiorosulfonic acid. More preferably the chlorosulfoflatiflg agent comprises chlorosulfoniC acid and a chlorinating agent. Preferably the chlorinating agent is an acid chloride. More preferably the chlorinating agent is selected from the group consisting of phosphorous trichloride, phosphorous pentachioride phosphorous oxychloride, thionyl chloride and mixtures thereof.

The chlorosulfonatiofl may be performed in a sequential manner whereby the copper phthalocyanine pigment is first reacted with an excess of chiorosulfoniC acid and later a chlorinating agent is added to the mixture of copper phthalocyaflifle pigment and chlorosulfonic acid to form the chlorosulfOnatiflg agent in situ. However it is preferred that the chlorosulfonation is performed in one step whereby the copper phthalocyanine pigment is in contact with the chlorosulfonating agent comprising both chiorosulfonic acid and chlorinating agent throughout the entire chiorosulfonatiOn step. This one step process is simpler and less prone to errors than operating in a sequential manner.

Preferably the chlorosulfonating agent comprises a mixture of chlorosulfOfliC acid and phosphorous oxychioride.

The preferred molar ratio of chlorosulfonic acid to chlorinating agent used in the chlorosulfonating agent depends to some extent on the ratio of chlorosultoniC acid to copper phthalocyanine pigment. In general, as the ratio of chlorosulfonic acid to copper phthalocyanine pigment increases the optimum ratio of chiorosulfonic acid to chlorinating agent in the chlorosulfonating agent also increases (i.e. less chlorinating agent is needed when more chlorosulfonic acid is used). Bearing the above factors in mind, when the molar ratio of chiorosulfonic acid to copper phthalocyanine pigment is in the range 10 to 75:1 then the molar ratio of chlorinating agent to copper phthalocyaflifle pigment is preferably in the range 10 to 0.5:1. More preferably, when the molar ratio of chiorosulfonic acid to copper phthalocyanine pigment is in the range 15 to 23:1 then the molar ratio of chlorinating agent to copper phthalocyanifle pigment is preferably in the range 5to 1:1.

In absolute terms, the molar ratio of chiorosulfonic acid to copper phthalocyaflifle pigment is preferably in the range 5:1 to 200:1, more preferably in the range 10:1 to 75:1 and especially in the range 15:1 to 75:1.

The molar ratio of chlorinating agent to copper phthalocyanifle is preferably in the range 0.5:1 to 10:1, more preferably in the range 0.75:1 to 7.5:1 and especially in the range 1:1 to 5:1.

Preferably chlorosulfonation is performed at a temperature in the range of from 90 to 180°C, more preferably 110 to 150°C, especially 110 to 130°C and more especially to 125°C.

Preferably the chlorosulfonation is performed for 0.5 to 16 hours, more preferably 1 to 8 hours, especially 1.5 to 7.0 hours. In a particularly preferred embodiment chlorosulfonatiOn is performed for 2 to 6 hours.

The length of time for which the chlorosulfonation is performed depends on the temperature used. For example higher temperatures require less time and lower temperatures require more time.

In a preferred embodiment chlorosulfonation is performed at a temperature of 110 to 130°C for a time of 1.5 to 7.0 (more preferably 2 to 6) hours.

The cholorosulfonating agent optionally comprises further ingredients, for example sulfuric acid. When sulfuric acid is present the molar ratio of sulfuric acid to copper phthatocyanine pigment is preferably in the range 0.3:1 to 2:1, more preferably 0.6:1 to 1.2:1. Condensation of the product of step (I) with ammonia is preferably performed using ammonia in aqueous solution, e.g. ammonium hydroxide of strength 3 to 35 weight %, preferably 7 to 13 weight %.

The ratio of the legs x, y and z is determined by the total amount of and molar ration of ammonia to 3-aminopropionic acid. Thus, the as total amount of ammonia and 3-aminopropionic acid is increased the aqueous hydrolysis of the -SO2CI groups becomes less likely and so the value of x decreases. When the molar ratio of ammonia to 3-aminopropionic acid is increased y will increase relative to z and when it decreases y will decrease relative to z. Preferably condensation of the product of step (i) with ammonia and 3-aminopropionic acid is performed at a temperature of 0 to 50°C, more preferably 10 to 45°C and especially 12 to 40°C.

The length of time for which the condensation of the product of step (i) with ammonia and 3-aminopropionic acid is performed depends on the temperature used. For example higher temperatures require less time and lower temperatures require more time.

In a preferred embodiment condensation of the product of step (i) with ammonia and 3-aminopropionic acid is performed at a temperature of 0 to 45°C for a time of 0.5 to 24 hours.

Acid or basic groups on the compounds of Formula (1), particularly acid groups, are preferably in the form of a salt. Thus, all Formulae shown herein include the compounds in salt form.

Preferred salts are alkali metal salts, especially lithium, sodium and potassium, ammonium and substituted ammonium salts (including quaternary amines such as ((CH3)4N) and mixtures thereof. Especially preferred are salts with sodium, lithium, ammonia and volatile amines, more especially sodium salts. Compounds of Formula (1) may be converted into a salt using known techniques.

The compounds of Formula (1) may exist in tautomeric forms other than those shown in this specification. These tautomers are included within the scope of the present invention.

The compounds of Formula (1) have an attractive strong cyan shade and are valuable colorants for use in the preparation of ink-jet printing inks. They benefit from a good balance of solubility, storage stability, resistance to bronzing and fastness to water, ozone and light. In particular they display excellent wet fastness and ozone fastness.

According to a second aspect of the present invention there is provided a composition comprising a compound of Formula (1) as described in the first aspect of the invention and a liquid medium.

Preferred compositions according to the second aspect of the invention comprise: (a) from 0.01 to 30 parts of a compound of Formula (1) according to the first aspect of the invention; and (b) from 70 to 99.99 parts of a liquid medium; wherein all parts are by weight.

Preferably 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 I to 5 parts. The number of parts of component (b) is preferably from 80 to 99.9, more preferably from 85 to 99.5 and especially from 95 to 99 parts.

Preferably component (a) is completely dissolved in component (b). Preferably component (a) has a solubility in component (b) at 20°C of at least 10%. This allows the preparation of liquid dye concentrates that may be used to prepare more dilute inks and reduces the chance of the dye precipitating if evaporation of the liquid medium occurs during storage.

The inks may be incorporated in an ink-jet printer as a high concentration cyan ink, a low concentration cyan ink or both a high concentration and a low concentration ink. In the latter case this can lead to improvements in the resolution and quality of printed images. Thus the present invention also provides a composition (preferably an ink) where component (a) is present in an amount of 2.5 to 7 parts, more preferably 2.5 to 5 parts (a high concentration ink) or component (a) is present in an amount of 0.5 to 2.4 parts, more preferably 0.5 to 1.5 parts (a low concentration ink).

Preferred liquid media include water, a mixture of water and organic solvent and organic solvent free from water. Preferably the liquid medium comprises a mixture of water and organic solvent or organic solvent free from water.

When the liquid medium (b) comprises a mixture of water and 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 C14-alkanols, preferably methanol, ethanol, n-propanol.

isopropanol, n-butanol, sec-butanol, . tert-butanol, n-pentanol. cyclopentanol and cyclohexanol; 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. tnethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetnol; mono-C11-alkyl ethers of diols, preferably mono-C14-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxyethanOl, 2-(2-methoxyethOxy)ethaflOl.

2-(2-ethoxyethoxy)-ethanOl. 2-[2(2methoxyethoxY)ethOXYIethaflOl. 2-[2-(2-ethoxyethoxy)-ettioxy]-ethaflol and ethylene glycol monoallyl ether; cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidofle, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidOfle; cyclic esters, preferably caprolactone; sulfoxides, preferably dimethyl sulfoxide; and sulfones. Preferably the liquid medium comprises water and 2 or more, especially from 2 to 8, water-miscible organic solvents.

Especially preferred water-miscible organic solvents are cyclic amides, especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; diols, especially I,5-pentane diol, ethylene glycol, thiodiglycol, diethylene glycol and triethylene glycol; and mono-Ci.ralkyl and Ci..ralkyl ethers of diols, more preferably mono-C14-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2methoxy-2-ethoxy-2-ethoxYethar1Ol.

Examples of further suitable liquid media comprising 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-A-425,150.

When the liquid medium comprises organic solvent free from water, (i.e. less than 1% water by weight) the solvent preferably has a boiling point of from 30° to 200°C. more preferably of from 40° to 150°C, especially from 50 to 125°C. The organic solvent may be water-immiscible, 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 CH2CI2; 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 mixture of phthalocyanine dyes in the liquid medium. Examples of polar solvents include C14-alcohols.

In view of the foregoing preferences it is especially preferred that where the liquid medium is organic solvent free from water it comprises a ketone (especially methyl ethyl ketone) and/or an alcohol (especially a C14-alkanol, 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 liquid medium is organic solvent free from water it is a mixture of 2 to 5 different organic solvents. This allows a liquid medium to be selected that gives good control over the drying characteristics and storage stability of the ink.

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

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

Although not usually necessary, further colorants may be added to the ink to modify the shade and performance properties. Examples of such colorants include C.l. Direct Yellow 86, 132, 142 and 173; C.l. Direct Blue 307; Ci. Food Black 2; C.l. Direct Black 168 and 195; and C.l. Acid Yellow 23.

It is preferred that the composition according to the invention is ink suitable for use in an ink-jet printer. Ink suitable for use in an ink-jet printer is ink which is able to repeatedly fire through an ink-jet printing head without causing blockage of the fine nozzles. To do this the ink must be particle free, stable (i.e. not precipitate on storage), free from corrosive elements (e.g. chloride) and have a viscosity which allows for good droplet formation at the print head.

Ink suitable for use in an ink-jet printer preferably has a viscosity of less than 20 cP, more preferably less than 10 cP, especially less than 5 cP, at 25°C.

Ink suitable for use in an ink-jet printer preferably contains less than 500ppm, more preferably less than 25Oppm, especially less than lOOppm, more especially less than lOppm in total of divalent and trivalent metal ions (other than any divalent and trivalent metal ions bound to a colorant of Formula (1) or any other colorant or additive incorporated in the ink).

Preferably ink suitable for use in an ink-jet printer has been filtered through a filter having a mean pore size below lOp.tm, more preferably below 3pm, especially below 21.tm, more especially below 1jm. This filtration removes particulate matter that could otherwise block the fine nozzles found in many ink-jet printers.

Preferably ink suitable for use in an ink-jet printer contains less than SOOppm, more preferably less than 25Oppm, especially less than lOOppm, more especially less than loppm in total of halide ions.

A third aspect of the invention provides a process for forming an image on a substrate comprising applying a composition, preferably ink suitable for use in an ink-jet printer, according to the second aspect of the invention, thereto by means of an ink-jet printer.

The ink-jet printer preferably applies the ink to the substrate in the form of droplets that are ejected through a small orifice onto the substrate. Preferred ink-jet printers are piezoelectnc 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 from the orifice 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. Alternately the ink can be ejected by an electromechanical actuator connected to a moveable paddle or plunger, for example as described in International Patent Application W000/48938 and International Patent Application W000/55089.

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. Glossy papers are especially preferred. Photographic quality papers are especially preferred.

A fourth aspect of the present invention provides a material preferably paper, plastic, a textile, metal or glass, more preferably paper, an overhead projector slide or a textile matenal, especially paper more especially plain, coated or treated papers printed with a compound as described in the first aspect of the invention, a composition according to the second aspect of the invention or by means of a process according to the third aspect of the invention.

It is especially preferred that the printed material of the fourth aspect of the invention is a print on a photographic quality paper printed using a process according to the third aspect of the invention.

A fifth aspect of the present invention provides an ink-jet printer cartridge comprising a chamber and a composition, preferably ink suitable for use in an ink-jet printer, wherein the composition is in the chamber and the composition is as defined and preferred in the second aspect of the present invention. The cartridge may contain a high concentration ink and a low concentration ink, as described in the second aspect of the invention, in different chambers.

Examplel

Preparation of the sodium salt of: CUPC-(SO2NH2)1.6 (SO2NHCH2CH2CO2H)07 Staae I Phosphorous oxychloride (11.9g) was added drop-wise to chlorosulfonic acid (1 20g) at room temperature. To this stirred mixture was added copper phthalocyanine (12g) over 20 minutes while maintaining the temperature below 60°C. After the addition was complete the reaction was stirred at 40-60°C for 20mm, then stirred at 120°C for 6h.

Reaction cooled overnight, mixture drowned into ice/water (1200g) and salt (12g) and conc hydrochloric acid (5ml), 0°C. Precipitated solid filtered off, washed with 5% brine (600m1) to give copper phthalocyanine sulfonyl chloride damp paste (78g).

Stage 2 Copper phthalocya nine sulfonyl chloride damp paste (38g), prepared as in Stage 1, was slumed in cold water (lOOml) was added to a solution of 3-aminopropionic acid (1.8g), ammonium chloride (3.2g) and water (5Oml) adjusted to pH 8.5. The reaction mixture was stirred at 0-10°C and the pH was raised to and maintained at pHlO with 2M sodium hydroxide solution. This mixture was stirred for 2 h. The reaction mixture was then stirred at room temperature overnight, at 40°C for 2h and finally at pH 12 and 75-80°C for 2h. The pH of the reaction mixture was then lowered to pHlO with dilute hydrochloric acid and filtered. Methanol (700ml) was added to the filtrate and the solid which precipitated was filtered off and washed with methanol (5Oml). The resultant solid was dissolved in water (1 5Oml), dialysed and then dried at 60°C to give the title product (6.5g).

Example 2

Preparation of the sodium salt of a compound of Formula 1 wherein x is 0.7. y is 2.3 and z is0.5 Prepared as in Example I except that in Stage I the final step of the chiorosulfonation reaction was carried out at 130°C instead of 120°C. Product yield (8.8g).

Example 3

Preparation of the sodium salt of a compound of Formula I wherein x is 0.6. y is 2.2 and z is 0.5 Prepared as in Example 2 except that in Stage 2 3.6g of 3-aminopropiofliC acid was used instead of 1.8g. Product yield (8.8g) Preparation of Inks Ink may be prepared by dissolving Ig of the dye of Examples 1 to 3 in 19g of a liquid medium comprising: Thiodiglycol 5 % Urea 2.5% 2-Pyrollidone 2.5 % SurfynolTM 465 1 % Water 89 % (all % by weight) and adjusting the pH of the ink to 8-10 using sodium hydroxide.

SurfynolRlM 465 is a surfactant from Air Products.

lnk-iet Printuig Ink prepared as described above may be filtered through a 0.45 micron nylon filter and then incorporated into empty print cartridges using a syringe.

This ink may be printed on to plain paper or a specialised ink-jet media.

The prints may be tested for ozone fastness by exposure to lppm ozone at 40°C, 50% relative humidity for 24hrs in a Hampden 903 Ozone cabinet. Fastness of the printed ink to ozone can be judged by the difference in the optical density before and after exposure to ozone.

Light-fastness of the printed image may be assessed by fading the printed image in an AtIasRTM Ci5000 Weatherometer for 100 hours and then measuring the change in the optical density.

Optical density measurements can be performed using a GretagRlM spectrolino spectrophotometer set to the following parameters: Measuring Geometry: 0°/45° Spectral Range: 380 -730nm Spectral Interval: lOnm Illuminant: 065 Observer: 2° (CIE 1931) Density: Ansi A External Filler: None Light and Ozone fastness may then be assessed by the percentage change in the optical density of the print, where a lower figure indicates higher fastness, and the degree of fade. The degree of fade is expressed as iE where a lower figure indicates higher light fastness. aE is defined as the overall change in the CIE colour co-ordinates L, a, b of the print and is expressed by the equation E = (L2 + a2 + b2)0.5 Bronzing of the printed image may be conveniently assessed visually using an arbitrary scale of 0 (no bronzing) to 10 (heavy bronzing).

Further Inks The Inks described in Tables A and B may be prepared using the Compound of Example 1. Numbers quoted refer to the number of parts of the relevant ingredient and all parts are by weight. The inks may be applied to paper or a specialist ink-jet media by ink-jet printing.

The following abbreviations are used in Tables A and B: PG = propylene glycol DEC = diethylene glycol NMP = N-methyl pyrrolidone DMK = dimethylketone IPA = isopropanol MEOH = methanol 2P = 2-pyrrolidone MIBK = methylisobutyl ketone P12 = propane-i,2-diol BDL = butane-2,3-diol CET= cetyl ammonium bromide PHO = Na2HPO4 and TBT = tertiary butanol TDG thiodiglycol

TABLE A

Dye Water PG DEG NMP DMK NaOH Na IPA MEOH 2P MIBK Content ______ ____ _____ _____ _____ ______ Stearate ____ ______ ____ ______ 2.0 80 5 6 4 5 3.0 90 5 5 0.2 10.0 85 3 3 3 5 1 2.1 91 8 1 3.1 86 5 0.2 4 5 1.1 81 9 0.5 0.5 9 2.5 60 4 15 3 3 6 10 5 4 65 20 10 2.4 75 5 4 5 6 5 4.1 80 3 5 2 10 0.3 3.2 65 5 4 6 5 4 6 5 5.1 96 4 10.8 90 5 5 10.0 80 2 6 2 5 1 4 1.8 80 5 15 2.6 84 11 5 3.3 80 2 10 2 6 12.0 90 7 0.3 3 5.4 69 2 20 2 1 3 3 6.0 91 ____ _____ 4 _____ ______ ________ ____ ______ 5 _____

TABLE B

Dye Water PG DEG NMP CET TBT TOG BDL PHO 2P P12 Content _______ ____ ______ ______ ______ ______ ______ ______ ______ _____ ____ 3.0 80 15 0.2 5 9.0 90 5 1.2 5 1.5 85 5 5 0.15 5.0 0.2 2.5 90 6 4 0.12 3.1 82 4 8 0.3 6 0.9 85 10 5 0.2 8.0 90 5 5 0.3 4.0 70 10 4 1 4 11 2.2 75 4 10 3 2 6 10.0 91 6 3 9.0 76 9 7 3.0 0.95 5 5.0 78 5 11 6 5.4 86 7 7 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 2.0 90 10 2 88 10 78 5 12 5 8 70 2 8 15 5 80 8 12 80 ____ 10 _____ _____ _____ _____ _____ _____ ____ ____

Claims

Claims 1. A compound of Formula (1) and salts thereof: CuPc -(SO NH) 2 2y (SO2NHCH2CH2CO2H)Z Formula (1) wherein: x, y and z are all greater than 0 and less than 4; x plus y plus z is in the range of 2 to 4; and Pc represents a phthalocyanine nucleus of formula; p Nh1\ obtainable by means of a process which comprises: (ii) chiorosulfonating copper phthalocyanine pigment using a chlorosulfonating agent; and (ii) condensing the product of step (i) with ammonia and 3-aminopropionic acid, either at the same time or sequentially, to give a mixture of copper phthalocyanine dyes of Formula (1).
2. A compound and salts thereof as claimed in claim 1 wherein x is in the range of 1 to 3.
3. A compound and salts thereof as claimed in either claim 1 or claim 2 wherein y is in the range of I to3.
4. A compound and salts thereof as claimed in any one of the preceding claims wherein z is in the range of 0.1 to 3.
5. A compound and salts thereof as claimed in any one of the preceding claims wherein the sum of x plus y plus z is in the range of 3 to 4.
6. A composition comprising a compound of Formula (1) as described any one of claims 1 to 5 and a liquid medium.
7. A composition as claimed in claim 6 wherein the liquid medium comprises a mixture of water and organic solvent or organic solvent free from water.
8. A composition as claimed in either claim 6 or claim 7 which is ink suitable for use in an ink-jet printer.
9. A process for forming an image on a substrate comprising applying ink suitable for use in an ink-jet printer, according to claim 8, thereto by means of an ink-jet printer.
10. A material printed by means of a process according to claim 9.
11. An ink-jet printer cartridge comprising a chamber and ink suitable for use in an ink-jet printer, according to claim 8, wherein the ink is in the chamber.