MX2007006693A - Phthalocyanines and their use in ink-jet printing - Google Patents

Abstract

A mixture of dyes of Formula (1) and salts thereof;wherein M is 2H, Si, a metal, an oxymetal group, a hydroxymetal group or a halometal group;Pc represents a phthalocyanine nucleus of formula (2);R1is methyl;R2is H or methyl;R3and R4independently are H or optionally substituted C1-4alkyl;L is a divalent linking group;A and B are independently H or a substituent. x is 0.1 to 3.8;y is 0.1 to 3.8;z is0.1 to 3.8;the sum of (x+y+z) is 2 to 4;and the substituents, represented by x, yand z, are only attached to aÿposition on the phthalocyanine ring and the dyes are free from fibre reactive groups. Also compositions, inks, printed material and in-jet processes and cartridges.

Description

FTALOCIA IÑAS AND ITS USE IN PRINTING BY INJECTION OF INK DESCRIPTION OF THE INVENTION This invention relates to dyes, compositions and inks, printing processes, printed materials and inkjet printer cartridges. Inkjet printing is a non-percussive printing technique in which droplets of ink are ejected through a thin nozzle into a substrate without putting the nozzle in contact with the substrate. Color inkjet printers typically use four different color inks; Magenta, yellow, cyan, and black. Other colors than these can be obtained using different combinations of these inks. Thus, for optimum printing quality, the dyes used must be able to form an ink with a specific precise tone. This can be achieved by mixing dyes, but selling is achieved by using a single dye with the exact tone required. While inkjet printers have many advantages over other forms of printing and image development, there are still technical challenges to be met. For example, there are contradictory requirements with respect to providing ink colorants that are soluble in the ink medium and still do not function or stain REF. 182153 excessively when printed on paper. The inks need to be dried quickly to prevent the sheets from sticking after they have been printed, but no crust should form on the microtip used in the printer. Storage stability is also important to avoid the formation of particles that could block the micro-jets used in the printer, since especially consumers can keep an ink cartridge for inkjet for several months. With the advent of high-resolution digital cameras and inkjet printers, it became increasingly common for consumers to print photographs using an inkjet printer. This avoids the expense and inconvenience of conventional silver halide photography and provides fast and convenient printing. However, this use of inkjet printers requires that the prints exhibit excellent stability to light and common oxidizing gases such as ozone. Photographs, once printed, are frequently kept on display for years and it has been found that even seemingly small changes in the light and ozone stability of an impression in test systems can be correlated to a significant improvement in the stability of the image in real life. Most of the dyes used in inkjet printing are based on phthalocyanines and the problems of discoloration and change of hue in exposure to light and contact with ozone are particularly acute with dyes of this kind. Phthalocyanines having sulfonate and sulphonamide substituents have found particular utility in inkjet printing. These dyes are commonly made by sulfating a phthalocyanine pigment followed by chlorination and then amination / amidation, the resulting product contains sulfonamide substituents substituted with sulfo and sulfonamide in any susceptible position (for example see Schofield, J and Asaf, in Journal of Chromatography , 1997, 770, pp345-348). However, we have found that certain substituted phthalocyanines, only in the β-position exhibit advantageous properties when used in inkjet printing. The present invention provides a mixture of dyes of formula (1) and salts thereof: Formula (1) where: M is 2H, Si, a metal, an oximetal group, hydroxymetal group or halometal group; Pe represents a phthalocyanine nucleus of formula R1 is methyl; R2 is H or methyl; R3 and R4 are independently H or optionally Ci_4 substituted alkyl; L is a divalent ligature group; A and B are independently H or a substituent. x is 0.1 to 3.8; and is 0.1 to 3.8; z is 0.1 to 3.8; the sum of (x + y + z) is 2 to 4; and the substituents, represented by x, y, and z, are only attached to a β-position on the phthalocyanine ring and the dyes are free of reactive fiber groups. M is preferably 2Li, 2Na, 2K, Mg, Ca, Ba, Al, Si, Sn, Pb, Rh, Se, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, AIX, GaX, InX or SiX2, where in X is OH or Cl, preferably Se, Ti, Va, Cr, Mn, Fe, Co, Zn, Ni and Cu, especially Cu or Ni and more especially Cu. Preferably R3 and R4 are independently H, methyl, ethyl, or hydroxyethyl or ethyl sulfonic acid. Preferably R3 and R4 are independently methyl or H. More preferably R3 and R4 are H. L is preferably -alkylene-, optionally substituted or optionally interrupted by a heteroatom or a double or triple bond of carbon to carbon; -arlene-optionally substituted; or -heterocyclylene- optionally substituted. More preferably L is optionally substituted Ci-4-alkylene, especially C-1 alkylene; or optionally substituted phenyl, especially phenyl. It is particularly preferred that L is alkylene Ci-4, especially -C2H4-. Optional substituents for R2, R3, R4 and L, when these comprise optionally substituted -alkylene- are preferably independently optionally substituted (preferably Ci_4 alkoxy) alkoxy, optionally substituted (preferably phenyl) aryl, optionally substituted aryloxy (preferably phenoxy ), optionally substituted (preferably triazinyl) heterocyclyl, polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), C02H, S03H, P03H2, nitro, cyano, halo (preferably Cl and Br), ureido, -S02F, hydroxy, ester , -NRaRb, -CORa, -CONRaRb, -NHCOR3, carboxester, sulfone, and -S02NRaRb wherein Ra and R are each independently H or optionally substituted alkyl (especially C1-4 alkyl). Optional substituents for any of the above substituents may be selected from the same list of substituents. Optional substituents for A and B, when different from H, and L, when -arylene is optionally substituted or -heterocyclylene- are optionally substituted, are preferably selected independently from; optionally substituted alkyl (preferably C1-4 alkyl), optionally substituted alkoxy (preferably C 1-4), optionally substituted aryl (preferably phenyl), optionally substituted (preferably phenoxy), optionally substituted heterocyclic, polyalkylene oxide (preferably aryloxy oxide polyethylene or polypropylene oxide), carboxy, phosphato, sulfo, nitro, cyano, halo, ureido, -S02F, hydroxy, ester, -NRaRb, -COR, -CONRaRb, -NHCOR3, carboxyester, sulfone, and -S02NRaRb, wherein Ra and R are each independently H or optionally substituted alkyl (especially Ci-4-alkyl). Optional substituents for any of the substituents described above may be selected from the same list of substituents. Preferably A and B are independently H, -OH, -SH, -NH2, or -0, -S or -N substituted. In an A and / or B embodiment they comprise at least one anionic group, especially carboxy and / or sulfa. Is especially preferred that when A and B are different from H are independently selected from the group consisting of -OH, -NHCH 3, -N (CH3) 2, -NHC2HS03H2, -N (CH3) C2H4S03H2, -NC3H6S03H, -NHdisulfofenilo, · -NHsulfofenilo, -NHcarboxifenilo or -NHdicarboxifenilo, -NHsulfonaftilo, -NHdisulfonaftilo, -NHtrisulfonaftilo, -NHcarboxionaftilo, NHdicarboxionaftilo, NHtricarboxionaftil-NHsulfoheterciclilo, -NHdisulfoheterciclilo or -NHtrisulfoheterciclilo. Preferably x is 0.1 to 3, more preferably 0.1 to 2.0, especially 0.2 to 1.5 and more especially 0.3 to 1.0. Preferably y is 0.1 to 0.9, more preferably 0. 2 to 0.8. Preferably z is 0.1 to 3.5, more preferably 0.5 to 3, especially 0.8 to 3.0 and more especially 1.0 to 3. The sum of (x + y + z) is preferably 3 to 4, more preferably the sum of (x + y + z) is 4. The dye mixture of formula (1) is free of reactive fiber groups. The term fiber reactive group is well known in the art and is described for example in EP 0356014 Al. Reactive fiber groups are capable, under suitable conditions, of reacting with the hydroxyl groups present in the cellulosic fibers or with the amino groups present in natural fibers to form a covalent bond between the fiber and the dye. According to the examples of reactive groups of the fiber excluded from the dye mixture of the formula (1), aliphatic sulfonyl groups containing a sulfate ester group in the beta position for the sulfide atom, for example beta-sulfate-ethylsulfonyl, alpha and beta-unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, alpha-chloro-acrylic acid, alpha-bromoacrylic acid, propiolic acid, maleic acid and mono and male dichloro; also acyl radicals of acids containing a substituent which reacts with cellulose in the presence of an alkali, for example the radical of a halogenated aliphatic acid such as chloroacetic acid, beta-chloro acids and beta-bromopropionic acids and alpha, beta-acids dichloro- and dibromopropionic acids or radicals of vinylsulfonyl- or beta-chloroethylsulfonyl- or beta-sulfatoethyl-sulfonyl-endo-methylene cyanocarboxylic acids. Other examples of the reactive cellulose groups are tetrafluorocyclobutylcarbonyl, trifluorocyclobutenylcarbonyl, tetrafluorocyclobutyletenylcarbonyl, trifluorocyclobutenyletenylcarbonyl; activated halogenated 1,3-dicyanobenzene radicals; and heterocyclic radicals containing 1, 2 or 3 nitrogen atoms in the heterocyclic ring and at least one reactive substituent of cellulose in a ring carbon atom, for example a triazinyl halide. The basic or acidic groups in the dye mixture of the formula (1), particularly the acid groups, are preferably in the form of a salt. Thus, the formulas shown herein include the mixture of dyes in salt form. Preferred salts are alkali metal salts, especially lithium, sodium and potassium, ammonium and substituted ammonium salts (which include quaternary amines such as ((CH3) 4N +) and mixtures thereof. Especially preferred are the salts with sodium, lithium, ammonia and volatile amines, more especially sodium salts The mixture of dyes of formula (1) can be converted to a salt using known techniques The dyes in the dye mixture of formula (1) can exist in tautomeric forms other than those shown in this specification These tautomers are included within the scope of the present invention.

The dye mixture of formula (1) is preferably prepared by a process comprising the cyclization of a β-substituted phthalic acid or analog thereof. Preferred β-substituted phthalic acid analogs include phthalonitrile, iminoisoindolino, phthalic anhydride, phthalimide and phthalimide or mixtures thereof. The cyclization reaction can be carried out in the presence of a suitable source of ammonia (if required), and (if required) a suitable metal salt, for example CuCl 2, and a base such as 1,8-diazabicyclo [5. .0] undec-7-ene (DBU) followed by, if required, additional synthetic steps, eg, chlorination and then amidation. The total amount of x + y + z can be controlled by varying the degree and ratio of substituted phthalic acid or analog thereof to unsubstituted phthalic acid or analog thereof. Thus, when the mono-substituted phthalic acid or analogue thereof is used in the cyclization reaction then x + y + z is 4. In a preferred synthetic preparation of phthalocyanine dyes of formula (1), the phthalocyanine ring is prepared by the cyclization of 4-sulfophthalic acid, preferably for the phthalocyanine β-tetrasulfonic acid. When a phthalocyanine β-sulfonic acid is an intermediate in a route for the dyes of the formula (1), it can be chlorinated by reacting it with any suitable chlorinating agent. The chlorination is preferably carried out by treating the phthalocyanine β-sulphonic acid with chlorosulfonic acid preferably in the presence of an acid halide such as thionyl chloride, sulfuryl chloride, phosphorus pentachloride, phosphorus oxychloride or phosphorus trichloride. The substituent -S02C1, thus formed, in the phthalocyanine ring is then further reacted with a compound of formula NHR1R2 and (sequentially or at the same time) a compound of the formula: or with a compound of formula NHR1! 2 and (sequentially or at the same time) a compound of formula HR3N-L-NR4H, which product can then be reacted with cyanuric chloride and then with A and B (or activated precursors thereof) individually or at the same time. An expert will appreciate that the product of these reactions will be a dispersed mixture and thus the values x, y, and z will represent an average of the groups present in the mixture.

The mixture of the dyes of the formula (1) have attractive and strong cyan shades, and are valuable dyes for use in the preparation of inkjet printing inks. They benefit from a good balance of solubility, storage stability and inalterability to light and water. According to the second aspect of the present invention there is provided a composition comprising a mixture of dyes of the formula (1) as described in the first aspect of the invention and a liquid medium. Preferred liquid media include water, a mixture of water and organic solvent and water-free organic solvent. Preferably the liquid medium comprises a mixture of water and organic solvent or organic solvent free of 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 be an organic solvent mixable in water or a mixture of such solvents. Preferred water-miscible organic solvents include Ci_6 alkanols, preferably methane, 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; ethers which can be mixed in water, 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-alkylene glycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol; C 1-4 mono-alkyl ethers of diols, preferably C 1-4 mono-alkyl ethers of diols having from 2 to 12 carbon atoms, especially 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2 ethoxyethoxy) -ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- [2- (2-ethoxyethoxy) -ethoxy] -ethanol and ethylene glycol monoallyl ether / amides. cyclics, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclic esters, preferably caprolactone; sulfoxides, preferably dimethylsulfoxide and sulfolane. The liquid medium preferably comprises water and 2 or more, especially from 2 to 8, organic solvents which can be mixed in water. Especially the preferred water-miscible organic solvents are cyclic amides, especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; diols, especially 1,5-pentanediol, ethylene glycol, thiodiglycol, diethyleneglycol and triethyleneglycol; and mono-alkyl C-i-4 and Ci-4 alkyl ethers of diols, more preferably C1-4 mono-alkyl ethers of diols having from 2 to 12 carbon atoms, especially 2-methoxy-2-ethoxy-2-ethoxyethanol. Examples of other 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 the free organic solvent of water, (ie less than 1% water by weight), preferably the solvent has a boiling point of 30 ° to 200 ° C, more preferably 40 ° to 150 ° C, especially 50 to 125 ° C. The organic solvent can be unblemished in water, mixed in water or a mixture of these solvents. Preferred water-miscible organic solvents are any of the water-miscible organic solvents described above and mixtures thereof. Preferred water-miscible solvents include, for example, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH 2 Cl 2; and ethers, preferably diethyl ether; and mixtures thereof. When the liquid medium comprises an organic solvent unmixable in water, preferably a polar solvent is included because it improves the solubility of the phthalocyanine dyes in the liquid medium. Examples of polar solvents include C1-4 alcohols. In view of the above preferences it is especially preferred that where the liquid medium is water-free organic solvent comprises a ketone (especially methyl ethyl ketone) and / or an alcohol (especially a C 1-4 alkanol, more especially ethanol or propanol). The water-free organic solvent can be an organic solvent alone or a mixture of two or more organic solvents. It is preferred that when the liquid medium is a water-free organic solvent it is a mixture of 2 to 5 different organic solvents. This allows a liquid medium to be selected so as to provide good control over the drying characteristics and storage stability of the ink. The liquid media comprising the water-free organic solvent are particularly useful where fast drying times are required and particularly when printing on non-absorbent and hydrophobic substrates, for example plastics, metal and glass.

Preferred compositions according to the second aspect of the invention comprise: (a) from 0.01 to 30 parts of a mixture of dyes of formula (1) according to the first aspect of the invention; and (b) from 70 to 99.99 parts of a liquid medium; where all the 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 1 to 5 parts. The number of parts of component (b) is preferably from 80 to 99.9, more preferably from 85 to 99.5, 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 to be used to prepare more diluted inks and reduce the risk of dye precipitation if the evaporation of the liquid medium occurs during storage. The liquid media can of course contain additional components conventionally used in inkjet printing inks, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, koga reduction additives and surfactants that can be ionic or non-ionic. . Although not commonly necessary, additional dyes can be added to the ink to modify the hue and performance properties. Examples of such dyes include C.I. Direct Yellow 86, 132, 142 and 173; C.I. Direct Blue 307; C.I. Food Black 2; C.I. Direct Black 168 and 195; And ci. Acid Yellow 23. It is preferred that the composition according to the invention be ink suitable for use in an inkjet printer. Ink suitable for use in an inkjet printer is an ink that is capable of being repeatedly triggered through an ink jet printhead without causing blockage of fine nozzles. The ink suitable for use in an inkjet printer preferably has a viscosity less than 20cP, preferably less than 10cP, especially less than 5cP, at 25 ° C. Ink suitable for use in an inkjet printer preferably contains less than 500ppm, preferably less than 250ppm, especially less than 100ppm, more especially less than 10ppm in total of trivalent and bivalent metal ions (unlike any metal ion) bivalent and trivalent linked to a dye of formula (1) or any other colorant or additive incorporated in the ink). Preferably the ink suitable for use in an ink jet printer has been filtered through a filter having an average pore size below 10 μp ?, more preferably below 3 μm, especially below 2 μp? / More especially under lpm. This filtration removes particulate matter that could otherwise block the fine nozzles found in many inkjet printers. Preferably the ink suitable for use in an ink jet printer contains less than 500ppm, preferably less than 250ppm, especially less than 100ppm, more especially less than 10ppm in total of halide ions. The inks can be incorporated in an inkjet printer such as a high concentration cyan ink, a low concentration cyan ink or both, a high concentration ink 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) wherein the 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 the 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). A third aspect of the invention provides a process for forming an image on a substrate comprising applying the ink suitable for use in an inkjet printer, according to the second aspect of the invention, thereto by means of an ink jet printer. The inkjet printer preferably applies the ink to the substrate in the form of droplets which are thrown through a small hole on the substrate. Preferred inkjet printers are piezoelectric inkjet printers and thermal ink jet printers. In thermal inkjet printers, the programmed heat pulsations are applied to the ink in a reservoir by means of a resistor adjacent to the orifice, in such a way that it causes the ink to be ejected from the orifice in the form of small droplets directed towards the ink. substrate during relative movement between the substrate and the hole. In piezoelectric inkjet printers the oscillation of a small crystal causes ejection of the ink from the hole. Alternatively the ink may be ejected by an electromechanical actuator connected to a movable vane or piston, for example as described in International Patent Application WO00 / 48938 and International Patent Application WOOO / 55089. The substrate is preferably paper, plastic, a textile, metal or glass, more preferably paper, a top projector slide or a textile material, especially paper.

The preferred papers are planes or treated papers that may have an acidic, alkaline or neutral character. Bright papers are especially preferred. Photo-quality papers are especially preferred. Examples of commercially available higher quality papers include, HP Premium Coated Paper, HP Photopaper ™ (both available from Hewlett Packard Inc.); Stylus ™ Pro 720 dpi Coated Paper, Epson Photo Quality ™ Glossy Film, Epson Photo Quality ™ Glossy Paper (all available from Seiko Epson Corp.); Canon HR 101 High Resolution ™ Paper, Canon GP 201 Glossy ™ Paper, Canon HG 101 and HG201 High Gloss ™ Film, Canon PR101 (all available from Canon); Kodak Premium ™ Photopaper, Kodak Premium ™ InkJetpaper (available from Kodak); Konica Injet Paper QP ™ Professional Photo Glossy, Konica Injet Paper QP ™ Professional Photo 2-sided Glossy, Konica InkJet Paper QP ™ Premium Photo Glossy, Konica InkJet Paper QP ™ Premium Photo Silky (available from Konica). A fourth aspect of the present invention provides a material preferably paper, plastic, textile, metal or glass, more preferably paper, a top projector slide or a textile material, especially paper, more especially coated or treated papers, flat, printed with a mixture of dyes as described in the first aspect of the invention, a composition as described in the second aspect of the invention or by means of a process as described in 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 as described in the third aspect of the invention.

A fifth aspect of the present invention provides an ink jet printer cartridge comprising a chamber and an ink suitable for use in an ink jet printer where the ink is in the chamber and the ink is as defined in 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.

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

EXAMPLES Dye analysis of formula (1) Confirmation of the dye structure of formula (1) is by mass spectrometry. Elemental analysis is used to determine the relationships of x, y, and z. Thus, in the dyes of the later examples, mass spectrometry has shown that in all cases x + y + z is 4. When the sum of x plus y and z, as determined by the elementary analysis is not exactly 4 this makes think that it is due to the presence of impurities. The presence of these impurities and their effect on the estimated values of x, y and z would be well known to one skilled in the art who would appreciate that the value of x plus z plus should not exceed 4 and would treat the experimentally determined values of x, yyz as indicative of the groups' relationships. Also with some dyes according to the present invention it is not possible, using elemental analysis, to exclude between the different sulfonamide substituents. In these cases x and y are shown as a sum of both sulfonamide groups ie (y + z).

Example 1 Stage 1 Preparation of copper tetra-β-sulfonate phthalocyanine mixed 4-sulfophthalic potassium acid (56.8g), urea (120g), CuCl2 (6.9g), ammonium molybdate (1.2g) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) (7.5g) in a container of reaction. The mixture was heated in stages (130 ° C / 30 minutes, 150 ° C / 30 minutes, 180 ° C / 30 minutes, 220 ° C / 30 minutes) for 2 hours and the melt that formed was stirred at 220 ° C. for 2 additional hours. The resulting solid was extracted 4 times with hot water (4 x 200ml) and the extract was filtered to remove the insoluble material. The filtrate was stirred at 60 ° C-70 ° C and then enough NaCl was added to give a 7% salt solution. Stirring was continued and the precipitate was filtered, washed with a 10% salt solution (200 ml) and extracted by vacuum drying. The resulting wet solid (77.6 g) was suspended in acetone, filtered and dried, first at room temperature and then at 50 ° C.

Stage 2 Preparation of: Cyanuric chloride (27.68 g) dissolved in actone (150 ml) was added to an ice / water suspension (100 g / 150 ml) at 0-5 ° C. Then a solution of 2,5-disulfoaniline (41.4 g) in water (150 ml) was added dropwise at a pH of 4 to 5. This reaction mixture was kept below 5 ° C and stirred at a pH of 4. to 5 for 2 hrs. The pH was then adjusted to pH 7 with 2M sodium hydroxide solution, the temperature was raised to 20-25 ° C and the reaction mixture was allowed to stand for 1 hour. Ammonia (9.1 ml) was then added and pH adjusted to pH 9 to 9.5 (with 2M sodium hydroxide) and the reaction mixture was stirred at room temperature overnight. The next day the reaction mixture was heated at 80 ° C for 1 h, and then ethylenediamine (99 ml) was added and the reaction mixture was heated at 80 ° C for 2 hrs more. The reaction mixture was then cooled, salted with 20% brine%, and the pH was decreased to 1 with concentrated HC1. The precipitate that formed was filtered and washed with 20% brine, this was suspended in methanol to filtrate and dried to give the previous product (56.1 g) Stage 3 Preparation of the title product Phosphorus oxychloride (5.16 ml) was added dropwise to chlorosulfonic acid (86g) for 5 to 10 minutes while keeping the temperature below 35 ° C. When all of P0C13 had been added, copper phthalocyanine tetra-sulfonate was added from step 1 (16 g) per portion while the reaction temperature was maintained below 55 ° C. The reaction mixture was stirred at 50-60 ° C for 15-20 minutes. The temperature of the reaction mixture was then gradually increased to 138-140 ° C for 30 minutes, maintained at this temperature for 6.5 h and then the reaction mixture was allowed to cool and stir overnight at room temperature. The mixture was added to water / ice (100 ml / 150 g) and the resulting precipitate was filtered, washed with ice water, removed dry using a vacuum pump and then dried in a desiccator (15 g). The dried solid (5g) in water (200ml) was then added to a mixture of the product of Step 2 (2.94g), in water (50ml) followed by 40% dimethylamine (0.9ml) at 0 ° -5 ° C. The resulting mixture was stirred 0 ° to 5 ° C and pH 9 to 9.5 for 1 hour while maintaining the pH by the addition of 2M sodium hydroxide. The reaction mixture was then stirred at room temperature overnight. The next day the reaction mixture was heated to 60 ° C, maintaining the temperature for 1 hour and then cooled to 40 ° C. The reaction mixture was then salted with 20% brine and the pH was decreased to pH 1 with concentrated HC1. The solid that was precipitated was filtered, washed with 20% brine, dissolved in deionized water, dialyzed, filtered and then dried at 70 ° C to give 4.7 g of product. The elemental analysis of the product gave x = 3.3 and (y + z) = 0.8. Example 2 The dye of Example 2 was prepared as described in Example 1 with the exception of step 3, 1 molar equivalent of methylamine was used in place of 2 molar equivalents of dimethylamine, and one molar equivalent of triazinyl amine formed in step 2 It was used instead of two molar equivalents. The elemental analysis of the product gave x = l .7 and (y + z) = 1.8.

Example 3 The dye of example 3 was prepared as described in example 1 except for stage 3, 1 molar equivalent of methylamine was used instead of 2 molar equivalents of dimethylamine and two molar equivalents of triazinyl amine formed in step 2 were used. instead of two molar equivalents. The elemental analysis of the product gave x = 1.2 and (y + z) = 3.0. Example 4 The dye of Example 4 was prepared as described in Example 1 with the exception of stage 3, one molar equivalent of methylamine was used in place of dimethylamine, in step 2, 2-sulfoaniline was used instead of 2,5-disulfoaniline and two molar equivalents of triazinyl amine so formed in step 2 were used instead of three molar equivalents. Ink and Inkjet Printing The ink can be prepared from the dyes of Examples 1 to 4, by dissolving 3g of dye in 97ml of a liquid medium consisting of 5 parts of 2-pyrrolidone.; 5 parts of thiodiethylene glycol; 1 part of Surfinol ™ 465 and 89 parts of water and adjusting the pH to pH between 8 to 9 with sodium hydroxide. Surfinol ™ 465 is an Air Products surfactant. Ink Jet Printing The ink, prepared as described above, can be filtered through a 0.45 micron nylon filter and then incorporated into an empty print cartridge using a syringe. The ink can then be printed by inkjet in either plain paper or specialized media. Print Evaluation Prints, formed by inkjet printing, can be tested for ozone stability by exposure to 1 ppm ozone at 40 ° C, 50% relative humidity, for 24 hours in a Hampden 903 cabinet Ozone The stability of the printed ink to ozone can be determined by fade by the difference in optical density before and after exposure to ozone. The light stability of the printed image can be determined by the discoloration of the printed image on a Atlas CÍ5000 Weatherometer for 100 hours and then measuring the change in optical density. Optical density measurements can be made using a Gretag spectrometer spectrophotometer operated at the following parameters: Geometric Measurement: 45 ° / 0 ° Spectral Range: 380-730 nm Spectral Range: 10 nm Illuminant: D65 Observer: 2 ° (CIE 1931 Density: Ansi To External Filler: None The stability to light and ozone should be determined by the percentage change in the optical density of the impression, where a lower figure indicates a higher stability, and the degree of discoloration. The degree of discoloration can be expressed as ?? and a lower figure indicates a higher light stability. ?? is defined as the total change in the coordinates L, a, b of CIE color of the impression and is expressed by the equation AE = (AL2 + Aa2 + Ab2) 0-5. Additional Inks The inks described in tables A and B can be prepared in which the Dye described in the first column is the Dye made in the previous example of the same number. The numbers shown in the second forward column refer to the number of parts of the relevant ingredient and all parts are by weight. Inks can be applied to paper by inkjet or thermal printing. The following abbreviations are used in tables A and B: PG = propylene glycol DEG = diethylene glycol NMP = N-methyl pyrrolidone DMK = dimethyl ketone IPA = isopropanol MEOH = 2P methanol = 2-pyrrolidone MIBK = methyl isobutyl ketone P12 = propane-1,2-diol BDL = butane-2, 3-diol CET = cetylammonium bromide PHO = Na2HP04 TBT = tertiary butanol TDG = thiodiglycol TABLE A TABLE B It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (16)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Mixture of dyes of formula (1) and salts thereof:
2. Formula 1) characterized in that: M is 2H, Si, a metal, an oximetal group, hydroxymetal group or halometal group; Pe represents a phthalocyanine nucleus of formula
3. R1 is methyl; R2 is H or methyl; R3 and R4 are independently H or optionally substituted Ci-4 alkyl; L is a bivalent ligature group; A and B are independently H or a substituent. x is 0.1 to 3. and is 0.1 to 3.8, z is 0.1 to 3. the sum of (x + y + z) is 2 to 4; and the substituents, represented by x, y and z, are attached only to a β-position on the phthalocyanine ring and the dyes are free of reactive groups on the fiber. 2. Mixture of dyes according to claim 1, characterized in that y is 0.1 to 0.9. 3. Mixture of dyes according to any of claim 1 or 2, characterized in that M is Cu.
4. 4. Mixture of dyes according to any of claim 1 or 2, characterized in that R3 and R4 are independently methyl or H.
5. 5. Mixture of dyes according to any of the preceding claims, characterized in that R3 and R4 are H.
6. 6. Mixture of dyes according to any of the preceding claims, characterized in that L is C1-4 alkylene.
7. 7. Dye mixture according to any of the preceding claims, characterized in that A and B are independently selected from the group consisting of -OH, -NHCH3, -N (CH3) 2, -NHC2H4SO3H2, -N (CH3) C2H4S03H2, -NC3H6S03H, -NHdisulfophenyl, -NHsulfophenyl, -NHcarboxyphenyl or -NHdicarboxyphenyl, -NHsulfonaphthyl, -NHdisulfonaphthyl, -NHtrisulfonaphthyl, -NHcarboxionaphthyl, -NHdicarboxiona tyl, NHtricarboxionaftil-NHsulfoheterciclilo, NHdisulfohetercicilil or -NHtrisulfohetercicilil.
8. 8. Mixture of dyes according to any of the preceding claims, characterized in that the sum of (x + y + z) is 4.
9. 9. Mixture of dyes according to any of the preceding claims, characterized in that it is prepared by a process comprising the cyclization of a β-substituted phthalic acid or analog thereof.
10. 10. Composition characterized in that it comprises a mixture of dyes of formula (1) according to any of claims 1 to 9 and a liquid medium.
11. 11. Composition according to claim 10, characterized in that the liquid medium comprises a mixture of water and organic solvent or organic solvent free of water.
12. 12. Composition according to any of claims 10 or 11, characterized in that it is an ink suitable for use in an inkjet printer.
13. 13. Process for forming an image on a substrate, characterized in that it comprises applying the ink suitable for use in an ink-jet printer, according to claim 12, thereto by means of an ink-jet printer.
14. 14. Material, characterized in that it is printed with a mixture of dyes according to any of claims 1 to 9, a composition according to any of claims 10 to 12 or by means of a process according to claim 13. 15 Material according to claim 14, characterized in that it is a print on a photographic quality paper printed using a process according to claim 13. 16. Inkjet printer cartridge characterized in that it comprises a chamber and an ink suitable for use in an inkjet printer wherein the ink is in the chamber and the ink is in accordance with claim 12.