HK1081585B - Phthalocyanine compounds, ink compositions comprising said compounds, and printing process therewith - Google Patents

Description

Phthalocyanine compounds, ink compositions containing said compounds and printing process thereof

The present invention relates to a process for ink jet printing, compositions and inks suitable for use in the process, novel compounds for preparing these compositions and inks, printing substrates and 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 the nozzle touching the substrate.

Ink jet printing places extremely high demands on the properties of the dyes and inks used. For example, they should provide clear, featherless images with excellent water resistance, light resistance, ozone resistance and optical density. Ink is typically applied to a substrate requiring rapid drying to prevent smudging of the ink, but the ink does not form a crust over the tip of the ink jet nozzle, which can hinder printer operation. The ink should also be stable in properties over time and not decompose or form precipitates which could block the fine nozzles of the printer.

Dyes containing a single copper phthalocyanine group and their use in ink jet printing are known. For example, in commercial ink jet printing inks, c.i. direct blue 199 and c.i. direct blue 86 are used as colorants. There are also more recent phthalocyanine dyes such as those described in US6,149,722. However, ink jet printing inks still need to deliver high performance colorants.

One particular problem with photorealistic quality printing is its permanence, i.e., the ability of the colorant to be used to produce photographic prints to maintain the color characteristics of the photograph for many years. The main factor that makes the printing less permanent is atmospheric contaminants, such as ozone, that quench the printed colorants.

We have now found that certain cyan colorants when used in an ink jet printing process produce prints having improved permanence and in particular improved ozone resistance.

Accordingly, in the present invention there is provided a method for imaging on a substrate, the method comprising applying to the substrate by an ink jet printer a composition comprising:

(a) a compound of formula (1) and salts thereof:

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or optionally substituted C_1-4An alkyl group;

R⁴is optionally substituted C_1-4-a hydroxyalkyl group;

x is greater than 0 and less than 1.8;

y and z are both greater than 0; and is

The sum of (x + y + z) is 2.4 to 4.5; and

(b) a liquid medium.

Preferably, the ink jet printer applies the composition 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, a programmed heat pulse is applied to the ink in a reservoir through a resistor near a small orifice during relative movement between the substrate and the orifice, causing the ink to be ejected from the orifice directly onto the substrate in the form of droplets. In piezoelectric ink jet printers, small crystal vibration (oscillation) causes ink to be ejected from a small orifice. Alternatively the ink may be ejected by a motor drive connected to a movable paddle or piston as described in international patent application WO00/48938 and international patent application WO 00/55089.

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

Preferred papers are plain, treated or coated papers and can be acidic, basic or neutral.

Photographic quality paper is particularly preferred.

A compound of formula (1) R¹、R²And R³Preferably independently hydrogen or methyl, more preferably a compound R of formula (1)¹、R²And R³Are both hydrogen.

A compound of formula (1) R⁴May contain more than 1 hydroxyl group, although R is preferred⁴Contains one hydroxyl group.

Preference is given to compounds R of the formula (1)⁴Is unsubstituted C_1-4Hydroxyalkyl, more preferably C₂-hydroxyalkyl groups.

Preferably R¹、R²、R³And R⁴The optional substituents on (a) are independently selected from: optionally substituted alkoxy (preferably C)_1-4-alkoxy), optionally substituted aryl (preferably phenyl), optionally substituted aryloxy (preferably phenoxy), optionally substituted heterocycle, polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), carboxy, phosphate, sulpho, nitro, cyano, halo, ureido, -SO₂F. Hydroxyl radicalRadical, ester, -NR⁵R⁶，-COR⁵，-CONR⁵R⁶，-NHCOR⁵Carboxylic acid esters, sulfones and-SO₂NR⁵R⁶Wherein R is⁵And R⁶Each independently hydrogen or optionally substituted alkyl (especially C)_1-4-an alkyl group). Any R¹、R²、R³And R⁴Optional substituents for the substituents may be selected from the same substituents listed.

Particular preference is given to compounds of the formula (1) in which R is¹、R²、R³Are all hydrogen, R⁴Is C_1-4-hydroxyalkyl, especially-CH₂CH₂OH。

Preferably, in the compound of formula (1), x is greater than 0 and less than 1.5, more preferably x is greater than 0 and less than 1.2, especially preferably x is greater than 0.05 and less than 1.0, more especially preferably x is greater than 0.05 and less than 0.8, and most preferably x is greater than 0.05 and less than 0.5.

Preferably the sum y + z in the compound of formula (1) is from 2.4 to 4.2, more preferably from 2.7 to 4.1.

Preferably, the sum (x + y + z) in the compound of formula (1) is from 3.5 to 4.5, more preferably the sum (x + y + z) is from 3.8 to 4.2, most preferably the sum (x + y + z) is 4.0.

The values for compounds of formula (1) x, y and z all represent statistical averages.

The substituents represented by x, y and z can be in any substitutable position of the phthalocyanine ring system.

In a preferred embodiment, provided that the compound of formula (1) is not a compound of the formula:

the acidic or basic group, especially the acidic group, in the compound of formula (1) is preferably in the form of a salt. Thus, the formulae shown herein include the free acid form of the compound and the salt form of the compound.

Preferred salts are alkali metal salts, especially lithium, sodium and potassium salts, ammonium and substituted ammonium salts (including quaternary ammonium salts such as (CH)₃)₄N⁺) And mixtures thereof. Particularly preferred are sodium salts, lithium salts, ammonia salts and volatile amine salts, more particularly sodium salts. These compounds can be converted to salts by known techniques.

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

The compound of formula (1) can be prepared by reacting a copper phthalocyanine or a nickel phthalocyanine having a sulfonyl chloride group and a sulfonic acid group with a compound of formula HNR¹R²And HNR³R⁴Prepared by condensation of compounds, wherein R¹、R²、R³And R⁴As defined above. Of the formula HNR¹R²And HNR³R⁴Many of the compounds of (a) are commercially available, e.g., ammonia and cholamine, and others can be readily prepared by one of ordinary skill. Preferably the condensation is carried out in water at a pH above 7. The condensation is generally carried out at from 30 to 70 ℃ and is generally completed in a time of less than 24 hours. Of the formula HNR¹R²And HNR³R⁴The compounds of (a) may be used as a mixture or condensed sequentially with the phthalocyanine compound.

Copper and nickel phthalocyanines with sulfonyl chloride groups and optionally sulfonic acid groups can be prepared from chlorosulfonated copper (chlorosulfonating coater) or nickel phthalocyanines, for example, using chlorosulfonic acid and optionally a chlorinating agent (e.g., POCl)₃、PCl₅Or thionyl chloride).

Preferred compositions comprise:

(a)0.01 to 30 parts of the compound of formula (1); and

(b)70-99.99 parts of liquid medium.

The fraction of component (a) is preferably from 0.1 to 20, more preferably from 0.5 to 15, and particularly preferably from 1 to 5. The fraction of component (b) is preferably from 99.9 to 8, more preferably from 99.5 to 85, and particularly preferably from 99 to 95.

Preferably component (a) is completely dissolved in component (b). Preferably, the solubility of component (a) in component (b) is at least 10% at 20 ℃. This allows the preparation of liquid dye concentrates which can be used to prepare thinner inks and reduces the chance of dye precipitation on storage due to evaporation of the liquid medium.

Preferred liquid media include water, mixtures of water and organic solvents, and anhydrous organic solvents.

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 particularly preferably from 95: 5 to 80: 20.

Preferably, the organic solvent 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 C_1-6Alkanols, 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, such as 1, 5-pentanediol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and thiodiglycol, and oligo-and poly-alkylene glycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; trihydric alcohols, preferably glycerol and 1, 2, 6-hexanetriol; mono-C of diols_1-4Alkyl ethers, preferably glycol mono-C having 2 to 12 carbon atoms_1-4Alkyl ethers, in particular 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) -ethanol, 2- [2- (2-methoxyethoxy) ethoxy ] ethanol]Ethanol, 2- [2- (2-ethoxyethoxy) -ethoxy]-ethanol and ethylene glycol monoallyl ether; cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1, 3-dimethylimidazolidinone; cyclic esters, preferably caprolactone; sulfoxides, preferably dimethyl sulfoxide and sulfolane. The liquid medium is preferablyComprising water and 2 or more, especially 2-8, water-miscible organic solvents.

Particularly preferred water-miscible organic solvents are cyclic amides, in particular 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; diols, in particular 1, 5-pentanediol, ethylene glycol, thiodiglycol, diethylene glycol and triethylene glycol; and mono-C of diols_1-4-alkyl and C_1-4Alkyl ethers, more preferably glycol mono-C having 2 to 12 carbon atoms_1-4Alkyl ethers, in particular 2-methoxy-2-ethoxy-2-ethoxyethanol.

Examples of more suitable liquid media comprise mixtures of water with one or more of the organic solvents described in US4,963,189, US4,703,113, US4,626,284 and EP4,251, 50A.

When the liquid medium comprises an anhydrous organic solvent (i.e. containing less than 1% by weight water), the boiling point of the solvent is preferably from 30 ℃ to 200 ℃, more preferably from 40 ℃ to 150 ℃, and most preferably from 50 ℃ to 125 ℃. The organic solvent may be water immiscible, water miscible or a mixture of such solvents. Preferred water miscible organic solvents are any of the aforementioned water miscible organic solvents and mixtures thereof. Preferred water immiscible solvents include, for example, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH₂Cl₂(ii) a And ethers, preferably diethyl ether; and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent, it is preferred to include a polar solvent, as this may enhance the solubility of the compound in the liquid medium. Examples of suitable polar solvents include C_1-4-an alcohol.

According to the preceding preferences, it is particularly preferred to include ketones (in particular methyl ethyl ketone) and/or alcohols (in particular C) when the liquid medium is an anhydrous organic solvent_1-4-an alcohol, more particularly ethanol or propanol).

The anhydrous organic solvent may be a single organic solvent or a mixture of two or more organic solvents. Preferably, when the medium is an anhydrous organic solvent, it is a mixture of 2 to 5 different organic solvents. This allows the media to be selected for good control over the drying characteristics and storage stability of the ink.

Liquid media comprising anhydrous organic solvents are particularly useful when rapid drying is required, especially when printing onto hydrophobic and non-absorbent substrates such as plastics, metals and glass.

The liquid medium may also contain other components conventionally used in ink jet printing inks, such as viscosity and surface tension modifiers, corrosion inhibitors, biocides, scale-reducing additives and ionic or nonionic surfactants.

Additional colorants can be added to the composition to adjust hue and performance characteristics, although it is generally not necessary to add additional colorants. Examples of such colorants are c.i.direct Yellow 86, 132, 142, and 173; c.i.direct Blue 199 and 307; C.I.food Black 2; c.i.directblack 168 and 195; acid Yellow 23; and any dye sold by Seiko Epson Corporation, Hewlett Packard Company, Canon Inc. & Lexmark International for use in ink jet printers. The addition of these additional dyes improves the overall solubility so that the resulting ink does not clog the nozzle.

In order not to allow the composition to clog the nozzles of an ink jet printer during use, the composition is preferably prepared with high purity ingredients and/or the composition is purified after preparation. Suitable purification techniques are well known such as ultrafiltration, reverse osmosis, ion exchange and combinations of these techniques, either added first or later to the compositions of the present invention. This purification results in the removal of substantially all inorganic salts and by-products of their synthesis. This purification facilitates the preparation of low viscosity aqueous solutions suitable for use in ink jet printers.

The viscosity of the composition at 25 ℃ is preferably less than 20cP, more preferably less than 10cP, and most preferably less than 5 cP. These low viscosity compositions are particularly suitable for application to a substrate by an ink jet printer.

Preferably the composition contains less than 500ppm total of divalent and trivalent metal ions (other than any divalent and trivalent metal ions incorporated into the ingredients of the composition), more preferably less than 250ppm, especially preferably less than 100ppm, most preferably less than 10 ppm. Free divalent and trivalent metals can form insoluble complexes upon storage that can clog inkjet printer nozzles.

Preferably the composition is filtered through a filter having an average pore size of less than 10 μm, more preferably less than 3 μm, especially preferably less than 2 μm, most preferably less than 1 μm. Filtration is found in many ink jet printers to remove particulate matter that could otherwise clog the fine nozzles.

Preferably the composition contains less than 500ppm, more preferably less than 250ppm, especially preferably less than 100ppm, most preferably less than 10ppm total halide ions. High levels of halide ions can cause deleterious results such as corrosion of the metal parts of the head of the ink jet printer.

In a second aspect, the present invention provides a composition comprising:

(a) a compound of formula (1) and salts thereof:

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or optionally substituted C_1-4An alkyl group;

R⁴is optionally substituted C_1-4-hydroxy radicalAn alkyl group;

x is greater than 0 and less than 1.8;

y and z are both greater than 0; and is

The sum of (x + y + z) is 2.4 to 4.5; and

(b) a liquid medium comprising water and an organic solvent or an anhydrous organic solvent.

Preferred compositions are as described in the first aspect of the invention.

Preference for the compound of formula (1) is as described and preferred in the first aspect of the invention.

The organic solvent in the mixture of water and organic solvent is as preferred in the first aspect of the invention.

Anhydrous organic solvents are preferred as in the first aspect of the invention.

It is particularly preferred that the composition of the second aspect of the invention is an ink jet printing ink or a liquid dye concentrate. The concentrate serves as a means of shipping the colorant and thus reduces the costs associated with drying the dye and shipping excess liquid.

In a third aspect, the present invention provides compounds of formula (1):

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or optionally substituted C_1-4An alkyl group;

R⁴is optionally substituted C_1-4-a hydroxyalkyl group;

x is greater than 0 and less than 1.8;

y and z are both greater than 0; and is

The sum of (x + y + z) is 2.4 to 4.5;

with the proviso that the compound of formula (1) is not a compound of formula

The compound of formula (1) is optimised according to the first aspect of the invention.

The compound of formula (1) may be prepared by a process according to the first aspect of the invention.

The compounds of formula (1) have an attractive dark cyan hue and are important colorants for use in the preparation of ink jet printing inks. They are to be gained in a good balance of solubility, storage stability and water and light resistance. In particular, they exhibit excellent light and ozone resistance. And they can be prepared from inexpensive intermediates, avoiding the complex process and expense of preparing some of the more complex phthalocyanine dyes.

In a fourth aspect the present invention provides a composition comprising a compound of formula (1) according to the third aspect of the invention and a liquid medium. Preferred liquid media include water, mixtures of water and organic solvents and anhydrous organic solvents as described in the first aspect of the invention.

A fifth aspect of the invention provides paper, plastic, textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, especially paper, more especially clear, coated or treated paper, most especially photo-quality paper, printed by a method of the first aspect of the invention with a composition of the second or fourth aspect of the invention or with a compound of the third aspect of the invention.

A sixth aspect of the invention provides an ink jet printer cartridge comprising a chamber and an ink, wherein the ink is in the chamber and the ink is as defined in the second or fourth aspects of the invention.

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

Example 1

The following dyes were prepared, where x was 0.8, (y + z) was 3.2:

step 1

Preparation:

copper phthalocyanine (118.7 g: molar ratio 1) was added in portions to a stirred mixture of chlorosulfonic acid (310 ml: molar ratio 23) and phosphorus oxychloride (37.8 ml: molar ratio 2) while maintaining the temperature in the range of 50 ℃ to 60 ℃. The mixture was gradually heated to 140 ℃ and stirred for 3 hours while maintaining this temperature. The reaction mixture was then poured into a mixture of ice (3Kg), water (1400ml) and NaCl (160 g). The precipitate formed was collected by filtration under reduced pressure, washed with 3% brine (500ml), and then used in step 2.

Step 2

Preparation of the title dye:

water (2L), ethanolamine (24.6g, mol 2) and 35% ammonia solution (20 g: mol 2) were mixed in a 5L beaker and then placed in an ice bath (pH 11.5, temperature 8 ℃). The phthalocyanine sulfonylchloride paste obtained in the above step 1 (molar ratio 1) was slowly added to the mixture while keeping the temperature below 5 ℃, and a 10% NaOH (V/V) solution was added to maintain the pH at 8. The reaction mixture was left overnight at room temperature and then heated at 40 ℃ for 4 hours. 50% NaCl (W/V) solution was added and the resulting precipitate was collected by filtration under reduced pressure and dialyzed to remove the salt to give the title dye, wherein x was 0.8 and (y + z) was 3.2.

Examples 2 to 9

Removing POCl₃The process of example 1 was repeated except that the molar ratios of ethanolamine and ammonia were as shown in Table 1.

Examples 10 to 16

Step 1

Except for the POCl used in the examples₃The method of example 1 and step 1 was repeated except for the molar ratio shown in Table 1.

Step 2

Water (1L) and ethanolamine (12g, mole ratio 1) were mixed and then placed in an ice bath. Phthalocyanine sulfonyl chloride paste (mole ratio 1) prepared as described in step 1 was slowly added to the mixture while maintaining the temperature below 5 deg.C, and 10% ammonia (V/V) solution was added to maintain the pH at 8. The reaction mixture was left overnight at room temperature and then heated at 40 ℃ for 4 hours. NaCl (20% W/V) solution was added, and the resulting precipitate was collected by filtration under reduced pressure and dialyzed to remove salts to obtain phthalocyanine dyes as described in examples 10 to 16 of Table 1 below.

TABLE 1

Examples	POCl3(molar ratio)	Ethanolamine (molar ratio)	Ammonia (molar ratio)	x	y+z
						2	2	4	2	0.1	4.0
3	2	6	2	0.1	4.0
						4	2	2	4	1.1	3.0
5	2	2	6	1.0	3.0
						6	2.5	2	4	0.4	3.4
7	2.5	4	2	0.2	3.6
						8	2.5	2	6	0.2	3.4
9	2.5	2	2	0.6	3.2
						10	1.5	1	AR	1.3	2.8
11	2	1	AR	0.8	3.2
						12	2.5	1	AR	1.4	2.6
13	3	1	AR	0.8	3.2
						14	3.5	1	AR	0.4	3.6
15	3.8	1	AR	0.4	3.8
						16	1	1	AR	0.7	3.4

AR-indicates that step (b) requires adjustment of pH to 8.0.

Comparative examples

Phthalocyanine dye:

prepared as described in example 1 of US6,149,722, which is incorporated herein by reference.

Examples 17 to 33

Preparation of inks 1 to 16

The compounds of examples 1-16 (3.5g) were dissolved in 100ml of a solution prepared from 2-pyrrolidone/thiodiglycol/Sufynol^TM465 in a liquid medium in a weight ratio of 5: 1. In Table 2 below, ink 1 contains the compound of example 1, ink 2 contains the compound of example 2, and so on.

Preparation of comparative inks

The compound of comparative example (3.5g) was dissolved in 100ml of a solution prepared from 2-pyrrolidone/thiodiglycol/Sufynol^TM465 in a liquid medium in a weight ratio of 5: 1.

Example 34

Ozone resistance

Using Canon 5800^TMThe IJ printer prints the inks of examples 1-16 and the comparative ink on various papers. The stability of the printed substrates to ozone was then evaluated using an ozone Test chamber from Hamcaden Test Equipment. The test was carried out in the presence of 1ppm ozone at 40 ℃ and 50% relative humidity for 24 hours. Ozone resistance was evaluated by comparing the difference in optical density before and after exposure of the printed ink to ozone with Gretag MacBeth Spectrolino. Thus, the lower the% OD loss, the stronger the ozone resistance. The results are shown in table 2 below and clearly show that inks based on the compounds of the present invention show good ozone resistance.

TABLE 2

Printing ink	Base material	% OD loss
			Ink 1	HP Premium Plus	2
Ink 1	Canon PR101	48
			Ink 1	SEC Premium Photo	53
Ink 2	HP Premium Plus	0
			Ink 2	Canon PR101	27
Ink 2	SEC Premium Photo	21
			Ink 3	HP Premium Plus	0
Ink 3	Canon PR101	27
			Ink 3	SEC Premium Photo	12
Ink 4	HP Premium Plus	2

Ink 4	Canon PR101	53
			Ink 4	SEC Premium Photo	54
Ink 5	HP Premium Plus	3
			Ink 5	Canon PR101	52
Ink 5	SEC Premium Photo	45
			Ink 6	HP Premium Plus	2
Ink 6	Canon PR101	39
			Ink 6	SEC Premium Photo	38
Ink 7	HP Premium Plus	3
			Ink 7	Canon PR101	30
Ink 7	SEC Premium Photo	28
			Ink 8	HP Premium Plus	2
Ink 8	Canon PR101	33
			Ink 8	SEC Premium Photo	33
Ink 9	HP Premium Plus	-1
			Ink 9	Canon PR101	41
Ink 9	SEC Premium Photo	41
			Ink 10	HP Premium Plus	2
Ink 10	Canon PR101	43
			Ink 10	SEC Premium Photo	45
Ink 11	HP Premium Plus	1
			Ink 11	Canon PR101	37
Ink 11	SEC Premium Photo	39
			Ink 12	HP Premium Plus	4
Ink 12	Canon PR101	55
			Ink 12	SEC Premium Photo	56
Ink 13	HP Premium Plus	3

Ink 13	Canon PR101	23
			Ink 13	SEC Premium Photo	19
Ink 14	HP Premium Plus	0
			Ink 14	Canon PR101	17
Ink 14	SEC Premium Photo	12
			Ink 15	HP Premium Plus	1
Ink 15	Canon PR101	15
			Ink 15	SEC Premium Photo	7
Ink 16	HP Premium Plus	2
			Ink 16	Canon PR101	28
Ink 16	SEC Premium Photo	25
			Comparative inks	HP Premium Plus	4
Comparative inks	Canon PR101	71
			Comparative inks	SEC Premium Photo	64

Additional ink

The inks described in tables A and B can be prepared using the compounds prepared in examples 1-16. The numbers quoted in the second column immediately above refer to the parts of the relevant ingredient and all parts are by weight. The ink may be applied to the paper by thermal or piezoelectric ink jet printing.

The following abbreviations are used in tables a and B:

PG ═ propylene glycol

DEG ═ diethylene glycol

NMP ═ N-methylpyrrolidone

DMK ═ acetone

IPA (isopropyl alcohol)

MEOH ═ methanol

2P ═ 2-pyrrolidone

MIBK ═ methyl isobutyl ketone

P12 ═ 1, 2-propanediol

BDL ═ 2, 3-butanediol

CET ═ hexadecylammonium bromide

PHO＝Na₂HPO₄And

TBT ═ tert-butanol

TDG (thiodiglycol)

TABLE A

Examples	Dye content	Water (W)	PG	DEG	NMP	DMK	NaOH	Sodium stearate	IPA	MEOH	2P	MIBK
													1	2.0	80	5		6	4					5
2	3.0	90		5	5		0.2
													3	10.0	85	3		3	3				5	1
4	2.1	91		8								1
													5	3.1	86	5					0.2	4			5
6	1.1	81			9		0.5	0.5			9
													7	2.5	60	4	15	3	3			6	10	5	4
8	5	65		20					10
													9	2.4	75	5	4		5				6		5
10	4.1	80	3	5	2	10		0.3
													11	3.2	65		5	4	6			5	4	6	5
12	5.1	96								4
													13	10.8	90	5						5
14	10.0	80	2	6	2	5			1		4
													15	1.8	80		5							15
16	2.6	84			11						5
													14	3.3	80	2			10				2		6
15	12.0	90				7	0.3		3
													14	5.4	69	2	20	2	1					3	3
15	6.0	91			4						5

TABLE B

Examples	Dye content	Water (W)	PG	DEG	NMP	CET	TBT	TDG	BDL	PHO	2P	PI2
													1	3.0	80	15			0.2					5
2	9.0	90		5						1.2		5
													3	1.5	85	5	5		0.15	5.0	0.2
4	2.5	90		6	4					0.12
													5	3.1	82	4	8		0.3						6
6	0.9	85		10					5	0.2
													7	8.0	90		5	5			0.3
8	4.0	70		10	4				1		4	11
													9	2.2	75	4	10	3				2		6
10	10.0	91			6						3
													11	9.0	76		9	7		3.0			0.95	5
12	5.0	78	5	11							6
													13	5.4	86			7						7
14	2.1	70	5	5	5	0.1	0.2	0.1	5	0.1	5
													15	2.0	90		10
16	2	88						10
													14	5	78			5			12			5
15	8	70	2		8			15			5
													14	10	80						8			12
15	10	80		10

Claims (19)

1. A method of forming an image on a substrate, the method comprising applying to the substrate via an ink jet printer a composition comprising:

(a) a compound of formula (1) or a salt thereof:

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or methyl;

R⁴is unsubstituted C_1-4-a hydroxyalkyl group;

x is greater than 0 and less than 1.2;

y and z are both greater than 0; and is

The sum of x + y + z is 2.4-4.5; and

(b) a liquid medium.

2. The method of claim 1, wherein R in the compound of formula (1)¹、R²And R³Are both hydrogen.

3. The method of claim 1, wherein R in the compound of formula (1)⁴Is C₂-hydroxyalkyl groups.

4. A process according to any one of claims 1 to 3 wherein in the compound of formula (1) x is greater than 0.05 and less than 1.0.

5. A process according to any one of claims 1 to 3 wherein in the compound of formula (1) x is greater than 0.05 and less than 0.5.

6. A composition, comprising:

(a) a compound of formula (1) or a salt thereof:

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or methyl;

R⁴is unsubstituted C_1-4-a hydroxyalkyl group;

x is greater than 0 and less than 1.2;

y and z are both greater than 0; and is

The sum of x + y + z is 2.4-4.5; and

(b) a liquid medium comprising water and an organic solvent or an anhydrous organic solvent.

7. The composition of claim 6, wherein R in the compound of formula (1)¹、R²And R³Are both hydrogen.

8. The composition of claim 6, wherein R in the compound of formula (1)⁴Is C₂-hydroxyalkyl groups.

9. The composition of any one of claims 6-8, wherein x in the compound of formula (1) is greater than 0.05 and less than 1.0.

10. The composition of any one of claims 6-8, wherein x in the compound of formula (1) is greater than 0.05 and less than 0.5.

11. A compound of formula (1) or a salt thereof:

formula (1)

Wherein:

m is copper or nickel;

pc represents a phthalocyanine nucleus of formula (2);

formula (2)

R¹、R²And R³Independently is hydrogen or methyl;

R⁴is unsubstituted C_1-4-a hydroxyalkyl group;

x is greater than 0 and less than 1.0;

y and z are both greater than 0; and is

The sum of x + y + z is 2.4-4.5.

12. The compound of claim 11, wherein R in the compound of formula (1)¹、R²And R³Are both hydrogen.

13. The compound of claim 11, wherein R in the compound of formula (1)⁴Is C₂-hydroxyalkyl groups.

14. The compound of any one of claims 11-13, wherein x in the compound of formula (1) is greater than 0.05 and less than 0.5.

15. A composition comprising a compound of formula (1) according to any one of claims 11 to 14 and a liquid medium.

16. A paper, plastic, textile, metal or glass material printed by the method of any one of claims 1 to 5.

17. A paper, plastic, textile, metal or glass material printed with a composition according to any one of claims 6 to 10 or 15.

18. A paper, plastic, textile, metal or glass material printed with a compound according to any one of claims 11 to 14.

19. An ink jet printer cartridge comprising a chamber and an ink, wherein the ink is within the chamber and the ink is a composition as defined in any one of claims 6 to 10 or 15.