HK1097284B

HK1097284B - Phthalocyanines and their use in ink-jet printers

Info

Publication number: HK1097284B
Application number: HK07104020.9A
Authority: HK
Inventors: Prakash Patel
Original assignee: Fujifilm Imaging Colorants Limited
Priority date: 2003-07-18
Filing date: 2004-07-02
Publication date: 2009-07-31

Description

Phthalocyanine dyes and their use in ink jet printers

The invention relates to a composition, a dye, a printing process, a printing substrate and an ink jet printer cartridge.

Ink jet printing is a non-impact printing technique in which the nozzle is not in contact with the substrate and ink droplets are ejected through a fine nozzle onto the substrate.

Color inkjet printers typically use four color inks: magenta, yellow, cyan, and black. Additional colors can be obtained using different combinations of these inks. The colorants used must therefore be capable of forming inks of a specific, precise hue in order to obtain optimum print quality. This can be achieved by mixing the colorants but is best achieved by using a single colorant having the exact hue desired.

With the development of high-definition digital cameras and inkjet printers, it has become more common to output photographs using inkjet printers. This avoids the expense of conventional silver chloride photographs and provides a quick and convenient way of printing.

Despite the many advantages of ink jet printers compared to other printing and image development, there are still technical challenges to be solved. For example, where the need for ink colorants is contradictory, it is desirable that the colorant be soluble in the ink medium on the one hand, and not flow out too quickly or smear the paper when printing on the paper on the other hand. After printing, the ink needs to dry quickly to avoid sticking together of the paper, but should not form a crust over the fine nozzles used in the printer. Storage stability is also important to avoid the formation of particles that can clog the fine nozzles used in the printer. In addition, it is desirable that the resulting image does not fade rapidly upon exposure to light or common oxidizing gases such as ozone.

Most cyan colorants used in ink-jet printing are based on phthalocyanines, and the problems of fading and hue change of such dyes are particularly pronounced.

The present invention therefore provides a composition comprising:

(a) a major dye component which is a mixture of phthalocyanine dyes of formula (1) and salts thereof:

wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or optionally substituted C_1-4An alkyl group;

R³is H or optionally substituted hydrocarbyl; and

R⁴is an optionally substituted hydrocarbyl group; or

R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted aliphatic or aromatic ring system;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

the sum of (x + y + z) is 4; and is

The substituents indicated by x, y and z are attached only in the beta-position of the phthalocyanine ring; and

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

Phthalocyanine dyes containing sulfo, sulfamoyl and substituted sulfamoyl substituents are usually prepared by sulfonation of phthalocyanine pigments followed by chlorination and then amination/amidation. The product of this reaction is a complex mixture containing sulfo, sulfamoyl and substituted sulfamoyl substituents at any sensitive (refractory) position on the phthalocyanine ring (see, for example, Schofield, J and Asaf, M, Journal of chromatography, 1997, 770, page 345-348).

Having sulfo and sulfamoyl substituents bound to the phthalocyanine ringThe phthalocyanine of formula (1) in the beta position of (A) can be prepared by any known method of the prior art, and in particular in a suitable nitrogen source (if desired), a copper salt or a nickel salt (e.g. CuCl)₂) And bases (e.g. 1, 8-diazabicyclo [5.4.0 ]]Undec-7-ene (DBU)) by cyclization of a suitable β -sulfo substituted phthalic acid, phthalonitrile, iminoisoindoline, phthalic anhydride, phthalimide or phthalamide followed by chlorination and then amination/amidation.

The phthalocyanine dyes of formula (1) with sulfo, sulfamoyl and substituted sulfamoyl substituents attached in the beta position of the phthalocyanine ring can preferably be prepared by reacting the phthalocyanine dye with a nitrogen source, such as urea, a copper salt or a nickel salt, such as CuCl₂) And bases (e.g. 1, 8-diazabicyclo [5.4.0 ]]Undec-7-ene (DBU)) in the presence of a catalyst to cyclize the 4-sulfo-phthalic acid to yield the phthalocyanine β -tetrasulfonic acid. Subsequent chlorination of the phthalocyanine beta-tetrasulfonic acid, the sulfonyl chloride group thus formed being reacted with a compound of the formula HNR¹R²And HNR³R⁴Compound (wherein R¹、R²、R³And R⁴As defined above). The reaction is preferably carried out in water at a pH above 7. The reaction is usually carried out at 30-70 ℃ and is usually completed in less than 24 hours. Of the formula HNR¹R²And HNR³R⁴The compounds may be used as a mixture or added sequentially.

A plurality of formula HNRs¹R²And HNR³R⁴The compounds are commercially available, for example ammonia and metanilic acid, others can be readily prepared by the skilled artisan using methods well known in the art.

The ratio of sulfo to sulfamoyl substituents can be varied depending on the amount and nature of chlorinating agent used, the formula HNR used¹R²And HNR³R⁴The relative amounts of the compounds and the reaction conditions in the two reactions.

The skilled person expects the product of these reactions to be a dispersed mixture (dispersemixure) such that the values x, y and z represent the average values of the groups in the mixture.

When phthalocyanine tetrasulfonic acid is an intermediate of the dye of formula (1) in the scheme, it may be reacted with any suitable chlorinating agent for chlorination.

Preferably, the chlorination is carried out by treating the phthalocyanine tetrasulfonic acid with chlorosulfonic acid, preferably in the presence of an acid halide such as thionyl chloride, sulfuryl chloride, phosphorus pentachloride, phosphorus oxychloride and phosphorus trichloride.

Preferably, M is Cu.

In a first preferred embodiment, R is preferred¹、R²And R³Independently H or methyl, more preferably R¹、R²And R³Are all H, R⁴Is an optionally substituted aryl group, in particular an optionally substituted phenyl or naphthyl group. More preferably R⁴Is optionally substituted phenyl, in particular phenyl which contains at least one sulfo, carboxy or phosphono substituent and has further optional substituents. Particular preference is given to R⁴Phenyl containing a single sulfo, carboxy or phosphono substituent is especially phenyl containing a single sulfo substituent.

In a second preferred embodiment, R¹And R²Independently H or methyl, more preferably R¹And R²Are all H, R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted mono-, bi-or tricyclic aliphatic or aromatic ring. More preferably R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 3-8 membered aliphatic or aromatic ring. Particular preference is given to R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 5-or 6-membered aliphatic or aromatic ring. From R³And R⁴The optionally substituted aromatic or aliphatic ring formed with the nitrogen atom to which it is attached may contain at least one other heteroatom. Examples of preferred ring systems include imidazole, pyrazole, pyrrole, benzimidazole, indole, tetrahydro (iso) quinoline, decahydro (iso) quinoline, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, indoline, isoindoline, thiazolidine and morpholine.

In a third embodiment, R¹And R²Independently H or methyl, more preferably R¹And R²Are all H; r³Is H or optionally substituted alkyl, preferably optionally substituted C_1-8Alkyl, more preferably optionally substituted C_1-4Alkyl radical, R⁴Is optionally substituted alkyl, preferably optionally substituted C_1-8Alkyl, more preferably optionally substituted C_1-4An alkyl group.

In a third preferred embodiment R is particularly preferred¹And R²Is H, R³Is H or contains at least one element selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4Alkyl radical, R⁴Is at least one selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group.

Can be at R¹、R²And R³(in a first preferred embodiment) and in R¹、R²、R³And R⁴Preferred optional substituents present (in a third preferred embodiment) are independently selected from:

optionally substituted alkoxy (preferably C)_1-4Alkoxy), optionally substituted aryl (preferably phenyl), optionally substituted aryloxy (preferably phenoxy), optionally substituted heterocycle, polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), carboxyl, phosphono, sulfo, nitro, cyano, halogen, ureido, -SO₂F. Hydroxy, ester (ester), -COR^a、-CONR^aR^bCarboxylic acid esters (carboxyester), sulfones (sulfone) and-SO₂NR^aR^bWherein R is^aAnd R^bEach independently of the other being H or optionally substituted alkyl (especially C)_1-4-an alkyl group). R^aAnd R^bOptional substituents of (A) may be selected from those described for R¹、R²And R³A substituent of (1).

In a first preferred embodiment may be at R⁴Or in a second preferred embodiment from R³And R⁴Preferred optional substituents present on the ring formed with the nitrogen atom to which they are attached are independently selected from: optionally substituted alkyl (preferably C)_1-4-alkyl), optionally substituted alkoxy (preferably C)_1-4Alkoxy), optionally substituted aryl (preferably phenyl), optionally substituted aryloxy (preferably phenoxy), optionally substituted heterocycle, polyalkylene oxide (preferably polyethylene oxide or polypropylene oxide), carboxyl, phosphono, sulfo, nitro, cyano, halogen, ureido, -SO₂F. Hydroxy, ester, -NR^aR^b、-COR^a、-CONR^aR^b、-NHCOR^aCarboxylic acid esters, sulfones and-SO₂NR^aR^bWherein R is^aAnd R^bEach independently of the other being H or optionally substituted alkyl (especially C)_1-4-an alkyl group). R^aAnd R^bOptional substituents of (A) may be selected from those described for R⁴A substituent of (1).

Preferably x is 0.5 to 3.5.

Preferably, y is 0.5 to 3.5.

Preferably z is 0.5-3.5.

Particular preference is given to dyes of the formula (1) in which x is from 0.5 to 3.5, y is from 0.5 to 3.5 and z is from 0.5 to 3.5.

The preferred mixtures of dyes of formula (1) in the first embodiment are mixtures of phthalocyanine dyes of formula (2) and salts thereof:

wherein:

m is Cu;

pc represents a phthalocyanine nucleus of the formula;

R¹、R²and R³Independently is H or methyl;

R⁴is phenyl containing at least one sulfo, carboxy or phosphono substituent and having other optional substituents in addition to amino or substituted amino;

x is 0.5-3.5;

y is 0.5 to 3.5;

z is 0.5-3.5;

the sum of (x + y + z) is 4; and the substituents indicated by x, y and z are attached only in the beta-position of the phthalocyanine ring.

R may be present in the dyes of formula (2)⁴The other optional substituents on (a) are independently selected from R exemplified for the dyes of formula (1)⁴A substituent of (1).

The preferred mixtures of dyes of formula (1) in the third embodiment are mixtures of phthalocyanine dyes of formula (3) and salts thereof:

wherein:

m is Cu;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

R³is H, methyl or contains at least one element selected from-SO₃H. -COOH or-PO₃H₂Acid of (2)C of a substituent_1-4Alkyl radical

R⁴Independently of at least one element selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group;

x is 0.5-3.5;

y is 0.5 to 3.5;

z is 0.5-3.5;

the sum of (x + y + z) is 4; and the substituents indicated by x, y and z are attached only in the beta position of the phthalocyanine ring.

In the dyes of formula (1) it is preferred that the alpha position of the phthalocyanine ring is unsubstituted, i.e. its substituent is hydrogen.

It is likewise preferred that the dyes of formula (1) do not contain fibre-reactive groups. The term "fibre-reactive group" is well known in the art and is described in e.g. EP 0356014 a 1. The fiber-reactive groups are capable of reacting with hydroxyl groups present in the cellulosic fibers or amino groups present in natural fibers under suitable conditions to form covalent bonds between the fibers and the dye. As examples of fiber-reactive radicals which are excluded from the dyes of the formula (1), mention may be made of aliphatic sulfonyl radicals having a sulfate group in the beta position with a sulfur atom (for example. beta. -sulfato-ethylsulfonyl), the alpha, beta-unsaturated acyl radicals of aliphatic carboxylic acids (for example the acyl radicals of acrylic acid,. alpha. -chloro-acrylic acid,. alpha. -bromoacrylic acid, propiolic acid, cis-butenedioic acid and mono-and dichlorocis-butenedioic acid) and the acyl radicals of acids containing substituents which react with cellulose in the presence of a base, for example the radicals of halogenated aliphatic acids, such as chloroacetic acid, beta-chloro-and beta-bromopropionic acid, alpha, beta-dichloro-and dibromopropionic acid, or the radicals of vinylsulfonyl-or beta-chloroethylsulfonyl-or beta-sulfatoethyl-sulfonyl-endo-methylenecyclohexanecarboxylic acid. Other examples of cellulose-reactive groups are tetrafluorocyclobutylcarbonyl, trifluorocyclobutenylcarbonyl, tetrafluorocyclobutylvinylcarbonyl, trifluorocyclobutenylvinylcarbonyl; an activated halogenated 1, 3-dicyanobenzene group; and heterocyclic groups containing 1, 2 or 3 nitrogen atoms in the heterocyclic ring and having at least one cellulose-reactive substituent on a carbon atom of the ring, such as halotriazines.

The acid or base groups, in particular the acid groups, in the dyes of formula (1) are preferably in the form of salts. Thus, the structural formulae presented herein include dyes in free acid and salt forms.

Preferred salts are alkali metal salts (particularly lithium, sodium and potassium), ammonium and substituted ammonium salts (including quaternary ammonium, e.g., (CH)₃)₄N⁺) ) and mixtures thereof. Sodium, lithium, ammonium and volatile amines (amines) are particularly preferred, more particularly the sodium salt. The dyes may be converted to salts using known techniques.

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

When the preferred route (as described above) is used for the synthesis of the dyes of formula (1), the ammonium salt is predominantly formed. However, any known technique can be used to convert the ammonium to other cations such as acidification, optionally followed by dialysis, followed by addition of an alternative cation (e.g., addition of an alkali metal hydroxide, ammonium salt or amine) to remove the original cation. Ion exchange resins and reverse osmosis are other well known techniques for cation exchange.

When the liquid medium (b) comprises a mixture of water and an organic solvent, it is preferred that the weight ratio of water to organic solvent is from 99: 1 to 1: 99, more preferably from 99: 1 to 50: 50, especially from 95: 5 to 80: 20.

Preferably, 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: 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 ketoalcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscible ethers, preferably tetrahydrofuranAnd dioxane; diols, preferably diols having 2 to 12 carbon atoms, such as 1, 5-pentanediol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, and thiodiglycol; oligo-and polyalkylene glycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1, 2, 6-hexanetriol; mono C of diols_1-4Alkyl ethers, preferably mono C of glycols 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) ethoxyethanol, 2- [2- (2-ethoxyethoxy) ethoxyethanol]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. Preferably the liquid medium comprises water and two or more, especially 2 to 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_1-4Alkyl ethers and C_1-4Alkyl ethers, more preferably mono C of glycols having 2 to 12 carbon atoms_1-4Alkyl ethers, in particular 2-methoxy-2-ethoxy-2-ethoxyethanol.

Examples of suitable other 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 425,150 a.

When the liquid medium comprises an anhydrous organic solvent (i.e. less than 1% by weight of water), it is preferred that the solvent has a boiling point in the range 30 to 200 deg.C, more preferably 40 to 150 deg.C, especially 50 to 125 deg.C. The organic solvent may be immiscible with water, miscible with water or a mixture of these solvents. Preferred water-miscible organic solvents are any of the water-miscible solvents mentioned above and mixtures thereof. Preferably immiscible with waterThe solvent of (b) includes, for example, aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinated hydrocarbons, preferably CH₂Cl₂(ii) a Ethers, preferably diethyl ether and mixtures thereof.

When the liquid medium comprises an organic solvent immiscible with water, it is preferred to include a polar solvent, as polar solvents increase the solubility of the dye in the liquid medium. Examples of the polar solvent include C_1-4An alcohol.

In the above-mentioned preferred cases, it is particularly preferred when the liquid medium is an anhydrous organic solvent comprising a ketone (in particular methyl ethyl ketone) and/or an alcohol (in particular C)_1-4Alkanols, more particularly ethanol or propanol).

The anhydrous organic solvent may be a single organic solvent or a mixture of two or more organic solvents. When the liquid medium is an organic solvent free from water, it is preferably a mixture of 2 to 5 different organic solvents. The liquid medium can thus be selected so as to adjust well the drying characteristics and storage stability of the ink.

Liquid media comprising anhydrous organic solvents are particularly useful in the following cases: fast drying is desirable, especially when printing on hydrophobic and non-absorbent substrates such as plastics, metals and glass.

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

Although not generally necessary, other colorants may also be added to the ink to improve hue and performance. Examples of such colorants include: c.i. direct yellow 86, 132, 142 and 173; c.i. direct blue 307; c.i. food black 2; c.i. direct blacks 168 and 195; acid yellow 23 and any of the dyes sold by Seiko Epson Corporation, Hewlett Packard Company, canoninc.

If the composition of the invention comprises a phthalocyanine dye other than that of formula (1), it is preferred that at least 70%, more preferably at least 80%, especially at least 90%, more especially at least 95% and especially at least 99% of the total weight of the phthalocyanine dye is of formula (1) wherein the substituents indicated by x, y and z are attached in the beta position to the phthalocyanine ring.

Preferably the composition of the invention is an ink suitable for ink jet printers. Suitable inks for ink jet printers are inks which can be repeatedly ejected from an ink jet print head without causing the clogging of the fine nozzles.

Inks suitable for ink jet printers preferably have a viscosity at 25 ℃ of less than 20cP, more preferably less than 10cP, especially less than 5 cP.

The surface tension of the ink is preferably 20 to 65 dynes/cm, more preferably 30 to 60 dynes/cm.

Preferably the ink suitable for ink jet printers comprises a total amount of divalent and trivalent metal ions (excluding any divalent and trivalent metal ions associated with the colorant of formula (1) or any other component of the ink) of less than 500ppm, more preferably less than 250ppm, especially less than 100ppm, more especially less than 10 ppm.

Preferably the ink suitable for ink jet printers is filtered using a filter having an average pore size of less than 10 μm, more preferably less than 3 μm, especially less than 2 μm, more especially less than 1 μm. Filtration removes particulate matter that can clog fine nozzles in many ink jet printers.

Preferably the total amount of halide ions, especially chloride ions, in the ink suitable for ink jet printers is less than 500ppm, more preferably less than 250ppm, especially less than 100ppm, more especially less than 10 ppm.

Preferred compositions comprise:

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

(b)70-99.99 parts of liquid medium;

wherein all parts are parts by weight.

The preferred parts (a) + (b) are 100.

The fraction of component (a) is preferably from 0.1 to 20, more preferably from 0.5 to 15, in particular from 1 to 5. The part of component (b) is preferably 99.9 to 80, more preferably 99.5 to 85, especially 99 to 95 parts.

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 that can be used to prepare more dilute inks and reduces the chance of dye precipitation if the liquid medium evaporates during storage.

The inks can be incorporated into an ink jet printer as high concentration cyan inks, low concentration cyan inks, or both high and low concentration inks. In the latter case, the sharpness and quality of the printed image may be improved. Accordingly, the present invention also provides a composition (preferably an ink) wherein the amount of component (a) is 2.5 to 7 parts, more preferably 2.5 to 5 parts (high concentration ink) or the amount of component (a) is 0.5 to 2.4 parts, more preferably 0.5 to 1.5 parts (low concentration ink).

In a second aspect the present invention provides a mixture of dyes of formula (4) and salts thereof:

wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or optionally substituted C_1-4An alkyl group;

R³is H or optionally substituted C_1-8An alkyl group;

R⁴is optionally substituted C_1-8Alkyl or phenyl containing at least one sulfo, carboxy or phosphono substituent and having other optional substituents in addition to amino or substituted amino; or

R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 5-or 6-membered alicyclic or aromatic ring;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

In the dye of formula (4) the alpha position on the phthalocyanine ring is unsubstituted, i.e. contains H.

M、R¹、R²、R³、R⁴X, y and z are as described and preferred for the dye of formula (1) in the first aspect of the invention.

Preferably the mixture of dyes of formula (4) is a mixture of dyes of formula (2) or formula (3) and salts thereof as defined and preferred in the first aspect of the invention.

Also preferred is a mixture of dyes as described in the second preferred embodiment of the first aspect of the invention, wherein R¹And R²Independently H or methyl, more preferably R¹And R²Are all H, R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted mono-, bi-or tricyclic aliphatic or aromatic ring. More preferably R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 3-8 membered aliphatic or aromatic ring. Particular preference is given to R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 5-or 6-membered aliphatic or aromatic ring.

In the formula (2), is excellentR is selected⁴Is phenyl containing a single sulfo substituent.

Particular preference is given to dyes of the formula (2) in which R is¹、R²And R³Are both H and R⁴A single sulfo substituent meta to the bridged sulfamoyl group.

R⁴The other optional substituents of (A) may be selected from the above groups R⁴Preferred substituents are.

Preferably the mixture of dyes of formula (4) is free of fibre-reactive groups, wherein the fibre-reactive groups are as described in the first aspect of the invention.

The dyes of formula (4) have an attractive, intense cyan hue and are valuable colorants for the preparation of ink jet printing inks. The advantage is a good balance of solubility, storage stability, water and light resistance, especially ozone resistance.

In a third aspect of the present invention there is provided a composition comprising a principal dye component which is a mixture of phthalocyanine dyes of formula (4) as defined in the second aspect of the invention and water.

Preferably the composition of the third aspect of the invention is an ink suitable for use in an ink jet printer. Such an ink is as described in the first aspect of the invention.

The inks of the third aspect of the present invention may comprise other ingredients conventionally used in ink jet printing inks, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, kogation reducing additives and ionic or non-ionic surfactants.

Although not generally necessary, other colorants may also be added to the inks of the third aspect of the present invention to improve hue and performance. Examples of such colorants include: c.i. direct yellow 86, 132, 142 and 173; c.i. direct blue 307; c.i. food black 2; c.i. direct blacks 168 and 195; acid yellow 23 and any of the inkjet printer dyes sold by Seiko Epson Corporation, Hewlett packard company, Canon inc.

If the composition of the third aspect of the present invention comprises a phthalocyanine dye other than that of formula (4) then preferably at least 70% by weight, more preferably at least 80% by weight, especially at least 90% by weight, more especially at least 95% by weight and especially at least 99% by weight of the total weight of the phthalocyanine dye is a dye of formula (4) wherein the substituents indicated by x, y and z are attached in the beta position of the phthalocyanine ring.

In a fourth aspect of the invention there is provided a method of imaging a substrate by applying to the substrate an ink suitable for use in an ink jet printer as described in the first or third aspects of the invention by means of an ink jet printer.

Preferably the ink is applied by an ink jet printer which ejects drops of ink through an orifice onto the substrate. Preferred inkjet printers are piezoelectric inkjet printers and thermal inkjet printers. In a thermal ink jet printer, a programmed thermal pulse is applied to the ink in the ink cartridge through a resistor adjacent an orifice, whereby an ink droplet is ejected from the orifice directly onto the substrate during relative movement between the substrate and the orifice. In piezoelectric ink jet printers, the oscillation of small crystals causes ink to be ejected from small orifices. Or may be ejected by an electromechanical actuator connected to a movable paddle or piston as described in international patent application WO 00/48938 and international patent application WO 00/55089.

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

Preferred papers are plain or treated papers which are acidic, alkaline or neutral. Glossy paper is particularly preferred.

A fifth aspect of the invention provides a material printed using the composition of the first or third aspect of the invention, using the dye of the third aspect of the invention or by the method of the fourth aspect of the invention, preferably paper, plastic, textile, metal or glass, more preferably paper, a projection slide or a textile material, especially paper, more especially plain paper, coated paper or treated paper.

It is particularly preferred that the printed material of the fifth aspect of the invention is a photograph printed by the method of the fourth aspect of the invention.

A sixth aspect of the invention provides an ink jet printer cartridge comprising an ink reservoir and an ink, wherein the ink is in the reservoir and the ink is suitable for use in an ink jet printer, the ink being as defined in the first or third aspects of the invention. The ink cartridge may contain the high-concentration ink and the low-concentration ink according to the first aspect of the present invention in different ink storage chambers.

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

Example 1

Preparation of a dye of formula substituted only in the beta position, wherein x is 1.1 and (y + z) is 2.2:

analysis of the dye of formula (1)

The dye structure of formula (1) was confirmed by mass spectrometry. Elemental analysis was used to determine the ratio of x to y + z. It is therefore considered to be due to the presence of impurities when the sum of x + y + z is not exactly 4. The presence of these impurities and their effect on the estimated values of x, y and z are well known to those skilled in the art who believe that the value of x + y + z should not exceed 4 and process the experimentally determined values of x, y and z to represent the true ratio of the groups. It is not possible to distinguish the differences between the different sulfamoyl substituents for some dyes of the present invention using these methods. In these cases, x and y are either the sum of the two sulfamoyl groups, i.e. (y + z), or half of the total number of sulfamoyl groups detected, i.e. y ═ 1.4av, in the latter case y and z usually take the same value.

Step 1 beta position is substituted by 4-SO ₃ Preparation of H-substituted copper phthalocyanines

In a reaction vessel, the following components were: 4-sulfo-Potassium phthalate (56.8g), Urea (120g), CuCl₂(6.9g), ammonium molybdate (1.2g) and 1, 8-diazabicyclo [5.4.0]Undec-7-ene (DBU) (7.5g) were mixed.

The mixture was then temperature programmed (130 ℃/30 min, 150 ℃/30 min, 180 ℃/30 min, 220 ℃) over 2 hours and the melt formed was stirred at 220 ℃ for a further 2 hours.

The solid formed was extracted with hot water (4 × 200ml) and the extract was filtered to remove insoluble material.

The resulting filtrate was stirred at 60-70 ℃ followed by addition of sufficient sodium chloride to give a 7% brine solution. The stirring was continued and the precipitated solid was filtered, washed with 10% brine solution (200ml) and dried in vacuo. The resulting wet solid (77.6g) was slurried in acetone, filtered and dried first at room temperature and then at 50 ℃. Analysis showed 3.8 sulfo groups per phthalocyanine ring.

Step 2 beta position is substituted by 4-SO ₃ Chlorosulfonation of H-substituted copper phthalocyanines

To chlorosulfonic acid (69.9g) was added phosphorus oxychloride (6.99g) at 28 ℃. The sulfonated phthalocyanine product of step 1 (11.8g) was then added to the mixture over a period of 10-15 minutes while maintaining the temperature below 60 ℃. The reaction mixture was stirred at 50 ℃ for 15-20 minutes and slowly warmed to and maintained at 120 ℃ and 125 ℃ while stirring for 3 hours. At this end the reaction mixture was cooled and stirred at room temperature overnight.

The next day the reaction melt was poured into a water/ice/salt/HCl (50ml/150g/10g/2.5ml) mixture, with external cooling and additional ice added if necessary to keep the temperature below 0 ℃. The resulting suspension was stirred at 0 ℃ for 30 minutes then filtered, washed with ice-cooled acidified 10% brine solution (100ml) and dried in vacuo to give the product as a wet paste.

Step 3 preparation of the target product

The wet paste (33g) prepared in step 2 was added portionwise to a stirred solution of metanilic acid (4.15g), concentrated ammonia (0.8g) and cold water (200ml) over 10-15 minutes at 0-5 ℃. The resulting reaction mixture was stirred at 0-10 ℃ for 30 minutes while maintaining the pH above 8.5 by addition of 2M NaOH. The mixture was allowed to warm to above room temperature and stirred at pH 8.5 overnight. The mixture was then heated to 60-70 ℃, adjusted to pH 12 using 2M NaOH and stirred for 4 hours 30 minutes. The mixture was filtered and sodium chloride was added to the filtrate to give a 20% aqueous salt solution, followed by adjustment of the pH to less than 1 with concentrated hydrochloric acid. The precipitated solid was filtered, washed with acidified (i.e. pH less than 1) 20% sodium chloride solution (200ml) and dried in vacuo. The resulting wet paste was dissolved in deionized water at pH 8 and dialyzed to low conductivity. The product was subsequently filtered and dried at 70 ℃.

Example 2

Preparation of a dye substituted only in the beta position, where x is 1.5 and (y + z) is 3.4：

Steps 1 and 2 were carried out as in example 1.

Step 3 preparation of the target product

The wet paste prepared in step 2 (47g) was slurried in 200ml cold (5 ℃) water. To this suspension was added a solution of M-aminobenzenesulfonic acid (8.65g) having a pH of 6.5 to 7 and concentrated ammonia (s.g.0.88, 0.34ml) in 100ml of water, stirred for 2 hours while keeping the temperature below 10 ℃, and the pH was kept around 7 with 2M NaOH solution. The mixture was then allowed to warm to room temperature and stirred at pH 7.8 overnight. The next day the reaction mixture was warmed to 40 ℃ and stirred at pH 7-8 for 2 hours. At this end the reaction mixture was filtered and to the filtrate was added sodium chloride to give a 25% salt solution. The temperature was raised to 50-60 ℃ and stirred and then the pH was adjusted to less than 1 with concentrated hydrochloric acid, 5% sodium chloride was added and the precipitate formed was collected by filtration after vacuum drying. The precipitate was dissolved in deionized water at pH 7 and dialyzed to low conductivity. The product was then filtered and dried at 50-60 ℃.

Examples 3 to 23

Examples 3-23 were prepared in a similar manner to that described in example 1, except that in step 3 the amino compound shown in table 1 was used in place of metanilic acid and the molar equivalents of the amino compound and ammonia were adjusted as shown in table 1. Table 1 also shows the ratios of substituents indicated by x, y and z.

TABLE 1

Examples 24 and 25

Examples 24 and 25 were prepared in a similar manner to that described in example 1, except that in step 3 the amino compound shown in table 2 was used in place of metanilic acid and methylamine was used in place of ammonia. Table 2 also shows the ratios of substituents indicated by x, y and z.

TABLE 2

Examples	Amines as pesticides	Equivalent of amine	Equivalent of methylamine	x	y	z
Examples	Amines as pesticides	Equivalent of amine	Equivalent of methylamine	x	y	z	Example 24	HNCHCHSOH	3	0.5	0.2	0.6	2.9
Example 25	HNCHCHSOH	2	1	ND	ND	ND	Example 24	HNCHCHSOH	3	0.5	0.2	0.6	2.9

Example 26

Example 26 was prepared in a similar manner to that described in example 1, except that in step 3 the amino compound shown in table 3 was used in place of metanilic acid and dimethylamine was used in place of ammonia. Table 3 also shows the ratios of substituents indicated by x, y and z.

TABLE 3

Examples	Amines as pesticides	Equivalent of amine	Equivalent of dimethylamine	x	y	z
Examples	Amines as pesticides	Equivalent of amine	Equivalent of dimethylamine	x	y	z	Example 26	HNCHCHSOH	3	0.5	ND	ND	ND

In tables 2 and 3, ND means not detected (not determined).

Control dye 1

Control dye 1 is Pro-jet^TMCyan 1 is c.i. direct blue 199 from Avecia ltd. which is provided as a compound of the formula:

c.i. direct blue 199 is the most widely used cyan inkjet dye and is prepared by sulfonation and amination of phthalocyanine pigments and contains dyes substituted in both the alpha and beta positions.

Control dye 2

Control dye 2 was prepared as in example 1 of international patent application WO 99/67334 via sulfonation of a copper phthalocyanine pigment followed by amination/amidation, which resulted in a complex dye mixture of the general formula:

wherein the substituents are in the alpha and beta positions and wherein x is 2.7, y is 0.5 and z is 0.8.

Example 27

Preparation of inks 1 and 2 and control ink

The dyes of examples 1 and 2 and the dyes of comparative example 1 and comparative example 2 were converted into inks by dissolving 3g of the dye in 100ml of a liquid medium comprising:

thiodiglycol 5%

2-pyrrolidone 5%

Surfynol^TM465 1％

89% Water (all percentages are by weight)

And adjusting the pH of the ink to 8 with sodium hydroxide. Preferably, the ink composition has a viscosity of 1 to 3 cp. Surfynol^TM465 is a surfactant from Air Products ltd.

Ink jet printing

The ink and the control ink were filtered through a 0.45 micron nylon filter and then added to an empty print cartridge using a syringe.

The inks were then inkjet printed onto Epson Premium Glossyphotopper ("SECPM") and Canon PR101 Photopper ("PR 101").

Ozone resistance was determined by exposing 100% of the print to 1ppm ozone for 24 hours in a Hamcaden 903 ozone test chamber at 40 ℃ and 50% relative humidity. The ozone resistance of the printing ink was judged by the difference in optical density before and after exposure to ozone.

The lightfastness of the printed images was evaluated by determining the change in optical density after 100 hours of fading of the printed images in an Atlas Ci5000 Weatherometer.

The optical density was measured using a Gretag spectrophotometer with the following parameters:

measurement mode (geometry): 0 DEG/45 DEG

Spectral range: 400-700nm

Spectral spacing: 20nm

Light source: d65

Observation angle: 2 ° (CIE1931)

Density: ansi A

An external filter: is free of

Light and ozone resistance was assessed by the percent change in optical density (with lower values indicating higher fastness) and degree of fade of the print. The degree of fade is indicated by Δ E (with lower values indicating higher lightfastness). Δ E is defined as the overall change in CIE color coordinates L, a, b of the print and is given by the equation Δ E ═ Δ L (Δ L)²+Δa²+Δb²)^0.5And (4) showing. The results of light and ozone resistance are shown below.

Light resistance

	Delta EPR101	Optical Density loss% PR101	Delta ESEC PM	Optical Density loss% SECPM
	Delta EPR101	Optical Density loss% PR101	Delta ESEC PM	Optical Density loss% SECPM	Ink 1	7	5	2	3
Ink 2	17	21	6	12	Ink 1	7	5	2	3
Ink 2	17	21	6	12	Control ink 1	21	30	4	9
Control ink 2	20	29	5	13	Control ink 1	21	30	4	9

Ozone resistance

	Delta EPR101	Optical Density loss% PR101	Delta ESEC PM	Optical Density loss% SECPM
	Delta EPR101	Optical Density loss% PR101	Delta ESEC PM	Optical Density loss% SECPM	Ink 1	5	5	4	5
Ink 2	13	21	5	15	Ink 1	5	5	4	5
Ink 2	13	21	5	15	Control ink 1	51	51	19	28
Control ink 2	51	58	23	41	Control ink 1	51	51	19	28

It is apparent that the dyes of the present invention have improved ozone resistance and equal or superior light fastness compared to dyes substituted at both the alpha and beta positions.

Other inks

The inks described in tables a and B can be prepared using the dyes prepared in examples 1 and 2. The numbers quoted in the second column refer to the parts of the relevant component, all parts being by weight. These inks can be applied to paper by thermal or piezo ink jet printers.

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-ammonium bromide

PHO＝Na₂HPO₄

TBT ═ tert-butanol

TDG (thiodiglycol)

Claims

1. A composition, comprising:

formula (1)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

R³is H, methyl or contains at least one element selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group; and

R⁴is phenyl, phenyl containing at least one sulfo, carboxyl or phosphono substituent, C with a nitrogen-containing 6-membered heterocycle_1-4Alkyl radical, containing at least one element selected from the group consisting of-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group; or

R³And R⁴Together with the nitrogen atom to which they are attached represent a ring system selected from: imidazole, pyrazole, pyrrole, benzimidazole, indole, tetrahydro (iso) quinoline, decahydro (iso) quinoline, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, indoline, isoindoline, thiazolidine and morpholine;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

the sum of (x + y + z) is 4; and is

2. The composition of claim 1, comprising:

formula (1)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

the sum of (x + y + z) is 4; and is

The substituents indicated by x, y and z are attached only in the beta-position of the phthalocyanine ring; and the mixture of phthalocyanine dyes of formula (1) is obtained by a process comprising cyclisation of a suitable beta-sulfo-substituted phthalic acid, phthalonitrile, iminoisoindoline, phthalic anhydride, phthalimide or phthalamide in the presence of a suitable nitrogen source, a copper or nickel salt and a base, followed by chlorination and then amination/amidation; and

3. The composition of claim 1, comprising:

formula (1)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

the sum of (x + y + z) is 4; and is

The substituents indicated by x, y and z are only attached toThe beta-position of the phthalocyanine ring; and the mixture of phthalocyanine dyes of formula (1) is obtained by a process comprising cyclizing 4-sulfo-phthalic acid in the presence of a nitrogen source, a copper or nickel salt and a base to give a phthalocyanine β -tetrasulfonic acid, and subsequently chlorinating the phthalocyanine β -tetrasulfonic acid, the sulfonyl chloride group thus formed being reacted with a compound of formula HNR¹R²And HNR³R⁴Wherein R is¹、R²、R³And R⁴As defined above; and

4. The composition of claim 1, comprising:

formula (1)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus;

R¹and R²Independently is H or methyl;

R³is H or methyl;

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

the sum of (x + y + z) is 4; and is

5. The composition of claim 1 wherein M is Cu.

6. The composition of claim 1 wherein x is from 0.5 to 3.5, y is from 0.5 to 3.5, and z is from 0.5 to 3.5.

7. The composition of claim 1, wherein R¹、R²And R³Independently is H or methyl, R⁴Is phenyl, phenyl containing at least one sulfo, carboxy or phosphono substituent.

8. The composition of claim 1, wherein R⁴Is a phenyl group containing at least one sulfo, carboxy or phosphono substituent.

9. The composition of claim 1, wherein R⁴Is phenyl containing a single sulfo substituent.

10. The composition of claim 1, wherein R¹And R²Is H, R³Is H or contains at least one element selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4Alkyl radical, R⁴Is at least one selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group.

11. The composition of claim 1, wherein R¹And R²Is H.

12. The composition of claim 1, wherein R¹、R²And R³Is H, R⁴is-CH₂CH₂SO₃H。

13. The composition of claim 1, wherein R¹Is H, R²Is CH₃，R³Is H, R⁴is-CH₂CH₂SO₃H。

14. The composition of claim 1, wherein R¹And R²Is CH₃，R³Is H, R⁴is-CH₂CH₂SO₃H。

15. The composition of claim 1, wherein at least 70% of the total weight of the phthalocyanine dye is the dye of formula (1).

16. The composition of claim 15, wherein at least 90% of the total weight of the phthalocyanine dye is the dye of formula (1).

17. The composition of claim 1, wherein the dye of formula (1) is free of fiber-reactive groups.

18. The composition of claim 1, comprising:

(a)0.1 to 20 parts of the compound of formula (1); and

(b)80-99.9 parts of liquid medium;

wherein all parts are parts by weight, and the parts (a) + (b) are 100.

19. The composition of claim 18, comprising:

(a)0.5 to 15 parts of the compound of formula (1); and

(b)85-99.5 parts of liquid medium;

wherein all parts are parts by weight, and the parts (a) + (b) are 100.

20. The composition of claim 18, comprising:

(a)1-5 parts of a compound of formula (1); and

(b)95-99 parts of liquid medium;

wherein all parts are parts by weight, and the parts (a) + (b) are 100.

21. The composition of claim 1, wherein the liquid medium may comprise other components conventionally used in ink jet printing inks.

22. The composition of claim 1, wherein the composition is an ink suitable for use in an ink jet printer.

23. A mixture of dyes of formula (4) and salts thereof:

formula (4)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

R³is H, methyl or contain at leastOne is selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group;

R⁴is phenyl containing at least one sulfo, carboxyl or phosphono substituent, C having a nitrogen-containing 6-membered heterocyclic ring_1-4Alkyl radical, containing at least one element selected from the group consisting of-SO₃H. -COOH or-PO₃H₂And C without amino or substituted amino_1-4An alkyl group; or

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 3.8;

24. A mixture of dyes according to claim 23 and salts thereof, of formula (4):

formula (4)

Wherein:

m is Cu or Ni;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

R³is H, methyl or contains at least one element selected from-SO₃H、-COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group;

R⁴phenyl containing at least one sulfo, carboxyl or phosphono substituent, C with a nitrogen-containing 6-membered heterocycle_1-4Alkyl radical, containing at least one element selected from the group consisting of-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group; or

x is 0.1-3.8;

y is 0.1 to 3.8;

z is 0.1 to 38;

the sum of (x + y + z) is 4; and the substituents indicated by x, y and z are only attached in the beta-position of the phthalocyanine ring, and mixtures of phthalocyanine dyes of formula (1) are prepared by a process comprising cyclisation of a suitable beta-sulfo substituted phthalic acid, phthalonitrile, iminoisoindoline, phthalic anhydride, phthalimide or phthalamide in the presence of a suitable nitrogen source, a copper or nickel salt and a base, followed by chlorination and then amination/amidation.

25. A mixture of dyes according to claim 23 and salts thereof, which is a mixture of dyes of formula (2):

formula (2)

Wherein:

m is Cu;

pc represents a phthalocyanine nucleus of formula:

R¹、R²and R³Independently is H or methyl;

R⁴is phenyl containing at least one sulfo, carboxy or phosphono substituent;

x is 0.5-3.5;

y is 0.5 to 3.5;

z is 0.5-3.5;

the sum of (x + y + z) is 4; and substituents indicated by x, y and z are attached only to the beta-position of the phthalocyanine ring; and mixtures of phthalocyanine dyes of formula (1) are prepared by a process which comprises cyclisation of a suitable beta-sulfo-substituted phthalic acid, phthalonitrile, iminoisoindoline, phthalic anhydride, phthalimide or phthalamide in the presence of a suitable nitrogen source, a copper or nickel salt and a base, followed by chlorination and then amination/amidation.

26. A mixture of dyes according to claim 23 and salts thereof, of the formula (3):

formula (3)

Wherein:

m is Cu;

pc represents a phthalocyanine nucleus of formula:

R¹and R²Independently is H or methyl;

R³and R⁴Independently of at least one element selected from-SO₃H. -COOH or-PO₃H₂C of an acid substituent of_1-4An alkyl group;

x is 0.5-3.5;

y is 0.5 to 3.5;

z is 0.5-3.5;

27. A mixture of dyes and salts thereof as claimed in claim 23 wherein R¹And R²Is H.

28. A mixture of dyes and salts thereof as claimed in claim 23 wherein R¹、R²And R³Is H, R⁴is-CH₂CH₂SO₃H。

29. A mixture of dyes and salts thereof as claimed in claim 23 wherein R¹Is H, R²Is CH₃，R³Is H, R⁴is-CH₂CH₂SO₃H。

30. A mixture of dyes and salts thereof as claimed in claim 23 wherein R¹And R²Is CH₃，R³Is H, R⁴is-CH₂CH₂SO₃H。

31. A mixture of dyes and salts thereof as claimed in claim 23 wherein R¹And R²Independently is H or methyl, R³And R⁴Together with the nitrogen atom to which they are attached represent an optionally substituted 5-or 6-membered alicyclic or aromatic ring.

32. A mixture of dyes according to claim 23 which are free of fibre-reactive groups and salts thereof.

33. A composition comprising a mixture of phthalocyanine dyes of formula (4) as defined in claim 23 as a main dye component and water.

34. The composition of claim 33 which is an ink suitable for use in an ink jet printer.

35. A method of imaging on a substrate, the method comprising applying to the substrate a composition according to claim 22 or claim 34 using an ink jet printer.

36. A material utilising a composition according to any one of claims 1 to 22, 33 or 34 or a dye according to any one of claims 23 to 32.

37. The material of claim 36 which is a photograph printed using the method of claim 35.

38. An ink jet printer cartridge comprising an ink reservoir and an ink, wherein the ink is in the ink reservoir and the ink is according to claim 22 or claim 34.