CN101432371A

CN101432371A - Trisazo dyes, compositions and ink jet printing processes

Info

Publication number: CN101432371A
Application number: CNA200780015809XA
Authority: CN
Inventors: P·M·米斯特里
Original assignee: Fujifilm Imaging Colorants Ltd
Current assignee: Fujifilm Imaging Colorants Ltd
Priority date: 2006-05-09
Filing date: 2007-04-27
Publication date: 2009-05-13
Also published as: ATE517153T1; TW200801125A; GB0609086D0

Abstract

A compound selected from the group consisting of compounds of Formula (1 ) and compounds of Formula (2) or a salt thereof: wherein: A is a beta naphthyl group of formula (X), wherein * is the point of attachment to the azo group in Formula (1) or (2) p and q are each independently 0, 1 or 2 and the sum of p + q is not zero; B is optionally substituted phenylene or naphthylene; n is 0 or 1; and D is an optionally substituted pyrazolyl group. The compound or salt is useful in an ink for ink jet printing. Also provided are printing processes, ink compositions and ink-jet cartridges for use in an ink-jet printer and substrates printed using an ink-jet printer.

Description

Trisazo dye, composition and ink jet printing method

The present invention relates to compound, relate to composition and their purposes in press, is not only ink jet printing (" IJP ") especially.IJP is a kind of wherein ink droplet by thin nozzle ejection on matrix and do not make the nonimpact printing technology on nozzle and matrix basis.

For dyestuff that is used for IJP and printing ink, there is the performance requirement of multiple expectation.For example, expect that they provide the image of sharp, the non-plumage traceization with good absorbancy, water tolerance, light resistance are provided and in the presence of oxidizing gas pollutent (for example ozone), resist and fade.In the time of on being applied to matrix,, need printing ink dry rapidly usually, but the tip that they are not taken in injection nozzle form duricrust, because this will stop printer work in order to prevent to blur.Printing ink is storage-stable for a long time also, can not decompose or form the precipitation that may block thin nozzle.

JP10195320 has described the trisazo dye that has the pyrazolyl azo group and they application in paper and paper pulp are painted.

United States Patent (USP) 6,749,674 have described the metal complexes that contains the trisazo-molecule deutero-trisazo dye of (replacement) pyrazolyl azo part by optional.It is said special preferably copper title complex.

WO2005/052065 has described the non-metallic trisazo dye that contains (replacement) pyrazolyl azo part.

We find shockingly that now some non-metallic compound with betanaphthyl of (replacement) pyrazolyl azo part and sulfo group replacement provides the valuable dyestuff that is used for ink jet printing printing ink.

The compound of the formula that is selected from (1) compound and formula (2) compound or its salt is provided according to a first aspect of the invention:

Formula (1)

Formula (2)

Wherein:

A is the β naphthyl of formula X,

Formula X

Wherein ^*For with formula (1) or (2) in the tie point of azo group,

P and q are 0,1 or 2 and p+q's and be not zero independently of one another;

B is optional phenylene or the naphthylidene that replaces;

N is 0 or 1; With

D is the optional pyrazolyl that replaces.

A is the β naphthyl, and promptly it is connected on the azo group on the naphthyl ring β position.In the art, the β position also is called the 2-position.

Preferred A not by non-sulfo group (promptly-SO ₃H) group replaces.

Preferably in formula X, p and q are 0,1 or 2 independently of one another, and condition is (p+q)＜4 (are p+q's and be 1,2 or 3).More preferably p+q's and be 2.Most preferably p=1 and q=1.

Preferably may reside in optional substituting group on the B be selected from independently of one another hydroxyl, halogen, nitro, cyano group, carboxyl (promptly-COOH), sulfo group (promptly-SO ₃H), phosphino-(promptly-PO ₃H ₂), the optional amino that replaces (particularly has one or more C _1-4The amino of-alkyl), the optional amide group that replaces (C particularly _1-4Amido or phenyl amido, optional separately sulfo group or the carboxyl of having), the optional urea groups that replaces (particularly has one or two C _1-4The urea groups of-alkyl), carboxylicesters, the optional alkyl that replaces (C particularly _1-6-alkyl), the optional cycloalkyl that replaces (C particularly _1-6-cycloalkyl), the optional alkoxyl group that replaces (C particularly _1-6-alkoxyl group), optional aryl that replaces or heteroaryl (particularly phenyl and naphthyl), the optional aryloxy that replaces, azo (particularly arylazo base, phenylazo or naphthyl azo base especially), OCOOR ⁸, OCOR ⁸, COR ⁸, CONR ⁸R ⁹, OCONR ⁸R ⁹, SR ⁸, SO ₂NR ⁸R ⁹Perhaps SO ₂R ⁸, R wherein ⁸And R ⁹Represent H, the optional alkyl that replaces (C particularly independently of one another _1-6-alkyl), optional cycloalkyl that replaces or the optional aryl that replaces.And unrestricted, such as sulfo group, phosphino-(phosphato) and or the group of carboxyl for example can exist with salt form.

Optional substituting group on the preferred B is selected from carboxyl, sulfo group, phosphino-(phosphato), the optional amino that replaces, the optional amide group that replaces, the optional urea groups that replaces, the optional alkyl that replaces (C particularly _1-6-alkyl), the optional alkoxyl group that replaces (C particularly _1-6-alkoxyl group) and the optional aryl that replaces.

When B was the phenylene that replaces, preferred phenylene endless belt had one or more to be selected from C _1-6-alkyl, the optional C that replaces _1-6-alkylthio, the optional C that replaces _1-6The group of-alkoxyl group, the optional amino that replaces, optional urea groups, carboxyl and the sulfo group that replaces.As B during for the phenylene that replaces, more preferably the phenylene endless belt has at least one, more preferably one or two, most preferably two are selected from the optional C that replace _1-6Alkyl (particularly optional methyl and the ethyl that replaces) and the optional C that replaces _1-6The substituting group of-alkoxyl group (particularly optional methoxyl group and the oxyethyl group that replaces).The optional C that replaces _1-6-alkyl and the optional C that replaces _1-6The preferred substituents of-alkoxyl group is-OH.

As B during for the naphthylidene that replaces, preferred naphthylidene endless belt has one or more water soluble group, more preferably one or more, particularly one or two are selected from the group of carboxyl, sulfo group and phosphino-(phosphato).

As the phenylene of the optional replacement of representing by B and the example of naphthylidene, what can mention is 2,5-two (2-hydroxyl-oxethyl) benzene-1,4-subunit, 2,5-dimethoxy benzene-1,4-subunit, 2,5-diethoxybenzene-1,4-subunit, 2-methoxyl group-5-amino-benzene-1,4-subunit, 2-methoxyl group-5-acetyl amino phenyl-1,4-subunit, 2-methyl-5-methoxyl group-benzene-1,4-subunit, 2,5-dimethyl-benzene-1,4-subunit, 7-sulfo group naphthalene-1,4-subunit, 6-sulfo group naphthalene-1,4-subunit and 2-oxyethyl group-6-sulfo group naphthalene-1,4-subunit.

Preferred B is the optional phenylene that replaces.Most preferably B is the phenylene of replacement, and preferably it is substituted as mentioned above.

Preferred D is for having the pyrazolyl of at least one carboxyl, sulfo group or phosphino-(phosphato).More preferably D is formula (3a), (3b) or group (3c), in addition more preferably D be formula (3a) or group (3b) and most preferably D be formula (3a):

Formula (3a) formula (3b) formula (3c)

Wherein

R ²And R ⁵Be H, carboxyl, cyano group or the optional C that replaces independently of one another _1-6-alkyl, the optional C that replaces _1-6-alkoxyl group, the optional acyl group that replaces, the optional aryl that replaces, the optional amino that replaces, the optional amido that replaces, optional substituted amido (CONR ⁶R ⁷), the optional carboxylicesters that replaces, the optional sulfoamido (SO that replaces ₂NR ⁶R ⁷) or the optional alkyl sulphonyl that replaces; (R wherein ⁶And R ⁷Be H or the optional C that replaces independently of one another _1-6Alkyl);

R ³And R ⁴(particularly have one or more C for H, hydroxyl, halogen, nitro, cyano group, carboxyl, sulfo group, phosphino-(phosphato), the optional amino that replaces independently of one another _1-4The amino of-alkyl), the optional amide group that replaces (C particularly _1-4Amide group or phenyl amide base, optional separately sulfo group or the carboxyl of having), the optional urea groups that replaces (particularly has one or two C _1-4The urea groups of-alkyl), the optional C that replaces _1-6-alkyl, the optional C that replaces _1-6-cycloalkyl, the optional C that replaces _1-6-alkoxyl group, the optional C that replaces _1-6-alkylthio, the optional aryl (particularly phenyl) that replaces, the optional C that replaces _1-6-alkyl sulphonyl and the optional sulfoamido that replaces (particularly have one or two C _1-4The sulfoamido of-alkyl); With

^*The tie point that expression is connected with azo linking group in formula (1) or (2).

R ²Be preferably H, the optional C that replaces _1-6Alkyl (particularly methyl), C _1-6-alkoxyl group, C _1-6-acyl group or amino or can (be CONR such as carboxyl or amide group with the group of free acid form with adjacent azo group formation hydrogen bond ⁶R ⁷, R wherein ⁶And R ⁷Be H or the optional C that replaces independently of one another _1-6Alkyl).

As R ²The most preferably examples of groups of expression can be mentioned methyl, carboxyl, CONR ⁶R ⁷And H.Yet, R most preferably ²Be carboxyl or CONR ⁶R ⁷(particularly carboxyl).

R most preferably ³And R ⁴Be the optional aryl that replaces independently of one another.More preferably R ³And R ⁴Be selected from carboxyl, sulfo group, nitro, phosphino-(phosphato), the optional C that replaces for having one or more independently of one another _1-4-alkyl, the optional C that replaces _1-4-alkoxyl group, the optional amino or optional C that replaces that replaces _1-4The phenyl of-amide group or naphthyl (particularly phenyl).R most preferably ³And R ⁴Independently of one another for having the phenyl or the naphthyl (particularly phenyl) of one or more sulfo group.

R ³And R ⁴The expression but the non-examples of groups that is limited to these, what can mention is 4-sulfo group phenyl and 2-sulfo group naphthyl.

R most preferably ⁵Be carboxyl or C _1-4The alkyl carboxylic acid ester group.

The preferred optional referred in this C that replaces _1-6-alkyl and C _1-6-alkoxyl group comprises the optional C that replaces respectively _1-4-alkyl or the optional C that replaces _1-4-alkoxyl group more preferably is not substituted or has the C of halogen atom or hydroxyl, carboxyl, sulfo group or phosphino-(phosphato) _1-4-alkyl or C _1-4-alkoxyl group.

R wherein ², R ³, R ⁴And/or R ⁵Be the optional aryl that replaces, preferably they are optional phenyl that replace, and choose wantonly by nitro, carboxyl, nitro, phosphino-(phosphato), the optional amino that replaces (particularly to have one or more C _1-4The amido of-alkyl), the optional amide group that replaces (C particularly _1-4-amide group or phenyl amide base, optional separately sulfo group or the carboxyl of having), the optional C that replaces _1-6-alkyl, the optional C that replaces _1-6-cycloalkyl and the optional C that replaces _1-6-alkoxyl group replaces.In addition, the preferred optional phenyl that replaces also has the water soluble group that at least one is selected from carboxyl, sulfo group and phosphino-(phosphato).

Preferably may reside in B, R ², R ³, R ⁴And R ⁵On substituted amido or sulfoamido be respectively formula CONR ⁶R ⁷Perhaps SO ₂NR ⁶R ⁷, R wherein ⁶And R ⁷Be H or the optional C that replaces independently of one another _1-6Alkyl.

Preferably may reside in B, R ², R ³, R ⁴And R ⁵On the amido of optional replacement be respectively the optional amide group, particularly C that replaces _1-4-amide group more preferably is not substituted or has the urea groups of the optional replacement of carboxyl, sulfo group or phosphino-(phosphato).

Preferably may reside in B, R ², R ³, R ⁴And R ⁵On carboxyl groups be respectively the optional C that replaces _1-4-alkyloyl, the optional phenyl acyl group that replaces, preferred ethanoyl or benzoyl.

Preferably may reside in B, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷In any C of the optional replacement on the group _1-6-alkyl, C _1-6-alkoxyl group, C _1-6-alkylthio, aryl and C _1-6Substituting group on the-alkyl sulphonyl is independently selected from hydroxyl, halogen, nitro, cyano group, carboxyl, sulfo group, phosphino-(phosphato), amide group, urea groups, C _1-6-alkyl (preferred C _1-6-alkyl, more preferably methyl or ethyl), C _1-6-alkoxyl group (preferred C _1-4-alkoxyl group, more preferably methoxyl group or oxyethyl group), C _1-10-alkylthio, aryl (preferred phenyl or naphthyl), C _1-6-alkyl sulphonyl and sulfoamido.

In preferred embodiment according to the compound of first aspect present invention or salt:

A not by any be not that the group of sulfo group replaces;

B is for having one or two substituting groups (particularly two s') phenylene or naphthylidene, and described substituting group is selected from sulfo group, the optional C that replaces _1-6Alkyl (particularly methyl), the optional C that replaces _1-6Alkoxyl group (particularly methoxyl group, oxyethyl group and 2-hydroxyl-oxethyl) and the optional amino that replaces (for example, the optional amide group that replaces);

N is 0 or 1;

D is formula (3a), (3b) or (3c), particularly (3a); Wherein:

Formula (3a) formula (3b) formula (3c);

R ²Be H, methyl, carboxyl or carbonamido (particularly carboxyl);

R ³And R ⁴Independently of one another for having one or two phenyl that is selected from sulfo group and carboxyl (particularly sulfo group) or naphthyls (particularly phenyl); With

R ⁵Be C _1-4The alkyl carboxylic acid ester.

In another preferred embodiment according to the compound of first aspect present invention or salt:

A is formula X ',

Formula X '

Wherein ^*For with formula (1) or (2) in the tie point of azo group, p and q are 0,1 or 2 and p+q's and be 1,2 or 3 independently of one another;

B has phenylene or the naphthylidene that one or two are selected from sulfo group, methyl, methoxyl group, oxyethyl group and 2-hydroxyl-oxethyl;

N is 0 or 1; With

D is formula (3a), (3b) or (3c), particularly (3a);

Formula (3a) formula (3b) formula (3c);

Wherein:

R ²Be H, methyl, carbonamido or carboxyl (particularly carboxyl);

R ⁵Be C _1-4The alkyl carboxylic acid ester.

Preferred compound according to first aspect present invention is formula (1A-1H) and salt thereof:

Formula 1A

Formula 1B

Formula 1C

Formula 1D

Formula 1E

Formula 1F

Formula 1G

Formula 1H

Particularly preferred compound is formula 1C, and preferred especially its salt.

Should be appreciated that formula (1) or formula (2) compound can prepare by methods known in the art.Obviously the salt of compound can similarly be prepared.For example, the salt of formula (1) compound can be prepared by the following method, diazotization formula (4) compound, wherein n, A and B as defined above, thereby provide diazonium salt and make gained diazonium salt and D wherein as defined above formula H-D compound carry out coupling:

Formula (4)

Preferred diazotization is carried out under 0 ℃～10 ℃ temperature.Preferred diazotization is carried out in water, preferably under less than 7 pH value.Diluted mineral acid, for example HCl or H ₂SO ₄Can be used to realize the pH value condition expected.

The salt of formula (4) compound can be prepared by the following method, at first diazotization formula A-NH ₂(NH wherein ₂Be connected among the formula X and be labeled as ^*The position on) and this compound is coupled at formula B-NH by methods known in the art ₂On the compound, thereby obtain formula A-N=N-B-NH ₂Compound.Continue this method then, diazotization formula A-N=N-B-NH ₂Compound, thus provide diazonium salt and make the gained diazonium salt with choose the 1-hydroxyl-3-sulfo group-6-amido naphthalene coupling that on the 5-position, has sulfo group wantonly, wherein A and B are as defined above.

For the salt of formula (2) compound, can use with the identical method of following formula (1) compound, but formula (4) compound can be prepared diazotization formula A-N=N-B-NH by the following method ₂Compound, thus provide diazonium salt and make the gained diazonium salt and choose 1-hydroxyl-3-sulfo group-7-amido naphthalene coupling that sulfo group is arranged at 5-or 6-bit strip wantonly.

In the other method of the salt of preparation formula (1) or (2) compound, to formula A-NH ₂Compound (NH wherein ₂Be connected among the formula X and be marked with ^*The position on) carry out diazotization and it be coupled at formula B-NH by methods known in the art ₂On the compound, thereby obtain formula A-N=N-B-NH ₂Compound.Individually, there is the 1-hydroxyl-3-sulfo group-6-amido naphthalene of sulfo group to carry out diazotization and it is coupled at wherein D as defined above on the formula H-D compound choosing wantonly then at the 5-bit strip, thus the formula of providing (5) compound:

Formula (5)

Then to formula A-N=N-B-NH ₂Compound carries out diazotization and then it is coupled on formula (5) compound.

The reaction conditions of all above methods is common those that use of dye field, for example described in EP0356080.

The compounds of this invention can provide with the form of salt.In view of the above, compound comprises its salt referred in this.Particularly, and non-limiting, and any sulfo group, carboxyl or phosphino-(phosphato) can exist with the form of salt.Preferred salt is an alkali metal salt (particularly lithium salts, sodium salt and sylvite), ammonium and substituted ammonium salt and composition thereof.Particularly preferred salt be sodium salt, sylvite and lithium salts, with salt of ammonia and volatile amine and composition thereof.Lithium salts has good solubility, forms the stable especially printing ink of storage that has hypotoxicity and do not block printing ink nozzle tendency.

The compounds of this invention can utilize known technology to change into the salt of expectation.For example, be dissolved in the water by an alkali metal salt compound, use the mineral acid acidifying, with with ammonia or amine the pH value of solution is adjusted to pH9～9.5, with by the dialysis or by utilizing ion exchange resin to remove alkali metal cation, an alkali metal salt of The compounds of this invention can change into ammonium salt or substituted ammonium salt.

The example that can be used to form the amine of described salt includes but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, piperidines, pyridine, morpholine, allylamine, diethylamine, triethylamine, tetramethyl-amine and composition thereof.The form that dyestuff of the present invention is entirely ammonium salt or substituted ammonium salt is not vital.The dyestuff that comprises mixed alkali metal salt and ammonium salt or substituted ammonium salt is that effectively particularly wherein at least 50% positively charged ion is ammonium ion or substituted ammonium ion.

Further salt be have the antagonism ionic described in US 5830265 claim 1 integral body (b) those, it is hereby incorporated by.

Compound of the present invention or salt can be with tautomeric forms, rather than the form shown in this specification sheets, exist.These tautomers are included in the claim scope of the present invention equally.

In a second aspect of the present invention, the compound that contains with good grounds first aspect present invention or the ink composite of its salt and liquid medium are provided.

The preferred liquid medium comprises water, the mixture of water and organic solvent and anhydrous organic solvent.The preferred liquid medium comprises the mixture of water and organic solvent.

Preferably the composition according to second aspect present invention comprises:

(a) 0.01～30 portion of compound or its salt according to aforesaid first aspect present invention; With

(b) 70～99.99 parts liquid medium;

Wherein liquid medium comprises that organic solvent and all umbers all are by weight and umber (a)+(b)=100.

The umber of preferred ingredient (a) is 0.1～20 part, more preferably 0.5～15 part and particularly 1～6 part.The umber of preferred ingredient (b) is 99.9～80 parts, more preferably 99.5～85 parts and particularly 99～94 parts.Preferred ingredient (a) is dissolved in the component (b) fully.Preferably under 20 ℃, the solubleness of component (a) in component (b) is at least 10%.Can prepare like this and be used to prepare the liquid pigment enriched material of printing ink and be reduced in memory period, if when there is evaporation in liquid medium, the possibility of dye precipitated.

The preferred liquid medium comprises water and organic solvent, and the weight ratio of preferably water and organic solvent is 99:1～1:99, more preferably 99:1～50:50 and particularly 95:5～80:20.

Preferred organic solvent be can with the miscible organic solvent of water or the mixture of described solvent.Preferably can comprise: C with the miscible organic solvent of water _1-6-alkanol, particular methanol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, cyclopentanol and hexalin; The straight chain acid amides, preferred dimethyl formamide or N,N-DIMETHYLACETAMIDE; Ketone and ketone-alcohol, preferred acetone, methyl ether ketone, pimelinketone and diacetone alcohol; Ether that can be miscible with water, preferred tetrahydrofuran (THF) and dioxane; Glycol, the glycol that preferably has 2～12 carbon atoms, pentane-1 for example, 5-glycol, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol and sulfo-glycol ether and oligomeric and poly-alkane glycol, preferred Diethylene Glycol, methylene glycol, polyoxyethylene glycol and polypropylene glycol; Triol, preferably glycerine and 1,2,6-hexanetriol; List-the C of glycol _1-4-alkyl oxide preferably has the nitrogen-C of 2～12 carbon atoms _1-4-alkyl oxide, particularly 2-methyl cellosolve, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy)-ethanol, 2-[2-(2-methoxy ethoxy) oxyethyl group] ethanol, 2-[2-(2-ethoxy ethoxy)-oxyethyl group]-ethanol and ethylene glycol monoallyl ether; Cyclic amide, preferred 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, hexanolactam and 1,3-methylimidazole alkane ketone; Cyclic ester, preferred caprolactone; Sulfoxide, preferred dimethyl sulfoxide (DMSO) and tetramethylene sulfone.The preferred liquid medium comprises water and 2 or more kinds of, particularly 2～8 kinds of water-miscible organic solvents.

Particularly preferred water-miscible organic solvent is cyclic amide, particularly 2-Pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; Glycol, particularly 1,5-pentanediol, ethylene glycol, sulfo-glycol ether, Diethylene Glycol and triethylene glycol; List-C with glycol _1-4-alkyl and C _1-4-alkyl oxide more preferably has the list-C of the glycol of 2～12 carbon atoms _1-4-alkyl oxide, particularly ((2-methoxyl group-2)-oxyethyl group)-cellosolvo.

Preferred liquid medium comprises:

(a) 75～95 parts of water; With

(b) altogether 25～5 parts one or more be selected from Diethylene Glycol, 2-Pyrrolidone, sulfo-glycol ether, N-Methyl pyrrolidone, hexalin, caprolactone, hexanolactam and pentane-1, the solvent of 5-glycol;

Wherein umber by weight and (a) and umber and=100 (b).

Another preferred liquid medium comprises:

(a) 60～80 parts of water;

(b) 2～20 parts of Diethylene Glycols; With

(c) altogether 0.5～20 part one or more be selected from 2-Pyrrolidone, N-Methyl pyrrolidone, hexalin, caprolactone, hexanolactam, pentane-1, the solvent of 5-two pure and mild sulfo-glycol ethers;

Wherein umber by weight, (a) and (b) and (c) umber and=100.

The case description of other suitable liquid medium of mixture that comprises water and one or more organic solvents is at US 4,963, and 189, US 4,703,113, US 4,626,284 and EP 4,251, among the 50A.

When liquid medium comprises anhydrous organic solvent (by weight less than 1% water), the boiling point of preferred solvent is 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, and particularly 50～125 ℃.

Organic solvent can be with the immiscible organic solvent of water, with the miscible organic solvent of water or the mixture of described solvent.Preferably can with the miscible organic solvent of water be any above-mentioned can with miscible organic solvent of water and composition thereof.Preferred do not comprise, for example aliphatic hydrocarbon with the miscible solvent of water; Ester, ethyl acetate; Hydrochloric ether, preferred CH ₂Cl ₂And ether, preferred ether; And composition thereof.

When liquid medium comprises not with the miscible organic solvent of water, preferably comprise polar solvent, because this strengthens the solvability of compound in liquid medium.The example of polar solvent comprises C _1-4-alcohol.In view of above-mentioned preferred, when liquid medium is anhydrous organic solvent, preferred especially it comprise ketone (particularly methyl ethyl ketone) and/or alcohol (C particularly _1-4-alkanol, more especially ethanol or propyl alcohol).

Anhydrous organic solvent can be the mixture of a kind of organic solvent or two or more organic solvents.When medium was anhydrous organic solvent, preferably it was the mixture of 2～5 kinds of different organic solvents.This allows medium to be selected such that and can well to control the anhydrous characteristic and the storage stability of ink composite.

When the needs fast drying time with particularly be printed on hydrophobic and nonabsorbable matrix (for example plastics, metal and glass) when going up, the liquid medium that contains anhydrous organic solvent is useful especially.

Preferred low melting point solid dielectric has 60 ℃～125 ℃ fusing point.Suitable low melting point solid comprises longer chain fatty acid or alcohol, preferably has C _18-24Chain, and sulfanilamide (SN).Formula (1) or (2) compound can be dissolved in the low melting point solid or can be its in small, broken bits being dispersed in wherein.

Because its tempting black colourity, so formula (1) or (2) compound or its salt can be used as single pigment in ink composite.Yet,, thereby reduce spray nozzle clogging (by improveing their solvability) if or colourity that need be slightly different during concrete final the application if expectation can merge formula (1) or (2) compound or other pigment of its salt and one or more.Thus, can obtain to comprise at least a other pigment according to printing ink of the present invention.Preferred other pigment is dyestuff.When merging to other pigment in the composition, preferably they are selected from black, scarlet, cyan, yellow, pansy, orange, blueness and veridian and combination thereof.

Other suitable black pigment comprises C.I.Food Black 2, C.I.Direct Black 19, C.I.Reactive Black 31, PRO-JET ^TMFast Black 2, C.I.Direct Black 195; C.I.Direct Black 168; By comprising Lexmark, Seiko, Epson, the original manufacturing firm (OEMs) of Canon and Hewlett-Packard or by comprising Fuji Photo FilmCo., the pigment manufacturer preparation of Nippon Kayaku and Mitsubishi or other black pigment of selling, with by OEMs or pigment manufacturer at other black pigment described in patent and the patent application, described OEMs comprises above-mentioned Lexmark, and (for example EP 0 539,178 A2, embodiment 1,2,3,4 and 5), Orient Chemicals (EP 0 347 803 A2 for example, pages 5-6, azoic dyestuff 3,4,5,6,7,8,12,13,14,15 and 16), Canon, Hewlett-Packard and Seiko Epson Corporation are perhaps by comprising Fuji Photo Film Co., the product that the dyestuff manufacturers of NipponKayaku and Mitsubishi makes.

Other suitable red lake pigment comprises PRO-JET ^TMFast Magenta 2 and by the OEMs that comprises Lexmark, Seiko, Epson, Canon and Hewlett-Packard or comprise the pigment manufacturer preparation of Fuji Photo Film Co., Nippon Kayaku and Mitsubishi, other red lake pigment of selling or in patent and patent application, describing.

Other suitable yellow ultramarine comprises C.I.Direct Yellow 142; C.I.Direct Yellow132; C.I.Direct Yellow 86; PRO-JET ^TMYellow OAM; PRO-JET ^TMFastYellow 2; C.I.Direct Yellow 85; C.I.Direct Yellow 173; With C.I.Acid Yellow23 and other by the OEMs that comprises Lexmark, Seiko, Epson, Canon and Hewlett-Packard or comprise the pigment manufacturer preparation of Fuji Photo Film Co., Nippon Kayaku and Mitsubishi, other yellow ultramarine of selling or in patent and patent application, describing.

Other suitable green pigment comprises phthalocyanine pigment, C.I.Direct Blue 199 and C.I.AcidBlue 9 and by the OEMs that comprises Lexmark, Seiko, Epson, Canon and Hewlett-Packard or comprise the pigment manufacturer preparation of Fuji Photo Film Co., Nippon Kayaku and Mitsubishi, other green pigment of selling or describing in patent and patent application.

Ink composite can also contain the other component that is generally used in the ink jet printing printing ink, and for example viscosity and surface tension modifier, sanitas, sterilant, dirt reduce additive and can be ion or non-ionic tensio-active agent.

Usually, liquid medium will further comprise one or more tensio-active agents, for example negatively charged ion and/or nonionic surface active agent.The example of ionic surface active agent comprises: sulfosalt surfactant, and such as sulfosuccinate (Aerosol ^TMOT, A196; AY and GP can be obtained from CYTEC) and sulfonate (Aerosol ^TMDPOS-45, OS can be obtained from CYTEC; Witconate ^TMC-50H can be obtained from WITCO; Dowfax ^TM8390, can be obtained from DOW); And fluorine surfactant (Fluorad ^TMFC99C can be obtained from 3M).The example of nonionic surface active agent comprises: fluorine surfactant (Fluorad ^TMFC170C can be obtained from 3M); Alkoxy-based surface-active agent (Tergitol ^TMSeries 15S-5,15S-7 and 15S-9 can be obtained from Union Carbide); And organic silicon surfactant (Silwet ^TML-77 and L-76-9 can be obtained from WITCO).Surfynol ^TMThe tensio-active agent of scope (can be obtained from Air Products) suits equally.

In one embodiment, the pH value according to printing ink of the present invention is about 3～about 5, preferred about 3.5～about 4.5.In another embodiment, more preferably the pH value of composition is 4～11, more preferably 7～10.The optional damping fluid that comprises of ink composite.

Can choose wantonly one or more damping fluids are integrated with in the liquid medium to regulate the pH value of printing ink.Described damping fluid can be organic-Ji biological buffer or inorganic damping fluid, and is preferably organic-the Ji biological buffer.The example of preferred damping fluid comprises can be obtained from (Milwaukee, three (methylol) aminomethane (TRIS) of company Wis.), 4-morpholino b acid (MES), 4-morpholine propanesulfonic acid (MOPS) and beta-hydroxy-4-morpholine propanesulfonic acid (MOPSO) such as Aldrich Chemical.In addition, in the present invention's practice, the preferred damping fluid that uses provides 3～10 pH value.

Can choose wantonly one or more sterilant that is generally used in the jetted ink are used for printing ink, such as Nuosept ^TM95, can be obtained from HuIs America (Piscataway, N.J.); Proxel ^TMGXL can be obtained from Arch Chemicals, and Inc. (Norwalk, Connecticut); And glutaraldehyde, can with trade(brand)name Ucarcide 250 be obtained from Union Carbide Company (Bound Brook, NJ.).

Can also choose wantonly according to printing ink of the present invention and to contain one or more metal chelators.Described sequestrant is used for the free transition-metal cation that may be present in printing ink in conjunction with any.The example of preferred metal chelator comprises: ethylenediamine tetraacetic acid (EDTA) (" EDTA "), two quadrol pentaacetic acids (" DPTA "), anti-form-1,2-diamines basic ring hexane tetraacethyl (" CDTA "), ethylidene nitrilo tetraacethyl (" EGTA ").Can also in addition or substitute and use other sequestrant.

Under 25 ℃, the viscosity of preferred printing ink is less than 50cP, is more preferably less than 20cP and particularly less than 5cP.

Preferably, be applicable to that the ink composite of the present invention in the ink-jet printer has filtered the following strainer of mean pore size 10 μ m, more preferably below the 3 μ m, particularly below the 2 μ m, more especially below the 1 μ m.This removes by filter otherwise may find to block the particulate matter of thin nozzle in multiple ink-jet printer.

In the time will being used as the ink jet printing composition according to the composition of second aspect present invention, the halogen ion concentration in the preferred composition is more preferably less than 100/1000000ths less than 500/1000000ths.Be applicable to that preferably ink composite of the present invention in the ink-jet printer contains altogether less than the divalence of 500ppm and trivalent metal ion (except any any divalence of other component bonded and trivalent metal ion of formula (1) compound or printing ink), be more preferably less than 250ppm, particularly less than 100ppm, more especially less than 10ppm.We have found that the described composition of purifying can reduce spray nozzle clogging in the ink jet printing head with the concentration that reduces these metal ions of not expecting, especially in hot ink jet printing head.

Another aspect of the present invention provides and has been used for the method for image printing on matrix, comprises by ink jet printing head and will be applied on the matrix according to the composition of second aspect present invention.

Preferred ink jet printing head is applied to the composition of droplet form on the matrix, and described droplet is ejected on the matrix by small nozzle.Preferred ink jet printing head is piezoelectricity ink jet printing head and hot ink jet printing head.In hot ink jet printing head, by the resistor adjacent with nozzle, the composition in container applies programpulse heating, thereby makes composition during the relative movement between matrix and the nozzle, is injected directly on the matrix with the form of droplet.In the piezoelectricity ink jet printing head, the vibrations of small-crystalline make composition be ejected from nozzle.

Preferred substrate is paper, plastics, fabric, metal or glass, is more preferably processed matrix, such as White Board or coated plastics, particularly White Board.

The paper of preferred planar or processing is for can have acidity, alkalescence or neutral paper.The example of commercially available plane and handling of paper comprises:

Photo Paper Pro (PR101), Photo Paper Plus (PP101), Glossy PhotoPaper (GP401), Semi Gloss Paper (SG101), Matte Photo Paper (MP101) (all are obtained from Canon); Premium Glossy Photo Paper, Premium Semi glossPhoto Paper, ColorLife ^TM, Photo Paper, Photo Quality Glossy Paper, two-sided Matte Paper, Matte Paper Heavyweight, Photo Quality InkJet Paper, Bright White InkJet Paper, Premium Plain Paper (all are obtained from Seiko EpsonCorp); HP All-ln-One Printing Paper, HP Everyday InkJet Paper, HPEveryday Photo Paper Semi-glossy, HP Office Paper, HP Photo Paper, HPPremium High-Gloss Film, HP Premium Paper, HP Premium Photo Paper, HP Premium Plus Photo Paper, HP Printing Paper, HP Superior InkJetPaper, HP Advanced Photo Paper (all are obtained from Hewlett Packard Inc.); Everyday Glossy Photo Paper, Premium Glossy Photo Paper (are obtained from Lexmark ^TMInc.); Matte Paper, Ultima Picture Paper, Premium PicturePaper, Picture Paper, Everyday Picture Paper (being obtained from Kodak Inc.).

The compounds of this invention described herein and composition provide tempting printing, are specially adapted to the neutral black chroma color of text and visual ink jet printing.Described composition has good storage stability and to the low obstruction proneness of the very thin nozzle that is used for ink jet printing head.In addition, the gained image has good absorbancy, colourity, light resistance, moisture resistivity, moisture resistance and fade resistance energy, particularly absorbancy and light resistance in the presence of oxidizing gas pollutent (for example ozone).

According to further aspect of the present invention, provide on it the matrix that is printed with image by the inventive method as defined above.Preferred described matrix comprises paper, elevated projecting slide plate or fabric.

When matrix was fabric, the method for preferred printed images comprised:

I) use ink jet printing head that ink composite is applied on the fabric; With

Ii) under 50 ℃～250 ℃ temperature, heat the gained printed fabric.

Preferred fabric is natural, synthetic and semi-synthetic material.The example of preferred natural fabric comprises fine hair, silk, hair and cellulosic material, particularly cotton, jute, hemp fibre, flax and linen.Preferred example synthetic and semi-synthetic material comprises polymeric amide, polyester, polyacrylonitrile and urethane.

Preferably in above step I) before, fabric has carried out handling and having carried out drying with the moisture pretreatment compositions that contains thickening material and optional water soluble alkali (base) and hydrophilic agent.

The composition of preferred pretreatment comprises and contains aqueous solution thickening material, alkali (base) and hydrophilic agent.Particularly preferred pretreatment compositions has carried out describing more comprehensively in european patent application No.534660A1.

The aspect further according to the present invention, the optional ink jet printing head cartridge that can refill is provided, comprise one or more chamber and ink composite, wherein ink composite be present at least one chamber and ink composite for according to ink composite of the present invention as herein defined.

According to a further aspect in the invention, provide the ink device that comprises black ink, scarlet printing ink, cyan ink and Yellow ink at least and wherein black ink comprise according to the compound of first aspect present invention as defined above or its salt and/or ink composite as defined above.

According to a further aspect in the invention, provide be used to provide according to the compound of first aspect present invention as defined above or its salt have a good absorbancy, photostabilization, wet fastness or in the presence of oxidizing gas, resist the purposes of the print image that fades.

In this application, unless clear and definite statement in addition in the context, the plural form of term is considered to comprise its singulative as used herein, and vice versa.

In the specification sheets and claim of this application, unless the clear and definite statement in addition of context, word " comprise " and " containing " with and variant, for example " comprise " expression and " include but not limited to ", and be not intended (with not) and get rid of other component.

Should be appreciated that and to change the above-mentioned embodiment of the present invention that this falls within the scope of the present invention equally.Except as otherwise noted, the further feature that disclosed each feature can be provided identical, equal or similar purpose in this application is replaced.Thus, except as otherwise noted, disclosed each feature only is a kind of example of on an equal basis serial or similar characteristics.

Disclosed all features can be merged into arbitrary combination in this application, except the combination that wherein at least some described features and/or step are repelled mutually.Particularly, preferred feature of the present invention is applicable to all aspects of the present invention and can be with any applied in any combination.Similarly, the feature of describing in inessential combination can be used (non-combination) separately.

The various features self that should be appreciated that aforesaid various features, particularly preferred embodiment is inventive point, but not only is the part of embodiment of the present invention.Except the invention or replacement scheme of any current requirement, can also seek independent protective to these features.

The present invention now further describes by following examples, and except as otherwise noted, wherein all umbers and per-cent are all by weight.Only illustrations the present invention of described embodiment does not limit the scope of the invention.

Embodiment 1

Preparation:

Steps A

A-N=N-B-NH ₂Mixing salt preparation:

With 2-amino naphthalenes-1, (49g, 0.1M MI=490) are dissolved in by adding 2N LiOH and make that pH value is in the water (500ml) of 7-8 the 5-disulfonic acid.Solution is filtered the GFA strainer and (6.9g 0.1M) joins in the filtrate with SODIUMNITRATE.Then, the gained mixture is joined in the mixture of the ice/water of stirring and cHCl (30ml), forms pH value and be 1 solution, with solution 0-10 ℃ of maintenance one hour down.After at this moment, remove excessive nitrite, test with the sulfone indicator by adding thionamic acid.

(13.7g, 0.1M MI=137) are dissolved in the acetone (200ml) and at 20 minutes and in the clock time this solution are joined in the previously prepared diazo solution, and keeping temperature is 0-10 ℃ with 2-methoxyl group-5-monomethylaniline.Then pyridine (10ml) is once added wherein and the gained mixture stirred and spend the night, make it be warming up to room temperature simultaneously.

Gained suspension inserted in the acetone (5L) and precipitation is filtered and it is carried out drying.In baking oven, products obtained therefrom is carried out drying, thereby provide A-N=N-B-NH ₂(32.5g).

Step B

Mixing salt preparation:

(26.5g, 0.1M MI=265) are dissolved in by adding 2N LiOH and make that pH value is in the water (400ml) of 7-8 with 7-amino-4-hydroxy naphthalene-2-sulfonic acid.Solution is filtered the GFA strainer and (6.9g 0.1M) joins in the filtrate with SODIUMNITRATE.Then, the gained mixture is joined in the mixture of the ice/water of stirring and cHCl (50ml), forms pH value and be 1 solution, with solution 0-10 ℃ of maintenance one hour down.After at this moment, remove excessive nitrite, test with the sulfone indicator by adding thionamic acid.

With 5-oxo-1-(4-sulfo group phenyl)-4, (40g, 0.114M MI=350) are dissolved in the water (400ml) that is added with 2N LiOH 5-dihydro-1 h-pyrazole-3-carboxylic acid.Join in the clock time in the previously prepared diazo solution at 20 minutes with this solution filtration GFA strainer with this solution, keeping temperature is 0-10 ℃.By adding pyridine (35ml) the pH value of this mixture is adjusted to 5 and the stirring of gained mixture spent the night, makes it be warming up to room temperature simultaneously.

Gained suspension is inserted in the acetone (5L) and precipitation is filtered, carried out drying with the small amount of acetone washing with to it.In baking oven, products obtained therefrom is carried out drying, thereby provides 4-[(5-hydroxyl-7-sulfo group-2-naphthyl) diazenyl]-5-oxo-1-(4-sulfophenyl)-4,5-dihydro-1 h-pyrazole-3-carboxylic acid (64g).

Step C-title dye

Product A-the N=N-B-NH of steps A will be obtained from ₂(12g, 0.02M MI=600) are suspended among the NMP (200ml), and SODIUMNITRATE (2g) is once added wherein.Mixture was stirred 15 minutes, thereby provides uniform suspension, then rare HCl[is prepared by cHCl (8ml) and water (200ml)] once add wherein.Again after an hour after, when stirring, make mixture from being cooled to room temperature.After at this moment, remove excessive nitrite, test with the sulfone indicator by adding thionamic acid.

(14g, 0.0186M MI=750) are dissolved in by adding 2N LiOH and make that the pH value is in 8 the water (200ml) with the product that is obtained from step B.Diazo suspension with above preparation in 30 fens clock times adds wherein, uses ice to keep temperature as 0-10 ℃ with use 2NLiOH maintenance pH value to be 8-9 simultaneously.The gained mixture was stirred 1 hour.

Gained suspension is inserted in the acetone (3L) and precipitation is filtered, carried out drying with the small amount of acetone washing with to it.Products obtained therefrom is soluble in water and dialysing with before the 0.45um nylon filter screening.Under 60 ℃ with gained solution evaporate to dryness, thereby provide title dye (17.1g, 6.3mM, MI1132, λ _Max=570nm).

Embodiment 2-9

Repeat with embodiment 1 in identical method prepare the salt that structure is presented at the dye composition in the following table 1.

Table 1

Embodiment 10-printing ink

Printing ink can be prepared according to following prescription, and it contains the dye composition of above embodiment 1～embodiment 9:

5 parts of 2-Pyrrolidones

5 parts of sulfo-glycol ethers

Surfynol ^TM465 1 parts

3 parts of dyestuffs

Water constitutes 100 parts of required amounts

Surfynol ^TMThe 465th, can be obtained from Air Products and Chemicals Inc., the tensio-active agent of USA.

Other printing ink can be prepared according to following table 2 and 3, and wherein the dyestuff of describing in first hurdle is the dyestuff for preparing among the embodiment of above identical numbering.The number that provides in second hurdle forward is meant the umber of related component and all umbers all by weight.Can printing ink be applied on the paper by for example heat or piezoelectric ink jet printing.Following shortenings is used for form:

The PG=propylene glycol

The DEG=Diethylene Glycol

The NMP=N-methyl-2-pyrrolidone

The DMK=Ketene dimethyl

The IPA=Virahol

MEOH=methyl alcohol

The 2P=2-pyrrolidone

The MIBK=methyl iso-butyl ketone (MIBK)

P12=propane-1, the 2-glycol

BDL=butane-2, the 3-glycol

CET=hexadecyl brometo de amonio

PHO=Na ₂HPO ₄With

The TBT=trimethyl carbinol

TDG=sulfo-glycol ether

Embodiment 11-14-printing test implementation example

Printing ink be prepared as described in example 10 above and use Canon i965 printing press with its ink jet printing on multiple matrix (paper).The CIE color coordinate of each time printing (A, B, L, chromaticity (C) and color (H)) uses Gretag Spectrolino photodensitometer to measure, simultaneously in the spectral range of 400-700nm, spectrum interval with 20nm uses light source D65 to carry out 0/45 degree measurement geometry, 2 degree (CIE1931) observing angle and density running status A.Be no less than 2 measurements with the size greater than 10mm x 10mm, described measurement diagonal angle passes list (solid) the look frame on the printed matter.

Above embodiment 1 and 5 dyestuff are used to prepare printing ink.

Except the printing ink that contains dye composition of the present invention, for sake of comparison, also prepared the printing ink that contains not dye composition (" comparative dye ") within the scope of the present invention.In each comparative dye, the A group is not a formula X group as defined herein.Comparative dye is as follows:

Comparative dye C1

Comparative dye C2

Absorbancy

The absorbancy of gained printed matter (OD) performance is shown in Table 4, and the embodiment numbering that wherein is used for preparing the dye composition of printing ink is shown in second hurdle.The result shows, shown the good absorbancy that is higher than based on the printing ink of control compounds based on the printing ink of The compounds of this invention.

The matrix of using in following form with below with reference to numeral:

Matrix title matrix numbering

HP Printing Pape r 1

HP Premium Plus Glossy Photo Media 2

Canon PR101 ^TMPrinting paper 3

Epson Premium Glossy Photo Media 4

Table 4

Embodiment number	Dyestuff	Matrix	Absorbancy (OD)
Embodiment number	Dyestuff	Matrix	Absorbancy (OD)	11	1	1	1.12
11	5	1	1.20	11	1	1	1.12
11	5	1	1.20	11	C1	1	1.03
11	C2	1	0.94	11	C1	1	1.03
11	C2	1	0.94
12	1	2	1.82
12	1	2	1.82	12	5	2	1.85
12	C1	2	1.76	12	5	2	1.85
12	C1	2	1.76	12	C2	2	1.55

Photostabilization

In order to measure photostabilization, aforesaid printed matter is at Atlas Ci5000Weatherometer ^TMIn shone 100 hours.The results are shown in the table 5, the embodiment numbering that wherein is used for preparing the dye composition of printing ink is shown in second hurdle.Fading extent after being exposed to light is with % absorbancy loss (OD) expression.The loss of % absorbancy is more little, and photostabilization is high more.The result shows, shown better photostabilization based on the printing ink of The compounds of this invention.

Table 5

Embodiment number	Dyestuff	Matrix	OD loses (%)
Embodiment number	Dyestuff	Matrix	OD loses (%)	13	1	3	26.9
13	5	3	29.9	13	1	3	26.9
13	5	3	29.9	13	C1	3	31.6
13	C2	3	32.4	13	C1	3	31.6
13	C2	3	32.4
14	1	4	16.5
14	1	4	16.5	14	5	4	16.5
14	C1	4	16.8	14	5	4	16.5
14	C1	4	16.8	14	C2	4	24.1

Claims

1. be selected from the compound of formula (1) compound and formula (2) compound or its salt:

Formula (1)

Formula (2)

Wherein:

A is the β naphthyl of formula X,

Formula X

Wherein ^*For with formula (1) or (2) in the tie point of azo group

P and q are 0,1 or 2 and p+q's and be not zero independently of one another;

B is optional phenylene or the naphthylidene that replaces;

N is 0 or 1; With

D is the optional pyrazolyl that replaces.

2. according to the compound or the salt of claim 1, wherein D is for having the pyrazolyl of at least one carboxyl, sulfo group or phosphino-(phosphato).

3. according to the compound or the salt of claim 1 or claim 2, wherein A does not have the group of non-sulfo group.

4. according to the compound or the salt of previous each claim, wherein p and q are 0,1 or 2 independently of one another, and condition is p+q's and be 1,2 or 3.

5. according to the compound or the salt of each previous claim, wherein B is the optional phenylene group that replaces.

6. according to the compound or the salt of previous each claim, wherein:

A is not replaced by the group of any non-sulfo group;

B has one or two to be selected from sulfo group, the optional C that replaces _1-6Alkyl, the optional C that replaces _1-6The substituent phenylene or the naphthylidene of alkoxyl group and the optional amino that replaces;

N is 0 or 1;

D is formula (3a), (3b) or (3c); Wherein:

Formula (3a) formula (3b) formula (3c);

R ²Be H, methyl, carbonamido or carboxyl;

R ³And R ⁴Independently of one another for having substituent phenyl or the naphthyl that one or two are selected from sulfo group and carboxyl; With

R ⁵Be C _1-4The alkyl carboxylic acid ester.

7. according to the compound or the salt of claim 6, wherein:

A is formula X ',

Formula X '

Wherein ^*For with formula (1) or (2) in the tie point of azo-group, p and q are 0,1 or 2 and p+q's and be 1,2 or 3 independently of one another;

B has substituent phenylene or the naphthylidene that one or two are selected from sulfo group, methyl, methoxyl group, oxyethyl group and 2-hydroxyl-oxethyl;

N is 0 or 1; With

D is formula (3a), (3b) or (3c):

Formula (3a) formula (3b) formula (3c);

Wherein:

R ²Be H, methyl, carbonamido or carboxyl;

R ⁵Be C _1-4The alkyl carboxylic acid ester.

8. according to the compound or the salt of previous each claim, wherein p+q's and be 2.

9. compound according to Claim 8 or salt, wherein p=1 and q=1.

10. compound according to Claim 8 or salt are formula 1C:

Formula 1C.

11. according to each salt of claim 1～10.

12. an ink composite comprises:

According to each compound or salt of claim 1～10; With

Liquid medium.

13., further comprise other pigment according to the ink composite of claim 12.

14., comprise by ink jet printing head on it, applying composition according to claim 12 or claim 13 with the method for image printing on matrix.

15. use paper, elevated projecting slide plate or fabric the composition printing or by printing according to the method for claim 14 according to claim 12 or claim 13.

16. an optional refillable ink jet printing head cartridge comprises one or more chamber and the composition according to claim 12 or claim 13 that is present at least one chamber.