HK1096114A - Organic solvent soluble metal complex azo dyes - Google Patents

Description

Organic solvent soluble metal complex azo dyes

Cross Reference to Related Applications

The present invention relates to and claims the benefit of the earlier filing date and priority of application No. 60/504,984 filed on 23/9/2003, which is hereby incorporated by reference in its entirety.

Technical Field

The present invention relates to organic solvent soluble dyes. In particular, the present invention relates to organic solvent soluble metal complex azo dyes containing chelated copper or nickel atoms.

Background

Metal complex azo compounds have been used for many years as organic solvent soluble dyes. A survey of the "color index" list published by the American Association of Textile Chemists and Society of dyers and Colourists (UK) shows that with one exception, all dyes are chelates of chromium and, to a lesser extent, cobalt and iron. The only exception appeared to be the non-ionic copper complex c.iSolvent Black 49. As these above-mentioned metals are in 3⁺As a result of the oxidation state, the dye chromophore is anionic accompanied by a cation derived from one of the alkali metals, such as sodium, or more commonly an organically substituted ammonium ion. Due to their ionic nature, most of these dyes have limited solubility in lower alcohols, glycol ethers, ketones and esters and similar materials, while generally not having significant solubility in aromatic and even more aliphatic hydrocarbons. These dyes also often have sulfonic acid groups which further limit their solubility, usually in weakly polar organic solvents. The dyes of the present invention are nonionic and contain no sulfonic acid groups.

It is therefore an advantage of some, but not necessarily all, embodiments of the present invention to provide a dye free of sulfonic acid groups that has a substantially broad solubility in organic solvents and can be converted to stable aqueous dispersions with or without the aid of conventional chemical dispersants.

Additional advantages of various embodiments of the invention are set forth in part in the description which follows and, in part, will be obvious to those having ordinary skill in the art from the description and/or from the practice of the invention.

Disclosure of Invention

One embodiment of the present invention is a dye composition comprising a dye represented by the formula:

one or more aromatic moieties wherein a and B are bonded through one or more azo and hydroazo groups; m is 2⁺A metal atom in an oxidized state; l is one or more water-soluble primary and/or secondary aliphatic amines; x and Y are independently one or more of oxygen and/or nitrogen. The aromatic moiety may be selected from the group consisting of: carbocyclic and heterocyclic moieties. The dye composition can be dissolved in an organic solvent. The dye composition may comprise an ionic or non-ionic metal complexed azo dye, the metal may be selected from, but not limited to, copper and/or nickel. The organic solvent may be selected from, but is not limited to, the following group: aliphatic hydrocarbons and lower alcohols.

One or more of a or B may be further substituted with a hydrocarbon chain containing from about 7 to about 24 carbon atoms, or may further comprise one or more hydrocarbon chains containing at least 6 carbon atoms. One or more of a or B may be further substituted by a group selected from the group consisting of: halogen, nitro, carbalkoxy, arylazo, sulfonamide, and substituted sulfonamide groups. L may be hydrophilic or hydrophobic. L may be selected from the group: di-, tri-and tetra-glycol amines, hydroxyethoxypropylamines, ethyleneamines, diethanolamine, glycol amines and more ethoxylated homologues, hydroxyalkoxypropylamine, N, N-dimethyl, diethylaminopropylamine and N, N, N, N-tetramethylethylenediamine. One or more of X and Y may be nitrogen, which nitrogen may be further substituted by alkyl or aryl.

Another embodiment of the present invention is a dye composition comprising a dye represented by the formula:

wherein C and D are one or more aromatic moieties bonded through one or more azo and hydroazo groups, and wherein one or more of C and D are substituted with a hydrophilic chain; m is 2⁺A metal atom in an oxidized state; n is one or more water-insoluble primary and/or secondary aliphatic amines; x and Y are independently one or more of oxygen and/or nitrogen. The hydrophilic chain may be derived from a water-soluble primary or secondary aliphatic amine, or from the condensation product of an aliphatic amine and ethylene oxide. One or more of C and D may further comprise other substituents selected from the group, but not limited to: halogen, nitro, carbalkoxy, arylazo, sulfonamide, and substituted sulfonamide groups. N may comprise from about 7 to 18 carbon atoms.

Another embodiment of the present invention is a dye composition represented by the formula:

the dye composition may comprise from about 10% to about 80% of a compatible solvent. The solvent may be selected from the group consisting of: n-propanol, 2-butanone, toluene, phenol glycol ether (phenol glycol ether), benzyl alcohol, and ethyl acetate, but is not limited thereto.

Another embodiment of the present invention is a dye composition comprising a copper or nickel complexed azo compound, having the general characteristics of a nonionic surfactant. I.e. one part of the molecule has covalently bonded hydrophobic or oleophilic alkyl chains comprising at least 7 carbon atoms, while another part of the same molecule has hydrophilic or oleophilic substituents.

Detailed Description

The present invention provides an organic solvent soluble non-ionic copper or nickel complexed azo dye having a broader range of solvent solubility and compatibility. In some embodiments, the dyes of the present invention have a very broad range of solvent solubilities from aliphatic hydrocarbons to lower alcohols, depending on the individual chemical composition. In other embodiments, the dyes are miscible in a variety of ratios with most organic solvents and are very resistant to crystallization or the formation of solid deposits when they are added, for example, to an ink. Embodiments of the dyes of the present invention are viscous liquids or tarry in their unsolvated state and are generally inconvenient to handle. It is expected that the dye will generally be provided as a stable flowable concentrate in a suitable solvent. The solvent may be partially, or even completely, substituted with a dispersant or surfactant or other suitable material so that the dye can be converted into a stable aqueous dispersion.

The broad solubility characteristics of the dye embodiments of the present invention are a result of their design as nonionic surfactants by incorporating into the molecule a hydrophobic hydrocarbon chain containing from 7 to 20, and in some embodiments 12, carbon atoms. Two or more hydrocarbon chains may be present, one of which may contain at least 6 carbon atoms.

Embodiments of the present invention also comprise a hydrophilic moiety, which may be provided by a primary or secondary aliphatic amino alcohol. For convenient access to industrial organic chemicals, this part of the molecule can be attached to the rest of the structure by an amine function acting as a ligand for the copper or nickel atom. In some embodiments, preferred ligands are di-, tri-, and tetra-glycol amines, hydroxyethoxypropylamines, or ethylene amines, or any other suitable amine. However, the opposite structure, in which the hydrophilic part of the molecule is part of an organic azo structure and the hydrophobic function is provided by an aliphatic amine as a ligand for the copper atom, is also effective.

The structure of the dyes of the embodiments of the present invention may be symbolically represented as:

FIG. 1 shows a schematic view of a

Wherein A and B are aromatic moieties to which an azo or hydrazo (hydrazo) group obtained by a conventional azo synthesis procedure is bonded. A and B, which are in close proximity to the azo bond, both carry X and Y atoms covalently bonded at 2⁺On the metal atom M in the oxidized state. In further embodiments of the present invention, the metal may be copper or nickel, but is not limited thereto. In addition, one of the nitrogen atoms of the azo bond acts as an electron donor to the metal atom. In yet another embodiment, the atoms X and Y may be oxygen or nitrogen. In the latter case, the nitrogen atom may be further substituted by a hydrocarbyl or aryl group, or be part of a heterocyclic ring structure.

In yet another embodiment, at least one of a or B is substituted with a hydrocarbon chain containing from 7 to 24, and in some examples about 12 carbon atoms. The total number of carbon atoms may be present in one or more of the components. Both a and B may also have other substituents that do not impart significant water solubility to the molecule, such as halogen, nitro, carbalkoxy, sulfonamide or substituted sulfonamide groups. Another substituent may be an arylazo group, which may or may not involve chelation of another copper or nickel atom.

L is a water-soluble primary or secondary aliphatic amine in which the nitrogen atom functions as a ligand for the metal atom. Suitable compounds include diethanolamine, glycol amine and more ethoxylated homologues, and hydroxyalkoxypropylamine and ethylene diamine.

Other useful ligands include N, N-dimethyl or diethylaminopropylamine and N, N, N, N-tetramethylethylenediamine. In some cases, the hydrophobic-hydrophilic equilibrium in a particular application may indicate the particular amine ligand used.

Alternative embodiments of the invention are illustrated below:

FIG. 2

Wherein C and D are aromatic moieties to which azo or hydrazo groups obtained by conventional azo synthesis procedures are bonded. C and D, both having X and Y atoms covalently bonded at 2, are immediately adjacent to the azo bond⁺On the metal atom M in the oxidized state. In some embodiments, the metal may be copper or nickel, but is not limited thereto. In addition, one of the nitrogen atoms of the azo bond acts as an electronic ligand for the metal atom. The atoms X and Y may be oxygen or nitrogen, but are not limited thereto. In the latter case, the nitrogen atom may be further substituted by a hydrocarbyl or aryl group, or be part of a heterocyclic ring structure.

At least one of C or D is substituted with a hydrophilic chain derived from a fully water-soluble primary or secondary aliphatic amine, or derived from the condensation product of an aliphatic amine and ethylene oxide. Both C and D may also have other substituents that do not impart significant water solubility to the molecule, such as halogen, nitro, carbalkoxy, sulfonamide or substituted sulfonamide groups. Another substituent may be an arylazo group, which may or may not involve chelation of other metal atoms.

N is a water-insoluble primary or secondary aliphatic amine in which the nitrogen atom acts as a ligand for the copper or nickel atom. Suitable compounds include aliphatic amines having 7 or more carbon atoms, in certain embodiments 12 to 18 carbon atoms. In some cases, the hydrophobic-hydrophilic equilibrium in a particular application may indicate the particular amine ligand used.

The following examples serve to illustrate, but not to limit the scope of the invention:

example 1

To a solution of 15g of sodium nitrite in 60ml of water was added 28g of technical grade (0.2 mole) 4-nitroaniline and stirred until a homogeneous slurry was obtained. The slurry was then added over about 5 minutes to 32% of hydrochloric acid, which had been cooled to-5 ℃ by the addition of ice. Additional ice was provided as a ligand system to prevent the temperature from rising above 5 ℃ during slurry addition. The mixture was then stirred for about 15 minutes until it became as clear as possible. At this point, a small amount of filter aid was added while still maintaining its temperature below 5 ℃ to filter the 4-nitrophenyldiazonium chloride. The filtered solution is then transferred to a stirred beaker or flask and any remaining nitrite ions are reduced with sulfamic acid. Next, 32g of 2, 5-dimethoxyaniline dissolved in 200ml of water and 25g of 32% hydrochloric acid are added via a dropping funnel over 15 minutes. Azo coupling begins immediately and a thick brown suspension forms. At the end of the addition of the 2, 5-dimethoxyaniline solution, a sufficient amount of 30% aqueous sodium acetate solution was added to raise and stabilize the pH at 3. The coupling, which is maintained at 5-10 ℃ by the addition of ice, proceeds rapidly, as detected by the disappearance of the diazo reaction to basic H acid.

At this point an additional 25g of 32% hydrochloric acid was added to the slurry of the aminoazo dye, followed by a slow addition of 15g of sodium nitrite dissolved in 60ml of water, during which the temperature may be raised to 20-25 ℃. The mixture was stirred for 30 minutes after nitrite addition to complete the diazotization process, after which any remaining nitrite ion was reduced by the addition of a small amount of sulfamic acid.

Next, a xylene solution containing 0.2 mole of 3-hydroxy-4' -dodecyldiphenylamine is prepared and added to the diazo compound. The diazo compound is rapidly transferred from the aqueous phase to the organic phase, wherein the azo coupling is essentially immediate. When all the brown azo compound had disappeared from the aqueous phase, the pH of the system was raised to about 5 by adding sodium hydroxide solution and the system was heated to 80 ℃. The stirring was then stopped and the mixture was allowed to separate into two phases. The lower aqueous phase was discarded and the upper organic phase was transferred to a heated stirred flask equipped with a distillation apparatus. To the flask was added 0.2g copper atoms in the form of basic copper carbonate, followed by 0.22g moles of diethanolamine. The contents of the flask were then heated to 140 ℃ and any water formed was distilled off. The cuprification process is monitored by thin layer chromatography ("TLC") during which conversion of the intermediate dark purple dye to its blue-black copper complex is observed.

After the reaction was complete, the reaction mixture was cooled and filtered. The filtered dye can then be cooled and calibrated to color intensity by adding xylene, or it can be placed in a clean flask and heated to 140 ℃ under vacuum to remove all xylene. The final weight of the viscous tarry dry dye is measured and thereafter can be diluted to a 60% or even 70% solution in ethanol, n-propanol, methyl ethyl ketone, ethyl acetate or toluene solvent, but the solvent is not limited thereto. It was found that all concentrates were resistant to crystallization even after long storage at-25 ℃. One of these concentrates was diluted to a 5% solution with the same solvent and then applied to white bond paper, drying to leave a strong blue-black film with excellent color age which did not penetrate into water even after prolonged immersion.

Example 2

To a 5 liter flask surrounded by an ice bath were added 300g of ice and 50g of water. The mixture was stirred and 130g of 96% sulfuric acid was added followed by 100g aniline, forming a white dispersion of aniline sulfate. The mixture was then cooled to-5 ℃ by the addition of ice and diazotized below 3 ℃ by the addition of 190g of 40% aqueous sodium nitrite solution. The mixture was stirred until all the aniline sulfate white particles dissolved to a clear solution. After approximately 5 minutes of agitation, unreacted nitrite ions were removed by adding a small amount of sulfamic acid. To the diazo compound was added 140g of 2-methoxy-5-methylaniline while the temperature was raised to 5-10 ℃. After 15 minutes of stirring, sufficient 30% aqueous sodium acetate was added to raise the pH of the reaction to 3.5. The reaction was stirred at 10-12 ℃ for 4 hours to substantially complete the azo coupling. Next, 600g of xylene was added, followed by 110g of concentrated sulfuric acid. After a few minutes of stirring, the amino azo compound is diazotized at 20-25 ℃ by adding 200g of a 40% sodium nitrite solution. The positive test for nitrite was maintained for 10 minutes and then eliminated with sulfamic acid.

The diazo compound will be a homogeneous brown solution in which most of the xylene is emulsified. To the diazo was added an 80% solution of 2- (4' -dodecylphenyl) aminonaphthalene having an azo coupling equivalent of 1.1 mole. The diazo rapidly transfers from the aqueous phase to the upper organic phase, forming a deep blue-violet dye. To the solution was added 30g of a 28% aqueous ammonia solution followed by about 350g of a 50% sodium hydroxide solution to raise the pH of the system to 7.5. The system was then heated to 80 ℃ and the reaction mixture allowed to separate into two phases when stirring was stopped. The lower aqueous phase was removed and discarded. To the dye phase were added 1g of copper atom in the form of copper hydroxide (cupric hydrate), followed by 40g of 2-ethylhexanoic acid and 200g of diethylene glycol-3-aminopropyl ether. The mixture was heated with stirring as in example 1. The cuprification process was monitored by TLC. After the reaction is complete, the dye is filtered and the color is calibrated with xylene to give about 1800g of product. Alternatively, the xylene may be stripped under vacuum and replaced with, but not limited to, n-propanol, 2-butanone, ethyl acetate, and phenoxyethanol to form a freeze-stable fluid concentrate. When diluted with solvent and dried on paper, the dye produced a thin purplish black film with the reminiscent shade of the azine dye Nigrosine.

Example 3

The synthesis of example 2 was repeated, except that 165g of diethylene glycol-3-aminopropyl ether was replaced by 220g of 1-propylamine-3, 3' - [ oxybis (2, 1-ethanedyloxy) ] bis. The resulting dye had very similar properties to example 2, except that it was significantly more blue in shade.

Example 4

The synthesis of example 2 was repeated except that diethylene glycol-3-aminopropyl ether was replaced by 100g of triethylenetetramine. Again, the final dye was similar, but was more blue in shade than example 1.

Example 5

52g of 3-aminobenzotrifluoride are mixed with 50g of 2-methyl-2-butanol and 200ml of water are added, followed by 38g of 96% sulfuric acid. The mixture was frozen to 5 ℃ and diazotized by adding 55g of 40% sodium nitrite solution. When the solution became clear, the remaining nitrous acid was reduced with sulfamic acid. The diazo compound is then added to 38g of 2-amino-p-cresol which has been dissolved in a mixture of 100g of 2-methyl-2-butanol and 100g of an aqueous solution containing 0.3 equivalents of naphthalenesulfonic acid, to which in each case 1g of acrylic acid and butyl methacrylate are added as free radical inhibitors. Coupling proceeds rapidly at 5-10 ℃ and is accomplished by adding sufficient sodium acetate solution to raise the pH to 2.5. When the azo coupling was complete, 150g of toluene and 55g of 32% hydrochloric acid were added to the reaction. At this point 60g of 40% sodium nitrite solution was added to diazotize the amino azo compound. When the reaction was complete, 0.3 equivalents of the composition prepared by condensing 0.3 equivalents of 3-aminophenol with 0.6 equivalents of 2-ethylhexyl glycidyl ether dissolved as an 80% solution in toluene was added to the system. The coupling proceeds rapidly and a magenta diazo dye is formed. At this point the coupling was adjusted to pH 9 by the addition of ammonia and heated to 60 ℃. At this point 0.3 molar equivalents of nickel chloride was added to the system with sufficient ammonia to prevent the pH from dropping below 8.0. The metal complex was formed substantially immediately as determined by TLC. At this point 2-ethylhexoxy propylamine was added to the system and after a few minutes the agitation was stopped allowing the dye layer to separate into the upper phase. The dye was then dried under vacuum to 110 ℃ to give a total weight of 700g containing n-propanol. The product is a violet black with very good colour age and solvent compatibility.

Example 6

47.2g of 98% active 4-nitro-2-aminophenol are dissolved in 150ml of cold water containing 75ml of 36% hydrochloric acid. At this point the solution was filtered to remove a small amount of insoluble material, which was then frozen to 0 ℃. The solution was diazotized at 0-10 c by addition of 55g of 40% aqueous sodium nitrite solution, which resulted in the precipitation of the diazo compound in its quinone diazide configuration. After destroying the remaining nitrous acid with sulfamic acid, a 50% potassium carbonate solution was carefully added to raise the pH of the system to 6.0. At this point, 34g of resorcinol (m-dihydroxybenzene or 1, 3-dihydroxybenzene; formula C6H6O2) solution in 100ml of water was added. The pH of the mixture was then adjusted to 8.0 by the addition of additional potassium carbonate solution. The coupling reaction was very fast, the monoazo compound started to dissolve in water and the coupling was terminated by adding 65g of 45% potassium hydroxide solution. To this solution was added a diazo compound prepared by diazotizing 80g of p-dodecylaniline in the presence of 150g of xylene. As the bisazo coupling proceeds, the resulting dye is emulsified into the xylene phase. When the coupling was complete, 0.3 molar equivalents of copper acetate was added and the pH was lowered to 4.5. When TLC indicated that metallization was complete, the system was heated to 80 ℃ and allowed to separate. The above organic dye phase was transferred to a dry flask and 25g of diglycolamine (2- (2-aminoethoxy) ethanol) was added. The resulting water and organic solvent were removed under vacuum to a temperature of c. The dye was diluted to a total of 400g with n-propanol and filtered. The product is a bright brown dye with good color age.

Example 7

Technical-grade 4, 4' -diaminobenzanilide (23g) was suspended in 200ml of stirred cold water. Then, 50g of 32% hydrochloric acid was added. The amine initially dissolves and then partially crystallizes as its dihydrochloride. The mixture was then cooled to 0-5 ℃ by the addition of ice and the diamine was diadzed by the addition of 35g of a 40% sodium nitrite solution while the temperature was maintained below 10 ℃ by the addition of ice. After a short stirring, a clear solution of the bisazo compound is obtained. Any remaining nitrite was reduced with a small amount of sulfamic acid and thereafter a solution containing 0.1 mole of 2, 5-dimethoxyaniline as prepared in example 1 was added. Azo coupling proceeds relatively quickly, and only one diazo group on the disazo 4, 4' -diaminobenzanilide is active under these conditions. When the coupling is complete, the aminoazo diazo compound formed is added to a solution of 27.5g of p-dodecylphenol and 15g of 45% aqueous potassium hydroxide dissolved in 150ml of water. Additional base was added as needed to maintain the coupling pH at 11-12. After the reaction was completed, 200g of xylene was added, followed by addition of hydrochloric acid to lower the pH to 5. The dye phase separated from the water, most of the water was removed and replaced with 150ml of clean water. Then 30g of hydrochloric acid was added, followed by ice to adjust the temperature to 20-25 ℃. At this time, 19g of a 40% sodium nitrite solution was added to diazotize the aminodisazo compound. When the nitrite remaining was reduced with sulfamic acid, diazotization was complete after about 30 minutes, after which a xylene solution containing 0.1 moles of 2- (4' -dodecylbenzene) aminonaphthalene was added. The coupling reaction proceeded rapidly to form a dark green-blue dye which was isolated and placed in a flask along with 0.1g moles of copper hydroxide and 53g of 2-aminoethoxyethanol. The reaction proceeded as in example 2 to produce a greenish black copperized azide dye. The dye has excellent solubility in most organic solvents and has good light fastness and water resistance.

Example 8

50g of 90% active 4, 4-diaminodiphenylamine sulfate are dissolved in 150ml of cold water and 50ml of 32% hydrochloric acid. The solution was frozen to 5 ℃ and at this temperature it was subjected to bisdiazotization by addition of 55g of a 40% sodium nitrite solution. After a clear, pale yellow solution was obtained, the remaining nitrous acid was reduced with sulfamic acid. To this diazo compound was added a solution of 25g of 2, 5-dimethoxyaniline previously prepared dissolved in a mixture of 15g of 70% nitric acid and 50ml of water, which was then cooled to 5 ℃. The coupling reaction was stirred until the bisazo diphenylamine could no longer be detected in the aqueous phase. At this point 0.15 molar equivalents of substantially mono heptylated 2-naphthol dissolved in 200ml of toluene was added to the reaction. A 50% sodium hydroxide solution was added dropwise until the pH reached 11, which allowed the bisazo coupling to be completed. The pH of the system was then adjusted to 7 with hydrochloric acid, after which 75ml of hydrochloric acid was added and the temperature was adjusted to 20 ℃. At this point 30g of a 40% solution of sodium nitrite is added at 20-25 ℃ which allows the pendant amino groups to be rapidly diazotized. At this point an additional 0.15 molar equivalent of heptylated β -naphthol was added and the pH raised to 4.5, yielding a deep blue black azide dye which separated into the upper organic phase. The azide dye was separated and placed in the reaction flask. At this point 50g of basic copper carbonate was added followed by 10g of 2-ethylhexanoic acid and 60g of 3-aminopropyldiglycol. The mixture was heated to 130 ℃ while water and solvent were distilled off from the system. Cuprification was monitored by TLC during which the organic dye was converted to a dark green compound. At the end of the reaction, all material volatilized to 110 ℃ was stripped under vacuum and the contents of the flask were diluted with an equal weight of toluene. The product produced a strong black shade in 5% solution in MEK-based inkjet inks. The prints obtained from the inks have excellent colour fastness and perfect water resistance.

Example 9

0.2 moles of 4-amino-N- (3' -propoxyethoxyethoxyethanol) phenylsulfamoyl, obtained by condensation of aminopropoxyethoxyethoxyethoxyethanol with N-p-acetamidophenylsulfamoyl chloride, followed by hydrolysis of the acetyl group, was diazotized and azo compounds were coupled to an equivalent amount of 2, 5-dimethoxyaniline using the techniques described in detail above. The newly formed amino azo compound is then diazotized and coupled to 2- (3' -propylmorpholino) aminonaphthalene. The resulting violet disazo dye was extracted under slightly basic conditions into a mixture of toluene and n-butanol. After separation from the aqueous phase, the compound is converted to its 1: 1 copper complex using bis 2-ethylhexylamine as a ligand. The final dye product is a reddish navy dye having good organic solvent solubility and relatively easy dispersibility in water to form a stable microemulsion. After it was diluted and applied to paper, it was dried to give a blue-black film that was completely resistant to water penetration.

Example 10

Small pieces of light oak wood were stained with a 5% solution of the brown dye detailed in example 6. After drying the wood appeared like antique oak. Exposure of the wood on a Q Panel weathering tester causes the sample pattern to become darker than the faded color after extended exposure.

Example 11

A simple permanent marker ink was formulated by mixing 20g of the unmetallized disazo dye synthesized in example 2 with 10g of a 50% n-propanol solution UNIREZ ® 7019(UNIREZ ® is a registered trademark of the Union-Camp Corporation), followed by 70g of n-propanol. A similar ink was then made with the finished cuprified dye. The two inks are loaded into a single permanent marker which is used to draw adjacent parallel lines on white adhesive paper. After drying, the paper was exposed to a Q-plate xenon arc lamp lightfastness tester according to the guidelines of method 16 in the American Association of Textile Chemists and Colorists. The unmetallized dye quickly started to fade and met a color age of 2 on the blue wood scale (scale). The comparative copper complex dyes started to fade only after a very long exposure period and were rated on the color age scale of 7-8.

Example 12

The solvent phenoxyethanol based ball-point pen ink was formulated to contain 20% of the dye synthesized in example 8. The ink was filled into a ball point pen cartridge and placed on a writing machine. Two very common brands of ball point pens were purchased and also placed in the machine which was set to write parallel written marks. The written sample was exposed to a Q-plate age tester, which showed that the ink in the purchased pen was very weak to light, since the ink was based on the very common c.i. solvent Black 46. In contrast, the ink made from the dye prepared in example 8 showed no loss of brightness (intensity), even though the ink in the other pens had photo-faded to colorless. In another test, 10% of its ink dye based primarily on c.i. solvent Black 46 was replaced with the dye of example 8. Further writing and exposure takes place. Even though c.1.solvent Black 46 has faded to colorless, the written content remains readily discernible due to the presence of the copper complex dye.

Example 13

The unsolvated dye (10g) prepared in example 2 was mixed with 4g of light vegetable oil and 6g of nonionic surfactant TRITON ® X100(TRITON ® is a registered trademark of Dow Corporation). The resulting mixture was slowly added to 200ml of gently stirred water in a disperser/mixer. After a short mixing, a homogeneous black dispersion was obtained. Samples of the dispersion were coated onto brown kraft paper, board, which is commonly used for packaging goods. A strong black coloration is formed, which has excellent water resistance.

Example 14

An n-propanol based industrial packaging inkjet ink was prepared from the dye synthesized in example 2. This ink was compared to a similar ink made from c.i. solvent Blacks 29 and 48, referred to in the art as a "baseline" product. The light fade resistance of the inks containing the competitive dyes was significantly poorer than that of the inks containing the dye of example 2.

The numerous features and advantages of the invention have been set forth in the foregoing description, together with details of the structure and function. The novel features set forth in the appended claims. The disclosure, however, is illustrative only, and changes may be made in detail, within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.

Claims (20)

1. A dye composition comprising a dye represented by the formula:

wherein a and B are one or more aromatic moieties bonded through one or more azo and hydroazo groups; m is 2⁺A metal atom in an oxidized state; l is one or more water-soluble primary and/or secondary aliphatic amines; x and Y are independently one or more of oxygen and/or nitrogen.

2. The dye composition of claim 1, wherein the aromatic moiety is selected from the group consisting of: carbocyclic and heterocyclic moieties.

3. The dye composition according to claim 1, wherein the dye composition is soluble in an organic solvent.

4. The dye composition according to claim 1, wherein the dye composition comprises a nonionic copper-complexed azo dye.

5. The dye composition according to claim 1, wherein the dye composition comprises a nonionic nickel complexed azo dye.

6. The dye composition according to claim 3, wherein the organic solvent is selected from the group consisting of: aliphatic hydrocarbons and lower alcohols.

7. The dye composition according to claim 1, wherein one or more of a or B is further substituted with a hydrocarbon chain containing from about 7 to about 24 carbon atoms.

8. The dye composition according to claim 1, further comprising one or more hydrocarbon chains containing at least 6 carbon atoms.

9. The dye composition according to claim 1, wherein one or more of a or B is further substituted by a group selected from the group consisting of: halogen, nitro, carbalkoxy, arylazo, sulfonamide, and substituted sulfonamide groups.

10. The dye composition according to claim 1, wherein L is hydrophilic.

11. The dye composition according to claim 1, wherein L is hydrophobic.

12. The dye composition according to claim 1, wherein L is selected from the group consisting of: di-, tri-and tetra-glycol amines, hydroxyethoxypropylamines, ethyleneamines, diethanolamine, glycol amines and more ethoxylated homologues, hydroxyalkoxypropylamine, N, N-dimethyl, diethylaminopropylamine and N, N, N, N-tetramethylethylenediamine.

13. The dye composition according to claim 1, wherein one or more of X and Y is nitrogen, and the nitrogen is further substituted by an alkyl or aryl group.

14. A dye composition comprising a dye represented by the formula:

wherein C and D are one or more aromatic moieties bonded through one or more azo and hydroazo groups, wherein one or more of C and D are substituted with a hydrophilic chain; m is 2⁺A metal atom in an oxidized state; n is one or more water-insoluble primary and/or secondary aliphatic amines; and X and Y are independently one or more of oxygen and/or nitrogen.

15. A dye composition according to claim 14 wherein the hydrophilic chain is derived from a water-soluble primary or secondary aliphatic amine or from the condensation product of an aliphatic amine and ethylene oxide.

16. The dye composition according to claim 14, wherein one or more of C and D may further comprise other substituents selected from the group consisting of: halogen, nitro, carbalkoxy, arylazo, sulfonamide, and substituted sulfonamide groups.

17. The dye composition according to claim 14, wherein N comprises from about 7 to about 18 carbon atoms.

18. A dye composition comprising a dye represented by the formula:

19. the dye composition of claim 18 further comprising from about 10% to about 80% of a compatible solvent.

20. The dye composition according to claim 19, wherein the solvent is selected from the group consisting of: n-propanol, 2-butanone, toluene, phenol glycol ether, benzyl alcohol, and ethyl acetate.