MXPA06013691A - Colorant compounds - Google Patents

Abstract

Disclosed are colorant compounds of the formulae wherein R1, R2, R3, M, A, E, G, J, m, n, and p are as defined herein.

Description

COLORING COMPOUNDS FIELD OF THE INVENTION Coloring compounds are described herein. More specifically, coloring compounds are described herein, particularly suitable for use in hot melt or phase change inks. One modality is directed to formulas coloring compounds where Ri, R2 and R3 each, independently of the others, is a hydrogen atom, an alkyl group, Ref .: 175557 including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms may or may not be present in the alkyl group, an arylalkyl group, including substituted and unsubstituted arylalkyl groups, wherein the alkyl portion of the Arylalkyl group can be linear or branched, saturated or unsaturated, cyclic or acyclic and substituted or unsubstituted and where heteroatoms may or may not be present in the aryl or alkyl portion of the aryl group, or an alkylaryl group, including substituted or unsubstituted alkylaryl groups , wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and wherein heteroatoms may or may not be present in the aryl or alkyl portion of the alkylaryl group, provided that the number total carbon atoms and heteroatoms, excluding the atoms in any substituents, in Ri + R2 + R3 is at least about 18, M is a metal atom, each A, each E and each G, independently of the other, represents a substituent on a phenyl or pyrazolone ring, where G can also be an atom of hydrogen, m is an integer of 0, 1 or 2, p is an integer of 0, 1, 2, 3 or 4, J represents (i) a hydrogen atom, (ii) an alkyl group (including linear and branched alkyl, saturated and unsaturated, cyclic and acyclic and substituted and not substituted, and where heteroatoms may or may not be present in the alkyl group), (iii) an aryl group (including substituted and unsubstituted aryl groups, and wherein heteroatoms may or may not be present in the aryl group (iv) an arylalkyl group ( including substituted and unsubstituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated and cyclic or acyclic and where heteroatoms may or may not be present in any of the aryl or alkyl portion of the arylalkyl group, or ( v) an alkylaryl group (including substituted and unsubstituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, and cyclic or acyclic, and where heteroatoms may or may not be present in any of the aryl moiety or alkyl of the alkylaryl group), wherein two or more substituents on the phenyl or pyrazolone rings may be attached to form a ring, and n represents an integer of 1, 2 or 3. BACKGROUND OF THE INVENTION In general, phase change inks (sometimes referred to as "hot-melt inks") are in solid phase at room temperature, but there are in liquid phase at the high operating temperature of an ink jet printing device. At the operating temperature of the jet, drops of water are ejected liquid inks of the printing device, and, when the ink drops come in contact with the surface of the recording substrate, either directly or via an intermediate hot transfer band or drum, they solidify rapidly to form a predetermined pattern of ink drops solidified. Phase change inks have also been used in other printing technologies, such as printing by engraving, as described, for example in U.S. Patent No. 5,496,879 and German Patent Publications DE 4205636AL and DE 4205713AL, the descriptions of each of which are fully incorporated here as a reference. Phase change inks for color printing typically comprise a phase change ink carrier composition which is combined with a colorant compatible with the phase change ink. In a specific modality, a series of colored phase change inks can be formed by combining ink-carrying compositions with compatible subtractive primary dyes. Phase change inks colored with subtractive primary dyes may comprise four component dyes, namely cyan, magenta, yellow and black, although the inks are not limited to those four colors. Those inks colored with subtractive primary dyes can be formed using a single dye or a mixture of dyes. By For example, magenta can be obtained by using a mixture of red solvent dyes or a black composition can be obtained by mixing several dyes. U.S. Patent No. 4,889,560, U.S. Patent No. 4,889,761 and U.S. Patent No. 5,372,852, the descriptions of which are all fully incorporated herein by reference, teach that the primary subtractive dyes employed may comprise dyes of the class of solvent dyes, disperse dyes, acid and modified direct dyes and basic color index (CI) dyes. U.S. Patent No. 5,621,022, the disclosure of which is incorporated herein by reference, describes the use of a specific class of polymeric dyes in phase change ink compositions. Phase change inks have also been used for applications such as postal marking, industrial marking and labeling. Phase change inks are desirable for inkjet printers because they remain in a solid phase at room temperature during shipping or transport, long-term storage and the like. In addition, the problems associated with nozzle clogging as a result of ink evaporation with liquid inkjet inks are largely eliminated, thereby improving the reliability of ink jet printing. inks In addition, in the phase change ink jet printers where the ink droplets are applied directly onto the final recording substrate (e.g., paper, transparency material, and the like), the droplets solidify immediately after contact with the ink. substrate, so that the migration of the ink along the print medium is avoided and improves the quality of the point. Compositions suitable for use as phase change ink carrier compositions are known. Some representative examples of references describing these materials include U.S. Patent No. 3,653,932, U.S. Patent No. 4,390,369, U.S. Patent No. 4,484,948, U.S. Patent No. 4,684,956, U.S. Patent No. 4,851,045, U.S. Patent No. 4,889,560, U.S. Patent No. 5,006,170, U.S. Patent No. 5,151,120, U.S. Patent No. 5,372,852, U.S. Patent No. 5,496,879, U.S. Patent Publication 0187352, U.S. Patent Publication 0206286, U.S. Patent Publication DE 4205636AL, German Patent Publication 4205636AL, German Patent Publication DE 4205713AL, and PCT Patent Application WO 94/04619, the descriptions of each of which are hereby fully incorporated by reference. The carrier materials suitable may include paraffins, microcrystalline waxes, polyethylene waxes, ester waxes, fatty acids and other waxy materials, materials containing fatty amide, sulfonamide materials, resinous materials made from different natural sources (liquid rosin resins and resin rosin esters). rosin, for example), and many synthetic resins, oligomers, polymers and copolymers. U.S. Patent No. 6,147,140 (Jaeger et al.) The disclosure of which is hereby incorporated by reference, discloses a phase change ink composition comprising a phase change ink carrier system in combination with a coloring system compatible, the coloring system comprising a combination (1) black dye having an absorbance in the region of 475 nanometers, which is less than 80 percent of the absorbance in the region of 580 nanometers and (2) a sufficient amount of minus another dye having an absorbance in the region of 475 nanometers, whereby the dye has an absorbance ratio in the region of 475 nanometers to the region of 580 nanometers from about 0.92: 1.0 to about 1.01: 1.0. Although known compositions and processes are suitable for their intended purposes, there remains a need for improved coloring compounds. In addition, there remains a need for coloring compounds particularly suitable for use in phase change inks. In addition, there remains a need for coloring compounds with a desirable degree of thermal stability. Additionally, there remains a need for coloring compounds that exhibit a desirable degree of solubility in the vesicles employed in phase change inks. There is also a need for coloring compounds that are compatible with phase change ink vehicles capable of operating at reduced energy requirements. In addition, there is a need for coloring compounds that exhibit a desirably high chromaticity in phase change inks. In addition, there is a need for coloring compounds that exhibit a satisfactory hue in phase change inks. Additionally, there is a need for coloring compounds that exhibit a high degree of light resistance in phase change inks. There also remains a need for coloring compounds that exhibit a relatively low degree of diffusion and shifting towards the attached printed areas of different colors when incorporated into phase change inks and printed. In addition, there remains a need for coloring compounds that are safe to handle. In addition, there remains a need for coloring compounds that allow the generation of prints with a reduced stack height.

SUMMARY OF THE INVENTION Coloring compounds of the formulas are described herein where Ri, R2 and R3 each, independently of the others, is a hydrogen atom, an alkyl group, including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms may be present or not in the alkyl group, an arylalkyl group, including substituted and unsubstituted arylalkyl groups, wherein the alkyl of the arylalkyl group can be linear or branched, saturated or unsaturated, cyclic or acyclic and substituted or unsubstituted and where heteroatoms may or may not be present in the aryl or alkyl portion of the aryl group, or an alkylaryl group, including substituted alkylaryl groups or unsubstituted, wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where heteroatoms may or may not be present in the aryl or alkyl portion of the alkylaryl group, provided that the total number of carbon atoms and heteroatoms, excluding the atoms in any substituents, in Ri + R2 + R3 is at least about 18, M is a metal atom, each A, each E and each G, independently of the other, represents a substituent on a phenyl or pyrazolone ring, where G can also be a hydrogen atom, m is an integer of 0, 1 or 2, p is? n integer of 0, 1, 2, 3 or 4, J represents (i) a hydrogen atom, (ii) an alkyl group (including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms may or may not be present in the alkyl group), (iii) an aryl group (including substituted and unsubstituted aryl groups, and where heteroatoms may or may not be present in the aryl group (iv) an arylalkyl group (including substituted and unsubstituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated and cyclic or acyclic and where they may or may not be present heteroatoms in either the aryl or alkyl portion of the arylalkyl group, or (v) an alkylaryl group (including substituted and unsubstituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, and cyclic or acyclic, and where heteroatoms may or may not be present in any of the aryl or alkyl portion of the alkylaryl group), where two or more substituents on the phenyl or pyrazolone rings may be joined to form a ring, and n represents an integer of 1. , 2 or 3. DETAILED DESCRIPTION OF THE INVENTION General compounds of the formulas are described herein where every A, every E and every G, independently they each represent a substituent on a phenyl or pyrazolone ring, such as (but not limited to) an alkyl group (including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where they may be present or non-heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like in the alkyl group) in an embodiment with at least one carbon atom and in an embodiment with not more than about 50 carbon atoms, in another embodiment with no more than about 18 carbon atoms, and in another embodiment with no more than about 2 carbon atoms, although the number of carbon atoms may be outside those ranges, an aryl group (including substituted and unsubstituted aryl groups and where heteroatoms may be present or not, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like in the aryl group), in an embodiment with at least about 5 carbon atoms and in another embodiment with at least about 6 carbon atoms and in an embodiment with no more than about 20 carbon atoms, in another embodiment with no more than about 14 carbon atoms and in another embodiment with no more than about 10 carbon atoms. carbon, although the number of carbon atoms may be outside those ranges, such as phenyl, naphthyl, anthryl or the like, an arylalkyl group (including substituted and unsubstituted arylalkyl, wherein the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated cyclic or acyclic, and where heteroatoms may be present or not, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like in any one of the aryl or alkyl portions of the arylalkyl group), in an embodiment with at least about 6 carbon atoms, and in another embodiment with at least about 7 carbon atoms and in an embodiment with not more than about 30 carbon atoms , in another embodiment with no more than about 18 carbon atoms, and in another embodiment with no more than about 12 carbon atoms, although the number of carbon atoms may be outside those ranges, such as benzyl or the like, a group alkylaryl (including substituted and unsubstituted alkylaryl groups, wherein the alkyl portion of the arylalkyl group can be linear or branched, saturated or unsaturated and cyclic or acyclic, and where heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like can be present in any of the aryl or alkyl portions of the alkylaryl group), in a mode with at least about 6 carbon atoms, and in another embodiment with at least about 7 carbon atoms, and in an embodiment with no more than about 30 carbon atoms, in another embodiment with no more than about 18 carbon atoms. carbon and in another embodiment with no more than about 12 carbon atoms, although the number of carbon atoms may be outside those ranges, such as tolyl or the like, a hydroxy group, a halogen atom, an amine group (including primary, secondary or tertiary amine), an imine group, an ammonium group, a cyano group, a pyridine group, a pyridinium group, an ether group, an aldehyde group, a ketone group, an ester group, an amide group, a group carbonyl, a thiocarbonyl group, a sulfate group, a GRAPO sulfonate, a sulfonic acid group, a sulfide group, a sulfoxide group, a phosphine group, a phosphonium group, a phosphate group, a nitrile group, a mercapto group, a group nitro, a nitroso group, a sulfone group, an acyl group, an azo group, a cyanate group, a carboxylate group, a carboxylic acid group, a urethane group, a urea group, and the like, where G can also be an atom of hydrogen, M is a whole number of 0, 1 or 2, p is an integer of 0, 1, 2, 3 or 4 and J represents (i) a hydrogen atom, (ii) an alkyl group (including linear and branched, saturated and unsaturated alkyl groups, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like may be present in the alkyl group), in a mode with at least one carbon atom, and in a modality with no more than about 50 carbon atoms, in another embodiment with no more than about 18 carbon atoms and in another embodiment with no more than about 2 carbon atoms, although the number of carbon atoms may be outside those ranges, (iii) an aryl group (including substituted and unsubstituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like may be present in the aryl group), in an embodiment with at least about 5 carbon atoms , and in another embodiment with at least about 6 carbon atoms, and in an embodiment with no more than about 20 carbon atoms, and in another embodiment with no more than about 14 carbon atoms, and in another embodiment with no more of about 10 carbon atoms, although the number of carbon atoms may be outside those ranges, such as phenyl, naphthyl, anthryl or the like, (iv) an arylalkyl group (including aryl groups) substituted and unsubstituted alkyl, wherein the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated and cyclic or acyclic and where heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like may be present in the any of the aryl or alkyl portions of the arylalkyl group), in an embodiment with at least about 6 carbon atoms and in another embodiment with at least about 7 carbon atoms; carbon, and in an embodiment with no more than about 30 carbon atoms, in another embodiment with no more than about 18 carbon atoms, and in another embodiment with no more than about 12 carbon atoms, although the number of carbon atoms carbon may be outside those ranges, such as benzyl or the like, or (v) an alkylaryl group (including substituted and unsubstituted alkylaryl groups, where the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, and cyclic or acyclic , and where heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like may be present in any of the aryl or alkyl portions of the alkylaryl group), in a mode with at least about 6 carbon atoms, and in another embodiment with at least about 7 carbon atoms, and in an embodiment with no more than about 30 carbon atoms, and in another embodiment with no more than about 18 carbon atoms, and in another embodiment with no more than about 12 carbon atoms, although the number of carbon atoms may be outside those ranges, such as tolyl or the like, where the substituents on the alkyl, aryl, substituted arylalkyl and alkylaryl can be (but are not limited to) hydroxy groups, halogen atoms, amine groups (including primary, secondary and tertiary amine groups), imine groups, ammonium groups, cyano groups, pyridine groups, pyridine groups, ether groups , aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups, acid groups sulphonic, sulfur groups, sulfoxide groups, phosphine groups, phosphonium groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, cyanate groups, carboxylate groups, carboxylic acid groups, groups urethane, urea groups and the like, wherein two or more substituents on the phenyl or pyrazolone rings can be joined to form a ring. These dyes include chromogenic compounds derived from the compounds of The integer wn "represents both the charge on the cramogenic compound complex and the number of countercations present.This integer is at least 1 and can also be 2 or 3. These compounds form complexes with metal compounds to form chromogenic compounds. Suitable M include any metals that complex with the compounds indicated above, where the complex will have a negative charge of at least 1. Examples of suitable metals include (but are not limited to) chromium, iron, cobalt, molybdenum, tungsten, osmium, rhodium, iridium, manganese, rhenium, vanadium, niobium, tantalum, titanium, zirconium, hafnium, scandium, yttrium, lanthanum, zinc, aluminum, metals of the Lanthanide series, and the like, as well as mixtures thereof. Although not limited to any particular theory, it is believed that the complexes formed are the following: where dotted lines and arrows represent coordination links between lone electron pairs on the nitrogen atoms and the metal atom. Since the oxygen atoms each impart a negative charge to the resulting complex, the resulting charge of the compound depends on the valence state of the metal. Some specific examples of complexes of chromogenic compounds suitable for the compounds described herein include (but are not limited to) the following: twenty and the like, as well as mixtures thereof. Complexes of chromogenic compounds have a negative charge of at least -1, and are consequently associated with a counterion. The counterion is formula where Ri, R2 and R3 each, independently of the others, can be (i) a hydrogen atom, (ii) an alkyl group (including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic, and substituted and not substituted, and where heteroatoms may be present, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like in the alkyl group), in an embodiment with at least 1 carbon atom, and in a mode with no more of about 150 carbon atoms, in another embodiment with no more than about 54 carbon atoms, and in another embodiment with no more than about 48 atoms carbon, although the number of carbon atoms may be outside those ranges, (iii) an arylalkyl group (including substituted and unsubstituted arylalkyl groups, where the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like can be present in any of the aryl or alkyl portions of the arylalkyl group), in one embodiment, at least about 6 carbon atoms, and in another embodiment, at least about 7 carbon atoms, and in an embodiment with no more than about 56 carbon atoms, and in another embodiment with no more than about 24 carbon atoms, and in another embodiment with no more than about 18 carbon atoms, although the number of carbon atoms may be outside those ranges, such as benzyl or the like, or (iv) a g alkylaryl radical (including substituted and unsubstituted alkylaryl groups, where the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where heteroatoms, such as oxygen, may or may not be present , nitrogen, sulfur, silicon, phosphorus, boron and the like in any of the aryl or alkyl portions of the alkylaryl group), in an embodiment with at least about 6 carbon atoms and in another embodiment with at least about 7 carbon atoms, in an embodiment with no more than about 56 carbon atoms, in another embodiment with no more than about 24 carbon atoms and in another embodiment with no more than about 18 carbon atoms , although the number of carbon atoms may be outside these ranges, such as tolyl or the like, provided that the total number of carbon atoms and heteroatoms (excluding the atoms in any substituent) in Rx + R2 + R3 is in a of at least about 18, in another embodiment of at least about 19, in another embodiment at least about 20, in another embodiment at least about 21, in another embodiment plus at least about 22, in another embodiment at least about 23, and in another embodiment at least about 24, where the total number of carbon atoms and heteroatoms (excluding the atoms in any substituent) in R? + R2 + R3 is in a mode not greater than about 150, in another mode no greater about 54, and in another embodiment no greater than about 48, although the total number of carbon atoms may be outside this range, where the substituents on the substituted alkyl, arylalkyl, and alkylaryl groups may be (but are not limited to) hydroxy groups, halogen atoms, amine groups, groups imine, ammonium groups, cyano groups, pyridine groups, pyridinium, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxide groups , phosphine groups, phosphonium groups, phosphate groups, nitrile groups, mercapto groups, nitro groups, nitroso groups, sulfone groups, acyl groups, azo groups, cyanate groups, carboxylate groups, carboxylic acid groups, urethane groups, urea groups, mixtures of the same, and the like, where two or more substituents can be linked to form a ring. In one embodiment, Ri, R2 and R are the same to each other, in another embodiment, at least two of Ri, R2 and R3 are different from each other. In yet another embodiment, the three of Ri, R2 and R3 as a whole are different from each other. The coloring compounds described herein can be prepared by any desired or effective method. For example, a chromogenic compound having a different counter ion or free acid form can be obtained commercially and the counter ion can be replaced with the desired counter ion. Azo metalizing dyes can be produced by any desired or effective method, such as those described in, for example, "British Intelligence Objectives Subcommittee Report 961," Publications Board No. 86139, Library of Congress, Washington, D.C. 1947, pp. 71-72, 110, 149-151, 160, 163, 164, the descriptions of which are hereby fully incorporated by reference. The desired counterions may be derived in general from commercially available amine compounds as well. Primary, secondary and tertiary amines can also be prepared as described in, for example, Comprehensive Organic Tronsformations - A Guide to Functional Group Preparations, 2nd Ed., Richard C. Larock, Wiley-VCH, 1999 ISBN 0-471-19031 -4 New York, NY, the description of which is fully incorporated here as a reference. For example, in one embodiment, the chromogenic compound and the amine compound from which the counterion is to be released can be heated together until the ion exchange is complete, followed by distillation of the solvent (if a solvent was used) and recovery of the coloring compound thus prepared. Any desired or effective relative amounts of the chromogenic compound and the amine compound from which the counterion is to be derived can be employed. When the charge on the chromogenic compound is -1, the relative amounts may be, for example, one embodiment at least about 0.1 mole of chromogenic compound per mole of amine compound, in another embodiment at least about 0.5 mole of chromogenic compound per each mole of amine compound, and in another modality more at least about 0.9 mole of chromogenic compound per mole of amine compound, and in one embodiment no more than about 3 moles of chromogenic compound per mole of amine compound, in another embodiment no more than about 2 moles of chromogenic compound per mole of amine compound, and in another embodiment no more than about 1.1 moles of chromogenic compound per mole of amine compound, although the relative amounts may be outside those ranges. When the charge on the chromogenic compound is -2, the amount of amine compound will, of course, be double, and where the charge of the chromogenic compound is higher, the amount of amine compound will, of course, be adjusted accordingly. When a solvent is used, any desired or effective solvent may be used. Examples of suitable solvents include methyl isobutyl ketone, methyl ethyl ketone, acetone, methanol, ethanol, n-propanol, isopropanol, butanol, and the like, as well as mixtures thereof. The reagents are present in the solvent in any desired or effective amount, in an embodiment at least about 1 gram of reagents per liter of solvent, in another embodiment at least about 225 grams of reagents per liter of solvent, and in another embodiment less approximately 450 grams of reagent per liter of solvent, and in one embodiment no more than about 2,000 grams of reagents per liter of solvent, in another embodiment no more than about 1,000 grams of reagent per liter of solvent, and in another embodiment no more than about 500 grams of reagent per liter of solvent, although the relative amounts of reagents and solvent may be outside those ranges. The reagents can be heated to any desired effective temperature, in a mode at least about 25 ° C, in another mode at least about 65 ° C, and in another mode more at least about 110 ° C, and in a more no more mode of about 150 ° C, in another embodiment no more than about 125 ° C, and in another embodiment no more than about 110 ° C, although the temperature may be outside those ranges. The reagents can be heated for any desired or effective period of time, in a mode at least about 1 hour, in another mode at least about 12 hours, and in another mode at least about 16 hours, and in a mode not more than about 7 days, in another modality no more than approximately 1 day and in another modality no more than approximately 18 hours, although the period of time may be outside those intervals.

Subsequently, the coloring compound thus prepared can be recovered by any desired or effective method, by distillation, vacuum, extinction in a solvent in which the product is not soluble (such as water) or the like. Now specific modalities will be described in detail. It is intended that those examples be illustrative, and the claims are not limited to the materials, conditions or process parameters set forth in those embodiments. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE IA a 2-liter, 3-neck, spherical bottom flask equipped with a magnet coated with TEFLON®, silicon oil bath, magnetically stirred heating plate and condenser was charged with 1,100 g of methyl isobutyl ketone (obtained from Aldrich Chemical Co. ., Milwaukee, Wl). Agitation was initiated and solvent black free acid dye 45 (approximately 250 g, 0.275 moles, obtained from Orient Chemical Industries Ltd, Osaka, Japan) was added to the flask of the formula The oil bath was heated at 120 ° C for about 2 hours until the dye completely dissolved. Subsequently, approximately 196.3 g (0.20 moles) of distearyl amine (ARMEEN® 2HT, obtained from Akzo Nobel, McCook, Illinois) were added and the reaction mixture was then refluxed for about 16 hours. Subsequently, the distillation apparatus was connected and the solvent was distilled with the help of a nitrogen inlet. When the distillation appeared complete, vacuum was applied to the system. The vacuum was gradually increased to prevent foaming and maintained for approximately 16 hours at 120 ° C. The flask was then transferred to an oven at 120 ° C and the top side secured down, and the product was collected. It was believed that the product was of the formula EXAMPLE II To a 100 milliliter three-neck spherical bottom flask, equipped with magnet coated with TEFLON®, oil-silicon bath, magnetically stirred heating plate, and condenser were charged 75 g of methyl isobutyl ketone (obtained from Aldrich Chemical Co., Milwaukee, Wl). Agitation was started and solvent black free acid dye 45 (approximately 10 g, 0.015 mol, obtained from Orient Chemical Industries Ltd, Osaka, Japan) was added to the flask. The oil bath was heated at 120 ° C for about 0.5 hour until the dye completely dissolved. About 6.2 g (0.015 moles) of PA28 (obtained from Tomoh Products Inc., Milton, Wisconsin) were then added and the reaction mixture was then refluxed for 16 hours. Subsequently, a distillation apparatus was connected and the solvent was distilled with the help of a nitrogen inlet. When the distillation appeared complete, the flask was then transferred to an oven at 120 ° C and secured with the upper side down for about 1 hour, and the product was collected. It was believed that the product was of the formula EXAMPLE III The process of Example II was repeated except that approximately 5.11 g (0.015 mole) of SA19.3 (obtained from Tomah Products Inc., Milton, Wisconsin) was replaced by the 6.2 g (0.015 mole) of PA28. It was believed that the product is of the formula EXAMPLE IV To a 100 milliliter three-neck spherical bottom flask equipped with TEFLON® coated magnet, silicon oil bath, magnetically stirred heating plate and condensers charging 35 g of methyl isobutyl ketone (obtained from Aldrich Chemical Co. ., Milwaukee, Wl). Agitation was started and solvent black free acid dye 45 (approximately 5 g, 0.0075 mol, obtained from Orient Chemical Industries Ltd, Osaka, Japan) was added to the flask. The oil bath was heated at 120 ° C for about 0.5 hour until the dye completely dissolved.

Subsequently, approximately 2.9 g (0.0075 mole) of PROPOMEEN 0/12 (obtained from Akzo Nobel, McCook, Illinois) was added and the reaction mixture was then refluxed for about 16 hours. Subsequently, a distillation apparatus was connected and the solvent was distilled with the help of a nitrogen inlet. When the distillation appeared complete, the flask was then transferred to an oven at 120 ° C and secured with the upper side down for about 1 hour, and the product was collected. It was believed that the product was of the formula EXAMPLE V The process of Example II was repeated except that approximately 10.3 g (0.015 mol) of trihexadecylamine (ARMEEN® 316 obtained from Akzo Nobel, McCook, Illinois) was replaced by 6.2 g (0.015 mol) of PA28. It was believed that the product is of the formula EXAMPLE VI The process of Example II was repeated except that approximately 7.8 g (0.015 mole) of tridodecane (ARMEEN 312 obtained from Akzo Nobel, McCook, Illinois) was replaced by 6.2 g (0.015 mole) of PA28. It was believed that the product is of the formula EXAMPLE VII The processes of Examples I through VI were repeated using Cl 12695 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained.

EXAMPLE VIII The processes of Examples I through VI were repeated using Cl 12696 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained.

EXAMPLE IX The processes of Examples I through VI were repeated using Cl 12716 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained. EXAMPLE X The processes of Examples I through VI were repeated using Cl 11836 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained.

EXAMPLE XI The processes of Examples I through VI were repeated using Cl 12196 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained.

EXAMPLE XII The processes of Examples I were repeated until VI using Cl 12205 as the free acid dye in place of Black Solvent 45 (Cl 12195). It is believed that similar results will be obtained. EXAMPLES OF INKS The ink compositions were prepared by the following process. All the ingredients except the dyes were loaded in a stainless steel beaker. The resulting mixture was then melted to fifty in an oven, followed by mixing and stirring in a temperature controlled blanket for the same temperature as the oven for about 0.3 hours, at a temperature of about 110 ° C for the A and B inks and the ink 1 Comparison and at a temperature of about 135 for the ink C. To this mixture the dyes were then added. After stirring for approximately 2 additional hours, the ink thus obtained was filtered through a hot MOTT® apparatus (obtained from Mott Metallurgical) using Whatman # 3 filter paper under a pressure of approximately 1.05465 kgf / cm2 (15 pounds per square inch). ). The filtered and formed phase change ink was cast into molds and allowed to solidify to form ink sticks. The inks were prepared from the following ingredients: polyethylene wax (PE500, obtained from Baker Petrolite, Tulsa, OK); polyethylene wax (PE655, obtained from Baker Petrolite, Tulsa, OK); a triamide Branched formula where p, q, and r each have an average value of about 35, prepared as described in Example II of U.S. Patent 6,860,930, the disclosure of which is hereby fully incorporated by reference; a tetramide (obtained from the reaction of an equivalent of a C-36 dimer acid obtained from Uniqema, New Castle, DE with ethylene diamine equivalents and UNICID® 700 (obtained from Baker Petrolite, Tulsa, OK, a chain hydrocarbon long having a terminal carboxylic acid group), prepared as described in Example 1 of US Pat. No. 6,174,937, the disclosure of which is hereby incorporated by reference); stearil stearamide wax (KEMAMIDE® S-180, obtained from Crompton Corporation, Greenwich, CT); KE-100 resin (triglycerides of hydrogenated abietic acid (rosin resin), commercially available from Arakawa Chemical Industries, Ltd); a urethane resin obtained from the reaction of two equivalents of hydroabietyl alcohol ABITOL® E (obtained from Hercules INc, Wilmington, DE) and one equivalent of isophorone dissociant, prepared as described in Example 1 of US Pat. No. 5,782,966, description of which fully incorporated herein by reference (hereinafter referred to as urethane resin # 1); a urethane resin that was the adduct of three stearyl isocyanate equivalents and the glycerol-based alcohol were prepared as described in Example 4 of U.S. Patent 6,309,453, the disclosure of which is hereby fully incorporated by reference (here subsequently referred to as urethane resin # 2); NAUGUARD® 445 antioxidant (obtained from Uhiroyal Chemical Co., Middlébury, CT); yellow disperse 47 dye (OD-47, obtained from Keystone Anilina Corporation, Chicago, IL), and the dye prepared as described in Example I. The amounts of each ingredient are listed in the following table for each ink: To evaluate the solubility of the dye at the base of the ink, the spectral forces at 580 nm of the inks were used as a measure of the solubility of the dye in the filtered and unfiltered inks. Any dye not dissolved in the ink was filtered, giving as a result the smaller spectral strength of the filtered ink compared to that of the unfiltered ink. Accordingly, the ratio of the spectral strength of the filtered ink to the spectral strength of the unfiltered ink ("SS ratio") is a measure of the solubility of the dye; to the extent that the SS ratio is significantly less than 1 indicates a poor solubility of the dye at the base of the ink. The transition temperature (TV) was measured by Dynamic Mechanical Analysis using a Rhesmetrics Solids Analyzer (RSA II). The melting point and freezing point were measured by Differential Scanning Calorimetry (DSC) using a DUPONT 2100 calorimeter.

Inks A and B were incorporated into the modified XEROX® PHASER® 8400 to print at 1102C and printed successfully. The C ink was incorporated into the XEROX® PHASER® 8400 by printing at the standard printing temperature and printing successfully. As indicated by the data, the dye prepared in Example I was well dissolved in the inks. In contrast, the commercial dye dissolved poorly, as indicated by the ratio of the spectral strength of the filtered and unfiltered ink at 580 nanometers of 0.69. Other embodiments and modifications of the present invention may occur to those skilled in the art after reviewing the information presented herein. Those embodiments and modifications, as well as the equivalents thereof, are also included within the scope of this invention. The exposed order of the elements or sequences of processing, or the use of numbers, letters, or other designations for the same, are not intended to limit a claimed process to any order except as specified in the claims themselves. It is noted that in relation to this date, the best method known to the applicant to carry out the said invention, which is clear from the present description of the invention.

Claims (49)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property.

1. Coloring compounds of formulas: characterized by Ri (R

2 R3 each, independently of the others, it is a hydrogen atom, an alkyl group, including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms may or may not be present in the alkyl group, a group arylalkyl, including substituted and unsubstituted arylalkyl groups, wherein the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated, cyclic or acyclic and substituted or unsubstituted and where heteroatoms may or may not be present in the aryl or alkyl portion of the arylalkyl group, or an alkylaryl group, including substituted or unsubstituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, and where they may or may not be present heteroatoms in the aryl or alkyl portion of the alkylaryl group, provided that the total number of atoms of carbon and heteroatoms, excluding the atoms in any substituents, in Ri + R2 + R3 is at least about 18, M is a metal atom, each A, each E and each G, independently of the other, represents a substituent on a ring of phenyl or pyrazolone, where G can also be a hydrogen atom, m is an integer of 0, 1 or 2, p is an integer of 0, 1, 2, 3 or 4, J represents (i) an atom of hydrogen, (ii) an alkyl group (including linear and branched alkyl, saturated and unsaturated, cyclic and acyclic and substituted and unsubstituted, and where heteroatoms may or may not be present in the alkyl group), (iii) an aryl group (including substituted and unsubstituted aryl groups, and where or heteroatoms are not present in the aryl group (iv) an arylalkyl group (including substituted and unsubstituted arylalkyl groups, where the alkyl portion of the arylalkyl group may be linear or branched, saturated or unsaturated and cyclic or acyclic and where they may or may not be present heteroatoms in either the aryl or alkyl portion of the arylalkyl group, or (v) an alkylaryl group (including substituted and unsubstituted alkylaryl groups, wherein the alkyl portion of the alkylaryl group may be linear or branched, saturated or unsaturated, and cyclic or acyclic, and where heteroatoms may or may not be present in any of the aryl or alkyl portion of the alkylaryl group), where s or more substituents on the phenyl or pyrazolone rings can be joined to form a ring, and n represents an integer of 1, 2 or 3. The coloring compound according to claim 1, characterized in that it has the formula:

3. The coloring compound according to claim 1, characterized in that it has the formula:

4. The coloring compounds according to claim 1, characterized in that at least one of A, E, G and J is an alkyl group, provided that, when A is at least one alkyl group, m is at least 1, and provided that, when E is at least one alkyl group, p is at least 1.

5. The coloring compounds according to claim 4, characterized in that the alkyl group is a substituted alkyl group.

6. The dye compounds according to claim 4, characterized in that the alkyl group is an unsubstituted alkyl group.

7. The dye compounds according to claim 4, characterized in that the alkyl group contains at least one heteroatom therein.

The coloring compounds according to claim 4, characterized in that the alkyl group does not contain heteroatoms therein.

9. The coloring compounds according to claim 1, characterized in that at least one of A, E, G and J is an aryl group, provided that, when A is at least one aryl group, m is at least 1, and provided, when E is at least one aryl group, p is at least 1.

The dye compounds according to claim 9, characterized in that the aryl group is a substituted aryl group.

The dye compounds according to claim 9, characterized in that the aryl group is an unsubstituted aryl group.

The coloring compounds according to claim 9, characterized in that the aryl group contains at least one heteroatom therein.

13. Coloring compounds in accordance with Claim 9, characterized in that the aryl group does not contain heteroatoms therein.

The dye compounds according to claim 1, characterized in that at least one of A, E, G and J is an arylalkyl or alkylaryl group, provided that, when A is at least one arylalkyl or alkylaryl group, m is at least 1, and provided that, when E is at least one arylalkyl or alkylaryl group, p is at least 1.

The coloring compounds according to claim 14, characterized in that the arylalkyl or alkylaryl group is an arylalkyl or substituted alkylaryl group.

16. The dye compounds according to claim 14, characterized in that the arylalkyl or alkylaryl group is an unsubstituted arylalkyl or alkylaryl group.

17. The dye compounds according to claim 14, characterized in that the arylalkyl or alkylaryl group contains at least one heteroatom therein.

18. The dye compounds according to claim 14, characterized in that the arylalkyl or alkylaryl group does not contain heteroatoms therein.

The dye compounds according to claim 1, characterized in that at least one of A, E and G is a substituent selected from the group consisting of of a hydroxy group, a halogen atom, an amine group, an imine group, an ammonium group, a cyano group, a pyridine group, a pyridinium group, an ether group, an aldehyde group, a ketone group, an ester group, an amide group, a carbonyl group, a thiocarbonyl group, a sulfate group, a sulfonate group, a sulfonic acid group, a sulfide group, a sulfoxide group, a phosphine group, a phosphonium group, a phosphate group, a nitrile group, a mercapto group, a nitro group, a nitroso group, a sulfone group, an acyl group, an azo group, a cyanate group, a carboxylate group, a carboxylic acid group, a urethane group, a urea group, or mixtures of the same, provided that, when A is at least one substituent, m is at least 1, and provided that, when E is at least one substituent, p is at least 1.

The coloring compounds according to claim 1, characterized in that n is 1.

21. The coloring compounds according to claim 1 ion 1, characterized in that n is 2.

22. The coloring compounds according to claim 1, characterized in that n is 3.

23. The coloring compounds according to claim 1, characterized in that M is a metal of the Lantánidos Series.

The coloring compounds according to claim 1, characterized in that M is chromium, iron, cobalt, molybdenum, tungsten, ruthenium, osmium, rhodium, iridium, manganese, rhenium, vanadium, niobium, tantalum, titanium, zirconium, hafnium, scandium, yttrium, lanthanum, zinc, aluminum or mixtures thereof.

25. The coloring compounds according to claim 1, characterized in that M is chromium, iron, cobalt or mixtures thereof.

26. The coloring compounds according to claim 1, characterized in that M is chromium.

27. A coloring compound according to claim 1, characterized in that it has the formula: 20 25 25 20 25

28. A coloring compound according to claim 1, characterized in that it has the formula:

29. The coloring compound according to claim 1, characterized in that Ri, R2, and R3 each, independently of the others, are hydrogen atoms or alkyl groups, including linear and branched alkyl groups, saturated and unsaturated, cyclic and acyclic, and substituted and unsubstituted, and where heteroatoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron and the like may or may not be present in the alkyl group.

30. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups is linear.

31. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups is branched.

32. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups is substituted.

33. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups is unsubstituted.

34. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups has heteroatoms therein.

35. The coloring compound according to claim 29, characterized in that at least one of the alkyl groups does not have heteroatoms therein.

36. The coloring compound according to claim 29, characterized in that Ri, R2 and R3 are the same as each other.

37. The coloring compound according to claim 29, characterized in that at least two of Rlf R2 and R3 are different from each other.

38. The coloring compound according to claim 29, characterized in that the three of Ri, R2 and R3, as a whole, are different from each other.

39. The coloring compound according to claim 29, characterized in that the compound has the formula:

40. The coloring compound according to claim 29, characterized in that the compound has the formula:

41. The coloring compound according to claim 29, characterized in that the compound has the formula:

42. The coloring compound according to claim 29, characterized in that the compound has the formula:

43. The coloring compound according to claim 29, characterized in that the compound has the formula:

44. The coloring compound according to claim 29, characterized in that the compound has the formula: or

45. The coloring compound according to claim 1, characterized in that at least one of R ?; R2 and R3 is an aryl group, an arylalkyl group or an alkylaryl group.

46. The coloring compound according to claim 45, characterized in that the aryl, arylalkyl or alkylaryl group is substituted.

47. The coloring compound according to claim 45, characterized in that the aryl, arylalkyl or alkylaryl group is not substituted.

48. The coloring compound in accordance with claim 45, characterized in that the aryl, arylalkyl or alkylaryl group contains at least one heteroatom therein.

49. The coloring compound according to claim 45, characterized in that the aryl, arylalkyl or alkylaryl group does not contain heteroatoms therein.