Method for synthesizing polymer dyes

Abstract

The present invention relates to a method for synthesizing polymer dyes by polymerization of polymerizable monomers having polymerizable functional groups and chromophore functional groups, such as acrylates, methacrylates, acrylamides, or methacrylamides, wherein the polymerization is carried out in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, and the obtained polymer dye is purified using a solvent selected from diisopropyl ether, methyl tert-butyl ether, dimethyl carbonate, ethyl acetate, and water. The present invention also relates to the obtained polymer dyes and ink compositions containing them.

Description

[Technical Field]

[0001] Field of Invention The present invention relates to a method for synthesizing polymer dyes, as well as polymer dyes obtained therefrom and related ink compositions containing the same.

[0002] More specifically, the present invention relates to a method for synthesizing polymer dyes by polymerization of polymerizable monomers having polymerizable functional groups and chromophore functional groups, such as acrylates, methacrylates, acrylamides, or methacrylamides, wherein the polymerization is carried out in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, and the obtained polymer dye is purified in a solvent selected from diisopropyl ether, methyl tert-butyl ether, dimethyl carbonate, ethyl acetate, and water. [Background technology]

[0003] Current Technical Status During inkjet printing, ink is typically ejected onto the substrate through components of the printhead (e.g., an array of nozzles). Many solvent-soluble dyes currently used in inkjet printing have been identified as hazardous materials for humans and the environment, raising long-term compliance issues.

[0004] These dyes are typically coordinated with heavy metals, and these heavy metals may be the cause of the toxicity of such dyes.

[0005] The black pigments currently used for inkjet printing are organometallic complexes. The organic portion contains a diazo functional group, and the metal cation is a trivalent chromium ion.

[0006] Some colored pigments, such as blue and red dyes, also contain metal cations like copper, cobalt, and iron.

[0007] This type of chemistry poses several concerns for human health, and several colorants have already been classified as CMR (carcinogenic, mutagenic, reprotoxic).

[0008] CMR chemical substances (as colorants) are prohibited from sensitive markets such as the food, beverage, pharmaceutical, and cosmetic industries, since chemical substances can migrate through packaging substrates and thus be found in products.

[0009] As explained in the REACh regulation, high molecular weight molecules such as polymers do not migrate through packaging substrates and are considered safe for sensitive markets such as the food, beverage, pharmaceutical, and cosmetic industries, so it would be desirable to have polymeric colorants.

[0010] Colored polymeric colorants are known in the art, for example from US7732509B2, US7273897B2, WO03089533, WO9961533, DE19651689, CN108071023B, and CN101787222A. However, such documents mainly disclose water-soluble polymeric colorants.

[0011] Therefore, there is a need to develop organic solvent-soluble polymeric colorants that do not contain heavy metals. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] Summary of the Invention The present applicant has faced the problem of developing organic solvent-soluble polymeric colorants that do not contain heavy metals. MEANS FOR SOLVING THE PROBLEM

[0013] After extensive experiments, the present applicant has found a solution that makes it possible to obtain organic solvent-soluble polymeric colorants that do not contain heavy metals.

[0014] The present applicant provides a method for synthesizing a polymeric colorant, comprising: (1) A step of functionalizing a dye with a polymerizable functional group to obtain a polymerizable monomer dye, (2) A step of copolymerizing at least one polymerizable monomer dye with a polymerizable monomer, (3) A step of recovering the obtained polymer dye and A concurrent European patent application, No. 23158134.9, was filed, claiming a method including the above.

[0015] EP Application No. 23158134.9 discloses a copolymerization step (2) carried out in dimethylformamide (DMF) and a recovery step (3) carried out using pentane, hexane, methanol, diethyl ether, or a mixture thereof.

[0016] While continuing the experiments, the applicant faced the challenge of avoiding the use of CMR chemicals such as DMF and methanol, as well as the challenge of avoiding the use of hazardous solvents with high flammability and explosive risk, such as diethyl ether.

[0017] After several tests, the applicant found, surprisingly, that by specifically selecting diisopropyl ether or methyl tert-butyl ether or dimethyl carbonate or ethyl acetate or water as the solvent for the purification step of the recovered polymer dye, along with specifically selecting a mixture of acetonitrile or methyl ethyl ketone and ethanol as the solvent for the copolymerization step (2), a significant increase in yield was also obtained, in addition to solving the aforementioned issues of toxicity and hazard.

[0018] Therefore, in one embodiment, the present invention is a method for synthesizing polymer dyes, (1) A dye containing a first reactive functional group is reacted with a polymerizable monomer containing a second reactive functional group to obtain the following formulas (I) to (III) and (V)

[0019] [ka]

[0020] (In the formula, M1, M2, M3, and M5 are either the same or different from each other and are reactive monomers, while C1 to C4 are different from each other and are chromophore units.) A step to obtain a polymerizable monomer dye having one of the following, (2) At least one polymerizable monomer dye (I) to (III) and (V) is given by the following formula (IV)

[0021] [ka]

[0022] (In the formula, M4 is a reactive monomer.) A step of copolymerizing with a polymerizable monomer having the following characteristics: (3) A step of recovering the obtained polymer dye and Includes, The copolymerization step (2) is carried out in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, and the recovery step (3) includes a purification step carried out using a solvent selected from diisopropyl ether, methyl tert-butyl ether, dimethyl carbonate, ethyl acetate, and water. Regarding the method.

[0023] In another aspect, the present invention relates to polymer dyes obtained using a synthesis method according to a first aspect of the present invention. Such polymer dyes can be used as dyes in continuous inkjet (CIJ) printing methods, drop-on-demand (DOD) printing methods (e.g., thermal inkjet (TIJ) printing methods), or hot-melt (HM) inkjet printing methods. Compared to conventional colorants (e.g., carbon black-metal complex dyes) used in printing methods (e.g., CIJ, DOD, TIJ, or HM), the polymer dyes of the present invention can form ink compositions with standard fastness without containing any toxic metal cations, while still possessing excellent stability, printability, solubility in organic solvents, and adhesion to various substrates.

[0024] In another aspect, the present invention relates to an ink composition comprising the polymer dye of the present invention and an organic solvent. The composition may be a solution.

[0025] The polymer dye of the present invention can be present in an amount of about 1% to about 70% by weight, preferably 3% to 50% by weight, relative to the weight of the ink composition.

[0026] In another aspect, the present invention relates to a product comprising a substrate (e.g., cardboard, glass, metal, or film) and a solid ink for drawing an image on the substrate, wherein the solid ink comprises an ink composition as described herein.

[0027] In another aspect, the present invention relates to a printing method comprising ejecting an ink composition described herein from a print head in an inkjet printer onto a substrate to form an image. [Modes for carrying out the invention]

[0028] Detailed description of the invention While the present invention can be implemented in many different forms, and certain embodiments are shown in the figures and further described herein, it should be understood that this disclosure is illustrative of the principles of the present invention and is not intended to limit the invention to the specific embodiments described herein.

[0029] Method for synthesizing polymer dyes The method for synthesizing polymer dyes according to the present invention is: (1) A dye containing a first reactive functional group is reacted with a polymerizable monomer containing a second reactive functional group to obtain the following formulas (I) to (III) and (V)

[0030] [ka]

[0031] (In the formula, M1, M2, M3, and M5 are either the same or different from each other and are reactive monomers, while C1 to C4 are different from each other and are chromophore units.) A step to obtain a polymerizable monomer dye having one of the following, (2) At least one polymerizable monomer dye (I) to (III) and (V) is given by the following formula (IV)

[0032] [ka]

[0033] (In the formula, M4 is a reactive monomer.) A step of copolymerizing with a polymerizable monomer having the following characteristics: (3) A step of recovering the obtained polymer dye and Includes, The copolymerization step (2) is carried out in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, and the recovery step (3) includes a purification step carried out using a solvent selected from diisopropyl ether, methyl tert-butyl ether, dimethyl carbonate, ethyl acetate, and water.

[0034] Polymerizable monomer dyes can be prepared by the synthesis methods described herein or by synthesis methods known in the art.

[0035] Polymerizable monomer dyes can be easily prepared by the reaction of one reactive functional group of the dye, such as a hydroxyl group, an amine group, or a carboxyl group, with a reactive functional group of the polymerizable monomer, such as a carboxylic acid group, an acyl chloride group, an anhydride group, an ester group, or a hydroxyl group or an amine group.

[0036] Any dye as described above can be used provided that it contains at least one reactive functional group capable of forming a covalent bond with the reactive functional group of the polymerizable monomer. In some embodiments, if the dye contains an alkali or alkaline earth sulfonate group or a carboxylate group, the alkali or alkaline earth ions are pre-replaced with tetraalkylammonium groups such as tetrabutylammonium, tetrahexylammonium, or tetraoctylammonium to improve solubility in organic solvents while decreasing solubility in water.

[0037] In some embodiments, polymerizable monomer dyes are obtained by reacting a dye having a hydroxyl group, a primary or secondary amine group, or a carboxylic acid group with a polymerizable monomer having a carboxylic acid group, an acyl chloride group, an anhydride group, an ester group, or an alcohol group or a phenol group.

[0038] In some embodiments, the polymerizable monomer has a polymerizable functional group represented by a vinyl group. In preferred embodiments, the polymerizable monomer is acrylic acid or methacrylic acid or a derivative thereof, such as acrylic acid or methacrylic acid ester.

[0039] In some embodiments, the reaction between the dye and the polymerizable monomer is carried out in a suitable solvent, preferably an aprotic solvent such as dichloromethane (DCM), acetone, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, or tetrahydrofuran.

[0040] In some embodiments, the reaction between the dye and the polymerizable monomer is an esterification reaction. In some embodiments, the esterification reaction is carried out in the presence of a catalyst, such as 4-dimethylaminopyridine. In some other embodiments, the esterification reaction is carried out in the presence of a carbodiimide as a coupling reagent, such as dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide (DIC), or 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide (EDC), and a catalyst, such as 4-dimethylaminopyridine.

[0041] The polymerizable monomer dyes obtained can be isolated from the reaction mixture by methods known in the art. For example, the polymerizable monomer dyes can be isolated by washing the reaction mixture with water and / or brine solution, separating the organic layer from the aqueous layer, and removing the solvent from the organic layer (e.g., by evaporation).

[0042] Starting from one or more different polymerizable monomer dyes, polymer dyes can be prepared by the synthesis methods described herein.

[0043] Copolymerization of one or more different polymerizable monomer dyes with polymerizable monomers can be achieved by free radical polymerization in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, in the presence of a suitable initiator.

[0044] When using a mixture of methyl ethyl ketone (MEK) and ethanol (EtOH), the weight ratio MEK / EtOH is preferably in the range of 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 45 / 55 to 55 / 45. Advantageously, the weight ratio MEK / EtOH is approximately 50 / 50.

[0045] In some embodiments, the volume ratio MEK / EtOH is preferably in the range of 30 / 70 to 70 / 30, more preferably in the range of 40 / 60 to 60 / 40, and even more preferably in the range of 45 / 55 to 55 / 45. Advantageously, the volume ratio MEK / EtOH is about 50 / 50.

[0046] In some embodiments, the reaction involves thermal decomposition of an initiator (e.g., organic peroxide (e.g., dicumyl peroxide) or azo compound), photodecomposition (e.g., metal iodide, metal alkyl, or azo compound (e.g., azoisobutylnitrile (AIBN) or 2,2'-azobis[2-methylbutyronitrile] (AMBN)), peroxide initiator (e.g., benzoyl peroxide), redox reaction (e.g., iron ions or, for example, Cr 2+ , V 2+ Ti 3+ Co 2+ , or Cu + The process may be initiated by an initiator composition that enables the reduction of hydrogen peroxide or alkyl hydrogen peroxide by means of other reducing agents, persulfate activation, ionizing radiation (e.g., by α, β, γ, or X-rays), electrochemical activation, plasma activation, or sonication (e.g., at approximately 16 kHz).

[0047] The obtained polymer dye can be recovered from the reaction mixture by methods known in the art. For example, the obtained polymer dye can be recovered by evaporation of the reaction solvent, i.e., by evaporation of acetonitrile or a mixture of methyl ethyl ketone and ethanol, or by precipitation using a suitable solvent.

[0048] According to the method of the present invention, the crude polymer dye is purified by precipitation from a reaction mixture using diisopropyl ether or methyl tert-butyl ether or dimethyl carbonate or ethyl acetate or water. The purification step can be repeated once or twice, after which the purified polymer dye can be separated from diisopropyl ether or methyl tert-butyl ether or dimethyl carbonate or ethyl acetate or water by methods known in the art, such as filtration, decantation or centrifugation.

[0049] If the purification step is carried out using water, the pH of the water can be adjusted by methods known in the art. In some embodiments, the purification step can be carried out using water with a neutral pH, or water with an acidic pH or a basic pH. Purification may be carried out using saline solution (e.g., brine solution).

[0050] In general, the reaction temperatures for steps (1), (2), and (3) can be adjusted as needed. In some embodiments, both steps (1) and (3) can be carried out at room temperature. In some embodiments, step (1) is carried out at room temperature and step (3) is carried out at 0°C. Step 2 is preferably carried out at a temperature in the range of 60°C to 85°C.

[0051] In general, the reaction times for steps (1) and (2) can be adjusted as needed. The progress of steps (1) and (2) can be monitored using methods known in the art, such as UV-Vis spectroscopy, NMR spectroscopy, or thin-layer chromatography (TLC).

[0052] The weight ratio of the amount of solvent used during synthesis to the amount of solvent used during the purification step is preferably in the range of 1 / 5 to 1 / 30, more preferably 1 / 10 to 1 / 25, even more preferably 1 / 10 to 1 / 20, and even more preferably 1 / 15 to 1 / 20.

[0053] In some embodiments, the volume ratio of the amount of solvent used during synthesis to the amount of solvent used during the purification step is preferably in the range of 1 / 5 to 1 / 30, more preferably 1 / 10 to 1 / 25, even more preferably 1 / 10 to 1 / 20, and even more preferably 1 / 15 to 1 / 20.

[0054] Polymer dyes In one embodiment, the polymer dye according to the present invention is a copolymer comprising at least one polymerizable monomer dye (I) to (III) and (V) as described above, which is copolymerized with a polymerizable monomer having formula (IV) as described above.

[0055] In one embodiment of the present invention, M1 to M5 are the same or different from each other and are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, vinylamine monomer, and the like.

[0056] In one embodiment of the present invention, one of C1 to C4 is Acid Blue 1, 3, 7, 9, 15, 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 52, 57, 58, 61:1, 62, 62:1, 63, 64, 65, 68, 69, 72, 74, 78, 78:1, 79, 80, 81, 81:1, 83, 90, 92, 96, 103, 104, 111, 112, 113, 114, 120, 124, 127, 127:1, 128, 129, 129:1, 138, 138:1, 1 40, 142, 145, 150, 156, 158, 171, 175, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 215, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277, 277:1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 344, 350, Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29 Direct Blue 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218, 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291, Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 77, 79, 79:1, 79:2, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 14 8, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 281, 284, 285, 287, 288, 291, 291:1, 293, 295, 297, 301, 315, 330, 333, 373, Hood Blue 1, 2, Reactive Blue 2, 3, 4, 5, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236, Solvent Blue 4, 5, 6, 35, 38, 48, 59, 67, 70, 104, and 136 It can be a blue chromophore unit derived from a commercially available dye selected from the group consisting of the following.

[0057] In one embodiment of the present invention, one of C1 to C4 is Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97:1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 143:1, 145, 151, 183, 195, 198, 211, 215, 2 17, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, 447, Basic Red 1, 2, 9, 12, 13, 37 Direct Red 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243, 254, Disperse threads 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 15 1, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328, 337, 343, Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106, Reactive Red 2, 3, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78, 83, 84, 106, 111, 312, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187, 190, 193, 194, 195, 198, 218, 220, 222, 223, 228, 235, Solvent Red 1, 23, 29, 49, 119, 122, 125, 127, 130, 132, 135, 149, 160, 164, 168, 169, 172, and 233 It can be a red chromophore unit derived from a commercially available dye selected from the group consisting of the following.

[0058] In one embodiment of the present invention, one of C1 to C4 is Acid Green 1, 3, 5, 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 50, 56, 73, 81, 84, 104, 108, 109, Basic Green 1, 4, 5 Direct Green 26, 28, 59, 80, 85, Disperse Green 9, Food Green 2, 3, Reactive Green 5, 7, 8, 12, 15, 19, 21 Solvent Green 1, 3, 7, and 11 It can be a green chromophore unit derived from a commercially available dye selected from the group consisting of the following.

[0059] In one embodiment of the present invention, one of C1 to C4 is Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40:1, 42, 44, 49, 59, 59:1, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219:1, 220, 230, 232, 235, 241, 242, 246, Basic Yellow 1, 2, 11, 12, 14, 21, 28, 32, 36, 57, 87 Direct Yellow 4, 7, 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 59, 62, 79, 86, 87, 98, 105, 106, 130, 132, 137, 142, 147, 153, Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 11 6, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227, 231, 232, Food Yellow 3, 4, 5 Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176, Solvent Yellow 2, 3, 7, 10, 13, 14, 19, 25, 28, 33, 88, 89, 114, 146, 163, Acid Orange 3, 6, 7, 8, 10, 12, 19, 20, 24, 51, 56, 63, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168, Basic Orange 2, 14, 15, 21, 22, 31, 69 Direct Orange 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118, Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, Reactive Orange 1, 4, 5, 7, 11, 2, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92, 93, 95, 107, Solvent Orange 1, 2, 3, 7, 11, 15, 20, 25, 54, 60, 62, 63, 86, 99, 105, Acid Violet 7, 9, 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126, Basic Violet 1, 2, 3, 4, 7, 10, 14 Direct Violet 9, 35, 51, 66, 94, 95 Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, Food Violet 2, Reactive Violet 1, 2, 4, 5, 6, 8, 9, 22, 23, 33, 36, 38, Solvent Violet 8, 9, 11, 13, 14, and 38 It can be a chromophore unit derived from a commercially available dye selected from the group consisting of the following.

[0060] Of the commercially available dyes listed above, preferred commercially available dyes contain at least one reactive functional group, such as a hydroxyl group, an amine group (primary or secondary amine group), or a carboxyl group, which can react with the reactive functional group of a polymerizable monomer. However, commercially available dyes that do not contain any reactive functional groups can be used within the scope of the present invention by derivatization to include a reactive functional group.

[0061] In some embodiments, the polymer dye according to the present invention may be a block copolymer, a random copolymer, or a graft copolymer. In preferred embodiments, the polymer dye according to the present invention is a random copolymer.

[0062] In some embodiments, the polymer dyes according to the present invention may have a weight-average molecular weight of at least about 1,000 Da (e.g., at least about 2,000 Da, at least about 5,000 Da, at least about 7,500 Da, at least about 10,000 Da, at least about 12,500 Da, at least about 15,000 Da, at least about 17,500 Da, or at least about 20,000 Da) to at most about 150,000 Da (e.g., at most about 140,000 Da, at most about 130,000 Da, at most about 120,000 Da, at most about 115,000 Da, at most about 110,000 Da, at most about 105,000 Da, at most about 100,000 Da, at most about 95,000 Da, or at most about 90,000 Da).

[0063] In some embodiments, the polymer dye according to the present invention may contain at least about 5% by weight (e.g., at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or at least about 50% by weight) to at most about 80% by weight (e.g., at most about 75% by weight, at most about 70% by weight, at most about 65% by weight, at most about 60% by weight, at most about 55% by weight, or at most about 50%) of any one of the monomer repeating units having formulas (I) to (V) with respect to the weight-average molecular weight of the polymer dye.

[0064] In one embodiment, the polymer dye according to the present invention comprises one of the monomer repeating units having formulas (I), (II), and (IV) in an amount of at least about 5% by weight (e.g., at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or at least about 50% by weight) to at most about 80% by weight (e.g., at most about 75% by weight, at most about 70% by weight, at most about 65% by weight, at most about 60% by weight, at most about 55% by weight, or at most about 50% by weight) relative to the weight-average molecular weight of the polymer dye.

[0065] In some embodiments, the polymer dye according to the present invention comprises monomer repeating units having formulas (I) and (II) in a total amount of at least about 10% by weight (e.g., at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or at least about 50% by weight) to at most about 90% by weight (e.g., at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, at most about 65% by weight, at most about 60% by weight, at most about 55% by weight, or at most about 50% by weight) relative to the weight-average molecular weight of the polymer dye, the remainder being represented by monomer repeating units having formula (IV) and optionally monomer repeating units having formulas (III) and (V).

[0066] Generally, the polymer dyes according to the present invention can have relatively high solubility in organic solvents at 25°C. The term "high solubility" refers to the ability of the polymer to dissolve in an organic solvent and form a homogeneous solution (without suspension or precipitation).

[0067] In some embodiments, the polymer dyes according to the present invention may have a solubility in an organic solvent at 25°C ranging from at least about 1% by weight (e.g., at least about 2% by weight, at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or at least about 50% by weight) to at most about 90% by weight (e.g., at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, at most about 65% by weight, at most about 60% by weight, at most about 55% by weight, or at most). As used herein, solubility refers to the weight percentage of the solute (e.g., polymer dye) based on the total weight of the solution (e.g., a solution containing the solute and an organic solvent) at 25°C.

[0068] In some embodiments, the organic solvent in which the polymer dye can be dissolved may include ketones, esters, acetals, ethers, carbonates, or combinations thereof. Examples of suitable organic solvents include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. In some embodiments, the organic solvent may include a single solvent or a combination of two or more (e.g., three or four) solvents.

[0069] In some embodiments, the polymer dye is substantially insoluble in water at 25°C (for example, having a solubility of less than 0.5 wt%, preferably less than 0.3 wt%, and more preferably less than 0.1 wt%).

[0070] In one embodiment, the polymer dye of the present invention is soluble in organic solvents, preferably having a solubility of at least 1 wt% in organic solvents at 25°C, and insoluble in water, preferably having a solubility of less than 0.1 wt% in water at 25°C.

[0071] Ink composition Generally, the polymer dyes according to the present invention can be incorporated into ink compositions (e.g., inkjet ink compositions). In some embodiments, the ink composition may be a homogeneous solution or liquid composition in which all solutes (including the polymer dyes according to the present invention) are dissolved. In some embodiments, the ink composition may be a dispersion or emulsion. In some further embodiments, the ink composition may be a solid composition.

[0072] In some embodiments, the polymer dye according to the present invention may be in the range of at least about 1% by weight (e.g., at least about 2% by weight, at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, or at least about 50% by weight) to as much as about 70% by weight (e.g., as much as about 65% by weight, as much as about 60% by weight, as much as about 55% by weight, as much as about 50% by weight, as much as about 45% by weight, as much as about 40% by weight, as much as about 35% by weight, or at least about 30%) of the ink composition.

[0073] Without being constrained by theory, it is conceivable that the polymer dyes according to the present invention can form ink compositions without using any metals (e.g., any heavy metals) or any colorants. Furthermore, without being constrained by theory, it is conceivable that ink compositions containing the polymer dyes according to the present invention can have excellent lightfastness, color intensity, and adhesive properties.

[0074] In some embodiments, the ink compositions described herein may contain an organic solvent in which the polymer dye according to the present invention is dissolved. In some embodiments, the organic solvent suitable for the ink composition may include ketones, esters, acetals, ethers, carbonates, or combinations thereof. Examples of suitable organic solvents include methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diethyl ketone, cyclopentanone, acetone, methyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol, dimethyl carbonate, propylene carbonate, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. In some embodiments, the organic solvent may include one solvent or a combination of two or more (e.g., three or four) solvents.

[0075] In some embodiments, the organic solvent may be in the range of at least about 30% by weight (e.g., at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight) to at most about 99% by weight (e.g., at most about 97% by weight, at most about 95% by weight, at most about 90% by weight, at most about 85% by weight, at most about 80% by weight, at most about 75% by weight, at most about 70% by weight, at most about 65% by weight, or at most about 60% by weight) of the ink composition.

[0076] In some embodiments, the ink composition is a liquid composition comprising the polymer dye and an organic solvent, wherein the polymer dye is present in an amount of 1% to 70% by weight, preferably 3% to 50% by weight, of the ink composition.

[0077] In some embodiments, the ink compositions described herein may include a fusible carrier for dispersing the polymer dyes according to the present invention. In some embodiments, the fusible carrier suitable for the ink composition may include waxes, resins, and / or long-chain fatty acids, esters, or alcohols. Suitable resins include, but are not limited to, copolyester resins, polyamide resins, rosin resins, polyesteramide resins, epoxy resins, polyvinyl alcohol resins, cellulose esters, cellulose ethers, and polyvinylpyridine resins. These resins may be used alone or in combination. Suitable waxes include, but are not limited to, polyalkylene waxes such as polyethylene wax or polypropylene wax, linear primary alcohols such as Fischer-Tropsch wax and Unilin® alcohol wax (available from Baker Hughes), microcrystalline waxes, fatty acids, carnauba wax, candelilla wax, stearamide, paraffin wax, and montan wax, as well as ethoxylated long-chain alcohols such as Unithox® (available from Baker Hughes). Waxes may be used alone or in combination. Suitable examples of long-chain fatty acids, esters, or alcohols include, but are not limited to, dialkyl esters of sebaciate, higher aliphatic alcohols, stearic acid, lauric acid, and behenic acid. Furthermore, waxes, resins, and / or combinations of long-chain fatty acids, esters, or alcohols may be used.

[0078] In some embodiments, the fusible carrier may be in the range of at least about 30% by weight (e.g., at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight) to as much as about 99% by weight (e.g., as much as about 97% by weight, as much as about 95% by weight, as much as about 90% by weight, as much as about 85% by weight, as much as about 80% by weight, as much as about 75% by weight, as much as about 70% by weight, as much as about 65% by weight, or as much as about 60%) of the ink composition.

[0079] In some embodiments, the ink composition is a solid composition comprising the polymer dye and a fusible carrier, wherein the polymer dye is present in an amount of 1% to 70% by weight, preferably 3% to 50% by weight, of the ink composition.

[0080] In some embodiments, the ink compositions described herein may contain only two components (i.e., a polymer dye and an organic solvent or fusible carrier according to the present invention). In some embodiments, the ink compositions may optionally contain one or more (e.g., two, three, or four) additives or additional components.

[0081] In some embodiments, the ink compositions described herein may optionally contain at least one conductive salt. Examples of suitable conductive salts include alkali metal salts, alkaline earth salts, and halides (chlorides, bromides, iodides, and fluorides), perchlorates, nitrates, thiocyanates, formates, acetates, sulfates, and propions.

[0082] In some embodiments, the ink compositions described herein may optionally contain at least one rheological agent. Examples of suitable rheological agents include nitrocellulose, cellulose acetate butyrate, cellulose acetate, shellac, rosin esters, polyurethanes, acrylics, or conductive polymers (e.g., polyaniline). In some embodiments, the rheological agent may be in the range of at least about 1% by weight (e.g., at least about 2% by weight, at least about 4% by weight, at least about 5% by weight, at least about 6% by weight, at least about 8% by weight, at least about 10% by weight, or at least about 15% by weight) to at most about 30% by weight (e.g., at most about 25% by weight, at most about 20% by weight, at most about 15% by weight, at most about 10% by weight, or at most about 5% by weight) of the ink composition. While we do not wish to be bound by theory, it is believed that by adding rheological agents to the ink compositions described herein, the viscosity of the ink composition can be increased, a structure for flow and droplet formation can be imparted, adhesion can be promoted, separation of other ink components can be delayed or prevented, and / or the amount of ink composition loaded can be changed.

[0083] In some embodiments, the ink compositions described herein may optionally include at least one additional colorant, such as a dye or pigment. The dye or pigment may be either an organic or inorganic material. In some embodiments, the ink composition may be substantially free of colorants other than the polymer dyes according to the present invention.

[0084] In some embodiments, the ink compositions described herein may optionally include one or more tackifiers. Generally, tackifiers can improve the adhesion between the ink composition and the substrate (e.g., cardboard, glass, metal, or film). Examples of tackifiers include glycerol esters, pentaerythritol esters, hydrocarbons, rosin, rosin esters, modified rosin esters (e.g., hydrogenated, acid, or phenol-modified rosin esters), coumarone-indene polymers, cyclic ketone polymers, styrene-allyl alcohol polymers, polystyrene, polyvinyltoluene / methylstyrene polymers, polyvinyl chloride, polyvinyl alcohol, ethylene / vinyl acetate, ethylene / acrylic acid, alkyl hydrocarbon polymers, aryl hydrocarbon polymers, alkylaryl hydrocarbon polymers, terpene polymers, ethylene carbon monoxide copolymers, vinyl chloride / vinyl alcohol copolymers Examples include polypolymers, polyvinyl butyral, polyketones, styrene / acrylic copolymers, polybutene, polybutadiene, styrene-isoprene-styrene, styrene-butadiene-styrene, polyvinylpyrrolidone, polyvinylpyridine, vinylpyrrolidone / vinyl acetate, polyurethane, polyester, polyamide, cellulose ester, cellulose ether, polyol, styrene-acrylate, polypropylene, chlorinated polypropylene, chlorinated paraffin, gilsonite and other asphalt materials, cyclic hydrocarbon polymers, halogenated polymers, acrylics, epoxides, novolacs, and other synthetic and natural resins. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and / or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of tackifier.

[0085] In some embodiments, the ink compositions described herein may optionally include one or more resins (e.g., binder resins). The resins can impart desired viscosity, thermal stability, flexibility, and adhesive properties to the ink composition. Examples of suitable resins include acacia (gum arabic); ghati gum; guar gum; locust bean gum; karaya gum (stelcuria gum); tragacanth gum; chicle; highly stabilized rosin esters; tall oil; manila copal; corn gluten; coumaron-indene resin; crown gum; damar gum; p,α-dimethylstyrene; elemi gum; ethylene oxide polymers and their adducts; ethylene oxide / propylene oxide copolymers and their adducts; galbanum resin; gellan gum; ghati gum; gluten gum; guaiac gum; guarana gum; heptylparaben; cellulose resins containing methyl and hydroxypropyl; hydroxypropyl methylcellulose resin; isobutylene-isoprene copolymer; mastic rubber; oat gum; opopanax rubber; polyacrylamide; modified polyacrylamide resin; polylimonene; polyisobutylene; polymaleic acid; polyoxyethylene derivatives; polypropylene Recall; polyvinyl acetate; polyvinyl alcohol; polyvinyl polypyrrolidone; polyvinylpyrrolidone; fumarate adduct rosin pentaerythritol ester; gum rosin glycerol ester; gum or wood rosin pentaerythritol ester; partially hydrogenated gum or wood rosin glycerol ester; partially hydrogenated gum or wood rosin pentaerythritol ester; partially hydrogenated rosin methyl ester; partially dimerized rosin glycerol ester; partially hydrogenated rosin; rosin and rosin derivatives; polymerized rosin glycerol ester; tall oil rosin glycerol ester; wood rosin; wood rosin glycerol ester; refined shellac; styrene; styrene terpolymer; styrene copolymer; sucrose acetate isobutyrate; natural and synthetic terpene resins; turpentine gum; vinyl acetate; vinyl chloride-vinylidene chloride copolymer; xanthan gum; and zein.In some embodiments, the ink composition contains a resin sufficient to achieve the desired viscosity, stability, flexibility, and adhesion. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 5 wt%, at least about 10 wt%, or at least about 15 wt%) and / or at most about 25 wt% (e.g., at most about 20 wt%, at most about 15 wt%, at most about 10 wt%, or at most about 5 wt%) of resin. In some embodiments, the ink composition contains substantially no resin other than the polymer dye according to the present invention.

[0086] In some embodiments, the ink compositions described herein may optionally contain one or more plasticizers. Generally, plasticizers can reduce the viscosity of the ink composition. Examples of plasticizers include aromatic sulfonamides, phthalates, acetates, adipicates, amides, azelaates, epoxides, glutarates, laurates, oleates, sebacates, stearates, sulfonicates, tallates, phosphates, benzoin ethers, and trimelliticates. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and / or at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of plasticizers.

[0087] In some embodiments, the ink compositions described herein may optionally contain one or more antioxidants. Generally, antioxidants can inhibit oxidation of the ink composition (e.g., thermally induced oxidation) (e.g., when the ink composition is in a high-temperature molten state during spraying). Examples of antioxidants include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, tert-butylhydroquinone (TBHQ), ethylenediaminetetraacetic acid (EDTA), methylparaben, and propylparaben. Commercial examples of antioxidants include Irganox 1010 (i.e., hindered phenol) and Irgafos 168 (i.e., tris(2,4-di-tert-butylphenyl) phosphite), available from BASF Corporation (Florham Park, NJ). In some embodiments, the ink composition contains at least about 0.1 wt% (e.g., at least about 0.5 wt%, at least about 1 wt%, or at least about 3 wt%) and at most about 5 wt% (e.g., at most about 4 wt%, at most about 3 wt%, at most about 2 wt%, or at most about 1 wt%) of antioxidants.

[0088] In some embodiments, the ink compositions described herein may optionally contain one or more dispersants. Generally, dispersants can help stabilize insoluble components (e.g., colorants) in the ink composition. For example, dispersants can prevent aggregation of colorants (e.g., pigments) in the ink composition. Examples of dispersants include Solsperse 13,650, 13,940, 17,000, J910; Byk 108; Tego Dispers 700; UNIQEMA 5543; and EFKA 5244, 5207, 6750, all of which are commercially available from Lubrizol, Byk, Evonik, Croda, and BASF, respectively. In some embodiments, the ink composition contains at least about 1 wt% (e.g., at least about 2 wt%, at least about 4 wt%, at least about 6 wt%, or at least about 8 wt%) and at most about 10 wt% (e.g., at most about 9 wt%, at most about 7 wt%, at most about 5 wt%, or at most about 3 wt%) of a dispersant.

[0089] In general, the ink compositions described herein may have any suitable apparent viscosity. In some embodiments, the ink compositions are 20°C and 73s -1 It can have an apparent viscosity ranging from at least about 1 centipoise (cP) (e.g., at least about 5 cP, at least about 10 cP, at least about 15 cP, or at least about 20 cP) to at most about 25 cP (e.g., at most about 20 cP, at most about 15 cP, or at most about 10 cP) as measured by [method / tool ​​name].

[0090] In some embodiments, the ink compositions described herein may optionally contain one or more conductive agents. In some embodiments, the conductive agent may be a salt (e.g., an organic salt or an inorganic salt). For example, the salt may be a quaternary phosphonium salt (e.g., a tetraalkylphosphonium or tetraarylphosphonium salt), a quaternary ammonium salt (e.g., a tetraalkylammonium or tetraarylammonium salt), an imidazolium salt, or an alkali salt (e.g., a Li, Na, K, or Cs salt).

[0091] In general, the ink compositions described herein can have any suitable conductivity. In some embodiments, the ink compositions can have conductivity ranging from at least about 0 μS / cm (e.g., at least about 10 μS / cm, at least about 50 μS / cm, at least about 100 μS / cm, at least about 200 μS / cm, at least about 300 μS / cm, at least about 400 μS / cm, at least about 500 μS / cm, or at least about 1000 μS / cm) to at most about 8000 μS / cm (e.g., at most about 7000 μS / cm, at most about 6000 μS / cm, at most about 5000 μS / cm, at most about 4000 μS / cm, at most about 3000 μS / cm, at most about 2000 μS / cm, or at most about 1000 μS / cm). For example, if an ink composition is designed for use in a continuous inkjet printing method, it may have a suitable conductivity (e.g., 100-8000 μS / cm) for printing in this method. As another example, if an ink composition is designed for use in a thermal inkjet printing method, it may have zero conductivity, as conductivity is not required in this printing method.

[0092] In some embodiments, the ink composition is substantially free of certain materials. For example, the ink composition may be substantially free of waxes (e.g., polyethylene wax), colorants other than polymer dyes according to the present invention (e.g., nonpolymer colorants), resins other than polymer dyes according to the present invention (e.g., nonpolymer resins), or conductive agents (e.g., salts).

[0093] In some embodiments, the ink composition may be a solution (in which all solutes (e.g., polymer dyes according to the present invention) are dissolved) or a dispersion (containing dispersed particles).

[0094] Printing methods and products In general, the ink compositions described herein can be used in any suitable printing method, such as continuous inkjet (CIJ) printing, drop-on-demand printing (e.g., thermal inkjet (TIJ) printing or piezo printing), hot melt printing, valve jet printing, flexographic printing, lithographic printing, gravure printing, screen printing, or pad printing, or offset printing. In some embodiments, the ink composition can be used in a printing method that involves ejecting the ink composition from a print head in an inkjet printer onto a substrate (continuously or on demand) to form an image.

[0095] In some embodiments, in a continuous inkjet printing method, a continuous stream of conductive ink droplets can be ejected from one or more nozzles of the printhead of an inkjet printer. The ink droplets are electrostatically deflected so as they are directed towards several pixels in the longitudinal direction as the substrate moves relative to the nozzle. CIJ inks generally have suitable conductivity, which allows for the deflection of ink droplets. The process of continuously ejecting ink droplets and directing unwanted droplets into the gutter has the effect of ensuring that the nozzle is never in a standby state while in operation, thus allowing the CIJ system to utilize fast-evaporating solvents (e.g., those having a relative evaporation rate (RER) greater than 1 for n-butyl acetate as determined by ASTM method D3359) without decapping (i.e., the ability to remain in a flowing state at the printhead nozzle opening exposed to air) and nozzle clogging problems.

[0096] In some embodiments, in a continuous inkjet printing method, a continuous ink stream ejected from a printhead is deflected by at least one electrode to which an electrostatic or sinusoidal high voltage is applied. Most of the ink stream is not printed and is directed towards an ink recovery gutter. During printing, segments of the ink stream are asynchronously sampled and deflected differently depending on the segment length (a length that provides a means of varying the distribution of embedded charge per unit length) and directed towards the substrate. These segments can be deformed into spherical droplets under the action of surface tension and are separated from the jet before their trajectories are deflected differently from the ink stream.

[0097] In some embodiments, in a drop-on-demand printing method, ink can be ejected by either a thermal inkjet cartridge or a piezo drop-on-demand printhead. For printing with ink, the ink is filled into a reservoir, where it is either pumped to the cartridge's ejection chamber or the printhead, or supplied by gravity. In the case of a thermal inkjet cartridge, the liquid ink is ejected from the printhead by rapidly heating, causing a rapid phase change from liquid to gas and rapid volume expansion, followed by the ejection of ink droplets from orifices. In the case of a piezo-based device, the liquid ink is ejected from the printhead by the operation of a piezoelectric transducer (PZT) which applies a pressure wave to the ink, and ink droplets can be ejected from orifices. Both devices are considered drop-on-demand because ink droplets are ejected only when the heater or PZT material is activated. Each cartridge or printhead contains an array of several orifices in the width direction. The operation of each orifice in such an array is performed in an orderly manner by the printer so that an image is formed drop by drop on a substrate positioned at a short distance from the orifice array. The printer is designed so that the orifice array and the substrate move relative to each other in order to form the image.

[0098] This disclosure also features products comprising a substrate and a solid ink for drawing an image on the substrate, wherein the solid ink comprises an ink composition described herein. The substrate can be any suitable material (e.g., porous or non-porous material) such as film, coated and uncoated paper, plastic, glass, metal, and cardboard. In some embodiments, the substrate can be a packaging material such as cardboard (e.g., corrugated cardboard) or film (e.g., shrink wrap). Examples of suitable substrates include flexible packaging films (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, or poly(lactic acid) films), rigid plastic materials (e.g., polypropylene, polyethylene, polyethylene terephthalate, polystyrene, poly(lactic acid), polyvinyl chloride materials), corrugated cardboard (e.g., bleached, unbleached, and coated cardboard), cardboard (e.g., glossy coated, matte coated, and uncoated cardboard), and bottle materials (e.g., glass, polyethylene terephthalate, polyethylene, polypropylene, and poly(lactic acid) materials). The contents of all publications cited herein (e.g., patents, patent application publications, and articles) are incorporated herein by reference in their entirety.

[0099] The present invention is further illustrated below by several preliminary embodiments, which are not intended to limit the present invention in any way and are shown solely for illustrative purposes. [Examples]

[0100] Experimental section Example 1 Synthesis of Disperse Red 1 Methacryloyloxyethyl Succinate The product described in the title is obtained by reacting Disperse Red 1 with methacryloyloxyethyl succinic acid according to the following reaction.

[0101] [ka]

[0102] EDC.HCl: 1-Ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride DMAP: Dimethylaminopyridine DCM: Dichloromethane In a round-bottom flask, Disperse Red 1 (10.0 g, 31.9 mmol, 1 equivalent) and 2-(methacryloyloxy)ethyl succinate (8.1 g, 35.0 mmol, 1.1 equivalents) were dissolved in 310 mL of dichloromethane. The mixture was cooled to 0°C in an ice bath, and then EDC.HCl (7.4 g, 38.5 mmol, 1.2 equivalents) and DMAP (0.78 g, 6.4 mmol, 0.2 equivalents) were added in fractions and continuously under a nitrogen flow. After the addition was complete, the mixture was left to stand at room temperature with stirring for 1 hour. At the end of the reaction, 100 mL of 0.5 M HCl was added, and the mixture was transferred to a separatory funnel. After decantation, the organic phase was recovered, dehydrated with anhydrous sodium sulfate, filtered on frit Por4, and concentrated under reduced pressure. After complete removal of dichloromethane, the polymerizable red monomer appeared as a red powder. The chemical structure of this monomer is: 1 Confirmed by 1H NMR (in chloroform-d).

[0103] 1 ¹H NMR (300 MHz, chloroform-d) δ (ppm) 8.34 - 8.14 (m, 2H), 7.92 - 7.68 (m, 4H), 6.81 - 6.63 (m, 2H), 6.05 (p, J = 1.1 Hz, 1H), 5.51 (p, J = 1.6 Hz, 1H), 4.26 (d, J = 8.1 Hz, 6H), 3.73 - 3.28 (m, 4H), 2.57 (h, J = 1.6 Hz, 4H), 1.87 (t, J = 1.2 Hz, 3H), 1.18 (t, J = 7.0 Hz, 3H). Example 2 Synthesis of Blue Patent V Methacryloyloxyethyl Succinate The product described in the title is obtained by reacting Blue Patent V with methacryloyloxyethyl succinic acid according to the following reaction.

[0104]

Chemical Formula

[0105] EDC.HCl: 1-Ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride DMAP: Dimethylaminopyridine DCM: Dichloromethane NBu: Tetrabutylammonium The first step consists in replacing the sodium counterion with tetrabutylammonium to reduce the hydrophilic properties of Patent Blue V. In a round-bottom flask, Patent Blue V sodium salt (20.0 g, 0.034 mol, 1 equivalent) and tetra-n-butylammonium bromide (22.1 g, 0.069 mol, 2 equivalents) were solubilized in 400 mL of a 3 / 1 v / v dichloromethane / water mixture. The biphasic mixture was vigorously stirred at room temperature for 3 hours, then 1 L of dichloromethane and 400 mL of 0.5 M HCl were added, and the solution was then transferred to a separatory funnel. After the two phases settled, the organic phase was collected, dried over anhydrous sodium sulfate, filtered on a Por4 frit, and concentrated under reduced pressure. After complete removal of dichloromethane, the intermediate product was obtained as a dark purple powder. This chemical structure was 1 confirmed by 1H NMR (in chloroform-d).

[0106] The second step involves the reaction of the dye with a polymerizable monomer. In a round-bottom flask, the product from the first step (20.9 g, 16.9 mmol, 1 equivalent) and 2-(methacryloyloxy)ethyl succinate (4.28 g, 18.6 mmol, 1.1 equivalents) were dissolved in 150 mL of dichloromethane. The mixture was cooled to 0°C in an ice bath, and then EDC.HCl (3.9 g, 20.4 mmol, 1.2 equivalents) and DMAP (0.41 g, 3.4 mmol, 0.2 equivalents) were added in fractions and continuously under a nitrogen flow. After the addition was complete, the mixture was left to stand at room temperature with stirring for 4 hours. At the end of the reaction, 200 mL of dichloromethane and 150 mL of 0.5 M HCl were added, and the mixture was transferred to a separatory funnel. After decantation, the organic phase was dehydrated with anhydrous sodium sulfate, filtered over frit Por4, and concentrated under reduced pressure. After complete removal of dichloromethane, the polymerizable blue monomer appeared as a dark blue powder. The chemical structure of this monomer is: 1 Confirmed by 1H NMR (in chloroform-d).

[0107] 1 ¹H NMR (300 MHz, chloroform-d) δ (ppm) 8.65 (s, 1H), 7.45 (dd, J = 9.1, 6.7 Hz, 4H), 6.80 - 6.57 (m, 5H), 6.14 - 5.96 (m, 1H), 5.50 (m, 1H), 4.24 (s, 4H), 3.52 (q, J = 7.1 Hz, 8H), 3.42 - 3.10 (m, 16H), 2.96 (t, J = 6.9 Hz, 2H), 2.75 (t, J = 6.9 Hz, 2H), 1.97 - 1.78 (m, 3H), 1.78 - 1.50 (m, 16H), 1.50 - 1.08 (m, 28H), 0.93 (t, J = 7.3 Hz, 24H). Example 3 - Comparison Synthesis of black polymer dyes Starting from the monomer dyes synthesized in Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to Scheme 1 below.

[0108] [ka]

[0109] In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (4.0 g, 1.77 mmol), Disperse Red 1 methacryloyloxyethyl succinate (1.37 g, 2.53 mmol), ethyl methacrylate (3.6 g, 31.5 mmol), and AIBN (0.12 g, 0.72 mmol) were dissolved in 40 mL of DMF. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was carried out overnight at 80°C. After polymerization was complete, the DMF was removed by evaporation under vacuum. The product was then dissolved in dichloromethane and precipitated twice in a cold mixture of 3 / 7 MeOH / Et2O, and then once in pentane. Before each precipitation, the product was redissolved in dichloromethane.

[0110] After drying in an oven at 40°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer is: 1 The molecular weight was confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC (gel permeation chromatography) using DMF as the eluent and PMMA (poly(methyl methacrylate)) (Mw=60,000 Da) as the standard.

[0111] The yield of the black polymer dye was approximately 48% w / w. 1 ¹H NMR (300 MHz, chloroform-d) δ (ppm) 8.70 (s, 1H x ), 8.34 (d, J = 8.6 Hz, 2H z ), 7.92 (t, J = 8.4 Hz, 4H z ), 7.51 (d, J = 9.1 Hz, 4H x ), 6.90 - 6.60 (m, 5H x + 2H z ), 4.54 - 3.83 (m, 4H x + 2Hy + 6H z ), 3.71 (s, 2H z ), 3.65 - 3.44 (m, 8H x + 2H z ), 3.34 (d, J = 8.6 Hz, 16H x ), 3.05 (s, 2H x ), 2.82 (s, 2H x ), 2.68 (s, 4H z ), 2.39 - 1.58 (m, 18H x + 2H y + 5H z), 1.56 - 1.15 (m, 28H x + 3 H y + 3H z ), 1.15 - 0.48(m, 27H x + 3H y + 3H z ). Example 4 - Comparison Synthesis of black polymer dyes Starting from the monomer dyes synthesized in Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to Scheme 1 under the following conditions.

[0112] In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (128 g, 0.66 mol), Disperse Red 1 methacryloyloxyethyl succinate (51.1 g, 0.097 mol), ethyl methacrylate (135.1 g, 1.18 mol), and AIBN (4.4 g, 0.027 mol) were dissolved in 1250 g of DMF. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was carried out overnight at 80°C. After polymerization was complete, the DMF was removed by evaporation under vacuum. The product was then dissolved in dichloromethane and precipitated twice in a cold mixture of MeOH / Et2O (3 / 7, 2 / 8 v / v) and then once in Et2O. Before each precipitation, the product was redissolved in dichloromethane.

[0113] After drying in an oven at 60°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer was as in Example 3. 1 The molecular weight was confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=63,400Da) as the standard.

[0114] The yield of the black polymer dye was approximately 67% w / w. Example 5 - Comparison Synthesis of black polymer dyes Starting from the monomer dyes synthesized in Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to Scheme 1 above under the following conditions.

[0115] In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (1.7 g, 1.4 mmol), Disperse Red 1 methacryloyloxyethyl succinate (1.0 g, 1.3 mmol), ethyl methacrylate (2.0 g, 17 mmol), and AIBN (0.17 g, 1.0 mmol) were dissolved in 19 g of DMF. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was then carried out at 80°C. After 6 hours, the DMF was removed by evaporation under vacuum. The product was then dissolved in acetonitrile and precipitated in 400 mL of diethyl ether.

[0116] After drying in an oven at 60°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer was as in Example 3. 1 The results were confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=46,600Da) as the standard.

[0117] The yield of the black polymer dye was approximately 80% w / w. Example 6 - Invention Synthesis of black polymer dyes Starting from the monomer dyes synthesized in Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to Scheme 1 above under the following conditions.

[0118] In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (4.5 g, 3.7 mmol), Disperse Red 1 methacryloyloxyethyl succinate (2.6 g, 4.7 mmol), ethyl methacrylate (5.3 g, 46.0 mmol), and AMBN (0.54 g, 2.7 mmol) were dissolved in 20 g of acetonitrile. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was carried out at 80°C. After 24 hours, the product was precipitated in diisopropyl ether at room temperature (20°C). The amount of diisopropyl ether was approximately 20 times the amount of the synthesis solvent acetonitrile (acetonitrile / diisopropyl ether volume ratio equal to approximately 1 / 20).

[0119] After drying in an oven at 60°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer was as in Example 3. 1 The results were confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=86,200Da) as the standard.

[0120] The yield of the black polymer dye was approximately 90% w / w. Example 7 - Invention Synthesis of black polymer dyes Starting from the monomer dyes synthesized in Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to Scheme 1 above under the following conditions.

[0121] In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (55.0 g, 45 mmol), Disperse Red 1 methacryloyloxyethyl succinate (32.3 g, 57 mmol), ethyl methacrylate (64.6 g, 566 mmol), and AMBN (6.6 g, 33 mmol) were dissolved in 270 g of acetonitrile. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was then carried out at 80°C. After 8 hours, the product was precipitated in diisopropyl ether at 0°C. The amount of diisopropyl ether was approximately 15 times the amount of the synthesis solvent acetonitrile (an acetonitrile / diisopropyl ether volume ratio equal to approximately 1 / 15).

[0122] After drying in an oven at 60°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer was as in Example 3. 1 The results were confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=66,300Da) as the standard.

[0123] The yield of the black polymer dye was approximately 99% w / w. Example 8 - Invention Synthesis of black polymer dyes In a round-bottom flask, Blue Patent V methacryloyloxyethyl succinate (55.0 g, 45 mmol), Disperse Red 1 methacryloyloxyethyl succinate (32.3 g, 57 mmol), ethyl methacrylate (64.6 g, 566 mmol), and AMBN (6.6 g, 33 mmol) were dissolved in 270 g of acetonitrile. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and polymerization was then carried out at 80°C. After 8 hours, the product was precipitated in methyl tert-butyl ether at 0°C. The amount of methyl tert-butyl ether was approximately 15 times the amount of the synthesis solvent acetonitrile (an acetonitrile / methyl tert-butyl ether volume ratio equal to approximately 1 / 15).

[0124] After drying in an oven at 60°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer was as in Example 3. 1 The results were confirmed by 1H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=68,700Da) as the standard.

[0125] The yield of the black polymer dye was approximately 92% w / w. In light of the above-described embodiments of the present invention, it will be understood that various modifications may be made by those skilled in the art. Such modifications are intended to be encompassed by the following claims.

Claims

1. A method for synthesizing polymer dyes, (1) A dye containing a first reactive functional group is reacted with a polymerizable monomer containing a second reactive functional group to obtain the following formulas (I) to (III) and (V) 【Chemistry 1】 (In the formula, M1, M2, M3, and M5 are either the same or different from each other and are reactive monomers, while C1 to C4 are different from each other and are chromophore units.) A step to obtain a polymerizable monomer dye having one of the following, (2) At least one polymerizable monomer dye (I) to (III) and (V) is given by the following formula (IV) 【Chemistry 2】 (In the formula, M4 is a reactive monomer.) A step of copolymerizing with a polymerizable monomer having the following characteristics: (3) A step of recovering the obtained polymer dye and Includes, The copolymerization step (2) is carried out in a solvent selected from acetonitrile or a mixture of methyl ethyl ketone and ethanol, and the recovery step (3) includes a purification step carried out using a solvent selected from diisopropyl ether, methyl tert-butyl ether, dimethyl carbonate, ethyl acetate, and water. method.

2. A method for synthesizing a polymer dye according to claim 1, wherein the first reactive functional group is selected from the group consisting of a hydroxyl group, an amine group, or a carboxyl group.

3. A method for synthesizing a polymer dye according to claim 1, wherein the second reactive functional group is selected from the group consisting of a carboxylic acid group, an acyl chloride, an anhydride group, an ester group, a hydroxyl group, or an amine group.

4. A method for synthesizing a polymer dye according to claim 1, wherein M1 to M5 are the same or different from each other and are selected from the group consisting of acrylic acid monomer, methacrylic acid monomer, acrylate monomer, methacrylate monomer, acrylamide monomer, methacrylamide monomer, vinyl alcohol monomer, and vinylamine monomer.

5. One of C1 to C4 is Acid Blue 1, 3, 7, 9, 15, 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 52, 57, 58, 61:1, 62, 62:1, 63, 64, 65, 68, 69, 72, 74, 78, 78:1, 79, 80, 81, 81:1, 83, 90, 92, 96, 103, 104, 111, 112, 113, 114, 120, 124, 127, 127:1, 128, 129, 129:1, 138, 138:1, 1 40, 142, 145, 150, 156, 158, 171, 175, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 215, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277, 277:1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 344, 350; Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29; Direct Blue 1, 15, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 160, 168, 189, 192, 193, 199, 200, 201, 202, 203, 218, 225, 229, 237, 244, 248, 251, 270, 273, 274, 290, 291; Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 77, 79, 79:1, 79:2, 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146, 14 8, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 281, 284, 285, 287, 288, 291, 291:1, 293, 295, 297, 301, 315, 330, 333, 373; Hood Blue 1, 2; Reactive Blue 2, 3, 4, 5, 7, 13, 14, 15, 19, 21, 25, 27, 28, 29, 38, 39, 41, 49, 50, 52, 63, 69, 71, 72, 77, 79, 89, 104, 109, 112, 113, 114, 116, 119, 120, 122, 137, 140, 143, 147, 160, 161, 162, 163, 168, 171, 176, 182, 184, 191, 194, 195, 198, 203, 204, 207, 209, 211, 214, 220, 221, 222, 231, 235, 236; Solvent Blue 4, 5, 6, 35, 38, 48, 59, 67, 70, 104, and 136 A method for synthesizing a polymer dye according to claim 1, which can be a blue chromophore unit derived from a commercially available dye selected from the group consisting of the following.

6. One of C1 to C4 is Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97:1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 143:1, 145, 151, 183, 195, 198, 211, 215, 2 17, 225, 226, 249, 251, 254, 256, 257, 260, 261, 265, 266, 274, 276, 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415, 447, Basic Red 1, 2, 9, 12, 13, 37 Direct Red 2, 4, 9, 23, 24, 31, 54, 62, 69, 79, 80, 81, 83, 84, 89, 95, 212, 224, 225, 226, 227, 239, 242, 243, 254, Disperse threads 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 15 1, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328, 337, 343, Food Red 2, 3, 7, 9, 14, 52, 87, 92, 94, 102, 104, 105, 106, Reactive Red 2, 3, 5, 8, 11, 21, 22, 23, 24, 28, 29, 31, 33, 35, 43, 45, 49, 55, 56, 58, 65, 66, 78, 83, 84, 106, 111, 312, 113, 114, 116, 120, 123, 124, 128, 130, 136, 141, 147, 158, 159, 171, 174, 180, 183, 184, 187, 190, 193, 194, 195, 198, 218, 220, 222, 223, 228, 235, Solvent Red 1, 23, 29, 49, 119, 122, 125, 127, 130, 132, 135, 149, 160, 164, 168, 169, 172 and 233 A method for synthesizing a polymer dye according to claim 1, which can be a red chromophore unit derived from a commercially available dye selected from the group consisting of the following.

7. One of C1 to C4 is Acid Green 1, 3, 5, 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 50, 56, 73, 81, 84, 104, 108, 109, Basic Green 1, 4, 5 Direct Green 26, 28, 59, 80, 85, Disperse Green 9, Food Green 2, 3 Reactive Green 5, 7, 8, 12, 15, 19, 21 Solvent Green 1, 3, 7, and 11 A method for synthesizing a polymer dye according to claim 1, which may be a green chromophore unit derived from a commercially available dye selected from the group consisting of the following.

8. One of C1 to C4 is Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40:1, 42, 44, 49, 59, 59:1, 61, 65, 72, 73, 79, 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219:1, 220, 230, 232, 235, 241, 242, 246, Basic Yellow 1, 2, 11, 12, 14, 21, 28, 32, 36, 57, 87 Direct Yellow 4, 7, 8, 9, 10, 11, 12, 22, 27, 28, 39, 44, 50, 58, 59, 62, 79, 86, 87, 98, 105, 106, 130, 132, 137, 142, 147, 153, Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 11 6, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, 227, 231, 232, Food Yellow 3, 4, 5 Reactive Yellow 2, 3, 7, 15, 17, 18, 22, 23, 24, 25, 27, 37, 39, 42, 57, 69, 76, 81, 84, 85, 86, 87, 92, 95, 102, 105, 111, 125, 135, 136, 137, 142, 143, 145, 151, 160, 161, 165, 167, 168, 175, 176 Solvent Yellow 2, 3, 7, 10, 13, 14, 19, 25, 28, 33, 88, 89, 114, 146, 163, Acid Orange 3, 6, 7, 8, 10, 12, 19, 20, 24, 51, 56, 63, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, 144, 149, 152, 156, 162, 166, 168, Basic Orange 2, 14, 15, 21, 22, 31, 69 Direct Orange 6, 26, 27, 34, 39, 40, 46, 102, 105, 107, 118, Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, Reactive Orange 1, 4, 5, 7, 11, 2, 13, 15, 16, 20, 30, 35, 56, 64, 67, 69, 70, 72, 74, 82, 84, 86, 87, 91, 92, 93, 95, 107 Solvent Orange 1, 2, 3, 7, 11, 15, 20, 25, 54, 60, 62, 63, 86, 99, 105, Acid Violet 7, 9, 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126, Basic Violet 1, 2, 3, 4, 7, 10, 14 Direct Violet 9, 35, 51, 66, 94, 95 Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, Food Violet 2, Reactive Violet 1, 2, 4, 5, 6, 8, 9, 22, 23, 33, 36, 38 Solvent violet 8, 9, 11, 13, 14, and 38 A method for synthesizing a polymer dye according to claim 1, wherein the chromophore unit may be derived from a commercially available dye selected from the group consisting of the following.

9. A polymer dye obtained by using a method for synthesizing a polymer dye according to any one of claims 1 to 8, wherein the polymer dye comprises at least one of the polymerizable monomer dyes (I) to (III) and (V) obtained by copolymerizing the polymer dye with the polymerizable monomer having formula (IV).

10. The polymer dye according to claim 9, wherein the polymer dye has high solubility in an organic solvent at 25°C.

11. The polymer dye according to claim 10, wherein the polymer dye has a solubility of at least 1 wt% in an organic solvent at 25°C.

12. The polymer dye according to claim 11, wherein the polymer dye has a solubility of less than 0.1 wt% in water at 25°C.

13. An ink composition comprising a polymer dye according to any one of claims 9 to 12, wherein the ink composition is a liquid composition, a dispersion composition, an emulsion composition, or a solid composition.

14. The ink composition according to claim 13, wherein the ink composition is a liquid composition comprising the polymer dye and an organic solvent, and the amount of the polymer dye is 1% to 70% by weight, preferably 3% to 50% by weight, of the ink composition.

15. The ink composition according to claim 13, wherein the ink composition is a solid composition comprising the polymer dye and a fusible carrier, and the amount of the polymer dye is 1% to 70% by weight, preferably 3% to 50% by weight, of the ink composition.

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