polymer dyes

Abstract

The present invention relates to polymeric dyes and related ink compositions, products, and methods.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to polymeric dyes and related ink compositions, products, and methods.

[0002] More particularly, the present invention relates to polymeric dyes obtained by polymerization of polymerizable monomers having a polymerizable functional group, such as an acrylate, methacrylate, acrylamide, or methacrylamide, and a chromophore functional group. [Background technology]

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

[0004] These pigments are usually coordinated with heavy metals, which may be the cause of the toxicity of such pigments.

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

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

[0007] This type of chemistry has raised several concerns for human health, with some dyes already classified as CMR (carcinogenic, mutagenic, reproductively toxic).

[0008] CMR chemicals (as dyes) are banned from sensitive markets such as the food, pharmaceutical, and cosmetic industries because the chemicals can migrate through packaging substrates and therefore be found in products.

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

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

[0011] Therefore, there is a need to develop organic solvent soluble polymeric dyes that do not contain heavy metals. Summary of the Invention [Problem to be solved by the invention]

[0012] Summary of the Invention The applicant faced the challenge of developing organic solvent-soluble polymeric dyes that are heavy metal-free. [Means for solving the problem]

[0013] After extensive experimentation, the applicant has found a solution that makes it possible to obtain organic solvent-soluble polymeric dyes that are free of heavy metals.

[0014] The solution is a method for synthesizing a polymer dye, comprising: (1) functionalizing a dye with a polymerizable functional group to obtain a polymerizable monomeric dye; (2) copolymerizing at least one polymerizable monomer dye with a polymerizable monomer; (3) recovering the resulting polymer dye; The present invention includes a method comprising the steps of:

[0015] Polymerizable monomeric dyes can be readily prepared by reaction of one reactive functional group of the dye, such as a hydroxyl, amine, or carboxyl group, with a reactive functional group of a polymerizable monomer, such as an acyl chloride or anhydride or an ester or a carboxylic acid, or a hydroxyl or amine group.

[0016] Copolymerization of at least one polymerizable monomer dye with a polymerizable monomer can be easily carried out in a suitable solvent in the presence of a suitable initiator.

[0017] Applicants have discovered that a wide range of polymeric dyes having different colors (black, cyan, magenta, yellow, blue, red, and green) can be obtained by copolymerizing two or more polymerizable monomeric dyes having different chromophores.

[0018] In one aspect, the present invention relates to polymeric dyes and methods for their preparation. Such polymeric dyes can be used as dyes in continuous ink jet (CIJ) printing methods, drop-on-demand (DOD) printing methods (e.g., thermal ink jet (TIJ) printing methods), or hot melt (HM) ink jet printing methods. Compared with conventional colorants (e.g., carbon black-metal complex dyes) used in printing methods (e.g., CIJ, DOD, TIJ, or HM), the polymeric dyes of the present invention can form ink compositions with standard fastness without containing any toxic metal cations, while still having excellent stability, printability, solubility in organic solvents, and adhesion to various substrates.

[0019] In another aspect, the present invention relates to an ink composition comprising the polymeric dye of the present invention and an organic solvent. The composition may be a solution.

[0020] The polymeric dye of the present invention can be present in an amount of from about 1% to about 70% by weight, preferably from 3% to 50% by weight, based on the weight of the ink composition.

[0021] In another aspect, the present invention relates to an article of manufacture comprising a substrate (e.g., cardboard, glass, metal, or film) and a solid ink defining an image on the substrate, wherein the solid ink comprises the ink composition described herein.

[0022] In another aspect, the present invention relates to a method of printing comprising ejecting the ink compositions described herein from a printhead in an ink jet printer onto a substrate to form an image. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 10 shows the immediate post-print results of the printing test described in Example 10. [Figure 2] FIG. 1 shows the results of the print test described in Example 10 after 10 hours of lightfastness aging. [Figure 3] FIG. 1 shows the results of the print test described in Example 10 after 18 hours of lightfastness aging. [Figure 4] FIG. 1 shows the results of the print test described in Example 10 after 28 hours of lightfastness aging. [Figure 5] FIG. 1 shows the results of the print test described in Example 10 after 35 hours of lightfastness aging. [Figure 6] FIG. 1 shows the results of the print test described in Example 10 after 50 hours of lightfastness aging. DETAILED DESCRIPTION OF THE INVENTION

[0024] Detailed Description of the Invention While the present invention may be embodied in many different forms, specific embodiments thereof are shown in the drawings and further described herein, it should be understood that the present disclosure exemplifies the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated and described.

[0025] polymer dyes In one embodiment, the polymeric dye according to the present invention has the following formulas (I) and (II):

[0026] [ka]

[0027] wherein M1 and M2 are the same or different and are reactive monomers, and C1 and C2 are different and are chromophore units. is a copolymer comprising a monomer repeat unit having the formula:

[0028] According to one embodiment, the polymeric dye according to the present invention has the following formulae (III) and (IV):

[0029] [ka]

[0030] wherein M3 and M4 are the same or different and are reactive monomers, and C3 is a chromophore unit different from C1 and C2. The monomer may optionally include a repeating unit having the formula:

[0031] In one embodiment of the present invention, the polymeric dye has the following formula (V):

[0032] [ka]

[0033] (wherein M5 is a reactive monomer, and C4 is a chromophore unit different from C1 to C3) The monomer may optionally include a repeating unit having the formula:

[0034] In one embodiment of the present invention, M1 to M5 are the same or different and are selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinylamine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, alkyl vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, and the like.

[0035] In one embodiment of the present invention, the styrene derivative monomer has the following general formula (VI):

[0036] [ka]

[0037] (wherein X1 to X3 may be the same or different and are selected from hydrogen, fluorine, chlorine, bromine, iodine, a hydroxy group, and a methyl group; and Y1 to Y5 may be the same or different and are selected from hydrogen, fluorine, chlorine, bromine, iodine, a hydroxy group, a methyl group, a hydroxymethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group). is expressed by

[0038] In one embodiment of the present invention, the chromophore unit may be selected from azo, metallized azo, diazo, polyazo, methine, arylidene, polymethine, azo-methine, anthraquinone, azamethine, anthrapyridone, anthrapyridine, phthaloylphenothiazine, benzanthrone, anthrapyrimidine, anthrapyrazole, anthraisothiazole, triphenodioxazine, thioxanthen-9-one, fluorindine, quinophthalone, phthalocyanine, naphthalocyanine, coumarin, coumarinimine, indophenone, as known by those skilled in the art. They can be represented by the following chromophore units: nol, perinone, nitroarylamine, benzodifuran, phthaloylphenoxazine, phthaloylacridone, anthraquinonethioxanthone, anthrapyridazone, indigo, thioindigo, xanthene, acridine, azine, oxazine, thiazine, 1,4- and 1,5-naphthoquinone, naphthotriazole, naphthoquinone, diiminoisoindoline, naphthopyran, aminonaphthalimide, diarylmethane, triarylmethane, acridene, indamine, and quinoline.

[0039] In preferred embodiments of the present invention, the chromophore units can be represented by azo, diazo, triarylmethane, and anthraquinone chromophore units.

[0040] In one embodiment of the present invention, any 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, 147 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, Food 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 The blue chromophore unit can be a blue chromophore unit contained in commercially available dyes selected from the group consisting of:

[0041] Specific examples of commercially available dyes containing blue chromophore units useful in the present invention are shown below along with their structural formulas.

[0042] [Table 1]

[0043] In one embodiment of the present invention, any 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 Red 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, Hood 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 The red chromophore unit can be a red chromophore unit contained in commercially available dyes selected from the group consisting of:

[0044] Specific examples of commercially available dyes containing red chromophore units useful in the present invention are shown below along with their structural formulas.

[0045] [Table 2]

[0046] In one embodiment of the present invention, any 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 The green chromophore unit can be a green chromophore unit contained in commercially available dyes selected from the group consisting of:

[0047] Specific examples of commercially available dyes containing green chromophore units useful in the present invention are shown below along with their structural formulas.

[0048] [Table 3]

[0049] In one embodiment of the present invention, any 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 The dye may be a chromophore unit contained in a commercially available dye selected from the group consisting of:

[0050] Specific examples of commercially available dyes containing other chromophore units useful in the present invention are shown below along with their structural formulas.

[0051] [Table 4]

[0052] Among the commercially available dyes listed above, preferred commercially available dyes are those that contain at least one reactive functional group, such as a hydroxyl group, an amine group, or a carboxyl group, that can react with the reactive functional group of the polymerizable monomer. However, commercially available dyes that do not have any reactive functional group can be used within the scope of the present invention by derivatization to contain a reactive functional group.

[0053] In some embodiments, the polymeric dyes according to the present invention can be block copolymers, random copolymers, or graft copolymers. In preferred embodiments, the polymeric dyes according to the present invention are random copolymers.

[0054] In some embodiments, the polymeric dyes according to the present invention can 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 120,000 Da (e.g., 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).

[0055] In some embodiments, the polymeric dye according to the present invention can comprise any one of the monomeric repeat units having Formulas (I)-(V) 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), based on the weight average molecular weight of the polymeric dye.

[0056] In one embodiment, a polymeric dye according to the present invention comprises any one of the monomeric repeat 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), based on the weight average molecular weight of the polymeric dye.

[0057] In some embodiments, the polymeric dye according to the present invention comprises a combined amount of monomeric repeat units having formulas (I) and (II) 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), based on the weight average molecular weight of the polymeric dye, with the remainder being represented by monomeric repeat units having formula (IV) and, optionally, monomeric repeat units having formulas (III) and (V).

[0058] Generally, the polymeric 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 be dissolved in an organic solvent to form a homogeneous solution (no suspension or precipitation).

[0059] In some embodiments, the polymeric dye according to the present invention can have a solubility in an organic solvent at 25° C. ranging from at least about 1 wt % (e.g., at least about 2 wt %, at least about 5 wt %, at least about 10 wt %, at least about 15 wt %, at least about 20 wt %, at least about 25 wt %, at least about 30 wt %, at least about 35 wt %, at least about 40 wt %, at least about 45 wt %, or at least about 50 wt %) to at most about 90 wt % (e.g., at most about 85 wt %, at most about 80 wt %, at most about 75 wt %, at most about 70 wt %, at most about 65 wt %, at most about 60 wt %, at most about 55 wt %, or at most about 50 wt %). As used herein, the solubility referred to herein refers to the weight percentage of the solute (e.g., the polymeric dye) based on the total weight of the solution (e.g., the solution containing the solute and the organic solvent) at 25° C.

[0060] In some embodiments, the organic solvent in which the polymeric dye can be dissolved can include a ketone, an ester, an acetal, an ether, a carbonate, an ester, or a combination 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 can include a single solvent or a combination of two or more (e.g., three or four) solvents.

[0061] In some embodiments, the polymeric dye is substantially insoluble in water at 25° C. (eg, has a solubility of less than 0.1 wt %, preferably less than 0.01 wt %).

[0062] In one embodiment, the polymeric dye of the present invention is The following formulas (I) to (III) and (V)

[0063] [ka]

[0064] (wherein M1, M2, M3, and M5 are the same or different from one another and are reactive monomers as described above, and C1 to C4 are different from one another and are chromophore units as described above). and at least one monomer repeat unit having the formula: ● The following formula (IV)

[0065] [ka]

[0066] where M4 is a reactive monomer as described above. and a monomer repeat unit having Including, The polymeric dye is soluble in organic solvents, preferably having a solubility of at least 1 wt% in organic solvents at 25°C, and is insoluble in water, preferably having a solubility of less than 0.1 wt% in water at 25°C.

[0067] How to Make Polymer Dyes The polymeric dye according to the present invention comprises (1) functionalizing a dye with a polymerizable functional group to obtain a polymerizable monomeric dye; (2) copolymerizing at least one polymerizable monomer dye with a polymerizable monomer; (3) recovering the resulting polymer dye; The compound can be prepared using a method comprising the steps of:

[0068] The polymerizable monomer dyes can be prepared by synthetic methods described herein or known in the art.

[0069] Polymerizable monomeric dyes can be readily prepared by reaction of one reactive functional group of the dye, such as a hydroxyl, amine, or carboxyl group, with a reactive functional group of a polymerizable monomer, such as a carboxylic acid group, acyl chloride, anhydride group, ester group, or hydroxyl or amine group.

[0070] 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, when the dye contains an alkali or alkaline earth sulfonate group or a carboxylate group, the alkali or alkaline earth ion is previously replaced with a tetraalkylammonium group, such as a tetrabutylammonium group, a tetrahexylammonium group, or a tetraoctylammonium group, to improve the solubility in organic solvents while decreasing the solubility in water.

[0071] In some embodiments, the polymerizable monomer dye is obtained by reacting a dye having a hydroxyl 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 or phenol group.

[0072] 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 an acrylic acid or methacrylic acid ester.

[0073] In some embodiments, the reaction is carried out in a suitable solvent, preferably an aprotic solvent such as dichloromethane (DCM), acetone, acetonitrile, dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.

[0074] In some embodiments, the reaction between the dye and the polymerizable monomer is an esterification reaction. In a preferred embodiment, 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 4-dimethylaminopyridine as a catalyst.

[0075] The resulting polymerizable monomer dye can be isolated from the reaction mixture by methods known in the art, for example, 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).

[0076] Starting with one or more different polymerizable monomeric dyes, the polymeric dyes can be prepared by synthetic methods described herein or known in the art.

[0077] Copolymerization of one or more different polymerizable monomer dyes with polymerizable monomers can be achieved by free radical polymerization in a suitable solvent in the presence of a suitable initiator.

[0078] In some embodiments, the reaction is carried out in a suitable solvent, preferably an aprotic solvent, such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethyl acetate, tetrahydrofuran, and the like.

[0079] In some embodiments, the reaction can be carried out by thermal decomposition of an initiator (e.g., organic peroxides (e.g., dicumyl peroxide) or azo compounds), photolysis (e.g., using metal iodides, metal alkyls, or azo compounds (e.g., azoisobutylnitrile (AIBN))), peroxide initiators (e.g., benzoyl peroxide), redox reactions (e.g., using iron ions or, e.g., Cr 2+ , V 2+ , Ti 3+ , Co2+ , or Cu + Initiation may also be by initiator compositions that allow for the reduction of hydrogen peroxide or alkyl hydrogen peroxides by means of other reducing agents such as persulfate activation, ionizing radiation (e.g., by alpha, beta, gamma, or x-rays), electrochemical activation, plasma activation, or sonication (e.g., at approximately 16 kHz).

[0080] The resulting polymeric dye can be isolated from the reaction mixture by methods known in the art, for example, by precipitating the resulting polymeric dye in a solvent in which it is insoluble and separating the precipitated polymer from the solvent by filtration, decantation, or centrifugation.

[0081] Generally, the reaction temperature for steps (1) and (2) can be adjusted as needed. In some embodiments, both steps (1) and (2) can be carried out at room temperature.

[0082] Generally, the reaction times for steps (1) and (2) can be adjusted as needed. The progress of steps (1) and (2) can be monitored by UV-Vis spectroscopy, NMR spectroscopy, or thin layer chromatography (TLC) using methods known in the art.

[0083] Ink composition Generally, the polymeric dyes according to the present invention can be formulated into ink compositions (e.g., ink-jet ink compositions). In some embodiments, the ink composition can be a homogeneous solution in which all solutes (including the polymeric dyes according to the present invention) are dissolved. In some embodiments, the ink composition can be a dispersion or emulsion. In some further embodiments, the ink composition can be a solid composition.

[0084] In some embodiments, the polymeric pigment according to the present invention can be present in a range of at least about 1 wt % (e.g., at least about 2 wt %, at least about 5 wt %, at least about 10 wt %, at least about 15 wt %, at least about 20 wt %, at least about 25 wt %, at least about 30 wt %, at least about 35 wt %, at least about 40 wt %, at least about 45 wt %, or at least about 50 wt %) to at most about 70 wt % (e.g., at most about 65 wt %, at most about 60 wt %, at most about 55 wt %, at most about 50 wt %, at most about 45 wt %, at most about 40 wt %, at most about 35 wt %, or at most about 30 wt %) of the ink composition.

[0085] Without wishing to be bound by theory, it is believed that the polymeric dyes according to the present invention can form ink compositions without the use of any metals (e.g., any heavy metals) or any colorants. Without wishing to be further bound by theory, it is believed that ink compositions containing the polymeric dyes according to the present invention can have excellent lightfastness, color strength, and adhesion properties.

[0086] In some embodiments, the ink compositions described herein can include an organic solvent in which the polymeric dye according to the present invention is dissolved. In some embodiments, organic solvents suitable for the ink compositions can include ketones, esters, acetals, ethers, carbonates, esters, 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 can include one solvent or a combination of two or more (e.g., three or four) solvents.

[0087] In some embodiments, the organic solvent can be in a 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.

[0088] In some embodiments, the ink compositions described herein can include a fusible carrier for dispersing the polymeric pigment according to the present invention. In some embodiments, suitable fusible carriers for ink compositions can include waxes, resins, and / or long-chain fatty acids, esters, or alcohols. Examples of 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. Examples of suitable waxes include, but are not limited to, polyalkylene waxes such as polyethylene wax or polypropylene wax, Fischer-Tropsch wax, linear primary alcohols such as Unilin™ alcohol wax (available from Baker Hughes), microcrystalline wax, fatty acids, carnauba wax, candelilla wax, stearamide, paraffin wax, and montan wax, and ethoxylated long-chain alcohols such as Unithox™ (available from Baker Hughes). Waxes may be used alone or in combination. Examples of suitable long chain fatty acids, esters, or alcohols include, but are not limited to, dialkyl esters of sebacic acid, higher fatty alcohols, stearic acid, lauric acid, and behenic acid. Additionally, combinations of waxes, resins, and / or long chain fatty acids, esters, or alcohols may be used.

[0089] In some embodiments, the fusible carrier can be in a 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.

[0090] In some embodiments, the ink compositions described herein may include only two components (i.e., a polymeric dye according to the present invention and an organic solvent or fusible carrier). In some embodiments, the ink compositions may optionally include one or more (e.g., two, three, or four) additives or additional components.

[0091] In some embodiments, the ink compositions described herein can optionally include at least one conductivity salt. Examples of suitable conductivity salts include alkali metal salts, alkaline earth salts, and simple or quaternary ammonium salts in the form of halides (chlorides, bromides, iodides, and fluorides), perchlorates, nitrates, thiocyanates, formates, acetates, sulfates, propionates, and the like.

[0092] In some embodiments, the ink compositions described herein can optionally include 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 can be present in a range of at least about 1 wt. % (e.g., at least about 2 wt. %, at least about 4 wt. %, at least about 5 wt. %, at least about 6 wt. %, at least about 8 wt. %, at least about 10 wt. %, or at least about 15 wt. %) to at most about 30 wt. % (e.g., at most about 25 wt. %, at most about 20 wt. %, at most about 15 wt. %, at most about 10 wt. %, or at most about 5 wt. %) of the ink composition. Without wishing to be bound by theory, it is believed that the addition of a rheology agent to the ink compositions described herein can increase the viscosity of the ink composition, provide structure for flow and droplet formation, promote adhesion, delay or prevent separation of other ink components, and / or modify the loading of the ink composition.

[0093] In some embodiments, the ink compositions described herein can optionally include at least one additional colorant, such as a dye or pigment. The dye or pigment can be either an organic or inorganic material. In some embodiments, the ink compositions can be substantially free of colorants other than the polymeric dyes according to the present invention.

[0094] In some embodiments, the ink compositions described herein can optionally include one or more tackifiers. Generally, tackifiers can improve adhesion between the ink composition and a 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, polyvinyl toluene / methyl styrene 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 polymers, and the like. Examples of suitable tackifiers include acrylic copolymers, polyvinyl butyral, polyketones, styrene / acrylic copolymers, polybutene, polybutadiene, styrene-isoprene-styrene, styrene-butadiene-styrene, polyvinylpyrrolidone, polyvinylpyridine, vinylpyrrolidone / vinyl acetate, polyurethanes, polyesters, polyamides, cellulose esters, cellulose ethers, polyols, styrene-acrylates, polypropylene, chlorinated polypropylene, chlorinated paraffins, Gilsonite and other asphaltic 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.

[0095] In some embodiments, the ink compositions described herein can optionally include one or more resins (e.g., binder resins), which can impart desired viscosity, thermal stability, flexibility, and adhesive properties to the ink composition. Examples of suitable resins include acacia (gum arabic); gum ghatti; guar gum; locust (carob) bean gum; Karaya gum (sterculia gum); tragacanth gum; chicle; highly stabilized rosin esters; tall oil; Manila copal; corn gluten; coumarone-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; gum ghatti; gluten gum; guaiac gum; guarana gum; heptylparaben; methyl- and hydroxypropyl-containing cellulose resins; hydroxypropylmethylcellulose resin; isobutylene-isoprene copolymer; mastic gum; oat gum; opopanax gum; polyacrylamide; modified polyacrylamide resins; polylimonene; polyisobutylene; polymaleic acid; polyoxyethylene derivatives; polypropylene gum Rosin and rosin derivatives include rosin glycerol esters; tall oil rosin glycerol esters; wood rosin; rosin and rosin derivatives; polymerized rosin glycerol esters; tall oil rosin glycerol esters; wood rosin; wood rosin glycerol esters; purified shellac; styrene; styrene terpolymers; styrene copolymers; sucrose acetate isobutyrate; natural and synthetic terpene resins; terpene gum; vinyl acetate; vinyl chloride-vinylidene chloride copolymers; xanthan gum; and zein.In some embodiments, the ink composition includes sufficient resin 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 is substantially free of any resin other than the polymeric pigment according to the present invention.

[0096] In some embodiments, the ink compositions described herein can optionally include one or more plasticizers. Generally, plasticizers can reduce the viscosity of the ink composition. Examples of plasticizers include aromatic sulfonamides, phthalates, acetates, adipates, amides, azelates, epoxides, glutarates, laurates, oleates, sebacates, stearates, sulfonates, tallates, phosphates, benzoin ethers, and trimellitates. 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 plasticizer.

[0097] In some embodiments, the ink compositions described herein can optionally include 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 jetting). Examples of antioxidants include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate, tert-butylhydroquinone (TBHQ), ethylenediaminetetraacetic acid (EDTA), methylparaben, and propylparaben. Commercially available examples of antioxidants include Irganox 1010 (i.e., a 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 %) antioxidant.

[0098] In some embodiments, the ink compositions described herein can 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 colorants (e.g., pigments) from agglomerating in the ink composition. Examples of dispersants include Solsperse 13,650, 13,940, 17,000, J910; Byk 108; Tego Disperse 700; UNIQEMA 5543; and EFKA 5244, 5207, and 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 dispersant.

[0099] In general, the ink compositions described herein can have any suitable apparent viscosity. In some embodiments, the ink compositions have a viscosity of 20° C. and 73 s -1 The viscosity may range 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 VI.

[0100] In some embodiments, the ink compositions described herein can optionally include one or more conductive agents. In some embodiments, the conductive agent can be a salt (e.g., an organic salt or an inorganic salt). For example, the salt can 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).

[0101] Generally, the ink compositions described herein can have any suitable conductivity. In some embodiments, the ink compositions can have a 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, when the ink composition is designed for use in a continuous ink jet printing method, it can have a conductivity suitable for being printed by this method (e.g., 100 to 8000 μS / cm). As another example, when the ink composition is designed for use in a thermal ink jet printing method, it can have zero conductivity, since conductivity is not required in this printing method.

[0102] 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 waxes), colorants other than the polymeric dyes according to the present invention (e.g., non-polymeric colorants), resins other than the polymeric dyes according to the present invention (e.g., non-polymeric resins), or conductive agents (e.g., salts).

[0103] In some embodiments, the ink composition can be a solution (in which all solutes (eg, polymeric pigments according to the present invention) are dissolved) or a dispersion (containing dispersed particles).

[0104] Printing methods and products In general, the ink compositions described herein can be used in any suitable printing method, including continuous ink jet (CIJ) printing, drop-on-demand printing (e.g., thermal ink jet (TIJ) 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 compositions can be used in a printing method that includes ejecting the ink composition (continuously or on demand) from a printhead in an ink jet printer onto a substrate to form an image.

[0105] In some embodiments, in a continuous inkjet printing method, a continuous stream of conductive ink droplets can be ejected from one or more nozzles in an inkjet printer's printhead. The ink droplets are electrostatically deflected to several pixels in the vertical direction as the substrate moves relative to the nozzle. CIJ inks generally have suitable electrical conductivity to allow the ink droplets to be deflected. The process of continuously ejecting ink droplets and directing unwanted droplets into a gutter has the effect of ensuring that the nozzles are never idle during operation, allowing CIJ systems to utilize fast-evaporating solvents (e.g., those with a relative evaporation rate (RER) greater than 1 relative to n-butyl acetate as determined by ASTM method D3359) without the problems of decapsulation (i.e., the ability to remain fluid in the printhead nozzle opening exposed to air) and nozzle clogging.

[0106] 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 to an ink collection gutter. During printing, segments of the ink stream are sampled asynchronously and deflected differently depending on the segment's length (which length provides a means for varying the distribution of incorporated charge per unit length) and directed toward the substrate. These segments can be transformed 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.

[0107] In some embodiments, in drop-on-demand printing methods, ink can be jetted by either a thermal inkjet cartridge or a piezo drop-on-demand printhead. To print with ink, the ink is filled into a reservoir, where it is either pumped or gravity-fed to the ejection chambers of the cartridge or printhead. In the case of a thermal inkjet cartridge, the liquid ink is ejected from the printhead by rapid heating, which causes a rapid phase change from liquid to gas, resulting in rapid volume expansion and subsequent ejection of ink droplets from the orifices. In the case of a piezo-based device, the liquid ink is ejected from the printhead by actuating a piezoelectric transducer (PZT) to exert a pressure wave on the ink, allowing ink droplets to be ejected from the orifices. Both devices are considered drop-on-demand because ink droplets are ejected only when the heater or PZT material is actuated. The cartridge or printhead each contains an array of several orifices across its width. The actuation of each orifice in such an array is carried out in an orderly manner by a printer so that an image is formed drop by drop on a substrate positioned a short distance from the orifice array, and the printer is designed so that the orifice array and the substrate move relative to one another to form the image.

[0108] The present disclosure also features an article of manufacture that includes a substrate and a solid ink that defines an image on the substrate, where the solid ink includes the 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 (eg, patents, patent application publications, and articles) cited herein are hereby incorporated by reference in their entirety.

[0109] The present invention will be further illustrated below by some preliminary examples which in no way limit the invention but are given for illustrative purposes only. [Example]

[0110] Experimental part Example 1 Synthesis of Disperse Red 1 Methacryloyloxyethyl Succinate The title product is obtained by reacting Disperse Red 1 with methacryloyloxyethyl succinate according to the following reaction:

[0111] [ka]

[0112] 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 equiv.) and 2-(methacryloyloxy)ethyl succinate (8.1 g, 35.0 mmol, 1.1 equiv.) 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 equiv.) and DMAP (0.78 g, 6.4 mmol, 0.2 equiv.) were added in small portions successively under nitrogen flow. Upon completion of the addition, the mixture was stirred at room temperature for 1 h. Upon completion 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 collected, dried over anhydrous sodium sulfate, filtered on a Por4 frit, and concentrated under reduced pressure. Upon complete removal of dichloromethane, the polymerizable blue monomer appeared as a red powder. The chemical structure of this monomer is: 1 Confirmed by 1 H NMR (in chloroform-d).

[0113] 1 H 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 title product is obtained by reacting Blue Patent V with methacryloyloxyethyl succinate according to the following reaction:

[0114] [ka]

[0115] EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride DMAP: dimethylaminopyridine DCM: dichloromethane nBu: tetrabutylammonium The first step was to reduce the hydrophilic properties of Patent Blue V by replacing the sodium counterion with tetrabutylammonium. In a round-bottom flask, Patent Blue V sodium salt (20.0 g, 0.034 mol, 1 eq.) and tetra-n-butylammonium bromide (22.1 g, 0.069 mol, 2 eq.) were solubilized in 400 mL of a 3 / 1 v / v mixture of dichloromethane and water. The biphasic mixture was vigorously stirred at room temperature for 3 hours, after which 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 had 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 the dichloromethane, the intermediate product was obtained as a dark purple powder. Its chemical structure is: 1 Confirmed by 1 H NMR (in chloroform-d).

[0116] The second step involves the reaction of the dye with a polymerizable monomer. In a round-bottom flask, the product of the first step (20.9 g, 16.9 mmol, 1 eq.) and 2-(methacryloyloxy)ethyl succinate (4.28 g, 18.6 mmol, 1.1 eq.) 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 eq.) and DMAP (0.41 g, 3.4 mmol, 0.2 eq.) were added in small portions in succession under nitrogen flow. Upon completion of the addition, the mixture was stirred at room temperature for 4 hours. Upon completion 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 dried over anhydrous sodium sulfate, filtered on a Por4 frit, and concentrated under reduced pressure. Once the dichloromethane was completely removed, the polymerizable blue monomer appeared as a dark blue powder. The chemical structure of this monomer is: 1 Confirmed by 1 H NMR (in chloroform-d).

[0117] 1 H 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 Synthesis of Solvent Violet 13 Methacryloyloxyethyl Succinate The title product is obtained by reacting Solvent Violet 13 with methacryloyloxyethyl succinate according to the following reaction:

[0118] [ka]

[0119] EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride DMAP: dimethylaminopyridine DCM: dichloromethane In a round-bottom flask, Solvent Violet 13 (5.0 g, 15.2 mmol, 1 equiv.) and 2-(methacryloyloxy)ethyl succinate (3.84 g, 16.7 mmol, 1.1 equiv.) were dissolved in 35 mL of dichloromethane. The mixture was cooled to 0 °C in an ice bath, and then EDC.HCl (3.49 g, 18.2 mmol, 1.2 equiv.) and DMAP (0.37 g, 3.04 mmol, 0.2 equiv.) were added in small portions in succession under nitrogen flow. Upon completion of the addition, the mixture was warmed to 30 °C and stirred at this temperature for 1 h. Upon completion of the reaction, 50 mL of dichloromethane and 50 mL of 0.5 M HCl were added, and the mixture was transferred to a separatory funnel. After decantation, the organic phase was washed with 50 mL of deionized water, then dried over anhydrous sodium sulfate, filtered on a Por4 frit, and concentrated under reduced pressure. Once the dichloromethane was completely removed, the polymerizable monomer appeared reddish purple in color. The chemical structure of this monomer is: 1 Confirmed by 1 H NMR (in chloroform-d).

[0120] 1H NMR (300 MHz, chloroform-d) δ (ppm) 11.55 (s, 1H), 8.42 - 8.07 (m, 2H), 7.88 - 7.59 (m, 2H), 7.43 (d, J = 9.4 Hz, 1H), 7.36 - 7.05 (m, 5H), 6.25 - 6.04 (m, 1H), 5.69 - 5.50 (m, 1H), 4.51 - 4.27 (m, 4H), 3.12 (t, J = 7.0 Hz, 2H), 2.91 (t, J = 7.0 Hz, 2H), 2.40 (s, 3H), 2.02 - 1.87 (m, 3H). Example 4 Synthesis of Disperse Red 60 methacryloyloxyethyl succinate The title product is obtained by reacting Disperse Red 60 with methacryloyloxyethyl succinate according to the following reaction:

[0121] [ka]

[0122] EDC.HCL: 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride DMAP: dimethylaminopyridine DCM: dichloromethane In a round-bottom flask, Disperse Red 60 (10.0 g, 28.4 mmol) and 2-(methacryloyloxy)ethyl succinate (7.84 g, 34.1 mmol) were dissolved in 40 mL of dichloromethane. The mixture was cooled to 0 °C and deoxygenated under a nitrogen flow, and then EDC.HCl (7.60 g, 39.6 mmol) and DMAP (1.74 g, 14.2 mmol) were added. The mixture was then heated to 40 °C and left under magnetic stirring for 8 h. Upon completion of the reaction, the mixture was diluted by adding 250 mL of dichloromethane and then washed successively with 100 mL of 1 M HCl, 100 mL of 1 M NaOH, and 100 mL of deionized water. The organic phase was dried over anhydrous sodium sulfate, filtered through a Por4 frit, and concentrated under vacuum until the solvent was completely removed. Disperse Red 60 methacryloyloxyethyl succinate was recovered as a red powder. The chemical structure of this monomer is: 1 Confirmed by 1 H NMR (in chloroform-d).

[0123] 1 H NMR (300 MHz, Chloroform-d) δ (ppm) 8.42 - 8.08 (m, 2H), 7.86 - 7.65 (m, 2H), 7.57 - 7.39 (m, 2H), 7.39 - 7.24 (m, 1H), 7.24 - 7.09 (m, 2H), 6.53 (s, 1H), 6.19 - 6.08 (m, 1H), 5.65 - 5.52 (m, 1H), 4.36 (d, J = 5.0 Hz, 4H), 3.05 (td, J = 7.0, 0.9 Hz, 2H), 2.85 (td, J = 7.0, 0.8Hz, 2H), 2.02 - 1.86 (m, 3H). Example 5 Synthesis of black polymer dyes Starting from the synthesized monomer dyes of Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to the following scheme:

[0124] [ka]

[0125] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide 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 then polymerization was carried out overnight at 80 °C. Upon completion of the polymerization, 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 v / v MeOH / EtO and once in pentane. 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 polymeric dye was characterized by H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=60,000 Da) as the standard. The polymeric dye was characterized as described in the ISO 12040 standard and showed an IWS value of 2.

[0126] 1 H 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 + 2H y + 6H z ), 3.71 (s, 2H z ), 3.65 - 3.44 (m, 8Hx + 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 + 3H y + 3H z ), 1.15 - 0.48 (m, 27H x + 3H y + 3H z ). Example 6 Synthesis of red polymer dyes Starting from the synthesized monomer dyes of Examples 1 and 3, red polymer dyes were obtained by free radical polymerization according to the following scheme:

[0127] [ka]

[0128] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide In a round-bottom flask, Solvent Violet 13 methacryloyloxyethyl succinate (2.0 g, 3.25 mmol), ethyl methacrylate (3.3 g, 28.9 mmol), Disperse Red 1 methacryloyloxyethyl succinate (1.2 g, 2.27 mmol), and AIBN (114 mg, 0.70 mmol) were dissolved in 27.5 mL of DMF. The mixture was deoxygenated under argon flow at room temperature for 15 minutes, and then polymerization was carried out overnight at 80 °C. Upon completion of the polymerization, the DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane and then precipitated in hexane. The polymer was allowed to settle, and the supernatant solvent was removed. After drying in an oven at 40 °C, the polymer was obtained as a dark red powder. The chemical structure of the synthesized polymer is 1 The polymeric dye was characterized by H NMR (in chloroform-d), while the molecular weight was evaluated by GPC using DMF as the eluent and PMMA (Mw=55,500 Da) as the standard. The polymeric dye was characterized as described in the ISO 12040 standard and showed an IWS value of 3.

[0129] 1 H NMR (300 MHz, chloroform-d) δ (ppm) 11.46 (s, 1H x ), 8.41 - 7.97 (m, 2H x + 2H z ), 7.97 - 7.56 (m, 2H x + 4H z ), 7.37 (d, J = 2.3 Hz, 1H x ), 7.25 - 6.88 (m, 5H x ), 6.73 (d, J = 9.1 Hz, 2H z ), 4.49 - 3.73 (m, 4H x + 2H y + 6H z ), 3.73 - 3.28 (m, 4H z ), 3.02 (d, J = 6.8 Hz, 2H x ), 2.82 (s, 2H x ), 2.59 (s, 4H z), 2.43 - 2.18 (m, 3H x ), 2.17 - 1.54 (m, 2H x + 5H y + 2H z ), 1.54 - 0.23 (m, 3H x + 3H y + 6H z ). Example 7 Synthesis of blue polymer dyes Starting from the synthesized monomer dyes of Examples 2 and 3, blue polymer dyes were obtained by free radical polymerization according to the following scheme:

[0130] [ka]

[0131] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide In a round-bottom flask, Patent Blue V methacryloyloxyethyl succinate (3.0 g, 1.48 mmol), Solvent Violet 13 methacryloyloxyethyl succinate (1.4 g, 2.11 mmol), ethyl methacrylate (3.0 g, 26.4 mmol), and AIBN (98 mg, 0.60 mmol) were dissolved in 32 mL of DMF. The mixture was deoxygenated under argon flux at room temperature for 30 minutes, and then polymerization was carried out overnight at 80 °C. Upon completion of the polymerization, the DMF was removed by evaporation under vacuum. The product was then dissolved in dichloromethane and precipitated twice in a 2:8 v / v mixture of methanol / diethyl ether and once in diethyl ether. After drying in an oven at 50 °C, the polymer was obtained as a dark blue powder. The chemical structure is 1 The product was confirmed by 1 H NMR (in chloroform-d), while the molecular weight was estimated by GPC using DMF as the eluent and PMMA (Mw=87,000 Da) as the standard.

[0132] 1H NMR (300 MHz, chloroform-d) δ (ppm) 11.54 (s, 1H z ), 8.69 (s, 1H x ), 8.42 - 8.07 (d, J = 8.7 Hz, 2H z ), 7.89 - 7.65 (d, J = 7.4 Hz, 2H z ), 7.62 - 7.35 (m, 4H x ), 7.32 - 7.01 (m, 5H z ), 6.88 - 6.57 (m, 5H x ), 4.56 - 3.84 (m, 4H x + 2H y + 4 H z ), 3.69 - 3.42 (m, 8H x ), 3.33 (m, 16H x ), 3.10 (m, 4H x ), 2.99 - 2.52 (m, 4H z ), 2.38 (s, 3H z ), 2.33 - 1.57 (m, 18H x + 2H y + 2H z ), 1.57 - 1.16 (m, 19H x + 3H y + 3H z ), 1.16 - 0.32 (m, 36H x + 3H y ). Example 8 Synthesis of green polymer dyes Starting from the synthesized monomer dyes of Examples 2 and 4, red polymer dyes were obtained by free radical polymerization according to the following scheme:

[0133] [ka]

[0134] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide In a round-bottom flask, Patent Blue V methacryloyloxyethyl succinate (1.0 g, 0.495 mmol), Disperse Red 60 methacryloyloxyethyl succinate (2.3 g, 3.8 mmol), ethyl methacrylate (2.7 g, 23.8 mmol), and AIBN (92 mg, 0.56 mmol) were dissolved in 26 mL of DMF. The mixture was deoxygenated under an argon flux at room temperature for 30 minutes, and then polymerization was carried out overnight at 80 °C. Upon completion of the polymerization, the DMF was removed by evaporation under vacuum. The product was then dissolved in dichloromethane and precipitated twice in a 2:8 v / v mixture of methanol / diethyl ether and once in diethyl ether. After drying in an oven at 50 °C, the polymer was obtained as a dark green powder. The chemical structure is 1 The product was confirmed by 1 H NMR (in chloroform-d), while the molecular weight was estimated by GPC using DMF as the eluent and PMMA (Mw=73,000 Da) as the standard.

[0135] 1 H NMR (300 MHz, chloroform-d) δ (ppm) 8.68 (s, 1H x ), 8.26 (s, 1H z ), 8.15 (s, 1H z ), 7.72 (s, 2H z ), 7.47 (m, 4H x + 2H z ), 7.28 (s, 1H z ), 7.15 (d, J = 7.5 Hz, 2H z ), 6.86 - 6.62 (m, 5H x ), 6.52 (s, 1H z ), 4.70 - 3.77 (m, 4H x + 2H y + 4H z ), 3.69 - 3.42 (m, 8H x ), 3.39 - 3.18 (m, 16H x ), 3.18 - 2.93 (m, 2H x + 2H z), 2.93 - 2.56 (m, 2H x + 2H z ), 2.16 - 0.53. Example 9 Inkjet ink formulation Inkjet inks were prepared by dissolving different amounts of the black polymeric dye of Example 5 in methyl ethyl ketone (MEK). Coatings were performed on coated white cardboard (opaque card from Leneta supplier) with a wet film deposition of 12 μm and a standard coating speed of 15 m / min. Table 1 below lists the lightness (L) values ​​assessed for the coatings. * ) and the viscosity (cP) of the resulting ink at several weight percentages are summarized.

[0136] [Table 5]

[0137] Example 10 Print test An inkjet ink was prepared by dissolving the conductive agent (1% wt) and the black polymer pigment of Example 5 (12.5% ​​wt) in MEK.

[0138] After printing on cardboard, the visual aspect was dark black, as shown in FIG. Light fastness resistance is 60±2W / m in a Suntest device as described in the ISO 16474-2 standard. 2 The results were visually evaluated by comparing photographs taken at different storage times at an irradiance of 1000 and a temperature of 65 ± 3 °C. The results are shown in Figures 2 to 6.

[0139] Under real-world indoor conditions, the results shown in Figures 2-6 correspond to a 30% decrease in color intensity of the printed samples after at least two years.

[0140] Example 11 An inkjet ink (INK1) according to the present invention was prepared by dissolving the black polymeric dye of Example 5 in methyl ethyl ketone (MEK) at 15 wt %. Two reference inkjet inks were prepared by dissolving commercially available Solvent Black 27 (INK2) and Solvent Black 27 (INK3) dyes at 6 wt % and a polymeric resin at 9 wt % in MEK. The polymeric resin was a solution of nitrocellulose in isopropyl alcohol in a ratio of nitrocellulose to isopropyl alcohol equal to 70:30.

[0141] Three different coatings were carried out on coated white cardboard (opaque card from Leneta supplier) with a wet film deposition of 12 μm and a standard coating speed of 15 m / min.

[0142] The inks were compared for regulatory compliance and viscosity, while the coatings were compared for brightness and visual aspects. The results are summarized in Table 3 below.

[0143] [Table 6]

[0144] The viscosity, brightness and visual data of the inventive INK1 show good results, being completely equivalent to the reference INK2 and INK3, and it also has the advantage of meeting the requirements of the REACH regulation.

[0145] Test Method viscosity The shear viscosity was measured by using a shear rate of 73 s −1 at 20° C. (for example by using a coaxial cylinder viscometer of the “Couette” type) as described in standard DIN 53019-1.

[0146] brightness Lightness (L * ) measurement, CIELAB (or CIE L * a * b *) was performed using a spectrophotometer (e.g., X-Rite eXact instrument). The CIELAB space is * is related to lightness, and a * is the red / green parameter, and b * is defined in three dimensions where is the yellow / blue parameter.

[0147] The synthesis of two additional black polymeric dyes with different molecular weights is shown in Examples 12 and 13 below.

[0148] Example 12 Starting from the synthesized monomer dyes of Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to the following scheme:

[0149] [ka]

[0150] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide In a round-bottom flask, Patent Blue V methacryloyloxyethyl succinate, ethyl methacrylate, Disperse Red 1 methacryloyloxyethyl succinate, dodecanethiol, and AIBN (2 mol% relative to the monomers) were dissolved in DMF (20 wt% dry extract). The mixture was deoxygenated under argon flow at room temperature for 15 minutes, and then polymerization was carried out at 70°C. After reaching approximately 80% conversion, an amount of AIBN was added to increase the conversion to over 95%. Upon completion of the polymerization, the DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane and then precipitated once in diethyl ether and twice in a mixture of methanol and diethyl ether. The polymer was allowed to settle, and the supernatant solvent was removed. After drying in an oven at 50°C, the polymer was obtained as a black powder. The chemical structure of the synthesized polymer is 1The polymeric dye was characterized as described in the ISO 12040 standard and showed an IWS value of 2.

[0151] 1 H NMR (300 MHz, chloroform-d) δ (ppm) 8.64 (s, 1H x ), 8.30 (d, J = 8.6 Hz, 2H z ), 7.85 (t, J = 8.4 Hz, 4H z ), 7.46 (d, J = 9.1 Hz, 4H x ), 6.90 - 6.60 (m, 5H x + 2H z ), 4.54 - 3.83 (m, 4H x + 2H y + 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 + 3H y + 3H z ), 1.15 - 0.45 (m, 27H x + 3H y + 3H z ). Example 13 Starting from the synthesized monomer dyes of Examples 1 and 2, black polymer dyes were obtained by free radical polymerization according to the following scheme:

[0152] [ka]

[0153] AIBN: 2,2'-azobis(2-methylpropionitrile) DMF: dimethylformamide In a round-bottom flask, Patent Blue V methacryloyloxyethyl succinate (2.0 g, 1.27 mmol), Disperse Red 1 methacryloyloxyethyl succinate (1.37 g, 2.54 mmol), butyl methacrylate (5.49 g, 38.6 mmol), and AIBN (70.0 mg, 0.42 mmol) were dissolved in 37 mL of DMF. The mixture was deoxygenated under argon flux at room temperature for 15 minutes, and then polymerization was carried out overnight at 70 °C. Upon completion of the polymerization, the DMF was removed by evaporation under vacuum, and the product was dissolved in dichloromethane and then precipitated in pentane. The polymer was then allowed to settle, and the supernatant solvent was removed. 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 product was confirmed by 1 H NMR (in chloroform-d), while the molecular weight was estimated by GPC (Mw=75,000 Da).

[0154] 1 H NMR (300 MHz, chloroform-d) δ (ppm) 8.67 (s, 1H x ), 8.30 (d, J = 8.8 Hz, 2H z ), 7.89 (t, J = 8.1 Hz, 4H z ), 7.48 (dd, J = 9.4, 6.9 Hz, 4H x ), 6.88 - 6.58 (m, 5H x + 2H z ), 4.40 - 4.03 (m, 4H x + 6H z ), 4.03 - 3.76 (m, 2H y ), 3.68 (t, J = 6.5 Hz, 2H z ), 3.52 (q, J = 7.0 Hz, 8Hx + 2H z ), 3.32 (dd, J = 11.0, 5.6 Hz, 16H x ), 3.09 - 2.48 (m, 4H x + 4H z ), 2.30 - 0.49 (m, 73H x + 12H y + 8H z ). It will be understood that various modifications may be made by those skilled in the art in view of the above description of embodiments of the invention, and such modifications are intended to be encompassed by the following claims.

Claims

1. Formulas (I) and (II) below 【Chemistry 1】 wherein M1 and M2 are the same or different and are reactive monomers, and C1 and C2 are different and are chromophore units. wherein the polymeric dye has a solubility of at least 1 wt % in an organic solvent at 25° C., and the reactive monomers M1 and M2 are selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinyl amine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, and alkyl-vinyl ether monomers.

2. The following formula (III) 【Chemistry 2】 wherein M3 is a reactive monomer and C3 is a chromophore unit different from C1 and C2. wherein the reactive monomer M3 is selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinyl amine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, and alkyl-vinyl ether monomers.

3. Formula (IV) below 【Transformation 3】 wherein M4 is a reactive monomer. wherein the reactive monomer M4 is selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinyl amine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, and alkyl-vinyl ether monomers.

4. The following formula (V) 【Chemistry 4】 wherein M5 is a reactive monomer and C4 is a chromophore unit different from C1-C3. wherein the reactive monomer M5 is selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinyl amine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, and alkyl-vinyl ether monomers.

5. Any 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, Food 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 10. The polymeric dye of claim 1, which can be a blue chromophore unit contained in a commercially available dye selected from the group consisting of:

6. Any 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 Red 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, Hood 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 10. The polymeric dye of claim 1, which can be a red chromophore unit contained in a commercially available dye selected from the group consisting of:

7. Any 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 10. The polymeric dye of claim 1, which can be a green chromophore unit contained in a commercially available dye selected from the group consisting of:

8. Any 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 10. The polymeric dye of claim 1, which can be a chromophore unit contained in a commercially available dye selected from the group consisting of:

9. (1) A dye containing a first reactive functional group selected from the group consisting of a hydroxyl group, an amine group, or a carboxyl group is reacted with a polymerizable monomer containing a second reactive functional group 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 to form a polymerizable monomer having the following formulae (I) to (III) and (V): 【Transformation 5】 wherein M1, M2, M3, and M5 are the same or different and are reactive monomers, and C1-C4 are different and are chromophore units. obtaining a polymerizable monomer dye having any one of: (2) At least one of the polymerizable monomer dyes (I) to (III) and (V) is a compound represented by the following formula (IV): 【Transformation 6】 wherein M4 is a reactive monomer. copolymerizing the compound with a polymerizable monomer having the formula: (3) recovering the resulting polymer dye; 1. A method for synthesizing a polymeric dye, comprising:

10. 10. The method for synthesizing a polymeric dye of claim 9, wherein M1 to M5 are the same or different from each other and are selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl alcohol monomers, vinylamine monomers, vinyl acetate monomers, vinyl glycol monomers, maleic acid monomers, maleic ester monomers, maleic amide monomers, maleic imide monomers, acryloyloxyethyl succinic acid monomers, methacryloyloxyethyl succinic acid, styrene monomers, styrene derivative monomers, and alkyl-vinyl ether monomers.

11. 9. An ink composition comprising the polymeric dye as defined in any one of claims 1 to 8, wherein the ink composition is a liquid composition, a dispersion composition, an emulsion composition, or a solid composition.

12. The ink composition according to claim 11, wherein the ink composition is a liquid composition comprising the polymer dye and an organic solvent, and the polymer dye is present in an amount of 1% by weight to 70% by weight, preferably 3% by weight to 50% by weight, of the ink composition.

13. 12. The ink composition according to claim 11, wherein the ink composition is a solid composition comprising the polymer dye and a fusible carrier, and the polymer dye is present in an amount of 1% to 70% by weight, preferably 3% to 50% by weight, of the ink composition.

14. Formulas (I) to (III) and (V) below 【Transformation 7】 wherein M1, M2, M3, and M5 are the same or different and are reactive monomers, and C1-C4 are different and are chromophore units. and at least one monomer repeat unit having the formula: The following formula (IV) 【Transformation 8】 wherein M4 is a reactive monomer. and a monomer repeat unit having 1. A polymeric dye comprising: having a solubility of at least 1 wt % in organic solvents at 25°C and a solubility of less than 0.1 wt % in water at 25°C; Polymer dyes.

15. 10. The method for synthesizing a polymeric dye of claim 9, wherein if the dye contains an alkali or alkaline earth sulfonate or carboxylate group, the alkali or alkaline earth ion is previously replaced with a tetraalkylammonium group, such as, for example, a tetrabutylammonium group, a tetrahexylammonium group, or a tetraoctylammonium group.

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