Modified colorant having a triazine structure and use thereof

Abstract

The application belongs to the field of pigment paste, and particularly relates to a modified colorant with a triazine structure and application thereof. The structure of the modified colorant is shown in general formula D1. Anchor groups L anchor the modified colorant on the surface of pigment particles in the form of physical adsorption or chemical bonds, so as to realize surface modification of the pigment. The modified colorant of the application realizes effective regulation of hydrophilicity or lipophilicity of the pigment by adjusting the types and numbers of triazine substituents. The nano pigment paste treated by the modified colorant has self-dispersing performance, does not need to add other additives, can effectively improve the dispersibility, stability and filterability of the nano pigment paste, and has excellent coloring capacity.

Description

Technical Field

[0001] This invention belongs to the field of pigment pastes, specifically relating to a modified colorant with a triazine structure and its application. Background Technology

[0002] Pigment pastes are produced by mixing pigments with water or solvents, adding dispersants and other additives to make them liquid, mixing them in a high-speed mixer, and then adding them to a nano-grinding mill where they are sheared at high speed with zirconium beads to achieve the desired final product. Pigments can be processed through pigmentation to adjust their wetting properties in the dispersion medium, thereby preparing high-quality pigment pastes with stable properties and superior performance.

[0003] The research and development of high-quality nano-water-based pigment pastes has always revolved around formulation and modification technologies. This involves adding additives to the paste to aid pigment dispersion and increase tinting strength, or attaching modifiers to the surface of dispersed particles, allowing the pigment particles to be uniformly dispersed in the medium through intermolecular forces and improving tinting strength. For example, patent CN112358749A proposes adding blue dye to carbon black paste to improve the blackness and tinting ability of the paste through bluish light. This approach makes the formulation system relatively complex, limiting the product's application range. Canon Corporation of Japan proposed mixing modifiers with pigments in a medium under heating conditions, allowing the modifiers to adhere to the surface of the pigment particles. However, this process requires subsequent refining to remove the influence of organic solvents, making the process relatively complex. Cabot Corporation's patents US5851280, US5672198, US6641656, US6328894, and US6506245 introduce a series of modifiers for pigment paste modification, but they have failed to achieve precise control of key parameters of pigment pastes under the action of a single modifier. Furthermore, a common problem with the above processes is that they have not explored the patterns of various indicators of pigment pastes. Although the above inventions provide methods for pigment surface modification, their pigment paste and ink products cannot simultaneously possess dispersibility, stability, and tinting ability. Moreover, the above modification methods cannot establish structure-property relationships for dispersibility, stability, and tinting ability, thereby failing to precisely control the various performance parameters of pigment pastes. Summary of the Invention

[0004] The purpose of this invention is to provide a modified colorant with a triazine structure and its application. This type of modified colorant can be used to prepare nano-aqueous pigment pastes of various colors such as blue, red, yellow, black, white, orange, green, purple, and brown, as well as the pigment varieties contained therein.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A modified colorant having a triazine structure, as shown in general formula D1:

[0007]

[0008] In the formula:

[0009] L is selected from -BZ-NH2;

[0010] B is selected from N or O;

[0011] Z is selected from C1-C6 alkyl, unsubstituted or further substituted aryl, heteroaryl, aralkyl, heteroaryl, alkylaryl, alkanearyl, and the following groups being hydroxyl, sulfonic acid, carboxylic acid, nitro, amino, secondary amino, tertiary amino, or halogen.

[0012] A 1 A 2 They may be the same or different, and are selected from halogens, -XQ, phosphate groups, phosphonic acid groups, and geminophosphonic acid groups, respectively.

[0013] X is selected from N or O;

[0014] Q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, unsubstituted or further substituted aryl, heteroaryl, aralkyl, heteroaryl, alkylaryl, alkanearyl, hydroxyl, sulfonic acid, carboxylic acid, nitro, amino, secondary amino, tertiary amino, or halogen.

[0015] Or a salt of the compound represented by general formula D1.

[0016] In the general formula D1:

[0017] L is selected from -BZ-NH2;

[0018] B is selected from N or O;

[0019] Z is selected from C1-C6 alkyl, unsubstituted or further substituted aryl, heteroaryl, the following groups being sulfonic acid group and carboxylic acid group;

[0020] A 1 A 2 They may be the same or different, and are respectively selected from chlorine, fluorine, bromine, -XQ or phosphate groups, phosphonic acid groups, and geminosphosphonic acid groups;

[0021] X is selected from N or O;

[0022] Q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, unsubstituted or further substituted aryl, heteroaryl, aralkyl, heteroaryl, alkylaryl, alkanearyl, hydroxyl, sulfonic acid, carboxylic acid, nitro, amino, secondary amino, tertiary amino, or halogen.

[0023] Or a salt of the compound represented by general formula D1.

[0024] The A 1 A 2 They may be the same or different, and are selected from chlorine, fluorine, bromine, -XQ, formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), and formula (g), respectively;

[0025] X is selected from N or O;

[0026] Q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, unsubstituted or further substituted aryl, heteroaryl, aralkyl, heteroaryl, alkylaryl, alkanearyl, hydroxyl, sulfonic acid, carboxylic acid, nitro, amino, secondary amino, tertiary amino, or halogen.

[0027] Equation (a) is -B-[(CH2)m(PO3H2)]2, where B is N or O, and m = 1-10;

[0028] Formula (b) is -B-CR=C(PO3H2)(CO2H), where B is N or O, and R is H, C1-C6 alkyl or unsubstituted or further substituted aryl or heteroaryl groups, such as sulfonic acid group or carboxylic acid group;

[0029] Formula (c) is -B-CQ(PO3H2)(CO2H), where B is N or O, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R1 and R2 can be the same or different, and are respectively selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl;

[0030] Formula (d) is -B-CR(PO3H2)(OH), where B is N or O, and R is H, C1-C6 alkyl or aryl, heteroaryl;

[0031] Formula (e) is -B-CQ(PO3H2)2, where B is N or O, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R1 and R2 can be the same or different, and are respectively selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl;

[0032] Equation (f) is -B-(CH2) n CQ(PO3H2)2, where B is N or O, n = 1-9, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R1 and R2 can be the same or different, and are respectively selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl;

[0033] Formula (g) is -B-Sp-(CH2) n CQ(PO3H2)2, where B is N or O, Sp is -CO2-, -O-, -NR', CO-, -CONR', -SO2NR', -SO2CH2CH2O-, -SO2CH2CH2S-; n = 1-9, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R1 and R2 can be the same or different, respectively selected from H, C1-C18 alkyl, C1-C18 acyl, aralkyl, heteroaryl or aryl, R' is cyanide or C1-C6 alkyl.

[0034] Preferably, formula (a) is -B-[(CH2)m(PO3H2)]2, where B is selected from N and m = 1-5;

[0035] Formula (b) is -B-CR=C(PO3H2)(CO2H), where B is selected from N, and R is H, C1-C6 alkyl or unsubstituted or further substituted aryl or heteroaryl groups, such as sulfonic acid group or carboxylic acid group;

[0036] Formula (c) is -B-CQ(PO3H2)(CO2H), where B is selected from N, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, and R1 and R2 can be the same or different, and are respectively selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl or aryl;

[0037] Formula (d) is -B-CR(PO3H2)(OH), where B is selected from N, and R is H, C1-C6 alkyl or aryl, heteroaryl;

[0038] Formula (e) is -B-CQ(PO3H2)2, where B is selected from N, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, and R1 and R2 can be the same or different, and are respectively selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl;

[0039] Equation (f) is -B-(CH2) n CQ(PO3H2)2, wherein B is selected from N, n = 1-6, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R1R2 can be the same or different, and are respectively selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl;

[0040] Formula (g) is -B-Sp-(CH2) n CQ(PO3H2)2, wherein B is selected from N, Sp is -CO2-, -O-, -NR', CO-, -CONR', -SO2NR', -SO2CH2CH2O-, -SO2CH2CH2S-; n = 1-9, Q is H, R, OR, SR or NR1R2, R is selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, R1 and R2 can be the same or different, and are respectively selected from H, C1-C6 alkyl, C1-C6 acyl, aralkyl, heteroaryl or aryl, and R' is cyanide or C1-C6 alkyl.

[0041] Furthermore, in general formula D1;

[0042] L is selected from -BZ-NH2;

[0043] B is selected from N or O;

[0044] Z is selected from C1-C6 alkyl, unsubstituted or further substituted phenyl, pyridine, the following groups being sulfonic acid group and carboxylic acid group;

[0045] A 1 A 2 They may be the same or different, and are selected from chlorine, fluorine, bromine, -XQ, formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), and formula (g), respectively;

[0046] X is selected from N or O;

[0047] Q is selected from hydrogen, alkoxy, C1-C18 alkyl, C1-C18 acyl, unsubstituted or further substituted phenyl, pyridine, and sulfonic acid or carboxylic acid groups.

[0048] Equation (a) is -B-[(CH2)m(PO3H2)]2, where B is selected from N and m = 1-3;

[0049] Formula (b) is -B-CR=C(PO3H2)(CO2H), where B is selected from N, and R is H, C1-C6 alkyl or unsubstituted or further substituted phenyl or pyridine, where the following groups are sulfonic acid group or carboxylic acid group;

[0050] Formula (c) is -B-CQ(PO3H2)(CO2H), where B is selected from N, Q is H, R, OR, SR or NR1R2, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl, and R1 and R2 can be the same or different, and are respectively selected from C1-C6 alkyl, phenyl, pyridine or benzyl;

[0051] Formula (d) is -B-CR(PO3H2)(OH), where B is selected from N, and R is H, C1-C6 alkyl or phenyl, or pyridine;

[0052] Formula (e) is -B-CQ(PO3H2)2, where B is selected from N, Q is H, R, OR, SR or NR1R2, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; R1 and R2 can be the same or different, and are respectively selected from C1-C6 alkyl, phenyl, pyridine or benzyl;

[0053] Equation (f) is -B-(CH2) n CQ(PO3H2)2, wherein B is selected from N, n = 1-6, Q is H, R, OR, SR or NR1R2, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; R1 and R2 can be the same or different, and are respectively selected from C1-C6 alkyl, phenyl, pyridine or benzyl;

[0054] Formula (g) is -B-Sp-(CH2) n CQ(PO3H2)2, wherein B is selected from N, Sp is -CO2-, -O-, -NR', CO-, -CONR', -SO2NR', -SO2CH2CH2O-, -SO2CH2CH2S-; n = 1-9, Q is H, R, OR, SR or NR1R2, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; R1 and R2 can be the same or different, respectively selected from C1-C6 alkyl, R is selected from C1-C6 alkyl, phenyl, pyridine or benzyl; R' is cyanide or C1-C6 alkyl;

[0055] Or a salt of the compound represented by general formula D1.

[0056] Table 1 lists some preferred examples of substituents in the compound of general formula D1 of this invention:

[0057] Table 1

[0058]

[0059]

[0060]

[0061] The application of the modified colorant allows the anchoring group L to anchor the modified colorant to the surface of pigment particles through physical adsorption or chemical bonding, thereby achieving surface modification of the pigment.

[0062] This invention relates to a specific triazine-structured modified colorant that can be applied to the modification of various known pigments, such as black, red, green, blue, orange, purple, brown, yellow, orange, and white. It includes, but is not limited to, the following pigment varieties: Pigment Black 1, 7, 31, 32, Carbon Black, Furnace Black, Lamp Black, Gas Black, etc.; Pigment Red 1, 2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 16, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 48, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 52:1, 53:1, 53:2, 53:3, 54, 57:1, 55, 58:1, 58:2. 60, 62, 63:1, 63:2, 68, 81, 88, 90, 112, 122, 123, 140, 141, 142, 143, 144, 146, 148, 149, 150, 151, 163, 164, 166, 168, 170, 170:1, 171, 175, 176, 177, 178, 179, 181, 183, 184, 185, 188, 189, 190, 194, 195, 196, 201, 202, 207, 208, 209, 214, 217, 218, 220, 221, 223, 224, 242, 245, 247, 248, 25 1, 253, 254, 255, 256, 260, 264, 266, 268, 269, 272, 279, etc.; Pigment Violet 1, 3, 5, 5: 1, 6, 7, 19, 20, 23, 27, 29, 31, 32, 33, 36, 37, 38, 39, 50, etc.; Pigment Yellow 1, 1: 1, 2, 3, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 23, 24, 55, 61, 62, 63, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 101, 108, 109, 110, 111, 113, 114, 117, 120, 121, etc. 123, 124, 126, 127, 128, 129, 138, 139, 147, 150, 151, 153, 154, 155, 156, 166, 168, 170, 171, 173, 174, 175, 176, 177, 179, 180, 181, 182, 183, 185, 188, 190, 191, 191:1, 192, 194, 202, 203, 213, etc.; Pigment Blue 1, 10, 15, 15:1, 15:6, 15:3, 15:4, 16, 17, 22, 26, 26, 60, 61, 64, 65, 75, 79, 80, etc.; Titanium Dioxide, Calcium White, Magnesium White, etc.Pigment orange: 1, 5, 13, 14, 15, 16, 18, 19, 22, 24, 31, 34, 36, 38, 40, 43, 44, 49, 55, 59, 61, 62, 64, 65, 66, 67, 68, 69, 71, 73, 74, 77, etc.; Pigment brown: 1, 23, 26, 27, 28, 38, 41, 42, etc.; Pigment green: 1, 4, 7, 8, 36, 37, 47, 58, etc.

[0063] Furthermore, the pigment is blue pigment, black pigment, brown pigment, cyan pigment, green pigment, white pigment, purple pigment, red pigment, yellow pigment, orange pigment, or a mixture thereof.

[0064] Furthermore, the pigments are pigment blue 15, pigment blue 15:3, pigment blue 15:4, pigment red 122, pigment purple 19, pigment yellow 74, pigment yellow 155, pigment yellow 128, pigment yellow 218, pigment yellow 220, pigment yellow 211, or carbon black.

[0065] To ensure modification efficiency and avoid repeated modification processes, the primary particle size of the selected pigment should preferably be between 5-100 nm, more preferably 10-80 nm, and most preferably 20-75 nm. Pretreatment of the coarse pigment particles can be performed using methods such as acid precipitation, wet grinding, ball milling, mixing, and ultrasonic dispersion to obtain fine pigment particles with suitable primary particle size. Furthermore, the BET surface area of ​​the pigment should preferably be 20 m². 2 / g-700m 2 / g, more preferably 30m 2 / g-500m 2 / g, the optimal value is 50m 2 / g-350m 2 / g, this value can be determined by nitrogen adsorption experiment. The oil absorption of pigment also affects the modification efficiency. Using linseed oil as the test medium, the preferred oil absorption of pigment is 0.5g / 100g-3g / 100g, more preferably 0.7g / 100g-1.5g / 100g, and most preferably 0.8g / 100g-1.1g / 100g.

[0066] Compared with the prior art, the advantages of this invention are as follows:

[0067] The surface properties of pigments have a significant impact on their application performance. This invention modifies the pigment surface by physically adhering or chemically bonding a modified colorant to the pigment surface, introducing various functional groups to achieve surface modification. For nano-aqueous pigment pastes, surface modification allows the resulting paste product to possess dispersibility, stability, and coloring ability. This requires the use of modified colorants containing different functional groups. This invention relates to specific pigment-modifying colorants with triazine structures. The chlorine groups in the aromatic ring structure of cyanuric chloride exhibit good activity and readily undergo substitution reactions to introduce various functional groups. Multiple functional groups can be incorporated into a single modified colorant structure, optimizing the pigment modification process, simplifying the formulation of nano-aqueous pigment pastes, and overcoming application limitations, thereby expanding its application range and improving its adaptability.

[0068] By bonding multiple pigment-modifying functional groups onto a single modified colorant molecule, on the one hand, modification efficiency can be effectively improved, modification formulation can be simplified, and pigment processing technology can be optimized. More importantly, the nano-aqueous pigment paste obtained after treatment with modified colorant can achieve self-dispersion function, that is, it can achieve nano-level dispersion without the addition of surfactants, dispersants, wetting agents and other additives, and can simultaneously have stability and coloring ability.

[0069] The modification method of the modified colorant with a special triazine structure involved in this invention can be achieved through physical methods, namely, mixing the pigment and the modified colorant during grinding, ball milling, ultrasonic dispersion, kneading, and mechanical stirring. The anchoring groups of the modified colorant adsorb onto the pigment molecule's conjugated structure through van der Waals forces and dispersion forces, causing the modified colorant to adhere to the pigment particle surface. Alternatively, the modified colorant can also form bonds with pigment molecules through chemical reactions such as diazotization, etherification, acylation, and esterification, generating modified pigment molecules that coat the outermost layer of the pigment particles during wetting. In the modified pigment particles, the functional groups of the modified colorant are exposed on the outer layer. On the one hand, they ionize in the dispersion medium, forming an electric double layer on the pigment particle surface, causing mutual repulsion between pigment particles. On the other hand, the hydrophilic functional groups can promote the wetting of pigment particles and the dispersion medium, thereby improving dispersibility. The pigment paste prepared using the modified colorant of this invention has advantages such as good filtration, strong coloring power, and stable thermal storage (small particle size change rate after 7 days of thermal storage), which are advantageous in the application of inkjet ink.

[0070] Functional group A 1 A 2The unique phosphate groups, phosphonic acid groups, sulfonic acid groups, carboxylic acid groups, and their salts can complex with metal ions, especially calcium ions, thereby improving coloring ability. Therefore, the calcium index value is introduced as a parameter, defined as the number of calcium ions that each molecule of modified colorant can complex (for cases where modified colorants are used in combination, it needs to be calculated after weighting according to the mass ratio). The calcium index value of the modified colorant is preferably 1.2-8, more preferably 1.5-6, and most preferably 2.5-5. In addition, functional group A... 1 A 2 The unique halogen, conjugated structure, and polymer groups have a steric hindrance effect, which to a certain extent inhibits the aggregation and flocculation between pigment particles.

[0071] The colorant modifier of this invention effectively controls the hydrophilicity or lipophilicity of pigments by adjusting the type and number of triazine substituents. The nano-pigment paste treated with this modifier exhibits self-dispersing properties, requiring no additional additives, and effectively improves the dispersibility, stability, and filterability of the nano-pigment paste, while also giving it excellent coloring ability. Detailed Implementation

[0072] This invention relates to specific pigment-modified colorants with triazine structures. The triazine host structure has an anchoring function, and by adjusting the type and number of triazine substituents, the hydrophilicity or oleophilicity of the pigment can be effectively controlled. This invention discloses such modified colorants and implementation schemes for their application in the preparation of nano-pigment pastes. The nano-pigment pastes treated with the modified colorants exhibit self-dispersing properties, requiring no additional additives, and effectively improving the dispersibility, stability, and filterability of the nano-pigment pastes, while also giving them excellent coloring ability.

[0073] The implementation plan includes the following aspects regarding the evaluation indicators and methods for nano-aqueous pigment pastes:

[0074] (1) Particle size and particle size distribution

[0075] Take a small amount of pigment paste, dilute it with distilled water to 300-500 kcps, prepare the sample in a 1 cm*1 cm cuvette, and test it using a NanoBrook nanoparticle size analyzer. Five sets of data were tested in parallel at 25℃, and the average value was taken.

[0076] (2) Viscosity

[0077] The color paste was placed in the sample cell, and the viscosity of the color paste sample was measured at 25°C using a Brookfield DV2T viscometer with rotor No. 0.

[0078] (3) Filterability

[0079] The color paste sample was placed in the filter and filtered using a 0.45μm pore size polypropylene filter membrane and a glass fiber filter membrane, respectively. The time required to filter 1L of color paste under the conditions of 25℃ and 0.3Mpa was recorded to measure the filterability of the color paste sample.

[0080] (4) Coloring ability

[0081] The color paste sample was formulated into ink, applied to a printer, and the resulting inkjet sample was tested for coloring ability using Lab assays.

[0082] (5) Stability of thermal and cold storage

[0083] Take two 20ml samples of color paste and place them in two separate PET sample bottles, sealing them with screw caps. Place each sample bottle in a 60℃ environment for 7 days, and then test its various parameters. If the relative change rate of each physicochemical index is less than 10%, the color paste is considered to be of acceptable stability.

[0084] Example 1: Preparation of Modified Colorant 1

[0085] Add 200 ml of distilled water and 21 g (0.1 mol) of sodium 2,4-diaminobenzenesulfonate to a 500 ml four-necked flask, stir and cool to 0-5 °C. Add 18.41 g (0.1 mol) of cyanuric chloride in portions and maintain the reaction temperature for 3 hours. Heat the reaction solution to 20-25 °C, add 29.7 g (0.1 mol) of p-(1,1-diphospho-1-hydroxyethane)aniline in portions, and stir and maintain the temperature for 3 hours. Adjust the pH of the reaction solution to less than 1 with concentrated hydrochloric acid, resulting in the precipitation of a reddish-brown solid. Filter and wash the filter cake with water, dry at 60 °C for 5 hours to obtain 56.2 g (0.91 mol) of modified colorant 1, a brown solid, with an HPLC purity of 98.55% and a yield of 91%. mp 265-268 °C. M / Z = 596.00

[0086] 1 H-NMR (600MHz, DMSO-D6) δ: 1.49-1.52ppm (s, 2H, CH2), 2.71ppm (s, 1H, COH), 3.35ppm (t, 2H, NHCH2CH2), 4.88ppm (s, 4H, POH), 5. 90ppm (s, 2H, NH2), 6.05ppm (d, 1H, CHCH), 6.60ppm (d, 1H, CHCH), 7.11ppm (s, 1H, NH2), 7.36ppm (d, 1H, CHCH), 8.33ppm (s, H, NH);

[0087]

[0088] Example 2: Preparation of Modified Colorant 2

[0089] Add 200 ml of distilled water, 18.8 g (0.1 mol) of 2,4-diaminobenzenesulfonic acid, and 8.4 g (0.1 mol) of sodium bicarbonate to a 500 ml four-necked flask, stir, and cool to 0-5 °C. Add 18.41 g (0.1 mol) of cyanuric chloride in portions and maintain the reaction temperature for 6 hours. Heat the reaction solution to 20-25 °C, and add 32.6 g (0.1 mol) of sodium phosphate trihydrate (4-amino-1-hydroxy-1-phospho-butyl) in portions. After stirring and maintaining the temperature for 8 hours, adjust the pH of the reaction solution to less than 1 using concentrated hydrochloric acid, resulting in the precipitation of a yellowish-brown solid. Filter, wash the filter cake with water, and dry at 60 °C for 5 hours to obtain 55 g (0.086 mol) of pale yellow solid modified colorant 2, with an HPLC purity of 97.36% and a yield of 86%. mp 245-247 °C. M / Z = 548.79

[0090] 1 H-NMR (600MHz, DMSO-D6) δ: 1.49-1.52ppm (m, 4H, CH2CH2), 2.21ppm (s, 1H, COH), 3.35ppm (t, 2H, NHCH2CH2), 4.88ppm (s, 4H, POH), 5 .90ppm (s, 2H, NH2), 6.05ppm (d, 1H, CHCH), 6.60ppm (d, 1H, CHCH), 7.11ppm (s, 1H, NH2), 7.36ppm (d, 1H, CHCH), 8.33ppm (s, 1H, NH);

[0091]

[0092] Example 3: Preparation of Modified Colorant 3

[0093] Add 200ml of distilled water, 7.51g (0.1mol) of glycine, and 8.4g (0.1mol) of sodium bicarbonate to a 500ml four-necked flask, stir, and cool to 0-5℃. Add 18.41g (0.1mol) of cyanuric chloride in batches and maintain the temperature for 2 hours. Heat the reaction solution to 10-15℃, add 29.7g (0.1mol) of (1,1-bisphosphono-1-hydroxyethane)amine in batches, and stir and maintain the temperature for 4 hours. Adjust the pH of the reaction solution to less than 1 with concentrated hydrochloric acid, and a yellowish-brown solid precipitates. Filter and wash the filter cake with water. Place the wet filter cake in a 500ml four-necked flask, add 200ml of distilled water to slurry, and add 10.8g (0.1mol) of p-phenylenediamine in batches, completing the addition in 15 minutes. Stir, heat to 20-25℃, and maintain the temperature for 3 hours. The filter cake was filtered and washed with water to obtain 34.7 g (0.0749 mol) of modified colorant 3, a reddish-brown solid. HPLC purity was 95.88%, and yield was 74.9%.

[0094] mp245-247℃. M / Z=548.79

[0095] 1 H-NMR (600MHz, DMSO-D6) δ: 1.12ppm (s, 3H, CCH3), 4.02ppm (s, 2H, NHCH2), 4.88ppm (s, 4H, POH), 5.90ppm (s, 2H, N H), 6.05ppm (d, 2H, CHCH), 6.25ppm (d, 2H, CHCH), 7.11ppm (s, 2H, PhNH2), 7.36ppm (d, 1H, CHCH), 8.33ppm (s, 1H, Ph NH);

[0096]

[0097] Example 4: Preparation of Modified Colorant 4

[0098] Add 200 ml of distilled water, 28.26 g (0.1 mol) of L-glutamic acid, and 16.8 g (0.2 mol) of sodium bicarbonate to a 500 ml four-necked flask, stir, and cool to 0-10 °C. Add 18.41 g (0.1 mol) of cyanuric chloride in portions and maintain the reaction temperature for 6 hours. Heat the reaction solution to 25-30 °C, add 6.0 g (0.1 mol) of ethylenediamine in portions, and stir and maintain the temperature for 4 hours. Adjust the pH of the reaction solution to less than 1 using concentrated hydrochloric acid, resulting in the precipitation of a pale yellow solid. Filter, wash the filter cake with water, and dry at 60 °C for 5 hours to obtain 38.5 g (0.089 mol) of modified colorant 4, a pale yellow solid. HPLC purity: 97.82%, yield: 89%. mp: 295-297 °C.

[0099] M / Z = 429.16

[0100] 1 H-NMR (600MHz, DMSO-D6) δ: 2.01ppm (q, 4H, CHCH2CH2), 2.33ppm (t, 4H, CHCH2CH2), 2.73ppm (t, 2H, CH2CH2NH2), 3.50ppm (t, 2H, NHCH2CH2NH2), 3.74ppm (t, 2H, NHCHCH2) 5.32ppm (s, 2H, NHPh), 5.62ppm (s, 1H, NHPh), 5.62ppm (s, 2H, NHCH2CH2NH2), 8.12ppm (s, 2H, OH); 8.35ppm (s, 1H, OH);

[0101]

[0102] Example 5: Preparation of Modified Colorant 5

[0103] Add 200 ml of distilled water, 13.8 g (0.1 mol) of 3-amino-2-carboxylic acid pyridine, and 8.4 g (0.1 mol) of sodium bicarbonate to a 500 ml four-necked flask. Stir and cool to 0-5 °C. Add 18.41 g (0.1 mol) of cyanuric chloride in portions and maintain the reaction temperature for 4 hours. Heat the reaction solution to 25-30 °C and add 6.0 g (0.1 mol) of ethylenediamine in portions. After stirring and maintaining the temperature for 4 hours, heat to 50 °C and maintain the temperature for 1 hour. Adjust the pH of the reaction solution to less than 1 using concentrated hydrochloric acid, and a white solid precipitates. Filter and wash the filter cake with water, then dry at 60 °C for 5 hours to obtain 22.2 g (0.763 mol) of modified colorant 5 as a white solid. HPLC purity: 98.32%, yield: 76.3%. mp: 154-156 °C. M / Z = 291.11

[0104]

[0105] 1 H-NMR (600MHz, DMSO-D6) δ: 2.25ppm (s, 2H, CH2CH2NH2), 2.73ppm (t, 2H, CH2CH2NH2), 3.50ppm (t, 2H, NHCH2CH2NH2), 6 .52ppm (s, 2H, NHCH2CH2NH2) 7.83ppm (d, 1H, CHPh), 7.93ppm (d, 1H, CHPh), 8.12ppm (s, 1H, NHPh) 8.51ppm (s, 1H, OHPh).

[0106] Example 6: Preparation of Modified Colorant 6

[0107] Add 200 ml of methanol, 27.2 g of water, and 16.8 g (0.2 mol) of sodium bicarbonate to a 500 ml four-necked flask. Stir and cool to -5 to 0 °C. Add 39.85 g (0.216 mol) of cyanuric chloride in portions and maintain the reaction temperature for 8 hours. Filter and wash the filter cake with 100 ml of cold water to obtain 29.54 g (0.164 mol) of white powdery solid; HPLC purity 94.30%, yield 82%. mp 124-125 °C. M / Z = 178.97

[0108]

[0109] 14.86 g (0.083 mol) of solid compound (1a), 40 g of acetone, 11.2 g (0.0896 mol) of taurine, 50 ml of water, and 9.0 g (0.0849 mol) of sodium carbonate were added sequentially to a 250 ml four-necked flask. The mixture was stirred at room temperature. The reaction solution first became clear, and then a white solid precipitated. After reacting for 5 hours, the mixture was filtered, and the filter cake was washed with acetone to obtain 22.29 g (0.0829 mol) of white powdery solid compound (1b); HPLC purity 98.30%, yield 92.59%. mp 221-223℃. M / Z = 268.00

[0110]

[0111] 1 H-NMR (600MHz, DMSO-D6) δ: 2.53ppm (s, 1H, SO3H), 3.62ppm (t, 2H, CH2CH2SO3H), 3.78ppm (t, 2H, CH2CH2SO3H), 3.83ppm (s, 3H, PhOCH3).

[0112] 11.0 g (0.041 mol) of compound (1b) and 100 ml of water were added to a 250 ml four-necked flask and stirred until completely dissolved. 4.32 g (0.041 mol) of p-phenylenediamine was added in portions at room temperature, completing the addition over 15 minutes. During the addition, the reaction mixture changed from a slightly reddish color to brown. The reaction was stirred for 3 hours, during which a white solid precipitated. The mixture was filtered and the filter cake was washed with water. After air-drying, 8.62 g (0.025 mol) of a gray powdery solid was obtained, which was the modified colorant 6. HPLC purity was 96.26%, yield was 63.38%. mp 258-260℃. M / Z = 340.10

[0113]

[0114] 1 H-NMR(600MHz, DMSO-D6)δ:2.53ppm(s,1H,SO3H),3.62ppm(t,2H,CH2CH2SO3H),3.78ppm(t,2H,CH2CH2SO3H),3.83ppm(s, 3H, PhOCH3), 6.05ppm (d, 2H, CHPh), 6.25ppm (d, 2H, CHPh), 7.11ppm (s, 2H, PhNH2), 7.36ppm (d, 1H, CHPh), 8.33ppm (s, 1H, Ph NH).

[0115] Example 7: Preparation of Modified Colorant 7

[0116] Add 18.42 g (0.1 mol) cyanuric chloride, 200 g distilled water, and 21.6 g (0.257 mol) sodium bicarbonate to a 500 ml four-necked flask. Stir at 15 °C for 10 min. Then, add 50.0 g (0.025 mol) polyetheramine (Mw = 2000) to the flask at a constant temperature and stir for 2 h. Next, add 32.7 g (4-amino-1-hydroxy-1-phospho-butyl) sodium phosphate trihydrate and 21.0 g (0.25 mol) sodium bicarbonate to the reaction system, stir, and heat to 35-40 °C, maintaining this temperature for 5 h. Finally, add 10.8 g (0.1 mol) p-phenylenediamine and 9.0 g (0.083 mol) sodium carbonate to the system, stir, and heat to 90 °C, maintaining this temperature for 12 h. The temperature was then lowered to 25°C, hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 1.0, and the mixture was stirred and kept at this temperature for 1 hour. The solution was then filtered, and the filter cake was dried in an 80°C forced-air drying oven for 2 hours to obtain 72.5 g of modified colorant 7 purple powder solid. Yield: 76.23%.

[0117] Example 8: Preparation of K-1 color paste modified with nano-carbon black

[0118] Add 100g of carbon black pigment powder, 34g (0.057mol) of modified colorant 1, 700g of distilled water, and 6.83g (0.068mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 23.23g (0.0673mol) of 20% sodium nitrite aqueous solution over one hour. Then, stir and heat to 40-45℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 with 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-1.

[0119] Example 9: Preparation of K-2 color paste modified with nano-carbon black

[0120] Add 100g of carbon black pigment powder, 27g (0.0453mol) of modified colorant 2, 700g of distilled water, and 4.77g (0.047mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 19.0g of 20% (0.055mol) sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 35-40℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-2.

[0121] Example 10: Preparation of K-3 color paste modified with nano-carbon black

[0122] Add 100g of carbon black pigment powder, 16.8g (0.036mol) of modified colorant 3, 700g of distilled water, and 6.9g (0.069mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 12.4g (0.036mol) of 20% sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 40-45℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-3.

[0123] Example 11: Preparation of K-4 color paste modified with nano-carbon black

[0124] Add 100g of carbon black pigment powder, 54g (0.090mol) of modified colorant 4, 700g of distilled water, and 9.62g (0.0962mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 31.5g (0.09mol) of 20% sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 40-45℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-4.

[0125] Example 12: Preparation of K-5 color paste modified with nano-carbon black

[0126] Add 100g of carbon black pigment powder, 16.8g (0.036mol) of modified colorant 5, 700g of distilled water, and 4.77g (0.0477mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 12.42g (0.056mol) of 20% sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 40℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-5.

[0127] Example 13: Preparation of K-6 color paste modified with nano-carbon black

[0128] 100g of carbon black pigment powder, 700g of distilled water, 19.4g (0.0322mol) of modified colorant 6, and 19.14g (0.055mol) of 20% sodium nitrite solution were added to a 2L four-necked flask. The mixture was then stirred and heated to 40℃ and maintained at this temperature for 16 hours. The color paste was cooled to room temperature, and the pH was adjusted to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, nano-aqueous carbon black pigment color paste K-6 was obtained.

[0129] Examples 14-21 are performed in the same manner as Examples 8-13, yielding nano-aqueous carbon black pigment pastes K-7 to K-15.

[0130] Example 22: Modification of M-16 with Nano-Pigments

[0131] Add 43g (0.0721mol) of modified colorant 1, 100g of distilled water, and 14.42g (0.144mol) of concentrated hydrochloric acid to a 1L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5℃. Then, slowly add 37.37g (0.0879mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 5-10℃ during the addition process. Separately, add 100g (0.294mol) of Pigment Red 122 dry powder and 600g of distilled water to a 2L four-necked flask, and stir to raise the temperature to 70℃. Then, add the diazo solution of modified colorant 1 to the Pigment Red 122 dispersion, maintaining the reaction temperature at 70-75℃ during the addition process, completing the addition within 1 hour, and maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. Subsequently, after membrane filtration, nano-waterborne pigment Red 122 color paste 16 was obtained.

[0132] Example 23: Pigment modification to prepare color paste sample M-17

[0133] Add 33g (0.060mol) of modified colorant 2, 100g of distilled water, and 12g (0.12mol) of concentrated hydrochloric acid to a 1L four-necked flask, and cool in an ice bath to 0-5℃. Then slowly add 28.66g (0.06mol) of 20% potassium nitrite aqueous solution, controlling the reaction temperature at 0-10℃, and react for 1 hour to obtain the modified diazonium solution.

[0134] Add 100g (0.294mol) of Pigment Red 122 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Add the modifier diazo solution in batches, maintaining the temperature at 70-75℃, and complete the addition within 1 hour. Maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Red 122 color paste 17.

[0135] Examples 24-27 were conducted in the same manner as Examples 22-23, yielding nano-aqueous pigment Red 122 color pastes M18-M21.

[0136] Example 28: Pigment modification to prepare color paste sample V-22

[0137] Add 43g (0.0721mol) of modified colorant 1, 100g of distilled water, and 14.42g (0.144mol) of concentrated hydrochloric acid to a 1L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5℃. Then, slowly add 37.37g (0.0879mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 0-10℃ throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0138] Add 100g (0.263mol) of Pigment Violet 19 dry powder and 600g of distilled water to another 2L four-necked flask, and heat to 70-75℃. Add the modifier diazo solution in batches, maintaining the temperature at 70-75℃, and complete the addition within 1 hour. Maintain the reaction temperature for 10-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Violet 19 color paste 22.

[0139] Example 29: Pigment modification for preparing color paste sample V-23

[0140] Add 39.0 g (0.114 mol) of modified colorant 6, 100 g of distilled water, and 22.4 g (0.228 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction temperature at 0-5 °C. Then slowly add 37.37 g (0.133 mol) of 20% potassium nitrite aqueous solution, controlling the reaction temperature at 0-5 °C throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0141] Add 100g (0.263mol) of Pigment Violet 19 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70-75℃ and stir. Add the modifier diazo solution in batches, maintaining the temperature at 70-75℃, and complete the addition within 1 hour. Maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Violet 19 color paste 23.

[0142] Example 30: Pigment modification to prepare color paste sample M-24

[0143] Add 43.0 g (0.0721 mol) of modified colorant 1, 100 g of distilled water, and 22.4 g (0.228 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction temperature at 0-5 °C. Then slowly add 37.37 g (0.133 mol) of 20% potassium nitrite aqueous solution, controlling the reaction temperature at 0-5 °C throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0144] Add 80.0 g (0.233 mol) of Pigment Red 122 dry powder, 20.0 g (0.052 mol) of Pigment Violet 19 dry powder, and 600 g of distilled water to another 2 L four-necked flask. Heat to 70-75 °C and stir. Then add the modifier diazo solution to the Pigment Red 122 / Pigment Violet 19 mixed dispersion, and maintain the temperature at 70-75 °C. The addition should be completed within 1 hour, and the reaction should be maintained at this temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Red 122 / Pigment Violet 19 composite color paste 24.

[0145] Example 31: Pigment modification to prepare color paste sample C-25

[0146] Add 43.0 g (0.0721 mol) of modified colorant 1, 100 g of distilled water, and 22.4 g (0.228 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction temperature at 0-5 °C. Then slowly add 19.0 g (0.0721 mol) of 20% potassium nitrite aqueous solution, controlling the reaction temperature at 0-5 °C throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0147] Add 100g (0.1721mol) of Pigment Blue 15:3 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the modifier diazonium solution to the Pigment Blue 15:3 dispersion, and maintain the temperature at 70-75℃, completing the addition within 1 hour, and maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Blue 15:3 color paste 25.

[0148] Example 32: Pigment modification to prepare color paste sample C-26

[0149] Add 43.0 g (0.0721 mol) of modified colorant 9, 100 g of distilled water and 22.4 g (0.228 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath and control the temperature of the reaction solution at 0-5 °C. Then slowly add 19.0 g (0.0721 mol) of 20% potassium nitrite aqueous solution, controlling the temperature of the reaction solution at 5-10 °C. React for 1 hour to obtain the modified colorant diazonium solution.

[0150] Add 100g (0.1721mol) of Pigment Blue 15:4 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the modifier diazonium solution to the Pigment Violet Pigment Blue 15:4 dispersion, and maintain the temperature at 70-75℃, completing the addition within 1 hour, and maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Blue 15:4 color paste 26.

[0151] Examples 33-37 are performed in the same manner as Examples 31-32.

[0152] Example 38: Pigment modification to prepare color paste sample Y-32

[0153] Add 43.0 g (0.0721 mol) of modified colorant 1, 100 g of distilled water, and 22.4 g (0.228 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5 °C. Then slowly add 19.0 g (0.0721 mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 5-10 °C throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0154] Add 100g (0.259mol) of Pigment Yellow 74 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70-75℃ and stir. Add the modifier diazo solution in batches, maintaining the temperature at 70-75℃, and complete the addition within 1 hour. Maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Yellow 74 color paste 32.

[0155] Example 39: Pigment modification to prepare color paste sample Y-33

[0156] Add 40g (0.06mol) of modified colorant 9, 100g of distilled water, and 12g (0.12mol) of concentrated hydrochloric acid to a 1L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5℃. Then slowly add 19.0g (0.0721mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 5-10℃ throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0157] Add 100g (0.139mol) of Pigment Yellow 155 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70-75℃ and stir. Add the modifier diazo solution in batches, maintaining the temperature at 70-75℃, and complete the addition within 1 hour. Maintain the reaction temperature for 12-14 hours. Cool to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Yellow 155 color paste 33.

[0158] Examples 40-43 were performed in the same manner as Examples 38-39, yielding nano-aqueous yellow pigments 34-37.

[0159] Example 44: Pigment modification to prepare color paste sample G-38

[0160] Add 43.0 g (0.0721 mol) of modified colorant 1, 100 g of distilled water, and 12.0 g (0.12 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5 °C. Then, slowly add 20.18 g (0.0721 mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 0-5 °C throughout the process. React for 1 hour to obtain the modified colorant diazonium solution.

[0161] Add 100g (0.060mol) of Pigment Green 36.0 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70-75℃ and stir. Then add the modified colorant 1 diazo solution to the Pigment Green 36 dispersion, stirring and maintaining the temperature at 70-75℃, and using a 30% potassium hydroxide aqueous solution to control the pH of the color paste to the range of 6-7. The modified colorant 1 diazo solution is added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, nano-aqueous Pigment Green 36 color paste 38 is obtained.

[0162] Example 45: Pigment modification to prepare color paste sample W-39

[0163] Add 40.0 g (0.06 mol) of modified colorant 9, 100.0 g of distilled water, and (0.12 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5 °C. Then, slowly add 20.18 g (0.0721 mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 5-10 °C throughout the process. After reacting for 1 hour, a diazonium solution of the modified colorant is obtained.

[0164] Add 100.0g of titanium dioxide and 600g of distilled water to a 2L four-necked flask, heat to 70℃ and stir. Then add the modified colorant 9 diazo solution to the titanium dioxide dispersion, stirring and maintaining the temperature at 70-75℃, using a 30% potassium hydroxide aqueous solution to control the pH of the color paste within the range of 6-7. The modified colorant 9 diazo solution is added completely over 12-14 hours. Cool the color paste to room temperature, and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, nano-aqueous titanium dioxide white paste 39 is obtained.

[0165] Examples 46-49 were prepared using the same procedures as Example 45, yielding nano-aqueous titanium white slurries W-40 to W-43.

[0166] Comparative Example 1

[0167] Add 100g of carbon black pigment powder, 13.0g (0.072mol) of p-aminophenyl butyric acid, 700g of distilled water, and 14.4g (0.144mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 23.23g (0.0721mol) of a 20% sodium nitrite aqueous solution over one hour. Then, stir and heat to 40℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste K-16.

[0168] Comparative Example 2

[0169] Add 100g of carbon black pigment powder, 11.7g (0.1mol) of p-aminobenzenesulfonic acid, 700g of distilled water, and 20g (0.2mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 34.5g (0.1mol) of 20% sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 35-40℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste 1.

[0170] Comparative Example 3

[0171] Add 100g of carbon black pigment powder, 13.7g (0.1mol) of p-aminobenzoic acid, 700g of distilled water, and 20g (0.2mol) of concentrated hydrochloric acid to a 2L four-necked flask. After stirring evenly, slowly add 34.5g (0.1mol) of 20% sodium nitrite aqueous solution dropwise over one hour. Then stir and heat to 35-40℃ and maintain this temperature for 16 hours. Cool the pigment paste to room temperature and adjust the pH to 8.0-9.0 using a 30% sodium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous carbon black pigment paste 1.

[0172] Comparative Example 4

[0173] Add 11.7 g (0.1 mol) of p-aminobenzenesulfonic acid, 100.0 g of distilled water, and 20.0 g (0.2 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, maintaining the reaction temperature at 0-5 °C. Then, slowly add 28.0 g (0.1 mol) of 20% potassium nitrite aqueous solution, keeping the reaction temperature below 10 °C throughout the process. React for 1 hour to obtain the modifier diazonium solution.

[0174] Add 100.0 g (0.294 mol) of Pigment Red 122 dry powder and 600 g of distilled water to another 2 L four-necked flask, heat to 70 °C and stir. Then add the diazo modifier to the Pigment Red 122 dispersion, stirring and maintaining the temperature at 70-75 °C, using a 30% potassium hydroxide aqueous solution to control the pH of the color paste within the range of 6-7. The diazo modifier should be added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Red 122 color paste.

[0175] Comparative Example 5

[0176] Add 11.7 g (0.1 mol) of p-aminobenzenesulfonic acid, 100 g of distilled water, and 20 g (0.2 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, maintaining the reaction temperature at 0-5 °C. Then, slowly add 28.0 g (0.1 mol) of a 20% potassium nitrite aqueous solution, keeping the reaction temperature below 10 °C throughout the process. After reacting for 1 hour, a diazonium solution of the modifier is obtained.

[0177] Add 100g (0.294mol) of Pigment Violet 19.0 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the diazo modifier solution to the Pigment Violet 19 dispersion, stirring and maintaining the temperature at 70-75℃, using a 30% potassium hydroxide aqueous solution to control the pH of the color paste within the range of 6-7. The diazo modifier solution is added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, the nano-aqueous Pigment Violet 19 color paste is obtained.

[0178] Comparative Example 6

[0179] Add 11.7 g (0.1 mol) of p-aminobenzenesulfonic acid, 100 g of distilled water, and 20.0 g (0.2 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction solution temperature at 0-5 °C. Then slowly add 28.0 g (0.1 mol) of 20% potassium nitrite aqueous solution, controlling the reaction solution temperature at 5-10 °C throughout the process. React for 1 hour to obtain the modifier diazonium solution.

[0180] Add 100g (0.1721mol) of Pigment Blue 15:3 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the diazo modifier to the Pigment Blue 15:3 dispersion, stirring and maintaining the temperature at 70-75℃, using a 30% potassium hydroxide aqueous solution to control the pH of the color paste within the range of 6-7. The diazo modifier should be added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, obtain nano-aqueous Pigment Blue 15:3 color paste.

[0181] Comparative Example 7

[0182] Add 11.7 g (0.1 mol) of p-aminobenzenesulfonic acid, 100 g of distilled water, and 20.0 g (0.2 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, maintaining the reaction temperature at 0-5 °C. Then, slowly add 28.0 g (0.1 mol) of 20% potassium nitrite aqueous solution, keeping the reaction temperature below 10 °C throughout the process. After reacting for 1 hour, a diazonium solution of the modifier is obtained.

[0183] Add 100g (0.259mol) of Pigment Yellow 74 dry powder and 600g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the diazo modifier to the Pigment Yellow 74 dispersion, keep at 70-75℃, and use a 30% potassium hydroxide aqueous solution to control the pH of the color paste at 6.0-7.0. The diazo modifier should be added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, nano-aqueous Pigment Yellow 74 color paste 32 is obtained.

[0184] Comparative Example 8

[0185] Add 11.7 g (0.1 mol) of p-aminobenzenesulfonic acid, 100 g of distilled water, and 20.0 g (0.2 mol) of concentrated hydrochloric acid to a 1 L four-necked flask. Stir in an ice bath, controlling the reaction temperature at 0-5 °C. Then slowly add 28.0 g (0.1 mol) of 20% potassium nitrite aqueous solution, keeping the reaction temperature below 10 °C throughout the process. React for 1 hour to obtain the modifier diazonium solution.

[0186] Add 100.0 g (0.139 mol) of Pigment Yellow 155 dry powder and 600.0 g of distilled water to another 2L four-necked flask, heat to 70℃ and stir. Then add the diazo modifier to the Pigment Yellow 155 dispersant, keep at 70-75℃, and use a 30% potassium hydroxide aqueous solution to control the pH of the color paste to the range of 6-7. The diazo modifier is added completely over 12-14 hours. Cool the color paste to room temperature and adjust the pH to 8.0-9.0 using a 30% potassium hydroxide aqueous solution. After membrane filtration, nano-aqueous Pigment Yellow 155 color paste 33 is obtained.

[0187] The test results of the pigment examples and comparative examples are shown in Table 1:

[0188] Table 1

[0189]

[0190]

[0191] As can be seen from the above examples and comparative data, the pigment paste prepared using the modified colorant of the present invention has advantages such as good filterability, strong tinting strength, and thermal stability (small particle size change rate after 7 days of thermal storage), which are advantageous in inkjet ink applications. Specifically, the modified colorant of the present invention has a triazine main structure and contains an anchoring group L and a functional group A. 1 A 2 The anchoring group L can be firmly anchored to the pigment surface through chemical bonds, and will not fall off even with changes in external temperature and additives, thus exhibiting good stability. The functional group A... 1 A 2 The hydrophilicity or oleophilicity of pigments can be effectively controlled by adjusting the type and number of functional groups. The functional groups of the modified colorant are exposed on the outer layer of the pigment particles. On the one hand, they ionize in the dispersion medium, forming an electric double layer on the surface of the pigment particles, causing mutual repulsion between them. On the other hand, the hydrophilic functional groups can promote the wetting of the pigment particles with the dispersion medium, thereby improving dispersibility. The functional group A in the triazine main structure... 1 A 2 It contains co-phosphoric acid groups with a high calcium index, which can complex with calcium ions in the application system and densely aggregate on the surface of the application system, thereby improving the coloring intensity.

[0192] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A modified colorant having a triazine structure, characterized in that: The modified colorant structure is shown in general formula D1: In the formula: L is selected from -BZ-NH2; B is selected from NH; Z is selected from unsubstituted aryl groups or those further substituted with sulfonic acid groups; A 1 Selected from A 2 Selected from halogens or -NHCH2CO2H; Or a salt of the compound represented by general formula D1.

2. The application of the modified colorant according to claim 1, characterized in that: The anchoring group L anchors the modified colorant to the surface of pigment particles through physical adsorption or chemical bonding, thereby achieving surface modification of the pigment.

3. The application of the modified colorant with a triazine structure according to claim 2, characterized in that: The pigments are blue pigments, black pigments, brown pigments, cyan pigments, green pigments, white pigments, purple pigments, red pigments, yellow pigments, orange pigments, or mixtures thereof.

4. The application of the modified colorant with a triazine structure according to claim 3, characterized in that: The pigments are Pigment Blue 15, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Red 122, Pigment Violet 19, Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 128, Pigment Yellow 218, Pigment Yellow 220, Pigment Yellow 211, or Carbon Black.

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