Hyperbranched dye, and preparation method and application thereof

Abstract

The application discloses a kind of hyperbranched dyes and its preparation method and application, it is related to fine chemical technology field.The preparation method includes the following steps: preparation contains active dye, tannin solution, under the condition of pH 7~12, 30 ℃~95 ℃ reaction, obtain the hyperbranched dye described in this application.Using natural plant extract tannin as hyperbranched core, grafting reaction is carried out with the hydroxyl group at the end of tannin hyperbranched structure and active dye to obtain hyperbranched dye, which can significantly improve the water resistance, light resistance and ozone resistance of active dye.

Description

Technical Field

[0001] This invention relates to the field of fine chemical technology, and in particular to a hyperbranched dye, its preparation method, and its application. Background Technology

[0002] Dyes possess advantages such as vibrant colors, high light transmittance and saturation, excellent color reproduction and resolution, water solubility, ease of use, environmental friendliness, and low cost. However, dyes also have disadvantages such as poor water resistance and poor weather resistance (poor resistance to ultraviolet light and ozone), making them unsuitable for outdoor use, especially in environments with water or ultraviolet light. When applying dyes to the preparation of inkjet inks, water-insoluble pigments are often used to improve water resistance. However, this results in the pigments being suspended in the ink in particulate form, which can easily lead to unstable dispersion, pigment precipitation, and printhead clogging, causing printer malfunctions. Patent CN103159904A discloses a polymer dye that improves the dye's water resistance, migration resistance, heat resistance, light resistance, and ozone resistance through the action of polymer resin. However, the preparation method of polymer resin is complex, the removal of residual monomers is difficult, and the high molecular weight results in high ink viscosity, which is not conducive to application. Furthermore, the polymer resin used is synthesized through petrochemicals and lacks green regeneration capabilities, resulting in poor environmental compatibility.

[0003] Therefore, it is very important to provide a dye with good water resistance and UV resistance that can be used in inkjet inks. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing hyperbranched dyes, the hyperbranched dyes of which have excellent water resistance, ultraviolet light resistance and ozone resistance.

[0005] The present invention also provides hyperbranched dyes prepared by the above preparation method.

[0006] The present invention also provides an inkjet ink comprising the above-described hyperbranched dyes.

[0007] The present invention also provides applications of the above-mentioned hyperbranched dyes or inkjet inks.

[0008] A method for preparing a hyperbranched dye according to a first aspect of the present invention includes the following steps:

[0009] A solution containing reactive dye and tannin was prepared and reacted at pH 7–12 and 30℃–95℃ to obtain the hyperbranched dye.

[0010] The preparation method according to embodiments of the present invention has at least the following beneficial effects:

[0011] The raw material tannin has the structure shown in Formula I. The core group of tannin is derived from a galloyl glucose-derived structure, possessing properties such as water resistance, light resistance, greenness, renewability, low toxicity, and natural environmental friendliness. It is also inexpensive and does not require high-molecular-weight resin synthesis. The preparation method in this example uses tannin, a natural plant extract, as the hyperbranched core. The hydroxyl groups at the ends of the hyperbranched tannin structure are grafted onto reactive dyes to obtain hyperbranched dyes, which significantly improves the water resistance, light resistance, and ozone resistance of the reactive dyes. Reaction conditions of pH 7–12 promote the dissociation of hydroxyl groups on the tannin to form anions, accelerating the nucleophilic reaction of the reactive dye and increasing the grafting coloring rate. If the pH is too high or too low, or the reaction temperature is too high, the hydrolysis reaction of the reactive dye will preferentially precede the grafting reaction, causing the reactive dye to lose its reactivity and become ungraftable, resulting in a hyperbranched dye with a low coloring rate. If the reaction temperature is too low, the initial reaction will not be achieved.

[0012]

[0013] According to some embodiments of the present invention, the reactive dye includes at least one of reactive yellow dye, reactive orange dye, reactive red dye, reactive purple dye, reactive blue dye, reactive green dye, reactive brown dye, and reactive black dye.

[0014] According to some embodiments of the present invention, the reactive yellow dyes include, but are not limited to, reactive yellow dyes 2, 3, 5, 13, 14, 15, 16, 17, 18, 37, 42, 57, 95, 145, 160, 167 or 186.

[0015] According to some embodiments of the present invention, the reactive orange dye includes, but is not limited to, reactive orange dyes 3, 5, 12, 13, 16, 72, 107 or 122.

[0016] According to some embodiments of the present invention, the reactive red dye includes, but is not limited to, reactive red dyes 3, 3:1, 15, 21, 24, 24:1, 31, 35, 43, 45, 106, 180, 194, 195, 198, 218, 222, 245 or 250.

[0017] According to some embodiments of the present invention, the reactive purple dye includes, but is not limited to, reactive purple dye 1, 2 or 5.

[0018] According to some embodiments of the present invention, the reactive blue dyes include, but are not limited to, reactive blue dyes 5, 13, 15, 19, 21, 49, 71, 72, 74, 194, 223 or 231.

[0019] According to some embodiments of the present invention, the reactive green dye includes, but is not limited to, reactive green dye 5, 8 or 35.

[0020] According to some embodiments of the present invention, the reactive brown dye includes, but is not limited to, reactive brown dyes 2, 11 or 18.

[0021] According to some embodiments of the present invention, the reactive black dye includes, but is not limited to, reactive black dyes 1, 5, 31, 39 or 45.

[0022] According to some embodiments of the present invention, the reaction molar ratio of the reactive dye to tannin is 1 to 15:1. For example, it can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, or 15:1. If the reaction molar ratio is less than 1, the grafting rate of the reactive dye on the tannin will be too low, resulting in insufficient color concentration of the ink. If the reaction molar ratio is greater than 15, it indicates that an excessive amount of reactive dye has been added. The grafted reactive dye will form a steric hindrance, preventing the excessive reactive dye from grafting onto the tannin, resulting in dye residue and affecting ink performance.

[0023] According to some embodiments of the present invention, the reaction molar ratio of the reactive dye and tannin is 3 to 12:1.

[0024] According to some embodiments of the present invention, the reaction molar ratio of the reactive dye and tannin is 5 to 10:1.

[0025] According to some embodiments of the present invention, the pH of the reaction is 8 to 11.5. For example, it can be 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.2, 11.4, or 11.5.

[0026] According to some embodiments of the present invention, the pH of the reaction is 9 to 11.

[0027] According to some embodiments of the present invention, the reaction temperature is 40°C to 90°C. For example, it can be 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C.

[0028] According to some embodiments of the present invention, the reaction temperature is 50°C to 85°C.

[0029] According to some embodiments of the present invention, the reaction time is 0.5h to 5h. For example, it can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.

[0030] According to some embodiments of the present invention, the reaction time is 0.7 to 3 hours.

[0031] According to some embodiments of the present invention, the reaction time is 0.9 to 2 hours.

[0032] According to some embodiments of the present invention, the solvent for the reaction includes water.

[0033] According to some embodiments of the present invention, the ratio of the mass of the solvent to the total mass of the reactive dye and tannin is 1 to 10:1. For example, it can be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10:1.

[0034] According to some embodiments of the present invention, the solution also includes a staining accelerator.

[0035] According to some embodiments of the present invention, the dyeing accelerator includes at least one selected from sodium chloride, ammonium chloride, sodium sulfate (sodium sulfate / glauber's salt), ammonium sulfate, sodium nitrate, and ammonium nitrate. Since the gallic acid on tannins dissociates into anions, it will electrostatically repel the anions dissociated from the sulfonates or carboxylates on reactive dyes, preventing them from approaching each other. The cations dissociated by the dyeing accelerator in water will adsorb around the anions, creating a charge shielding effect that reduces electrostatic repulsion, making it easier for the dye to adsorb onto the tannin surface for grafting reaction, thus increasing the dye grafting coloring rate.

[0036] According to some embodiments of the present invention, the amount of the dyeing accelerator added to the solution is 5–70 g / L. For example, it can be 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, 50 g / L, 55 g / L, 60 g / L, 65 g / L, or 70 g / L.

[0037] According to some embodiments of the present invention, the amount of the dyeing accelerator added to the solution is 10 to 60 g / L.

[0038] According to some embodiments of the present invention, the amount of the dyeing accelerator added to the solution is 15 to 50 g / L.

[0039] According to some embodiments of the present invention, the preparation method further includes post-reaction treatment.

[0040] According to some embodiments of the present invention, the post-reaction treatment includes purification.

[0041] According to some embodiments of the present invention, the purification includes ultrafiltration. The ultrafiltration has a molecular weight cutoff of greater than 1000 kDa; preferably greater than 1500 kDa; more preferably greater than 2000 kDa. This allows dyeing accelerators, unreacted reactive dyes, unreacted tannins, etc., to pass through the filter membrane, removing impurities and achieving purification.

[0042] According to some embodiments of the present invention, the preparation method includes: adjusting the pH of the solution using an alkaline substance.

[0043] According to some embodiments of the present invention, the alkaline substance includes at least one of organic bases and inorganic bases.

[0044] According to some embodiments of the present invention, the inorganic base includes at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium phosphate, and potassium phosphate.

[0045] According to some embodiments of the present invention, the organic base includes at least one selected from ethanolamine, triethanolamine, diethylamine, triethylamine, sodium methoxide, potassium ethoxide, 2-amino-2-methyl-1-propanol, potassium tert-butoxide, and sodium tert-butoxide.

[0046] A hyperbranched dye according to a second aspect of the present invention is prepared by the above-described preparation method.

[0047] Hyperbranched dyes according to embodiments of the present invention have at least the following beneficial effects:

[0048] The hyperbranched dyes described in this example exhibit advantages such as water resistance, light resistance, and ozone resistance. Their aqueous solutions have low viscosity, making them promising candidates for applications in inkjet inks and other fields. Furthermore, the polyphenolic structure of tannins acts as a natural antibacterial agent, free radical scavenger, and antioxidant, further enhancing the storage stability of the hyperbranched dyes.

[0049] According to some embodiments of the present invention, the solid content of the hyperbranched dye is 10% to 40%. For example, it can be 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0050] An inkjet ink according to a third aspect embodiment of the present invention includes hyperbranched dyes as described in the second aspect embodiment above. Since the inkjet ink employs all the technical solutions of the hyperbranched dyes described in the above embodiments, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments.

[0051] According to some embodiments of the present invention, the inkjet ink further includes additives and water.

[0052] According to some embodiments of the present invention, the additives include at least one of bactericides, wetting agents, humectants, penetrants, surface tension adjusters, pH adjusters, defoamers, adhesion promoters, and leveling agents.

[0053] According to some embodiments of the present invention, the inkjet ink comprises, by weight parts:

[0054] 20-85 parts water;

[0055] Additives: 0.1–30 parts;

[0056] 10 to 50 parts of the above-mentioned hyperbranched dyes.

[0057] According to some embodiments of the present invention, the solid content of the hyperbranched dye is 10% to 40%.

[0058] According to some embodiments of the present invention, the method for preparing the inkjet ink includes the following steps:

[0059] The inkjet ink is obtained by mixing the components.

[0060] According to some embodiments of the present invention, the method for preparing the inkjet ink further includes a post-mixing treatment. The post-mixing treatment includes filtration and degassing.

[0061] The application of the above-described hyperbranched dyes according to the fourth aspect of the present invention in the preparation of inkjet inks.

[0062] Application of the above-described hyperbranched dyes or inkjet inks in dyeing according to the fifth aspect of the present invention.

[0063] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Detailed Implementation

[0064] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0065] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0066] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0067] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (K is any number representing a multiplier). It is important to understand that, unlike the number of parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0068] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0069] In the embodiments of the present invention, the tannin has a purity of 80% and a molecular weight of 1701.2;

[0070] The purity of Reactive Blue 21 is 95%, and the molecular weight is 1079.6.

[0071] The purity of Reactive Blue 5 is 95%, and the molecular weight is 774.2.

[0072] The purity of Reactive Red 195 is 95%, and the molecular weight is 1136.3.

[0073] The purity of Reactive Red 180 is 95%, and the molecular weight is 933.8.

[0074] The purity of Active Yellow 17 is 95%, and the molecular weight is 682.8.

[0075] The purity of Active Yellow 2 is 95%, and the molecular weight is 873.0;

[0076] The purity of Active Black 31 is 95%, and the molecular weight is 1022.3.

[0077] Example 1

[0078] This example provides a hyperbranched dye (Reactive Blue 21 / tannin = 3.6 in molar ratio), and its preparation method is as follows:

[0079] In a reaction flask equipped with a reflux condenser, 19.0 g of Reactive Blue 21, 10 g of tannin, and 181.0 g of deionized water were mixed and stirred, then heated to 40°C to dissolve, yielding a premixed solution. Then, 5 g of sodium sulfate (approximately 27.6 g / L) was added and stirred for 30 min. Sodium hydroxide was added to adjust the pH to 10, and the mixture was heated to 60°C for dye grafting reaction. The reaction was carried out for 1 h to obtain an aqueous solution of hyperbranched dye. The hyperbranched dye aqueous solution was then concentrated and purified by ultrafiltration (molecular weight cutoff greater than 2000 kDa) to obtain a blue pigment paste containing hyperbranched dye (HBD1, solids concentration 12%).

[0080] Example 2

[0081] This example provides a hyperbranched dye (reactive blue 5 / tannin = 5.9 molar ratio), and its preparation method is as follows:

[0082] In a reaction flask equipped with a reflux condenser, 22.8 g of Reactive Blue 5, 10 g of tannin, and 57.2 g of deionized water were mixed and stirred. Potassium carbonate was added to adjust the pH to 10.5, and the mixture was heated to 80°C for dye grafting reaction. The reaction was carried out for 0.7 h to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by ultrafiltration (molecular weight cutoff greater than 2000 kDa) to obtain a blue pigment paste (HBD2, solids concentration 30%) containing hyperbranched dye.

[0083] Example 3

[0084] This example provides a hyperbranched dye (reactive red 195 / tannin = 11.9 molar ratio), and its preparation method is as follows:

[0085] In a reaction flask equipped with a reflux condenser, 66.8 g of Reactive Red 195, 10 g of tannin, and 663.2 g of deionized water were mixed and stirred. Sodium carbonate was added to adjust the pH to 10, and the mixture was heated to 60°C for dye grafting reaction. The reaction was carried out for 5 hours to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by ultrafiltration (molecular weight cutoff greater than 2000 kDa) to obtain a red pigment paste (HBD3, solids concentration 12%) containing hyperbranched dye.

[0086] Example 4

[0087] This example provides a hyperbranched dye (reactive red 180 / tannin = 5.9 molar ratio), and its preparation method is as follows:

[0088] In a reaction flask equipped with a reflux condenser, 27.4 g of Reactive Red 180, 10 g of tannin, and 172.6 g of deionized water were mixed and stirred. Sodium carbonate was added to adjust the pH to 9, and the mixture was heated to 60°C for dye grafting reaction. The reaction was carried out for 3 hours to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by ultrafiltration (molecular weight cutoff greater than 2000 kDa) to obtain a red pigment paste (HBD4, solids concentration 15%) containing hyperbranched dye.

[0089] Example 5

[0090] This example provides a hyperbranched dye (reactive yellow 17 / tannin = 8.3 molar ratio), and its preparation method is as follows:

[0091] In a reaction flask equipped with a reflux condenser, 28.1 g of Reactive Yellow 17, 10 g of tannin, and 271.9 g of deionized water were mixed and stirred. Sodium carbonate was added to adjust the pH to 10, and the mixture was heated to 50°C for dye grafting reaction. The reaction was carried out for 5 hours to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by ultrafiltration (molecular weight cutoff greater than 2000 kDa) to obtain a yellow pigment paste (HBD5, solids concentration 12%) containing hyperbranched dye.

[0092] Example 6

[0093] This example provides a hyperbranched dye (Molar ratio of Reactive Yellow 17 / Tannin = 7.1), and its preparation method is as follows:

[0094] In a reaction flask equipped with a reflux condenser, 30.8 g of Reactive Yellow 2, 10 g of tannin, and 269.2 g of deionized water were mixed and stirred. Sodium phosphate was added to adjust the pH to 8, and the mixture was heated to 70°C for dye grafting reaction. The reaction was carried out for 4 hours to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by passing it through an ultrafiltration membrane (molecular weight cutoff greater than 2000 kDa) to obtain a yellow pigment paste (HBD6, solids concentration 15%) containing hyperbranched dye.

[0095] Example 7

[0096] This example provides a hyperbranched dye (reactive black 31 / tannin = 11.9 molar ratio), and its preparation method is as follows:

[0097] In a reaction flask equipped with a reflux condenser, 60.1 g of Reactive Black 31, 10 g of tannin, and 439.9 g of deionized water were mixed and stirred. Sodium hydroxide was added to adjust the pH to 10.5, and the mixture was heated to 50°C for dye grafting reaction. The reaction was carried out for 2 hours to obtain an aqueous solution of hyperbranched dye. The aqueous solution of hyperbranched dye was then concentrated and purified by passing it through an ultrafiltration membrane (molecular weight cutoff greater than 2000 kDa) to obtain a black pigment paste (HBD7, solids concentration 15%) containing hyperbranched dye.

[0098] Comparative Example 1

[0099] This embodiment provides a hyperbranched dye (reactive blue 21 / tannin = 3.6 in molar ratio), the preparation method of which is basically the same as that in Example 1, except that the reaction condition pH is changed to 6, while other conditions remain unchanged.

[0100] The obtained hyperbranched dye aqueous solution was concentrated and purified by passing it through an ultrafiltration membrane (with a molecular weight cutoff greater than 2000 kDa), and a blue pigment paste (HBD1-CP1) was obtained after the same concentration time.

[0101] The color concentration ratio HBD1-CP1 / HBD1 was determined to be 17% using an X-Rite Ci7600 spectrophotometer.

[0102] The grafting rate of the dye was low due to an unsuitable reaction pH. Most of the dye was not grafted with tannins and was filtered out during ultrafiltration, resulting in a low color concentration in the pigment paste.

[0103] Comparative Example 2

[0104] This embodiment provides a hyperbranched dye (reactive blue 21 / tannin = 3.6 in molar ratio), the preparation method of which is basically the same as that in Example 1, except that the reaction temperature is changed to 25°C, while other conditions remain unchanged.

[0105] The obtained hyperbranched dye aqueous solution was concentrated and purified by passing it through an ultrafiltration membrane (with a molecular weight cutoff greater than 2000 kDa), and a blue pigment paste (HBD1-CP2) was obtained after the same concentration time.

[0106] The color concentration ratio HBD1-CP2 / HBD1 was determined to be 3% using an X-Rite Ci7600 spectrophotometer.

[0107] Due to unsuitable reaction temperature, the grafting rate of the dye was low. Most of the dye was not grafted with tannin and was filtered out during ultrafiltration, resulting in a low color concentration of the pigment paste.

[0108] Application Example 1

[0109] This application example provides an inkjet ink (INK1) with the following formulation:

[0110]

[0111] The theoretical content of Reactive Blue 21 in the blue pigment HBD1 is 3.6g.

[0112] This application example also provides a method for preparing the inkjet ink, the steps of which are as follows:

[0113] Mix all components thoroughly to obtain a semi-finished ink product; then pass the ink through a 0.45μm PP filter membrane and a 0.22μm PP filter membrane in sequence, and use a degassing membrane to remove air bubbles to obtain inkjet ink.

[0114] Application Example 2

[0115] This example provides an inkjet ink (INK2) with the following formula:

[0116]

[0117] The theoretical content of Reactive Blue 5 in the blue pigment HBD2 is 3.5g.

[0118] The preparation method of this inkjet ink is the same as in Application Example 1.

[0119] Application Example 3

[0120] This application example provides an inkjet ink (INK3) with the following formulation:

[0121]

[0122]

[0123] The theoretical content of Reactive Red 195 in the red pigment HBD3 is 3.6g.

[0124] The preparation method of this inkjet ink is the same as in Application Example 1.

[0125] Application Example 4

[0126] This application example provides an inkjet ink (INK4) with the following formulation:

[0127]

[0128] The theoretical content of Reactive Red 180 in the red pigment HBD4 is 3.6g, and the theoretical content of tannin is 1.3g. The preparation method of this inkjet ink is the same as in Application Example 1.

[0129] Application Example 5

[0130] This application example provides an inkjet ink (INK5) with the following formulation:

[0131]

[0132] The theoretical content of Active Yellow 17 in the yellow pigment HBD5 is 3.6g.

[0133] The preparation method of this inkjet ink is the same as in Application Example 1.

[0134] Application Example 6

[0135] This application example provides an inkjet ink (INK6) with the following formulation:

[0136]

[0137] The theoretical content of Active Yellow 2 in the yellow pigment HBD6 is 3.6g.

[0138] The preparation method of this inkjet ink is the same as in Application Example 1.

[0139] Application Example 7

[0140] This application example provides an inkjet ink (INK7) with the following formulation:

[0141]

[0142] The theoretical content of active black 31 in the black pigment HBD7 is 3.6g.

[0143] The preparation method of this inkjet ink is the same as in Application Example 1.

[0144] Application Comparative Example 1

[0145] This application example provides an inkjet ink (INK1-CP) with a formulation that is basically the same as that in application example 1, except that 46g of the blue pigment HBD1 in example 1 is replaced with 3.6g of Reactive Blue 21 and 42.4g of deionized water.

[0146] The preparation method of this inkjet ink is the same as in Application Example 1.

[0147] Application Comparative Example 2

[0148] This application example provides an inkjet ink (INK2-CP) with a formulation that is basically the same as that in application example 1, except that 17g of the blue pigment HBD2 in example 2 is replaced with 3.5g of Reactive Blue 5 and 13.5g of deionized water.

[0149] The preparation method of this inkjet ink is the same as in Application Example 1.

[0150] Application Comparative Example 3

[0151] This application example provides an inkjet ink (INK3-CP) with a formulation that is basically the same as that in application example 3, except that 34.5g of the red pigment HBD3 in example 3 is replaced with 3.6g of Reactive Red 195 and 30.9g of deionized water.

[0152] The preparation method of this inkjet ink is the same as in Application Example 1.

[0153] Application Comparative Example 4

[0154] This application example provides an inkjet ink (INK4-CP) with a formulation that is basically the same as that in application example 4, except that 33g of the red pigment HBD4 in example 4 is replaced with 3.6g of Reactive Red 180 and 29.4g of deionized water.

[0155] The preparation method of this inkjet ink is the same as in Application Example 1.

[0156] Application Comparative Example 5

[0157] This application example provides an inkjet ink (INK5-CP) with a formulation that is basically the same as that in application example 5, except that 41g of the yellow pigment HBD5 in example 5 is replaced with 3.6g of Reactive Yellow 17 and 37.4g of deionized water.

[0158] The preparation method of this inkjet ink is the same as in Application Example 1.

[0159] Application Comparative Example 6

[0160] This application example provides an inkjet ink (INK6-CP) with a formulation that is basically the same as that in application example 6, except that 32g of the yellow pigment HBD6 in example 6 is replaced with 3.6g of Reactive Yellow 2 and 28.4g of deionized water.

[0161] The preparation method of this inkjet ink is the same as in Application Example 1.

[0162] Application Comparative Example 7

[0163] This application example provides an inkjet ink (INK7-CP) with a formulation that is basically the same as that in application example 6, except that 28g of the black pigment HBD7 in example 7 is replaced with 3.6g of reactive black 31 and 24.4g of deionized water.

[0164] The preparation method of this inkjet ink is the same as in Application Example 1.

[0165] Application Comparative Example 8

[0166] This application example provides an inkjet ink (INK8-CP) with a formulation that is basically the same as that in application example 4, except that 33g of the red pigment HBD4 in example 4 is replaced with 3.6g of Reactive Red 180, 1.3g of tannin and 28.1g of deionized water.

[0167] The preparation method of this inkjet ink is the same as in Application Example 1.

[0168] Test case

[0169] This example tests the dyeing performance of the inkjet inks used in Examples 1-7 and Comparative Examples 1-8. The inkjet ink was scraped onto A4 80g plain paper using a No. 15 thread stick and allowed to stand for 24 hours until completely dry. The following tests were then conducted:

[0170] (1) Water resistance test: 1g of deionized water was added to the ink scraping strip. After drying, the color difference ΔE before and after the water drop was measured using an X-Rite Ci7600 spectrophotometer, and the relative water resistance improvement rate (%) was calculated. The formula for calculating the relative water resistance improvement rate is as follows:

[0171] Relative water resistance improvement rate = (△E0-△E1) / △E0×100%.

[0172] (2) Lightfastness Test: Six Philips TUVF17T8 UV-C lamps with wavelengths of 200-280nm were used. The lamps were placed 15cm away from the irradiated object, and the chamber temperature was 45±3℃. After 1 hour of exposure, the color difference ΔE before and after exposure was measured using an X-Rite Ci7600 spectrophotometer. The relative lightfastness improvement rate (%) was calculated. The formula for calculating the relative lightfastness improvement rate is as follows:

[0173] Relative lightfastness improvement rate = (△E0-△E1) / △E0×100%.

[0174] (3) Ozone resistance: Ozone concentration 250 PPhm, chamber temperature 25±3℃, chamber humidity 65±5%, chamber gas flow rate 8-16 mm / s, after 2 hours of exposure, the color difference ΔE before and after exposure was measured using an X-Rite Ci7600 spectrophotometer, and the relative ozone resistance improvement rate (%) was calculated. The formula for calculating the relative ozone resistance improvement rate is as follows:

[0175] Relative ozone resistance improvement rate = (△E0-△E1) / △E0×100%.

[0176] When calculating the relative improvement rate of water resistance, relative improvement rate of light resistance, and relative improvement rate of ozone resistance, △E1 represents Application Example 1, and △E0 represents Application Comparative Example 1; △E1 represents Application Example 2, and △E0 represents Application Comparative Example 2; △E1 represents Application Example 3, and △E0 represents Application Comparative Example 3; △E1 represents Application Example 4 or Application Comparative Example 8, and △E0 represents Application Comparative Example 4; △E1 represents Application Example 5, and △E0 represents Application Comparative Example 5; △E1 represents Application Example 6, and △E0 represents Application Comparative Example 6; △E1 represents Application Example 7, and △E0 represents Application Comparative Example 7.

[0177] The test results are shown in Table 1.

[0178] Table 1

[0179] Test Project Relative water resistance improvement rate Relative lightfastness improvement rate Relative ozone resistance improvement rate Application Example 1 68.90％ 41.50％ 56.40％ Application Example 2 72.30％ 42.70％ 54.30％ Application Example 3 66.80％ 32.10％ 40.80％ Application Example 4 67.10％ 31.80％ 41.70％ Application Example 5 76.60％ 41.20％ 52.90％ Application Example 6 77.20％ 43.60％ 50.70％ Application Example 7 73.60％ 44.90％ 55.20％ Application Comparative Example 8 2.30％ 24.30％ 32.80％

[0180] The hyperbranched dyes prepared in Examples 1-7 are far superior to those before hyperbranching in terms of lightfastness, waterfastness, and ozonefastness.

[0181] Given the same amount of Reactive Red 180 added, grafting Reactive Red 180 onto tannins yields significantly better results than adding tannins externally. This is likely because grafting Reactive Red 180 onto tannins restricts migration and improves water resistance; and the antioxidant and free radical scavenging capabilities of tannins enhance its light and ozone resistance.

[0182] The embodiments of the present invention have been described in detail above with reference to the examples. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A method for preparing a hyperbranched dye, characterized in that, Includes the following steps: A solution containing reactive dye and tannin is prepared and reacted at pH 8-11.5 and 40℃-90℃ to obtain the hyperbranched dye.

2. The preparation method according to claim 1, characterized in that, The reactive dyes include at least one of the following: reactive yellow dyes, reactive orange dyes, reactive red dyes, reactive purple dyes, reactive blue dyes, reactive green dyes, reactive brown dyes, and reactive black dyes.

3. The preparation method according to claim 2, characterized in that, The reactive yellow dye includes at least one of reactive yellow dyes 2, 3, 5, 13, 14, 15, 16, 17, 18, 37, 42, 57, 95, 145, 160, 167, and 186; And / or, the reactive orange dye includes at least one of reactive orange dyes 3, 5, 12, 13, 16, 72, 107, and 122; And / or, the reactive red dye includes at least one of reactive red dyes 3, 3:1, 15, 21, 24, 24:1, 31, 35, 43, 45, 106, 180, 194, 195, 198, 218, 222, 245, and 250; And / or, the reactive purple dye includes at least one of reactive purple dyes 1, 2, and 5; And / or, the reactive blue dye includes at least one of reactive blue dyes 5, 13, 15, 19, 21, 49, 71, 72, 74, 194, 223, and 231; And / or, the reactive green dye includes at least one of reactive green dyes 5, 8, and 35; And / or, the reactive brown dye includes at least one of reactive brown dyes 2, 11, and 18; And / or, the reactive black dye includes at least one of reactive black dyes 1, 5, 31, 39 or 45.

4. The preparation method according to claim 1, characterized in that, The reaction molar ratio of the reactive dye to tannin is 1~15:1; And / or, the reaction time is 0.5 h to 5 h.

5. The preparation method according to claim 1, characterized in that, The solution also includes a dyeing accelerator.

6. The preparation method according to claim 5, characterized in that, The dyeing accelerator includes at least one of sodium chloride, ammonium chloride, sodium sulfate, and ammonium sulfate; And / or, in the solution, the amount of the dyeing accelerator added is 5~70 g / L.

7. A hyperbranched dye, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 6.

8. An inkjet ink, characterized in that, Includes the hyperbranched dyes as described in claim 7.

9. The application of the hyperbranched dye according to claim 7 in the preparation of inkjet ink.

10. The application of the hyperbranched dye of claim 7 or the inkjet ink of claim 8 in dyeing.

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