High-stability cold transfer printing active ink, preparation method thereof and cold transfer printing and dyeing process

Abstract

The invention provides high-stability cold transfer printing active ink, a preparation method thereof and a cold transfer printing and dyeing process. The cold transfer printing active ink comprises an active mixed dye, wherein the active mixed dye comprises a metal complex type active dye, a P type active dye and a double-active-group dye; wherein the metal complex type reactive dye comprises one of a copper complex dye, a chromium complex dye, a cobalt complex dye, a nickel complex dye and a vanadium complex dye, and the P type reactive dye comprises a phosphonic acid group. The active group of the double-active-group dye is composed of two of monochlorotriazine, vinyl sulfone, halogenated pyrimidine active group, quinoxaline active group and alpha-bromo acrylamide active group. The cold transfer printing active ink disclosed by the invention has high stability while ensuring high fixation rate.

Description

Technical Field

[0001] The invention relates to the field of inkjet printing ink preparation, and in particular to a high-stability cold transfer active ink and a preparation method thereof, and a cold transfer printing and dyeing process. Background Art

[0002] Traditional reactive ink printing and dyeing requires processes such as steaming and washing. Multiple washing steps not only waste water resources, but the dye wastewater washed out will also have an impact on the environment.

[0003] To better align with environmental protection and energy conservation, transfer printing has emerged as a new printing technology. It primarily involves heat transfer and cold transfer printing. Heat transfer printing primarily uses disperse dyes on polyester fabrics. Cold transfer printing has been a research hotspot in recent years, with improvements in equipment and processes now allowing printing on cotton fabrics. Compared to traditional printing processes, cold transfer printing eliminates the need for steaming and washing, effectively reducing the discharge of colored wastewater.

[0004] However, cold transfer printing technology is not yet fully mature, and there are still challenges to be solved when applying cold transfer printing to cotton fabrics or cotton-polyester blends. Because the cold transfer printing process eliminates the steaming process and allows the reactive dye to react with cellulose at room temperature, this process places higher demands on the fixation rate of the reactive dye.

[0005] Currently, most research focuses on increasing the number of reactive dye groups to enhance their reaction with cellulose, thereby improving color fixation. While this approach can improve color fastness, the presence of multiple reactive groups can also pose ink stability issues: dyes with multiple active sites are more susceptible to hydrolysis during ink storage, leading to abnormally high conductivity and even the risk of printhead crystallization. Furthermore, a high density of reactive groups can trigger self-condensation of dye molecules, forming larger colloidal particles and increasing the risk of printhead clogging.

[0006] Therefore, solving the stability problem of cold transfer reactive ink has become an important research direction. Summary of the Invention

[0007] The first object of the present invention is to provide a highly stable cold transfer active ink, which is used to solve the problem that the existing cold transfer active ink has a high color fixation rate but poor stability.

[0008] The second object of the present invention is to provide a method for preparing a cold transfer active ink, which is used to prepare the above-mentioned high-stability cold transfer active ink.

[0009] The third object of the present invention is to provide a cold transfer printing and dyeing process, which is achieved by using the above-mentioned high-stability cold transfer reactive ink.

[0010] To achieve the first object of the present invention, a high-stability cold transfer reactive ink of the present invention includes reactive mixed dyes, and the reactive mixed dyes include metal complex type reactive dyes, P type reactive dyes and double reactive base dyes.

[0011] As can be seen from the above scheme, the reactive mixed dye includes three different types of reactive groups with differentiated reaction kinetics. The intermolecular charge-removal effect and steric hindrance can inhibit the aggregation and precipitation of the reactive dyes, thus giving the reactive ink long-term stability. Furthermore, the metal complex dye reduces the hydrolysis loss of the reactive dye during the dyeing process through coordination, while the phosphonic acid group of the P-type reactive dye is not easily hydrolyzed. These properties all contribute to improving the ink's color fixation rate and stability. In addition, the dual-reactive group reactive dye has high reactivity and can quickly react with the fiber, which helps enhance the ink's color fixation rate. However, due to its large molecular weight and rapid reaction rate, the dye cannot penetrate the fiber interior, resulting in uneven coloring. Therefore, the metal complex dye with a smaller molecular weight and slower reaction rate and the P-type reactive dye are combined to avoid the uneven coloring caused by excessive reaction. More importantly, the combination of the three dyes forms a multidimensional cross-linked network of "ester bond + covalent bond + coordination bond", which significantly improves the binding strength of the dye to the fiber, reduces the dye hydrolysis ratio and polycondensation, and makes the cold transfer reactive ink of the present invention highly stable while ensuring high color fixation rate.

[0012] A further solution is that the metal complex reactive dye includes one of a copper complex dye, a chromium complex dye, a cobalt complex dye, a nickel complex dye and a vanadium complex dye, the P-type reactive dye includes a phosphonic acid group, and the double reactive group dye includes two of a monochlorotriazine, a vinyl sulfone, a halogenated pyrimidine reactive group, a quinoxaline reactive group and an α-bromoacrylamide reactive group; wherein the double reactive group dye also includes a water-soluble group, and the water-soluble group is selected from one or more of a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an amide group, an amino group and an imino group.

[0013] As can be seen from the above scheme, the active groups of the dual active groups are selected from two of monochlorotriazine, vinyl sulfone, halogenated pyrimidine active groups, quinoxaline active groups and α-bromoacrylamide active groups, and have high reaction activity; the active dye contains a water-soluble group, which makes the active dye more water-soluble, further avoiding the probability of nozzle clogging during printing due to poor water solubility.

[0014] A further solution is that, by mass percentage, the cold transfer reactive ink contains 1% to 5% of metal complex reactive dye, 1% to 5% of P type reactive dye and 5% to 10% of double reactive base dye.

[0015] Preferably, the cold transfer reactive ink comprises, by mass percentage, 1% to 5% of a metal complex reactive dye, 1% to 3% of a P-type reactive dye, and 8% to 10% of a double reactive base dye.

[0016] It can be seen from the above scheme that under the above ratio, the printing color vividness of the cold transfer active ink of the present invention and the stability of the ink itself reach a balance point, with excellent color development and color fixation rate. Under this ratio, the cross-linking reaction of the active groups of the three can be avoided. The synergistic effect of the three makes the ink more stable, the color fixation rate better, and the color fastness higher.

[0017] In a further embodiment, the cold transfer active ink further comprises a pH adjuster, wherein the pH adjuster comprises an alkaline adjuster and an acidic adjuster. The alkaline pH adjuster comprises at least one of triethanolamine, diethanolamine, monoethanolamine, 2-aminoethanol, phosphate, sodium tartrate, and sodium citrate; and the acidic pH adjuster comprises at least one of acetic acid, formic acid, citric acid, tartaric acid, oxalic acid, ammonium sulfate, and ammonium chloride. By weight, the cold transfer active ink comprises 0.5% to 0.7% of the acidic adjuster and 0.3% to 0.5% of the alkaline adjuster.

[0018] As can be seen from the above scheme, the pH value of the cold transfer active ink can be controlled within a certain range by using the pH regulator in the above content, thereby inhibiting the hydrolysis of the active mixed dye, thereby ensuring the stability and fixation rate of the ink.

[0019] A further solution is that the cold transfer active ink also includes a chelating agent, which is at least one of an aminocarboxylic acid chelating agent, an organic phosphonic acid chelating agent, a hydroxycarboxylic acid chelating agent, a polyphosphate chelating agent and a polycarboxylic acid chelating agent. In terms of mass percentage, the cold transfer active ink contains 0.08% to 0.1% of the chelating agent.

[0020] A further embodiment is that the chelating agent is preferably at least one of glutamic acid diacetic acid tetrasodium salt, aminotriacetic acid trisodium salt, diethylenetriamine pentaacetic acid pentasodium salt, ethylenediamine tetramethylene phosphonate sodium, diethylenetriamine pentamethylene phosphonate sodium, triethylenetetraamine hexamethylene phosphonate sodium, and bis(1,6-hexylene)triamine pentamethylene phosphonate sodium.

[0021] As can be seen from the above scheme, chelating agents can form stable water-soluble complexes with calcium and magnesium ions in water, preventing these ions from reacting with reactive dyes or other ingredients to form precipitates, thereby improving the stability and fluidity of the ink. The above-mentioned chelating agents are alkaline compounds. When added in excessive amounts, they can exceed the capacity of the pH buffer system, leading to an increase in pH. This increased pH triggers hydrolysis of the reactive dyes, affecting the stability of the ink. Within the above-mentioned content, the chelating agent will not exceed the capacity of the pH buffer system and will not affect the stability of the ink.

[0022] A further solution is that the cold transfer active ink further includes a surfactant, which is a non-ionic surfactant. Calculated by mass percentage, the cold transfer active ink contains 1% to 3% of the surfactant.

[0023] Preferably, the surfactant is selected from nonionic surfactants containing ethoxy chains, such as acetylenic glycol ethoxy compounds and / or polyethylene glycol octylphenyl ether compounds.

[0024] As can be seen from the above scheme, the acetylene glycol ethoxylate can reduce dynamic surface tension, making it suitable for rapid substrate wetting during high-speed printing. The structure of polyethylene glycol octylphenyl ether gives it stronger interfacial adsorption capacity, which helps prevent stratification during long-term ink storage. The synergistic effect of these two compounds can better maintain ink stability. Within the above surfactant content range, excellent ink stability and appropriate surface tension are achieved.

[0025] A further solution is that, by mass percentage, the cold transfer active ink includes 10% to 15% of active mixed dye, 0.5% to 1% of pH adjuster, 0.08% to 0.1% of chelating agent, 1% to 3% of surfactant, 30% to 50% of organic solvent, 0.5% to 1% of auxiliary agent and the balance water; the cation content in the active mixed dye does not exceed 20 ppm, and the anion content does not exceed 100 ppm; the conductivity of the cold transfer active ink is 2.3 mS / cm to 2.8 mS / cm, and the pH value is 6 to 6.5.

[0026] Preferably, the cold transfer active ink has a conductivity of 2.3 mS / cm to 2.5 mS / cm and a pH value of 6 to 6.3.

[0027] It can be seen from the above scheme that under the above ratio, the ink can maintain stability for a long time. After the purification operation, the cation content of the reactive mixed dye does not exceed 20ppm, and the anion content does not exceed 100ppm. The reactive dyes within this range have high purity and low salt content, which avoids the formation of crystals due to excessive salt content, further improving the stability of the ink. Cold transfer reactive ink is not prone to chemical changes and precipitation under the above conductivity, which helps to ensure smooth printing and long-term preservation of the ink. The ink within the above pH range is weakly acidic. Under weakly acidic conditions, it can effectively inhibit the hydrolysis of the reactive dye, thereby improving the stability and color fixation rate of the ink.

[0028] To achieve the second purpose of the present invention, a method for preparing a cold transfer active ink of the present invention is used to prepare a high-stability cold transfer active ink described in any of the above schemes, and the preparation method comprises the following steps: S1: mixing an organic solvent, a surfactant, a chelating agent, an auxiliary agent and the remainder of water according to mass percentage to obtain a first mixed solution, stirring at a speed of 800 rpm to 1000 rpm for 20 min to 40 min until the first mixed solution becomes clear and transparent; at the same time, slowly adding an acidic pH regulator dropwise to the first mixed solution during the stirring process to adjust the pH of the first mixed solution. The pH value of the liquid is increased to 4-5; S2: adding the active mixed dye paste to the first mixed solution to obtain a second mixed solution, and stirring at a speed of 2000-3000 rpm for 20-40 minutes to make the particle size of the active mixed dye in the active mixed dye paste ≤200 nm. The active mixed dye paste is prepared by mixing the active mixed dye and water; at the same time, adding an alkaline pH regulator to the second mixed solution in three batches during the stirring process until the pH value of the second mixed solution reaches 6-6.5; S3: filtering the uniformly stirred second mixed solution through a filter membrane to obtain a cold transfer active ink.

[0029] Preferably, the filter membrane is a 0.3 μm filter membrane.

[0030] As can be seen from the above scheme, the active ink is first prepared as a base solution, then an acidic pH adjuster is added to adjust the solution to acidity. The reactive mixed dye is then added in an acidic environment, preventing hydrolysis of the reactive mixed dye during the preparation process. Finally, an alkaline pH adjuster buffer is used to adjust the active ink to a slightly acidic environment, preventing overly acidic ink from corroding the printhead and increasing production and maintenance costs.

[0031] A further solution is that the active mixed dye paste in step S2 is an active mixed dye paste that has undergone a purification operation, and the purification operation steps include: first, adding activated carbon to the active mixed dye paste to remove oil and impurities, then using food-grade macroporous weak acid sodium resin to remove calcium ions and magnesium ions, and finally using an ultrafiltration membrane to filter chloride ions, sulfate ions and phosphate ions to obtain the active mixed dye paste that has undergone a purification operation.

[0032] It can be seen from the above scheme that after the above purification steps, the ion content, impurities and oily substances contained in the reactive mixed dye are greatly reduced, which helps to stabilize the ink and reduces the differences between different production batches of dyes.

[0033] To achieve the third purpose of the present invention, a cold transfer printing and dyeing process of the present invention is implemented using a high-stability cold transfer active ink described in any of the above schemes. The cold transfer printing and dyeing process includes the following steps: spraying the cold transfer active ink onto a cold transfer film and waiting for drying to form an ink layer; laminating the ink layer to the pretreated fabric, applying a pressure of 0.2MPa to 0.4MPa, and pressing for 10s to 30s; then cold stacking and fixing at room temperature for 12h to 24h, and then washing and drying to complete the process.

[0034] As can be seen from the above scheme, the above cold transfer printing and dyeing process is simple to operate and the obtained fabric has bright colors. DETAILED DESCRIPTION

[0035] The high-stability cold transfer active ink provided by the present invention comprises, by mass percentage, 10% to 15% of active mixed dye, 0.5% to 1% of pH regulator, 0.08% to 0.1% of chelating agent, 1% to 3% of surfactant, 30% to 50% of organic solvent, 0.5% to 1% of auxiliary agent and the balance of water.

[0036] The reactive mixed dye includes a metal complex reactive dye, a P-type reactive dye, and a double reactive group dye; the metal complex reactive dye includes one of a copper complex dye, a chromium complex dye, a cobalt complex dye, a nickel complex dye, and a vanadium complex dye; the P-type reactive dye includes a phosphonic acid group; the reactive group of the double reactive group dye is composed of two of a monochloro-s-triazine, a vinyl sulfone, a halogenated pyrimidine reactive group, a quinoxaline reactive group, and an α-bromoacrylamide reactive group; the double reactive group dye also includes a water-soluble group, wherein the water-soluble group is selected from at least one of a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an amide group, an amino group, and an imino group. In terms of mass percentage, the cold transfer reactive ink contains 1% to 5% of the metal complex reactive dye, 1% to 5% of the P-type reactive dye, and 5% to 10% of the double reactive group dye. Preferably, in terms of mass percentage, the cold transfer reactive ink contains 1% to 5% of the metal complex reactive dye, 1% to 3% of the P-type reactive dye, and 8% to 10% of the double reactive group dye.

[0037] Among them, metal complex type reactive dyes can be purchased from Clariant's Savinyl Yellow RLSN, SavinylRed RLSN, Savinyl Black RLSN 01, Savinyl Blue RS, BASF's BASF Orasol Blue 825 / GN, BASF Orasol Black X55 / RLI, BASF Orasol Red 471, Runba's Ranbar Black D51-V, Ranbar Red D330, Ranbar Red D363; P-type reactive dyes were purchased from Jiangsu Jinji Industrial Co., Ltd., including reactive yellow PF-6GS, reactive yellow P-SN, reactive orange PG, and reactive red PB; dual-reactive base dyes were purchased from Jiangsu Jinji Industrial Co., Ltd., including reactive red 245, Shanghai Dyeing and Chemical Factory No. 8, reactive blue M-BR, reactive red M-3BE, Shanghai Wonder's reactive red B-3BF, reactive yellow B-4RFN, domestic dyes KE type, domestic dyes KP type, domestic dyes KD type, Yongguang HE type, Korean Jingren HL type, Archroma Drimarene K series, and DyStar Levafix EA series.

[0038] The pH regulator is selected from an acidic pH regulator and an alkaline pH regulator, wherein the alkaline pH regulator is selected from at least one of triethanolamine, diethanolamine, monoethanolamine, 2-aminoethanol, phosphate, sodium tartrate and sodium citrate, and the acidic pH regulator is selected from at least one of acetic acid, formic acid, citric acid, tartaric acid, oxalic acid, ammonium sulfate and ammonium chloride. In terms of mass percentage, the cold transfer active ink includes 0.5% to 0.7% of the acidic pH regulator and 0.3% to 0.5% of the alkaline pH regulator.

[0039] The chelating agent is at least one of an aminocarboxylic acid chelating agent, an organic phosphonic acid chelating agent, a hydroxycarboxylic acid chelating agent, a polyphosphate chelating agent, and a polycarboxylic acid chelating agent, and is preferably selected from tetrasodium glutamate diacetate, trisodium aminotriacetate, pentasodium diethylenetriaminepentaacetate, sodium ethylenediaminetetramethylenephosphonate, sodium diethylenetriaminepentamethylenephosphonate, sodium triethylenetetraaminehexamethylenephosphonate, and sodium bis(1,6-hexylene)triaminepentamethylenephosphonate. The cold transfer active ink contains 0.08% to 0.1% of the chelating agent by mass.

[0040] The surfactant is a nonionic surfactant, preferably a nonionic surfactant containing an ethoxy chain, more preferably an acetylene glycol ethoxylate and / or a polyethylene glycol octylphenyl ether compound. The cold transfer active ink contains 1% to 3% of the surfactant by mass. The acetylene glycol ethoxylate is selected from one of Surfynol 465, Surfynol 485, Dynol 604, Dynol 607, and ZY-1440, and the polyethylene glycol octylphenyl ether compound is selected from one of Triton X-100, Triton X-114, OP-10, and Triton X-705. Preferably, the acetylene glycol ethoxylate is Surfynol 465 purchased from Air Products, Inc., and the polyethylene glycol octylphenyl ether surface compound is Triton X-100 purchased from The Dow Chemical Company.

[0041] The organic solvent is selected from at least one of ethylene glycol, propylene glycol and glycerol.

[0042] The auxiliary agent includes an antibacterial agent, and the antibacterial agent is selected from one of Preventol D7, PROXEL GXL, and Kasong.

[0043] The method for preparing the high-stability cold transfer active ink of the present invention comprises the following steps:

[0044] S1: Mixing 30% to 50% of an organic solvent, 1% to 3% of a surfactant, 0.08% to 0.1% of a chelating agent, 0.5% to 1% of an auxiliary agent, and the balance of water to obtain a first mixed solution, and stirring the mixture at a speed of 800 rpm to 1000 rpm for 20 min to 40 min until the first mixed solution becomes clear and transparent;

[0045] At the same time, slowly adding 0.5% to 0.7% of an acidic regulator to the first mixed solution during stirring to adjust the pH of the first mixed solution to 4 to 5;

[0046] S2: adding a reactive mixed dye paste to the first mixed solution to obtain a second mixed solution, stirring the mixture at a speed of 2000 to 3000 rpm for 20 to 40 minutes to adjust the particle size of the reactive mixed dye in the reactive mixed dye paste to ≤ 200 nm. The reactive mixed dye paste is prepared by mixing the reactive mixed dye and water;

[0047] At the same time, adding 0.5% to 1% of an alkaline regulator to the second mixed solution in three batches during the stirring process until the pH of the second mixed solution reaches 6 to 6.5;

[0048] S3: Filter the uniformly stirred second mixed solution through a 0.3 μm filter membrane to obtain a cold transfer active ink.

[0049] Among them, the active mixed dye paste in step S2 is an active mixed dye paste that has undergone a purification operation, and the steps of the purification operation include: first, adding activated carbon to the active mixed dye paste to remove oil and impurities, then using food-grade macroporous weak acid sodium resin to remove calcium ions and magnesium ions, and finally using an ultrafiltration membrane to filter chloride ions, sulfate ions and phosphate ions to obtain the active mixed dye paste that has undergone a purification operation.

[0050] The specific steps for removing calcium and magnesium ions are as follows: Soak a food-grade macroporous weakly acidic sodium resin (such as D113) in deionized water for 24 hours to allow it to fully swell. Then, alternately soak the resin in 4% to 5% HCl solution and 2% to 5% NaOH solution for 4 to 8 hours to remove residual organic impurities and adjust the resin to the sodium form. Finally, rinse with deionized water until the pH is neutral (6-7). The pretreated resin is loaded into an ion exchange column, and a reactive dye solution is passed through the column at 5-10 mL / min, allowing the calcium and magnesium ions in the solution to exchange with the sodium ions on the resin. Adsorption can be stopped when the effluent conductivity approaches that of the raw water.

[0051] The reactive mixed dye in the cold transfer reactive ink prepared by the above method has a cation content of no more than 20 ppm and an anion content of no more than 100 ppm. The cold transfer reactive ink has an electrical conductivity of 2.3 mS / cm to 2.8 mS / cm and a pH of 6 to 6.5. More preferably, the cold transfer reactive ink has an electrical conductivity of 2.3 mS / cm to 2.5 mS / cm and a pH of 6 to 6.3.

[0052] The high-stability cold transfer reactive ink of the present invention can be used in a cold transfer printing and dyeing process, which comprises the following steps:

[0053] The cold transfer active ink is sprayed onto the cold transfer film and dried to form an ink layer;

[0054] Laminating the ink layer to the pretreated fabric, applying a pressure of 0.2MPa to 0.4MPa, and pressing for 10s to 30s, wherein the pretreated fabric can be cotton, polyester-cotton blended fabric, etc.;

[0055] Then, after cold-stacking at room temperature for 12 to 24 hours, washing and drying are completed.

[0056] The present invention is described in detail below with reference to Examples and Comparative Examples.

[0057] Cold transfer active ink was prepared according to the mass percentage in Table 1 below using the above-mentioned cold transfer active ink preparation method.

[0058] Table 1

[0059]

[0060]

[0061] Prepare the cold transfer active ink according to the mass percentages in Table 2 and Table 3 below.

[0062] Table 2

[0063]

[0064]

[0065] Table 3

[0066]

[0067]

[0068] It should be noted that Comparative Examples 1 to 6, 8, and 9 were prepared by the above-mentioned cold transfer active ink preparation method, and Comparative Example 7 was prepared by the following method:

[0069] S1: Mixing 30% to 50% of an organic solvent, 1% to 3% of a surfactant, 0.08% to 0.1% of a chelating agent, 0.5% to 1% of an auxiliary agent, and the balance of water to obtain a first mixed solution, and stirring the mixture at a speed of 800 rpm to 1000 rpm for 20 min to 40 min until the first mixed solution becomes clear and transparent;

[0070] S2: adding a reactive mixed dye paste to the first mixed solution to obtain a second mixed solution, and stirring the mixture at a speed of 2000 to 3000 rpm for 20 to 40 minutes to adjust the particle size of the reactive mixed dye in the reactive mixed dye paste to ≤ 200 nm. The reactive mixed dye paste is prepared by mixing the reactive mixed dye and water and undergoing a purification operation;

[0071] At the same time, during the stirring process, 0.5% to 0.7% of an acidic pH regulator is slowly added dropwise to the second mixed solution to adjust the pH of the first mixed solution to 4 to 5; then 0.5% to 1% of the acidic pH regulator is added in three batches until the pH of the second mixed solution is finally adjusted to 6 to 6.5;

[0072] S3: The uniformly stirred second mixed solution is filtered through a 0.3 μm filter membrane to obtain the cold transfer active ink of Comparative Example 7.

[0073] The cold transfer reactive inks of the above examples and comparative examples were subjected to performance tests.

[0074] 1. Physical and chemical parameters

[0075] (1) pH

[0076] Use a PHS-3C precision pH meter, insert its composite electrode into the ink to be tested, stir the ink to make it uniform, and when the value displayed on the instrument is stable, the value is the pH value of the ink.

[0077] (2) Conductivity

[0078] Use the Leici DDS-307 conductivity meter and immerse its electrode in the ink to be tested. When the value displayed by the instrument is stable, the value is the conductivity of the ink.

[0079] (3) Viscosity

[0080] Use a Brookfield digital viscometer. Inject 0.5ml to 1ml of ink sample into the sample cup of the viscometer, taking care to avoid creating bubbles. Then slowly immerse the rotor in the sample. Connect the viscometer to the water bath circulation system. After the sample temperature stabilizes, start the measurement and record the measured readings.

[0081] 2. Stability test

[0082] (1) Standby performance test

[0083] After the high-intensity printing test is completed, under the conditions of an ambient temperature of 18℃ to 30℃ and a humidity of 50% to 80%, turn off the inkjet and wait for 24 hours before continuing to print and test the mesh status.

[0084] (2) Printing fluency test

[0085] Under the conditions of ambient temperature of 18℃~30℃ and humidity of 50%~80%, test the mesh status after continuous printing for 2000m.

[0086] (3) Storage stability test

[0087] Store the ink for one year at an ambient temperature of 18°C to 30°C. Test the ink viscosity before and after one year of storage. A viscosity change rate of less than 5% is considered acceptable.

[0088] 3. Determination of dye fixation rate and color fastness to rubbing

[0089] The dye fixation rate is determined according to GB / T 2391-2024 “Determination of the fixation rate of reactive dyes”; the color fastness to rubbing of fabrics is determined according to GB / T3920-2008 “Textiles—Tests for color fastness—Color fastness to rubbing”.

[0090] The test results of physical and chemical parameters are shown in Table 4 below.

[0091] Table 4

[0092]

[0093]

[0094] The stability test results are shown in Table 5 below.

[0095] Table 5

[0096]

[0097]

[0098]

[0099] It should be noted that the conductivity of the ink in Comparative Example 9 is too high, and printing can easily damage the digital printing nozzle, so relevant tests on printing performance are not performed.

[0100] The test results of dye fixation rate and color fastness to rubbing are shown in Table 6.

[0101] Table 6

[0102]

[0103]

[0104] As can be seen from above-mentioned Table 4 to Table 6, Comparative Example 1 has only added double reactive base dyes compared with Example 2, Comparative Example 2 does not add P type reactive dyes compared with Example 1, Comparative Example 3 does not add metal complex type reactive dyes compared with Example 1, the addition of double reactive base dyes in Comparative Example 4 exceeds proportional range compared with Example 3, Comparative Example 5 does not add alkaline regulator compared with Example 1, Comparative Example 6 does not add acid regulator compared with Example 1, Comparative Example 7 directly adjusts pH value after reactive mixed dyes prior to other components mixing, Comparative Example 8 exceeds proportional range compared with the addition of chelating agent in Example 1, and Comparative Example 9 is not purified compared with the reactive dyes in Example 1. These comparative examples perform all not as well as embodiment in performance test. The present invention is by composite three kinds of reactive dyes, i.e. metal complex reactive dyes, double reactive base dyes and P type dyes, and the reactive groups of these three kinds of dyes repel each other, avoid cross-linking reaction between dyestuff and produce the larger micelle of particle diameter, strengthen the stability of ink. More importantly, metal complex reactive dyes and P-type dyes are not prone to hydrolysis reaction. In combination with bireactive group reactive dyes, a multidimensional cross-linked network of "ester bond+covalent bond+coordinate bond" is formed, thereby improving the bonding strength of dye and fiber and improving color fixation rate. Further, reactive dyes are purified so that the cation amount of reactive dyes is less than 20ppm and the anion amount is less than 100ppm. Under this content, the stability of the active ink is excellent. By pH adjusting agent, the pH of the ink is adjusted to weak acidity. Under weak acidity, the reactive dyes are not prone to hydrolysis, which indirectly increases the number of active groups while improving the stability of the ink. Moreover, the metal complex reactive dyes develop color more vividly under acidic conditions. In addition, the effect of adding a chelating agent is to react with the ions in the reactive ink to form a stable chelate, thereby reducing the probability that the reactive dyes react with these impurity ions to generate a precipitation, effectively enhancing the stability and fluidity of the ink. Finally, the preparation method of the present invention is optimized to effectively suppress the hydrolysis of the reactive dyes and further enhance the stability of the ink.

[0105] The above are only specific embodiments of the present application, but the scope of protection of the present application is not limited thereto. Any person skilled in the art can easily conceive of various modifications or substitutions within the technical scope disclosed in this application, and such modifications or substitutions should be included in the scope of protection of the present application. Therefore, the scope of protection of the present application should be based on the scope of protection of the claims.

Claims

1. A highly stable cold transfer reactive ink, characterized by: The cold transfer reactive ink comprises reactive mixed dyes, wherein the reactive mixed dyes comprise metal complex type reactive dyes, P type reactive dyes and double reactive base dyes.

2. The high-stability cold transfer active ink according to claim 1, characterized in that: The metal complex type reactive dye comprises one of a copper complex dye, a chromium complex dye, a cobalt complex dye, a nickel complex dye and a vanadium complex dye; the P type reactive dye comprises a phosphonic acid group; the reactive group of the double reactive group dye comprises two of a monochloro-s-triazine, a vinyl sulfone, a halogenated pyrimidine reactive group, a quinoxaline reactive group and an α-bromoacrylamide reactive group; The dual-reactive group dye further comprises a water-soluble group, and the water-soluble group is selected from at least one of a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an amide group, an amine group, and an imino group.

3. The high-stability cold transfer active ink according to claim 1, characterized in that: Calculated by mass percentage, the cold transfer reactive ink contains 1% to 5% of the metal complex reactive dye, 1% to 5% of the P type reactive dye and 5% to 10% of the double reactive base dye.

4. A high-stability cold transfer active ink according to any one of claims 1 to 3, characterized in that: The cold transfer active ink further includes a pH regulator, wherein the pH regulator includes an alkaline pH regulator and an acidic pH regulator, wherein the alkaline pH regulator includes at least one of triethanolamine, diethanolamine, monoethanolamine, 2-aminoethanol, phosphate, sodium tartrate and sodium citrate, and the acidic pH regulator includes at least one of acetic acid, formic acid, citric acid, tartaric acid, oxalic acid, ammonium sulfate and ammonium chloride; Calculated by mass percentage, the cold transfer active ink includes 0.5% to 0.7% of the acidic pH regulator and 0.3% to 0.5% of the alkaline pH regulator.

5. The high-stability cold transfer active ink according to any one of claims 1 to 3, characterized in that: The cold transfer active ink also includes a chelating agent, which includes at least one of an aminocarboxylic acid chelating agent, an organic phosphonic acid chelating agent, a hydroxycarboxylic acid chelating agent, a polyphosphate chelating agent and a polycarboxylic acid chelating agent. In terms of mass percentage, the cold transfer active ink contains 0.08% to 0.1% of the chelating agent.

6. A high-stability cold transfer active ink according to any one of claims 1 to 3, characterized in that: The cold transfer active ink further includes a surfactant, which is a nonionic surfactant. Calculated by mass percentage, the cold transfer active ink contains 1% to 3% of the surfactant.

7. A high-stability cold transfer active ink according to any one of claims 1 to 3, characterized in that: The cold transfer active ink comprises, by mass percentage, 10% to 15% of active mixed dye, 0.5% to 1% of pH regulator, 0.08% to 0.1% of chelating agent, 1% to 3% of surfactant, 30% to 50% of organic solvent, 0.5% to 1% of auxiliary agent and the balance of water; The cation content of the reactive mixed dye does not exceed 20ppm, and the anion content does not exceed 100ppm; The cold transfer active ink has an electrical conductivity of 2.3 mS / cm to 2.8 mS / cm and a pH value of 6 to 6.

5.

8. A method for preparing a cold transfer active ink, characterized in that: The preparation method is used to prepare a high-stability cold transfer active ink as described in any one of claims 1 to 7, and the preparation method comprises the following steps: S1: mixing an organic solvent, a surfactant, a chelating agent, an auxiliary agent and the balance water according to mass percentage to obtain a first mixed solution, and stirring at a speed of 800 rpm to 1000 rpm for 20 min to 40 min until the first mixed solution becomes clear and transparent; Simultaneously, during the stirring process, an acidic pH regulator is added dropwise to the first mixed solution to adjust the pH of the first mixed solution to 4-5; S2: adding a reactive mixed dye paste to the first mixed solution to obtain a second mixed solution, and stirring the mixture at a speed of 2000 to 3000 rpm for 20 to 40 minutes to adjust the particle size of the reactive mixed dye in the reactive mixed dye paste to ≤ 200 nm. The reactive mixed dye paste is prepared by mixing the reactive mixed dye and water. At the same time, adding an alkaline pH regulator to the second mixed solution in batches during the stirring process until the pH of the second mixed solution reaches 6 to 6.5; S3: Filtering the uniformly stirred second mixed solution through a filter membrane to obtain the cold transfer active ink.

9. The method for preparing a cold transfer active ink according to claim 8, wherein: The reactive mixed dye paste in step S2 is a reactive mixed dye paste that has been purified, and the purification steps include: First, activated carbon is added to the active mixed dye paste to remove oil and impurities, then food-grade macroporous weak acid sodium resin is used to remove calcium ions and magnesium ions, and finally, chloride ions, sulfate ions and phosphate ions are filtered out using an ultrafiltration membrane to obtain a purified active mixed dye paste.

10. A cold transfer printing and dyeing process, characterized in that: The cold transfer printing and dyeing process is implemented using a high-stability cold transfer reactive ink as described in any one of claims 1 to 7, and the cold transfer printing and dyeing process comprises the following steps: The cold transfer active ink is sprayed onto the cold transfer film and dried to form an ink layer; Lay the ink layer on the pretreated fabric, apply a pressure of 0.2MPa to 0.4MPa, and press for 10s to 30s; Then, after cold-stacking at room temperature for 12 to 24 hours, washing and drying are completed.

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