A quick-drying water-based ink and preparation method thereof

Abstract

The invention discloses a quick-drying water-based ink and a preparation method thereof, and relates to the technical field of ink. The present invention first utilizes 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazine-2-amine and ethylene sulfonamide to participate in the polymerization reaction of acrylic acid and butyl acrylate, and obtains a core-shell structure modified polyester emulsion with 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazine-2-amine and ethylene sulfonamide as soft shells and acrylic acid and butyl acrylate as hard cores through a two-step emulsion polymerization method, thereby improving the wear resistance and durability of the ink. Then, allyl polyether is reacted with 2-(p-chlorophenyl) ethylene oxide to accelerate the drying time and improve the wear resistance of the ink; then, by reactant, bis(2-hydroxyethyl) dimethyl ammonium chloride and hydrogenated silicone oil addition reaction, a modified silicone oil leveling agent modified by epoxy-amino-polyether is formed, which has both hydrophilicity and hydrophobicity, accelerates the drying speed, and improves the wear-resistant effect.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, in particular to a quick-drying water-based ink and a preparation method thereof. Background Art

[0002] Traditional quick-drying inks are mainly composed of organic solvents, resins, pigments, and fillers. However, organic solvents may be harmful to human health, and there are also safety hazards such as volatile pollution, flammability, and explosion. It is necessary to seek environmentally friendly alternatives. Water-based, non-volatile, and low-volatile environmentally friendly organic solvents are gradually becoming a more ideal choice. At present, water-based acrylic resins are widely used as water-based ink binders. Although they have good gloss, adhesion, film-forming properties, and printability, the surfactants or hydrophilic groups introduced into the water-based system can easily make the printed products less resistant to water, steam, and stains. In particular, poor water resistance may cause the ink to fall off and spread when it comes into contact with water. Therefore, the modification of water-based acrylic resins is mainly aimed at improving their adhesion and water resistance.

[0003] Meanwhile, antimicrobial inks on the market are primarily achieved by adding antimicrobial agents, while durable inks improve their weather resistance and adhesion by optimizing ink formulations and production processes. However, these inks often have limitations, such as the potential for antimicrobial agents to affect other ink properties, the high cost of heat-resistant resins and pigments, the difficulty in optimizing ink formulations and production processes, and the limited ability of existing technologies to achieve the single antimicrobial, heat-resistant, and durable properties of inks. Therefore, there is an urgent need to develop a new type of antimicrobial, durable, and quick-drying water-based ink to address the limitations of existing technologies. Summary of the Invention

[0004] The purpose of the present invention is to provide a quick-drying water-based ink and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a quick-drying water-based ink, which mainly includes 30 to 40 parts of modified emulsion, 1.4 to 3.6 parts of modified silicone oil leveling agent, 0.6 to 1.4 parts of film-forming aid, 2 to 4 parts of wax slurry, 10 to 14 parts of pigment, 20 to 26 parts of ethanol, and 36 to 44 parts of deionized water.

[0006] Furthermore, the modified emulsion is prepared by a two-step emulsion polymerization method in which 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylene sulfonamide participate in the polymerization reaction of acrylic acid and butyl acrylate to form a core-shell structure.

[0007] Furthermore, the core-shell structure has 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylenesulfonamide as the soft shell, and acrylic acid and butyl acrylate as the hard core.

[0008] Furthermore, the modified silicone oil leveling agent is prepared by reacting allyl polyether with 2-(p-chlorophenyl)ethylene oxide to form a composite polyether, which is then reacted with bis(2-hydroxyethyl)dimethylammonium chloride and hydrogen-containing silicone oil.

[0009] Furthermore, a method for preparing a quick-drying water-based ink comprises the following steps:

[0010] 1.2-3.4 parts of Gemini emulsifier HL-03 and 84-136 parts of deionized water were mixed uniformly, 5-9 parts of acrylic acid and 14-26 parts of butyl acrylate were added, and the mixture was stirred at 800 rpm for 10-20 minutes. The rotation speed was adjusted to 200 rpm, and the temperature was raised to 80-90° C., 3-7 parts of initiator were added dropwise, and the mixture was reacted for 1-2 hours. Subsequently, 21-35 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and 18-30 parts of ethylenesulfonamide were added, and 6-10 parts of initiator were added. The mixture was reacted for 2-4 hours, and the mixture was cooled to 25° C. The pH of the solution was adjusted to 7-8 with a 2 mol / L sodium hydroxide aqueous solution to prepare a modified emulsion.

[0011] 8-12 parts of allyl polyether were degassed at 70°C and a vacuum degree of -0.06 MPa for 10-20 min, 0.4-0.6 parts of stannous chloride were added under nitrogen protection, 7-11 parts of 2-(p-chlorophenyl)ethylene oxide were added dropwise, and the mixture was stirred at 70°C and 160 rpm for 3-5 h. 75-115 parts of toluene were added, the temperature was lowered to 40°C, 16-22 parts of a 30% wt aqueous sodium hydroxide solution were added, stirring was continued for 2-4 h, 150-230 parts of deionized water were added, and the mixture was extracted twice. The organic phase was collected, the pH was adjusted to 6-7 with glacial acetic acid, and the mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 3-5 h to obtain a composite polyether.

[0012] 12-18 parts of composite polyether and 11-17 parts of hydrogenated silicone oil were mixed evenly, 1-3 parts of chloroplatinic acid aqueous solution were added under stirring at 55-65°C and 170 rpm, the temperature was raised to 90-100°C, the reaction was carried out for 1-3 hours, 10-16 parts of bis(2-hydroxyethyl)dimethylammonium chloride were added, the reaction was carried out for 2-4 hours, and the mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 3-5 hours to prepare a modified silicone oil leveling agent;

[0013] 30-40 parts of modified emulsion, 1.4-3.6 parts of modified silicone oil leveling agent, 0.6-1.4 parts of film-forming aid, 2-4 parts of wax slurry, 10-14 parts of pigment, 20-26 parts of ethanol and 36-44 parts of deionized water are mixed uniformly to prepare a quick-drying water-based ink.

[0014] Furthermore, the preparation step of the initiator in step (1) is as follows: 0.3 parts of ammonium persulfate, 0.4 parts of sodium bicarbonate, and 10 parts of deionized water are mixed uniformly to prepare the initiator.

[0015] Furthermore, the dripping rate in step (2) is 0.5 drops / s.

[0016] Furthermore, the content of chloroplatinic acid in the chloroplatinic acid aqueous solution in step (3) is 0.2 wt%.

[0017] Furthermore, the hydrogen-containing silicone oil in step (3) is any one of 202 high hydrogen-containing silicone oil, WS61M high hydrogen-containing silicone oil, and KF99 high hydrogen-containing silicone oil.

[0018] Furthermore, the film-forming aid in step (4) is of model Dynol960; and the wax slurry is of model AQUACER513.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The invention achieves the effects of quick drying, wear resistance, high temperature resistance and antibacterial by mixing the modified emulsion with the modified silicone oil leveling agent.

[0021] First, 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylene sulfonamide were used to participate in the polymerization reaction of acrylic acid and butyl acrylate. A core-shell structure modified emulsion with 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylene sulfonamide as soft shell and acrylic acid and butyl acrylate as hard core was prepared by two-step emulsion polymerization. The dense molecular structure makes it more difficult for surface water or solvent to penetrate into the interface between ink and substrate, slowing down the initial adhesion. The decrease of adhesion force significantly improves the wear resistance and durability of the ink; the thiazine group introduced by 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine has a lactam unit on the heterocyclic ring in the molecule, which is easy to form hydrogen bonds with other molecules, thereby improving the structural stability and achieving a wear-resistant effect; combined with the sulfonamide group, it improves the compatibility of the ink and the substrate, improves the wettability of the ink during the printing process, makes the ink more easily adhere to the substrate surface, and thus improves the drying speed and wear resistance of the ink.

[0022] Secondly, the modified silicone oil leveling agent uses the hydroxyl group of allyl polyether to react with the epoxy group in 2-(p-chlorophenyl) ethylene oxide to introduce phenyl groups, thereby improving thermal stability, reducing ink surface tension, improving anti-cratering ability, and increasing the slipperiness of the ink film, thereby improving the fluidity of the ink, making it easier for the ink to penetrate into the fiber gaps and speeding up the drying time. At the same time, the polyether chain segment can improve the hydrophilicity and antistatic properties of the silicone oil, and tightly and firmly combine with the amino, hydroxyl and other groups in the fiber in the form of chemical bonds, significantly improving the wear resistance of the ink; then the reactants, diisocyanate, (2-Hydroxyethyl)dimethylammonium chloride and hydrogenated silicone oil undergo an addition reaction to form an epoxy-amino-polyether modified silicone oil leveling agent, which has both hydrophilic and hydrophobic properties, improves wettability to materials, and accelerates drying speed; the chloride ions introduced by bis(2-hydroxyethyl)dimethylammonium chloride can form ionic bonds with cations in ink molecules, strengthening the binding force with fibers, further improving adhesion, and thus improving wear resistance. On this basis, the ammonium group can destroy bacterial cell walls and cell membranes, thereby killing the bacteria and achieving an antibacterial effect. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the quick-drying water-based ink prepared in the following examples.

[0025] Adhesion fastness: Take the same weight of the embodiment and the comparative example and evenly apply them on the test piece. After curing, test according to GB / T13217.7.

[0026] Initial drying properties: Take the same weight of the embodiment and the comparative example and test them according to GB / T 13217.5.

[0027] Viscosity: The same weight of the embodiment and the comparative example were tested according to GB / T 13217.4.

[0028] Antibacterial activity value: The same weight of the embodiment and the comparative example were evenly coated on a test piece. After curing, the antibacterial activity value of the ink against Staphylococcus aureus was tested according to the Japanese Industrial Standard JIS Z2801. Example 1

[0029] An initiator was prepared by mixing 0.3 parts of ammonium persulfate, 0.4 parts of sodium bicarbonate, and 10 parts of deionized water.

[0030] 1.2 parts of Gemini emulsifier HL-03 and 84 parts of deionized water were mixed evenly, 5 parts of acrylic acid and 14 parts of butyl acrylate were added, and the mixture was stirred at 800 rpm for 10 minutes. The rotation speed was adjusted to 200 rpm, and the temperature was raised to 80°C. 3 parts of initiator were added dropwise at a rate of 0.5 drops / s, and the mixture was reacted for 1 hour. Subsequently, 21 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and 18 parts of ethylenesulfonamide were added, and 6 parts of initiator were added. The mixture was reacted for 2 hours, and the mixture was cooled to 25°C. The pH of the solution was adjusted to 7 with a 2 mol / L sodium hydroxide aqueous solution to prepare a modified emulsion.

[0031] 8 parts of allyl polyether were vacuum degassed at 70°C and a vacuum degree of -0.06 MPa for 10 min, 0.4 parts of stannous chloride were added under nitrogen protection, 7 parts of 2-(p-chlorophenyl)ethylene oxide were added dropwise, and the mixture was stirred at 70°C and 160 rpm for 3 h. 75 parts of toluene were added, the temperature was lowered to 40°C, 16 parts of a 30% wt aqueous sodium hydroxide solution were added, and the mixture was stirred for 2 h. 150 parts of deionized water were added, and the mixture was extracted twice. The organic phase was collected, the pH was adjusted to 6 with glacial acetic acid, and the mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 3 h to obtain a composite polyether.

[0032] 12 parts of composite polyether and 11 parts of 202 high hydrogen silicone oil were mixed evenly, and 1 part of 0.2 wt% chloroplatinic acid aqueous solution was added under stirring at 55°C and 170 rpm. The temperature was raised to 90°C and the reaction was continued for 1 hour. 10 parts of bis(2-hydroxyethyl)dimethylammonium chloride were added and the reaction was continued for 2 hours. The mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 3 hours to prepare a modified silicone oil leveling agent.

[0033] 30 parts of modified emulsion, 1.4 parts of modified silicone oil leveling agent, 0.6 parts of Dynol960 film-forming aid, 2 parts of AQUACER513 wax paste, 10 parts of pigment, 20 parts of ethanol and 36 parts of deionized water were mixed uniformly to prepare a quick-drying water-based ink. Example 2

[0034] An initiator was prepared by mixing 0.3 parts of ammonium persulfate, 0.4 parts of sodium bicarbonate, and 10 parts of deionized water.

[0035] 2.3 parts of Gemini emulsifier HL-03 and 110 parts of deionized water were mixed evenly, 7 parts of acrylic acid and 20 parts of butyl acrylate were added, and the mixture was stirred at 800 rpm for 15 minutes. The rotation speed was adjusted to 200 rpm, and the temperature was raised to 85°C. 5 parts of initiator were added dropwise at a rate of 0.5 drops / s, and the reaction was continued for 1.5 hours. Subsequently, 28 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and 24 parts of ethylenesulfonamide were added, and 8 parts of initiator were added. The reaction was continued for 3 hours, and the mixture was cooled to 25°C. The pH of the solution was adjusted to 7.5 with a 2 mol / L sodium hydroxide aqueous solution to prepare a modified emulsion.

[0036] 10 parts of allyl polyether were vacuum degassed at 70°C and a vacuum degree of -0.06 MPa for 15 minutes, 0.5 parts of stannous chloride were added under nitrogen protection, 9 parts of 2-(p-chlorophenyl)ethylene oxide were added dropwise, and the mixture was stirred at 70°C and 160 rpm for 4 hours. 95 parts of toluene were added, the temperature was lowered to 40°C, 19 parts of a 30% wt aqueous sodium hydroxide solution were added, and the mixture was stirred for 3 hours. 190 parts of deionized water were added, and the mixture was extracted twice. The organic phase was collected, the pH was adjusted to 6.5 with glacial acetic acid, and the mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 4 hours to obtain a composite polyether.

[0037] 15 parts of composite polyether and 14 parts of WS61M high hydrogen silicone oil were mixed evenly, and 2 parts of 0.2 wt% chloroplatinic acid aqueous solution were added under stirring at 60°C and 170 rpm. The temperature was raised to 95°C and the reaction was carried out for 2 hours. 13 parts of bis(2-hydroxyethyl)dimethylammonium chloride were added and the reaction was carried out for 3 hours. The mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 4 hours to prepare a modified silicone oil leveling agent.

[0038] 35 parts of modified emulsion, 2.5 parts of modified silicone oil leveling agent, 1.0 part of Dynol960 film-forming aid, 3 parts of AQUACER513 wax paste, 12 parts of pigment, 23 parts of ethanol and 40 parts of deionized water were mixed uniformly to prepare a quick-drying water-based ink. Example 3

[0039] An initiator was prepared by mixing 0.3 parts of ammonium persulfate, 0.4 parts of sodium bicarbonate, and 10 parts of deionized water.

[0040] 3.4 parts of Gemini emulsifier HL-03 and 136 parts of deionized water were mixed evenly, 9 parts of acrylic acid and 26 parts of butyl acrylate were added, and the mixture was stirred at 800 rpm for 20 minutes. The rotation speed was adjusted to 200 rpm, and the temperature was raised to 90°C. 7 parts of initiator were added dropwise at a rate of 0.5 drops / s, and the mixture was reacted for 2 hours. Subsequently, 35 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and 30 parts of ethylenesulfonamide were added, and 10 parts of initiator were added. The mixture was reacted for another 4 hours, and the mixture was cooled to 25°C. The pH of the solution was adjusted to 8 with a 2 mol / L sodium hydroxide aqueous solution to prepare a modified emulsion.

[0041] 12 parts of allyl polyether were vacuum degassed at 70°C and a vacuum degree of -0.06 MPa for 20 minutes. Under nitrogen protection, 0.6 parts of stannous chloride were added, and 11 parts of 2-(p-chlorophenyl)ethylene oxide were added dropwise. The mixture was stirred at 70°C and 160 rpm for 5 hours. 115 parts of toluene were added, the temperature was lowered to 40°C, 22 parts of a 30% wt aqueous sodium hydroxide solution were added, and stirring was continued for 4 hours. 230 parts of deionized water were added, and the mixture was extracted twice. The organic phase was collected, the pH was adjusted to 7 with glacial acetic acid, and the mixture was concentrated at 35°C and a vacuum degree of -0.08 MPa for 5 hours to obtain a composite polyether.

[0042] 18 parts of composite polyether and 17 parts of KF99 high hydrogen silicone oil were mixed evenly, 3 parts of 0.2 wt% chloroplatinic acid aqueous solution were added under stirring at 65°C and 170 rpm, the temperature was raised to 100°C, the reaction was continued for 3 hours, 16 parts of bis(2-hydroxyethyl)dimethylammonium chloride were added, the reaction was continued for 4 hours, and the mixture was concentrated at 35°C and vacuum degree of -0.08 MPa for 5 hours to prepare a modified silicone oil leveling agent;

[0043] 40 parts of modified emulsion, 3.6 parts of modified silicone oil leveling agent, 1.4 parts of Dynol960 film-forming aid, 4 parts of AQUACER513 wax paste, 14 parts of pigment, 26 parts of ethanol and 44 parts of deionized water were mixed uniformly to prepare a quick-drying water-based ink.

[0044] Comparative Example 1

[0045] The difference between Comparative Example 1 and Example 2 lies in step (2). Step (2) is modified as follows: 2.3 parts of Gemini emulsifier HL-03 and 110 parts of deionized water are mixed uniformly, 7 parts of acrylic acid and 20 parts of butyl acrylate are added, and the mixture is stirred at 800 rpm for 15 min. The rotation speed is adjusted to 200 rpm, the temperature is raised to 85°C, 5 parts of initiator are added dropwise at a rate of 0.5 drops / s, the reaction is carried out for 1.5 h, 52 parts of ethylene sulfonamide are subsequently added, 8 parts of initiator are added, the reaction is continued for 3 h, the mixture is cooled to 25°C, and the pH of the solution is adjusted to 7.5 with a 2 mol / L sodium hydroxide aqueous solution to obtain a modified emulsion. The remaining steps are the same as those in Example 2.

[0046] Comparative Example 2

[0047] The difference between Comparative Example 2 and Example 2 lies in the difference in step (2). Step (2) is modified as follows: 2.3 parts of Gemini emulsifier HL-03 and 110 parts of deionized water are mixed uniformly, 7 parts of acrylic acid and 20 parts of butyl acrylate are added, and the mixture is stirred at 800 rpm for 15 min. The rotation speed is adjusted to 200 rpm, the temperature is raised to 85°C, 5 parts of initiator are added dropwise at a rate of 0.5 drops / s, and the reaction is carried out for 1.5 h. Subsequently, 52 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine are added, 8 parts of initiator are added, the reaction is continued for 3 h, the mixture is cooled to 25°C, and the pH of the solution is adjusted to 7.5 with a 2 mol / L sodium hydroxide aqueous solution to obtain a modified emulsion. The remaining steps are the same as those in Example 2.

[0048] Comparative Example 3

[0049] The difference between Comparative Example 3 and Example 2 lies in the difference in step (2). Step (2) is changed to: 2.3 parts of Gemini emulsifier HL-03 and 110 parts of deionized water are mixed evenly, 7 parts of acrylic acid, 20 parts of butyl acrylate, 28 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine, and 24 parts of ethylenesulfonamide are added, and the mixture is stirred at 800 rpm for 15 min. The rotation speed is adjusted to 200 rpm, the temperature is raised to 85°C, 13 parts of initiator are added dropwise at a rate of 0.5 drops / s, the reaction is carried out for 4.5 hours, the mixture is cooled to 25°C, and the pH of the solution is adjusted to 7.5 with a 2 mol / L sodium hydroxide aqueous solution to obtain a modified emulsion. The remaining steps are the same as those in Example 2.

[0050] Comparative Example 4

[0051] Comparative Example 4 differs from Example 2 in that step (3) is omitted, and step (4) is modified as follows: 15 parts of allyl polyether and 14 parts of WS61M high hydrogen silicone oil are uniformly mixed, 2 parts of a 0.2 wt% chloroplatinic acid aqueous solution are added under stirring at 60°C and 170 rpm, the temperature is raised to 95°C, the reaction is carried out for 2 h, 13 parts of bis(2-hydroxyethyl)dimethylammonium chloride are added, the reaction is carried out for 3 h, and the mixture is concentrated at 35°C and a vacuum degree of -0.08 MPa for 4 h to obtain a modified silicone oil leveling agent. The remaining steps are the same as those in Example 2.

[0052] Comparative Example 5

[0053] The difference between Comparative Example 5 and Example 2 lies in step (4), which is modified as follows: 15 parts of the composite polyether and 14 parts of WS61M high hydrogen silicone oil are mixed uniformly, 2 parts of a 0.2 wt% chloroplatinic acid aqueous solution are added under stirring at 60°C and 170 rpm, the temperature is raised to 95°C, the reaction is carried out for 2 h, and the mixture is concentrated at 35°C and a vacuum degree of -0.08 MPa for 4 h to obtain a modified silicone oil leveling agent. The remaining steps are the same as those in Example 2.

[0054] Comparative Example 6

[0055] The difference between Comparative Example 6 and Example 2 lies in step (4), which is modified as follows: 14 parts of WS61M high hydrogen silicone oil are placed in a container, 2 parts of a 0.2 wt% chloroplatinic acid aqueous solution are added under stirring at 60°C and 170 rpm, the temperature is raised to 95°C, 13 parts of bis(2-hydroxyethyl)dimethylammonium chloride are added, the reaction is carried out for 3 hours, and the mixture is concentrated at 35°C and a vacuum degree of -0.08 MPa for 4 hours to obtain a modified silicone oil leveling agent. The remaining steps are the same as those in Example 2.

[0056] Effect Examples

[0057] Table 1 below shows the performance analysis results of the quick-drying water-based inks of Examples 1 to 3 of the present invention and Comparative Examples 1 to 6.

[0058] Table 1

[0059]

[0060] From the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 1, it can be found that the thiazine group introduced by using 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine has a lactam unit on the heterocyclic ring in the molecule, which is easy to form hydrogen bonds with other molecules, thereby improving the structural stability and achieving a wear-resistant effect; from the comparison of the experimental data of Examples 1, 2, and 3 with those of Comparative Example 2, it can be found that the sulfonamide group is introduced by using ethylenesulfonamide, which improves the compatibility of the ink with the substrate and improves the lubricity of the ink during printing. The wettability makes it easier for the ink to adhere to the surface of the substrate, thereby improving the drying speed and wear resistance of the ink; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 3, it can be found that the core-shell structure modified emulsion with 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylenesulfonamide as the soft shell and acrylic acid and butyl acrylate as the hard core is prepared by a two-step emulsion polymerization method. The dense molecular structure makes it more difficult for surface water or solvent to penetrate into the interface between the ink and the substrate, slowing down the decline in initial adhesion, and significantly improving the wear resistance of the ink. The ink wear resistance and durability are significantly improved; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 4, it can be found that the introduction of phenyl groups by 2-(p-chlorophenyl)ethylene oxide improves thermal stability, reduces ink surface tension, enhances anti-cratering ability, and increases the slipperiness of the ink film, thereby improving the fluidity of the ink, making it easier for the ink to penetrate into the fiber gaps and accelerating the drying time; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 5, it can be found that the chloride ions introduced by bis(2-hydroxyethyl)dimethylammonium chloride can form ionic bonds with cations in the ink molecules, enhance the binding force with the fibers, further improve the adhesion, and thus improve the wear resistance. On this basis, the ammonium group can destroy the bacterial cell wall and cell membrane, thereby killing the bacteria and achieving an antibacterial effect; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 6, it can be found that the polyether segment can improve the hydrophilicity and antistatic properties of the silicone oil, and tightly and firmly combine with amino, hydroxyl and other groups in the fiber in the form of chemical bonds, thereby significantly improving the wear resistance of the ink.

[0061] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A quick-drying water-based ink, characterized in that: The quick-drying water-based ink mainly comprises, by weight, 30 to 40 parts of modified emulsion, 1.4 to 3.6 parts of modified silicone oil leveling agent, 0.6 to 1.4 parts of film-forming aid, 2 to 4 parts of wax slurry, 10 to 14 parts of pigment, 20 to 26 parts of ethanol, and 36 to 44 parts of deionized water; The modified emulsion is prepared by a two-step emulsion polymerization method in which 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylene sulfonamide participate in the polymerization reaction of acrylic acid and butyl acrylate to form a core-shell structure. The core-shell structure is composed of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and ethylenesulfonamide as a soft shell and acrylic acid and butyl acrylate as a hard core; The modified silicone oil leveling agent is prepared by reacting allyl polyether with 2-(p-chlorophenyl)ethylene oxide to form a composite polyether, which is then reacted with bis(2-hydroxyethyl)dimethylammonium chloride and hydrogen-containing silicone oil.

2. A method for preparing a quick-drying water-based ink, characterized in that: The method comprises the following preparation steps: (1) 1.2~3.4 parts of Gemini emulsifier HL-03 and 84~136 parts of deionized water were mixed evenly, 5~9 parts of acrylic acid and 14~26 parts of butyl acrylate were added, stirred at 800 rpm for 10~20 min, the speed was adjusted to 200 rpm, the temperature was raised to 80~90 ° C, 3~7 parts of initiator were added dropwise, and the reaction was carried out for 1~2 h, followed by the addition of 21~35 parts of 4,6-bis(allyloxy)-n-butyl-1,3,5-thiazin-2-amine and 18~30 parts of ethylenesulfonamide, 6~10 parts of initiator, and the reaction was continued for 2~4 h, cooled to 25 ° C, and the pH of the solution was adjusted to 7~8 with a 2 mol / L sodium hydroxide aqueous solution to obtain a modified emulsion; (2) 8-12 parts of allyl polyether were degassed at 70°C and vacuum degree of -0.06 MPa for 10-20 min. Under nitrogen protection, 0.4-0.6 parts of stannous chloride were added, and 7-11 parts of 2-(p-chlorophenyl)ethylene oxide were added dropwise. The mixture was stirred at 70°C and 160 rpm for 3-5 h. 75-115 parts of toluene were added, and the temperature was lowered to 40°C. 16-22 parts of 30% wt sodium hydroxide aqueous solution were added, and the mixture was stirred for 2-4 h. 150-230 parts of deionized water were added, and the mixture was extracted twice. The organic phase was taken, and the pH was adjusted to 6-7 with glacial acetic acid. The mixture was concentrated at 35°C and vacuum degree of -0.08 MPa for 3-5 h to obtain a composite polyether. (3) 12-18 parts of composite polyether and 11-17 parts of hydrogenated silicone oil were mixed evenly, 1-3 parts of chloroplatinic acid aqueous solution were added under stirring at 55-65°C and 170 rpm, the temperature was raised to 90-100°C, the reaction was continued for 1-3 hours, 10-16 parts of bis(2-hydroxyethyl)dimethylammonium chloride were added, the reaction was continued for 2-4 hours, and the mixture was concentrated at 35°C and vacuum degree of -0.08 MPa for 3-5 hours to obtain a modified silicone oil leveling agent; (4) 30-40 parts of modified emulsion, 1.4-3.6 parts of modified silicone oil leveling agent, 0.6-1.4 parts of film-forming aid, 2-4 parts of wax slurry, 10-14 parts of pigment, 20-26 parts of ethanol, and 36-44 parts of deionized water are mixed evenly to prepare a quick-drying water-based ink.

3. The method for preparing a quick-drying water-based ink according to claim 2, wherein: The preparation step of the initiator in step (1) is as follows: 0.3 parts of ammonium persulfate, 0.4 parts of sodium bicarbonate, and 10 parts of deionized water are mixed evenly to prepare the initiator.

4. The method for preparing a quick-drying water-based ink according to claim 2, wherein: The dripping rate in step (2) is 0.5 drops / s.

5. The method for preparing a quick-drying water-based ink according to claim 2, wherein: The content of chloroplatinic acid in the chloroplatinic acid aqueous solution in step (3) is 0.2 wt %.

6. The method for preparing a quick-drying water-based ink according to claim 2, wherein: The hydrogen-containing silicone oil in step (3) is any one of 202 high hydrogen-containing silicone oil, WS61M high hydrogen-containing silicone oil, and KF99 high hydrogen-containing silicone oil.

7. The method for preparing a quick-drying water-based ink according to claim 2, wherein: The film-forming aid model in step (4) is Dynol960; the wax slurry model is AQUACER513.

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