Aqueous ink and method for its preparation
Patent Information
- Application Number
- CN202611272858.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-21
- Publication Date
- 2026-10-27
AI Technical Summary
[0003]然而，当细菌在水性油墨中繁殖时，会消耗油墨中的成分，并产生代谢物，这会直接导致油墨的pH值迅速下降，进而破坏整个体系的稳定性，直观的表现就是油墨出现发臭、结块、产生沉淀、粘度异常变化等问题，最终无法使用，且变质的油墨和发霉的印刷品可能会释放出有害物质或霉菌孢子，对操作工人的健康构成潜在威胁，同时也对环境不友好，这与水性油墨主打的环保、安全理念背道而驰，因此，本申请介绍了一种具有抗菌性能的水性油墨
本发明在制备水性油墨时，将1,3,5-三氨基苯和2,5-二羟基对苯二甲醛在二氧化硅表面反应再与DOPO反应，最后与锌离子配合，制得抗菌二氧化硅；将2-甲基-2-碘乙基丙烯酸酯和N,N-二甲基-3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-辛胺反应，再与甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟丙酯、甲基丙烯酸羟乙酯聚合，制得聚丙烯酸酯乳液；将抗菌二氧化硅、聚丙烯酸酯乳液、颜料、润湿分散剂DISPERBYK-181、磷酸三丁酯混合，制得水性油墨。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of water-based ink technology, specifically to a water-based ink and its preparation method. Background Technology
[0002] Water-based inks use water as the main solvent. Their main components include inorganic or organic pigments, rosin or acrylic resins, and various additives such as defoamers, dispersants, leveling agents, and stabilizers. Due to their environmentally friendly, safe, and non-toxic properties, water-based inks are widely used in many fields. In the paper printing industry, water-based inks have good adhesion to absorbent materials such as paper and cardboard, and are widely used in products such as books, brochures, newspapers, and corrugated boxes. In the textile printing industry, water-based printing technology is suitable for various materials such as cotton, polyester, and blended fabrics, and has the characteristics of strong color coverage and soft hand feel.
[0003] However, when bacteria multiply in water-based inks, they consume the ink's components and produce metabolites. This directly leads to a rapid drop in the ink's pH value, thereby disrupting the stability of the entire system. The most obvious manifestations are that the ink develops a foul odor, clumps, produces sediment, and exhibits abnormal viscosity changes, ultimately rendering it unusable. Furthermore, deteriorated inks and moldy printed materials may release harmful substances or mold spores, posing a potential threat to the health of operators and being environmentally unfriendly. This contradicts the environmentally friendly and safe principles that water-based inks emphasize. Therefore, this application introduces a water-based ink with antibacterial properties. Summary of the Invention
[0004] The purpose of this invention is to provide a water-based ink and its preparation method to solve the problems existing in the prior art.
[0005] A water-based ink, wherein the water-based ink is prepared by mixing antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181, and tributyl phosphate; The antibacterial silica is prepared by reacting 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde on the surface of silica, then reacting it with DOPO, and finally combining it with zinc ions. The polyacrylate emulsion is prepared by reacting 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine, followed by polymerization with methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, and hydroxyethyl methacrylate.
[0006] A method for preparing a water-based ink, the method mainly comprising the following preparation steps: (1) Zinc acetate and deionized water are mixed evenly at a mass ratio of 1:14~16 to obtain zinc acetate solution; modified silica is immersed in zinc acetate solution for 14~16h, filtered, washed with deionized water 3~5 times, and vacuum dried at -5~0℃ for 24~26h to obtain antibacterial silica. (2) Mix acrylate monomer, emulsifier, sodium bicarbonate and deionized water in a mass ratio of 48~52:3~4:0.1:28~32 and stir at room temperature for 40~60 min to obtain pre-emulsified polyacrylate; stir 1 / 3 of the pre-emulsified polyacrylate at 78~82℃ and 200~300 r / min for 3~5 min, add ammonium persulfate at 0.004~0.006 times the mass of acrylate monomer and continue stirring for 4~6 min, add the remaining 2 / 3 of the pre-emulsified polyacrylate at a uniform rate over 40~50 min, continue stirring for 180~200 min, add ammonium persulfate at 0.008~0.012 times the mass of acrylate monomer, continue stirring for 8~10 min, cool to room temperature, and adjust the pH to 7~8 with ammonia water to obtain polyacrylate emulsion; (3) Antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181 and tributyl phosphate are mixed evenly in a mass ratio of 1:8~10:2~3:0.22~0.26:0.16~0.2 to obtain water-based ink.
[0007] As an optimization, the modified silica in step (1) is prepared by mixing pre-modified silica, DOPO and THF in a mass ratio of 1:0.8~0.9:14~16, heating to 63~67℃ at 200~300r / min, stirring for 4~5h, cooling to room temperature, filtering, washing with ethanol 3~5 times, and vacuum drying at -5~0℃ for 24~26h.
[0008] As an optimization, the pre-modified silica is prepared by mixing 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde in a molar ratio of 2:3, adding 10 to 12 times the mass of 1,3,5-triaminobenzene in ethanol and an equal mass of 1,3,5-triaminobenzene in silica, heating to 73 to 77°C at 200 to 300 r / min under nitrogen protection, stirring for 4 to 5 hours, cooling to room temperature, filtering, washing 3 to 5 times with deionized water, and vacuum drying at -5 to 0°C for 24 to 26 hours.
[0009] As an optimization, the silica is silica with a particle size of 200~300nm.
[0010] As an optimization, the modified acrylate monomer in step (2) is prepared by mixing 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tetrafluoro-1-octylamine in a molar ratio of 1:1, adding acetonitrile in 18 to 22 times the mass of 2-methyl-2-iodoethyl-2-acrylate, stirring at 50 to 55°C and 200 to 300 r / min for 15 to 16 h, and then vacuum drying at room temperature for 24 to 26 h.
[0011] As an optimization, the acrylate monomer in step (2) is prepared by mixing methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, and modified acrylate monomer in a mass ratio of 30~34:23~25:6~8:2~3:1~1.5:6~8.
[0012] As an optimization, the emulsifier in step (2) is prepared by mixing alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1:1.
[0013] As an optimization, the pigments in step (3) are phthalocyanine blue, phthalocyanine green, phthalocyanine red, etc.
[0014] As an optimization, the reaction mechanism of modified silica is as follows:
[0015]
[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing water-based inks, this invention involves reacting 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde on a silica surface, followed by a reaction with DOPO, and finally combining with zinc ions to obtain antibacterial silica. 2-Methyl-2-iodoethyl acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tetrafluoro-1-octylamine are reacted, and then polymerized with methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, and hydroxyethyl methacrylate to obtain a polyacrylate emulsion. The antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181, and tributyl phosphate are mixed to obtain the water-based ink.
[0017] First, 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde are reacted on a silica surface, then reacted with DOPO, and finally combined with zinc ions to prepare antibacterial silica. The reaction of 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde on a silica surface creates a cross-linked network structure rich in imine bonds on the nano-silica surface. These imine bonds can react with DOPO, and the attached phosphate esters can decompose at high temperatures to generate phosphorus-containing free radicals, efficiently capturing hydrogen and hydroxyl free radicals in the combustion chain reaction, interrupting the combustion chain reaction. Simultaneously, the phosphoric acid substances generated at high temperatures catalyze the dehydration of the polyacrylate matrix in the ink to form carbon, creating a stable heat-insulating and oxygen-barrier carbon layer on the material surface. This reduces heat and oxygen exchange between the matrix and the external environment, enhancing the flame retardant ability of the ink. Finally, combined with zinc ions, the zinc ions in the ink can bind to the negatively charged bacterial cell membrane, altering the permeability of the bacterial cell membrane, causing leakage of cell contents, directly damaging the bacterial structure, and enhancing the antibacterial ability of the ink.
[0018] Next, 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine are reacted, and then polymerized with methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, and hydroxyethyl methacrylate to obtain a polyacrylate emulsion; antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181, and tributyl phosphate are mixed to obtain a water-based ink; through the reaction of 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro- The reaction of 1-octylamine introduces both fluorine and quaternary ammonium salt into the ink. Fluorine, being the most electronegative element, has a high CF bond energy, which reduces the surface energy of the material and effectively blocks moisture penetration, giving the ink good water resistance. Furthermore, the high CF bond energy makes it extremely difficult to break, making it difficult for the molecular chain to undergo pyrolysis and produce flammable volatiles, further enhancing the flame retardancy of the ink. At the same time, the introduction of quaternary ammonium salt, with its positively charged groups, can strongly adsorb the negatively charged bacterial cell wall surface through electrostatic force. Simultaneously, the hydrophobic alkyl chain can also insert into the lipid bilayer of the cell membrane, altering membrane permeability and causing intracellular enzymes, coenzymes, and metabolites to leak out, initiating cell lysis, thereby enhancing the antibacterial ability of the ink. Detailed Implementation
[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0020] The silica used in the following examples and comparative examples is silica with a particle size of 300 nm; the pigment used is phthalocyanine blue. Example
[0021] A method for preparing a water-based ink mainly includes the following steps: (1) Mix 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde in a molar ratio of 2:3, add 10 times the mass of ethanol of 1,3,5-triaminobenzene and an equal mass of silica of 1,3,5-triaminobenzene, heat to 73°C at 200 r / min under nitrogen protection, stir for 4 h, cool to room temperature, filter, wash 3 times with deionized water, and vacuum dry at 0°C for 24 h to obtain pre-modified silica; combine pre-modified silica, DOPO and T HF was mixed at a mass ratio of 1:0.8:14, heated to 63℃ at 200 r / min, stirred for 4 h, cooled to room temperature, filtered, washed three times with ethanol, and vacuum dried at -5℃ for 24 h to obtain modified silica; zinc acetate and deionized water were mixed evenly at a mass ratio of 1:14 to obtain zinc acetate solution; the modified silica was immersed in zinc acetate solution for 14 h, filtered, washed three times with deionized water, and vacuum dried at 0℃ for 24 h to obtain antibacterial silica; (2) 2-Methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine were mixed in a molar ratio of 1:1, and acetonitrile was added in 18 times the mass of 2-methyl-2-iodoethyl-2-acrylate. The mixture was stirred at 50°C and 200 r / min for 15 h, and then vacuum dried at room temperature for 24 h to obtain the modified acrylate monomer. Methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, and the modified acrylate monomer were mixed evenly in a mass ratio of 30:23:6:2:1:6 to obtain the acrylate monomer. Alkylphenol polyoxyethylene ether and sodium dodecyl sulfate were mixed evenly. The emulsifier was prepared by mixing the acrylate monomer, emulsifier, sodium bicarbonate and deionized water at a mass ratio of 1:1. The mixture was stirred at room temperature for 40 min to prepare pre-emulsified polyacrylate. One-third of the pre-emulsified polyacrylate was stirred at 78℃ and 200 r / min for 3 min. Ammonium persulfate with a mass ratio of 0.004 times that of the acrylate monomer was added and stirring was continued for 4 min. The remaining two-thirds of the pre-emulsified polyacrylate was added uniformly over 40 min and stirring was continued for 180 min. Ammonium persulfate with a mass ratio of 0.008 times that of the acrylate monomer was added and stirring was continued for 8 min. The mixture was cooled to room temperature and the pH was adjusted to 7 with ammonia water to obtain polyacrylate emulsion. (3) Antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181 and tributyl phosphate are mixed evenly in a mass ratio of 1:8:2:0.22:0.16 to obtain water-based ink. Example
[0022] A method for preparing a water-based ink mainly includes the following steps: (1) Mix 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde in a molar ratio of 2:3, add 11 times the mass of ethanol of 1,3,5-triaminobenzene and an equal mass of silica of 1,3,5-triaminobenzene, heat to 75°C at 250 r / min under nitrogen protection, stir for 4.5 h, cool to room temperature, filter, wash 4 times with deionized water, and vacuum dry at -3°C for 25 h to obtain pre-modified silica; combine pre-modified silica, DOPO and TH F was mixed at a mass ratio of 1:0.85:15, heated to 65℃ at 250 r / min, stirred for 4.5 h, cooled to room temperature, filtered, washed 4 times with ethanol, and vacuum dried at -3℃ for 25 h to obtain modified silica; zinc acetate and deionized water were mixed evenly at a mass ratio of 1:15 to obtain zinc acetate solution; the modified silica was immersed in zinc acetate solution for 15 h, filtered, washed 4 times with deionized water, and vacuum dried at -3℃ for 25 h to obtain antibacterial silica; (2) 2-Methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine were mixed in a molar ratio of 1:1, and acetonitrile was added in 20 times the mass of 2-methyl-2-iodoethyl-2-acrylate. The mixture was stirred at 53°C and 250 r / min for 15.5 h, and then vacuum dried at room temperature for 25 h to obtain the modified acrylate monomer. Methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, and the modified acrylate monomer were mixed evenly in a mass ratio of 32:24:7:2.5:1.3:7 to obtain the acrylate monomer. Alkylphenol polyoxyethylene ether and dodecyl sulfate were mixed evenly. Sodium was mixed evenly at a mass ratio of 1:1 to prepare an emulsifier. Acrylate monomers, emulsifiers, sodium bicarbonate and deionized water were mixed at a mass ratio of 50:3.5:0.1:30 and stirred at room temperature for 50 min to prepare pre-emulsified polyacrylate. 1 / 3 of the pre-emulsified polyacrylate was stirred at 80℃ and 250 r / min for 4 min. Ammonium persulfate with a mass ratio of 0.005 times that of the acrylate monomers was added and stirring was continued for 5 min. The remaining 2 / 3 of the pre-emulsified polyacrylate was added uniformly over 45 min and stirring was continued for 190 min. Ammonium persulfate with a mass ratio of 0.01 times that of the acrylate monomers was added and stirring was continued for 9 min. The mixture was cooled to room temperature and the pH was adjusted to 7.5 with ammonia water to obtain a polyacrylate emulsion. (3) Antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181 and tributyl phosphate are mixed evenly in a mass ratio of 1:9:2.5:0.24:0.18 to obtain water-based ink. Example
[0023] A method for preparing a water-based ink mainly includes the following steps: (1) Mix 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde in a molar ratio of 2:3, add 12 times the mass of ethanol of 1,3,5-triaminobenzene and an equal mass of silica of 1,3,5-triaminobenzene, heat to 77°C at 300 r / min under nitrogen protection, stir for 5 h, cool to room temperature, filter, wash 5 times with deionized water, and vacuum dry at -5°C for 26 h to obtain pre-modified silica; combine pre-modified silica, DOPO and T HF was mixed at a mass ratio of 1:0.9:6, heated to 67℃ at 300 r / min, stirred for 5 h, cooled to room temperature, filtered, washed 5 times with ethanol, and vacuum dried at -5℃ for 26 h to obtain modified silica; zinc acetate and deionized water were mixed evenly at a mass ratio of 1:16 to obtain zinc acetate solution; the modified silica was immersed in zinc acetate solution for 16 h, filtered, washed 5 times with deionized water, and vacuum dried at -5℃ for 26 h to obtain antibacterial silica; (2) 2-Methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine were mixed in a molar ratio of 1:1, and acetonitrile was added in 22 times the mass of 2-methyl-2-iodoethyl-2-acrylate. The mixture was stirred at 55°C and 300 r / min for 16 h, and then vacuum dried at room temperature for 26 h to obtain the modified acrylate monomer. Methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, and the modified acrylate monomer were mixed evenly in a mass ratio of 34:25:8:3:1.5:8 to obtain the acrylate monomer. Alkylphenol polyoxyethylene ether and sodium dodecyl sulfate were mixed evenly. The emulsifier was prepared by mixing the acrylate monomer, emulsifier, sodium bicarbonate and deionized water at a mass ratio of 52:4:0.1:32 and stirring at room temperature for 60 min. One-third of the pre-emulsified polyacrylate was stirred at 82℃ and 300 r / min for 5 min. Ammonium persulfate (0.006 times the mass of the acrylate monomer) was added and stirring continued for 6 min. The remaining two-thirds of the pre-emulsified polyacrylate was added uniformly over 50 min and stirring continued for 200 min. Ammonium persulfate (0.012 times the mass of the acrylate monomer) was added and stirring continued for 10 min. The mixture was cooled to room temperature, and the pH was adjusted to 8 with ammonia to obtain the polyacrylate emulsion. (3) Antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181 and tributyl phosphate are mixed evenly in a mass ratio of 1:10:3:0.26:0.2 to obtain water-based ink.
[0024] Comparative Example 1 The difference between the preparation method of the modified polyester fiber in Comparative Example 1 and Example 2 lies in step (1). Step (1) is modified as follows: 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde are mixed in a molar ratio of 2:3, and ethanol (11 times the mass of 1,3,5-triaminobenzene) and silica (equal mass of 1,3,5-triaminobenzene) are added. The mixture is heated to 75°C at 250 r / min under nitrogen protection, stirred for 4.5 h, cooled to room temperature, filtered, washed four times with deionized water, and vacuum dried at -3°C for 25 h to obtain pre-modified silica. The pre-modified silica, DOPO, and THF are mixed in a mass ratio of 1:0.85:15, heated to 65°C at 250 r / min, stirred for 4.5 h, cooled to room temperature, filtered, washed four times with ethanol, and vacuum dried at -3°C for 25 h to obtain antibacterial silica. The remaining steps are the same as in Example 2.
[0025] Comparative Example 2 The difference between the preparation method of the modified polyester fiber in Comparative Example 2 and that in Example 2 lies in step (1). Step (1) is modified as follows: 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde are mixed in a molar ratio of 2:3, and ethanol (11 times the mass of 1,3,5-triaminobenzene) and silicon dioxide (equal in mass to 1,3,5-triaminobenzene) are added. The mixture is heated to 75°C at 250 r / min under nitrogen protection, stirred for 4.5 h, cooled to room temperature, filtered, washed four times with deionized water, and vacuum dried at -3°C for 25 h to obtain antibacterial silicon dioxide. The remaining steps are the same as in Example 2.
[0026] Comparative Example 3 The preparation method of the modified polyester fiber in Comparative Example 3 differs from that in Example 2 in that antibacterial silica is not added. The remaining steps are the same as in Example 2.
[0027] Comparative Example 4 A method for preparing a water-based ink mainly includes the following preparation steps: The preparation method of the modified polyester fiber in Comparative Example 4 differs from that in Example 2 in that no modified acrylate monomer is added. The remaining steps are the same as in Example 2.
[0028] Test Example 1 Water resistance and flame retardancy tests Water resistance test: Coat a layer of ink on PET, leave it for 3 days until it is completely dry, then wipe the surface of the ink strip repeatedly with a damp cotton cloth and record the number of times white appears. Flame retardancy test: A layer of ink was coated on the PET film and left to dry completely for 3 days. Then, a flame retardancy test was conducted according to UL94 standard. The results are shown in Table 1.
[0029] Table 1
[0030] A comparison of the experimental data in Table 1 shows that the ink prepared by this invention has good water resistance and flame retardancy.
[0031] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Example 2 in Table 1 reveals that Examples 1, 2, and 3 exhibit high flame retardancy ratings. The difference between Comparative Example 2 and the Examples is the absence of DOPO, indicating that DOPO reacts with imine bonds. The introduced phosphate ester can decompose at high temperatures to generate phosphorus-containing free radicals, which efficiently capture hydrogen and hydroxyl free radicals in the combustion chain reaction, interrupting the combustion chain reaction. Simultaneously, the phosphoric acid substances generated at high temperatures catalyze the dehydration of the polyacrylate matrix in the ink into carbon, forming a stable heat-insulating and oxygen-barrier carbon layer on the material surface, reducing the exchange of heat and oxygen between the matrix and the outside world, and enhancing the flame retardancy of the ink. A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 4 reveals that Examples 1, 2, and 3 exhibit high flame retardancy and good water resistance. The difference between Comparative Example 4 and the Examples is the absence of fluorine. Fluorine is the most electronegative element, with a high CF bond energy, which reduces the surface energy of the material and effectively blocks the penetration of moisture, giving the ink good water resistance. Furthermore, due to the high bond energy, the CF bond is extremely difficult to break, making it difficult for the molecular chain to pyrolyze and produce flammable volatiles, further enhancing the flame retardancy of the ink.
[0032] Test Example 2 Antibacterial test Test method: The ink was dried in polytetrafluoroethylene for 3 days and tested according to GB / T31402, with Staphylococcus aureus and Escherichia coli selected as the bacterial strains. The results are shown in Table 2.
[0033] Table 2
[0034] A comparison of the experimental data in Table 2 shows that the ink prepared by this invention has good antibacterial properties.
[0035] A comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 2 shows that Examples 1, 2, and 3 have higher antibacterial rates. The difference between Comparative Example 1 and Examples is that zinc ions were not introduced, indicating that zinc ions in the ink can bind to the negatively charged bacterial cell membrane, change the permeability of the bacterial cell membrane, cause leakage of cell contents, directly damage the bacterial cell structure, and enhance the antibacterial ability of the ink. A comparison of the experimental data from Examples 1, 2, 3 and Comparative Example 4 reveals that Examples 1, 2, and 3 exhibit high antibacterial rates. The difference between Comparative Example 4 and the Examples is that no quaternary ammonium salt was introduced. This indicates that the quaternary ammonium salt carries a positive charge and can strongly adsorb the negatively charged bacterial cell wall surface through electrostatic force. At the same time, the hydrophobic alkyl chain can also insert into the lipid bilayer of the cell membrane, altering membrane permeability and causing the leakage of intracellular enzymes, coenzymes, and metabolites, inducing cell lysis, thereby enhancing the antibacterial ability of the ink.
[0036] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A water-based ink, characterized in that, The water-based ink is prepared by mixing antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181, and tributyl phosphate; The antibacterial silica is prepared by reacting 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde on the surface of silica, then reacting it with DOPO, and finally combining it with zinc ions. The polyacrylate emulsion is prepared by reacting 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octylamine, followed by polymerization with methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, and hydroxyethyl methacrylate.
2. A method for preparing a water-based ink, characterized in that, The preparation method of the water-based ink mainly includes the following preparation steps: (1) Zinc acetate and deionized water are mixed evenly at a mass ratio of 1:14~16 to obtain zinc acetate solution; modified silica is immersed in zinc acetate solution for 14~16h, filtered, washed with deionized water 3~5 times, and vacuum dried at -5~0℃ for 24~26h to obtain antibacterial silica. (2) Mix acrylate monomer, emulsifier, sodium bicarbonate and deionized water in a mass ratio of 48~52:3~4:0.1:28~32 and stir at room temperature for 40~60 min to obtain pre-emulsified polyacrylate; stir 1 / 3 of the pre-emulsified polyacrylate at 78~82℃ and 200~300 r / min for 3~5 min, add ammonium persulfate at 0.004~0.006 times the mass of acrylate monomer and continue stirring for 4~6 min, add the remaining 2 / 3 of the pre-emulsified polyacrylate at a uniform rate over 40~50 min, continue stirring for 180~200 min, add ammonium persulfate at 0.008~0.012 times the mass of acrylate monomer, continue stirring for 8~10 min, cool to room temperature, and adjust the pH to 7~8 with ammonia water to obtain polyacrylate emulsion; (3) Antibacterial silica, polyacrylate emulsion, pigment, wetting and dispersing agent DISPERBYK-181 and tributyl phosphate are mixed evenly in a mass ratio of 1:8~10:2~3:0.22~0.26:0.16~0.2 to obtain water-based ink.
3. The method for preparing a water-based ink according to claim 2, characterized in that, The modified silica in step (1) is prepared by mixing pre-modified silica, DOPO and THF in a mass ratio of 1:0.8~0.9:14~16, heating to 63~67℃ at 200~300r / min, stirring for 4~5h, cooling to room temperature, filtering, washing with ethanol 3~5 times, and vacuum drying at -5~0℃ for 24~26h.
4. The method for preparing a water-based ink according to claim 3, characterized in that, The pre-modified silica is prepared by mixing 1,3,5-triaminobenzene and 2,5-dihydroxyterephthalaldehyde in a molar ratio of 2:3, adding 10 to 12 times the mass of 1,3,5-triaminobenzene in ethanol and an equal mass of 1,3,5-triaminobenzene in silica, heating to 73 to 77°C at 200 to 300 r / min under nitrogen protection, stirring for 4 to 5 hours, cooling to room temperature, filtering, washing 3 to 5 times with deionized water, and vacuum drying at -5 to 0°C for 24 to 26 hours.
5. The method for preparing a water-based ink according to claim 4, characterized in that, The silica is silica with a particle size of 200~300nm.
6. The method for preparing a water-based ink according to claim 2, characterized in that, The modified acrylate monomer in step (2) is prepared by mixing 2-methyl-2-iodoethyl-2-acrylate and N,N-dimethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tetrafluoro-1-octylamine in a molar ratio of 1:1, adding acetonitrile in 18 to 22 times the mass of 2-methyl-2-iodoethyl-2-acrylate, stirring at 50 to 55°C and 200 to 300 r / min for 15 to 16 h, and then vacuum drying at room temperature for 24 to 26 h.
7. The method for preparing a water-based ink according to claim 2, characterized in that, The acrylate monomers in step (2) are prepared by mixing methyl methacrylate, butyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxyethyl methacrylate, and modified acrylate monomers in a mass ratio of 30~34:23~25:6~8:2~3:1~1.5:6~8.
8. The method for preparing a water-based ink according to claim 2, characterized in that, The emulsifier in step (2) is prepared by mixing alkylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 1:
1.
9. The method for preparing a water-based ink according to claim 2, characterized in that, The pigments mentioned in step (3) are phthalocyanine blue, phthalocyanine green, phthalocyanine red, etc.