Antibacterial water-based gravure ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, and discloses antibacterial water-based gravure ink and a preparation method thereof.The antibacterial water-based gravure ink is prepared by adding acrylic resin, nano-zinc oxide, an organic silicon defoaming agent, hydroxyethyl cellulose, polyether modified siloxane, quaternary ammonium salt modified triazole and deionized water into a stirrer and stirring for 15-20 min; the antibacterial water-based gravure ink is obtained after the reaction is finished. Ammonium salt in quaternary ammonium salt modified triazole can be adsorbed to thalli with negative charges, high-concentration ionic groups are formed on the surfaces of bacteria, normal functions of bacterial cells are directly affected, permeability of cell walls is destroyed, cell dissolution and death are caused, and the antibacterial effect is achieved; the triazole group causes death by destroying the structure of a cell membrane, and also has a relatively good antibacterial effect; wherein the nano zinc oxide has a relatively good antibacterial effect.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and particularly to an antibacterial water-based gravure ink and a preparation method thereof. Background Art

[0002] With the increasingly strict global environmental protection regulations, water-based gravure inks, as an alternative to traditional solvent-based inks, have seen a surge in demand in hygiene-sensitive fields such as food packaging and medical consumables. However, the inherently high water content (usually > 40%) and organic components (such as acrylic resins and wetting agents) in the water-based system provide an ideal environment for microbial growth. According to ISO16869 standard testing, after 28 days of storage at 30°C / 65%RH, the total colony count of untreated water-based inks can reach 10 6 CFU / mL, directly leading to a decrease in ink viscosity ( Δη > 30%), deterioration of printing adaptability, and the risk of secondary pollution of packaging materials.

[0003] The current industry's antibacterial modification of water-based gravure inks mainly focuses on the following technical paths: Inorganic nano-antibacterial agents: Nano-particles represented by silver and zinc oxides achieve broad-spectrum antibacterial effects through ion release mechanisms. For example, Patent CN109233439A discloses an ink, an antibacterial resin for ink, and a preparation method thereof. First, acrylic resin is dissolved in ethanol to obtain a first mixture, then silver is dissolved in ethanol to obtain a second mixture. After mixing the first mixture and the second mixture and filtering, an antibacterial resin for ink is obtained, enabling the ink to achieve an antibacterial rate of 97% against Escherichia coli and 94% against Staphylococcus aureus. Patent CN112852205A discloses a coating with an automatic sterilization function and a manufacturing method thereof, including a coating solution and silver ions, copper ions, or zinc ions, and one of silver ions, copper ions, or zinc ions is attached or mixed in the coating. It includes step S1: preliminarily processing the coating through coating processing machinery and equipment; S2: when manufacturing the coating, a silver ion generator is set beside the processing area for manufacturing the coating. Silver ions are ionized by the silver ion generator, attached to water, and then the water attached with silver ions is combined with or attached to the coating bath solution, and the silver ions are evenly distributed in the coating to make the coating have an automatic sterilization effect. However, it has defects such as nanoparticle aggregation (when D50 > 200nm, the clogging rate of 80μm mesh holes increases by 15%) and excessive migration of heavy metal ions (the migration amount of Ag⁺ exceeds 2.3 times the limit value of EU EC 10 / 2011).

[0004] Organic quaternary ammonium salt modification: For example, Patent CN106565912B discloses a polyquaternary ammonium salt polymer emulsion antibacterial agent and its preparation method and application, including: cationic antibacterial monomers, and the cationic antibacterial monomers are at least one of dodecyl dimethyl allyl ammonium chloride cationic antibacterial monomer, tetradecyl dimethyl allyl ammonium chloride cationic antibacterial monomer, hexadecyl dimethyl allyl ammonium chloride cationic antibacterial monomer, and octadecyl dimethyl allyl ammonium chloride cationic antibacterial monomer. Although this technology avoids heavy metal risks, the quaternary ammonium salt has poor thermal stability (decomposition temperature < 120°C), and the inactivation rate is as high as 60% during the high-temperature drying (130 - 150°C) process of the ink, and phase separation of the resin system is likely to occur during long-term storage; Photocatalytic antibacterial system: Based on TiO 2 / WO 3 The photocatalytic free radical sterilization technology of heterojunction materials can achieve dynamic antibacterial under UV irradiation. However, such materials need to be activated by a specific wavelength light source, and their applicability is limited in the actual use scenarios of packaging materials. Moreover, the nano-catalyst increases the surface tension of the ink to 38 mN / m (benchmark value 32 mN / m), resulting in the gravure transfer rate decreasing from 78% to 63%.

[0005] Therefore, developing a new antibacterial system with both high antibacterial properties and good storage stability has become the key technical bottleneck for the popularization and application of water-based gravure inks in the high-end sanitary packaging field. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the present invention provides an antibacterial water-based gravure ink with good antibacterial effect and good storage stability and its preparation method.

[0007] To achieve the above object, the present invention provides the following technical solutions: The antibacterial water-based gravure ink includes the following weight components: 35 - 50 parts by weight of acrylic resin, 0.4 - 0.6 parts by weight of nano-zinc oxide, 0.3 - 0.5 parts by weight of organosilicon defoamer, 0.5 - 0.6 parts by weight of hydroxyethyl cellulose, 1 - 2 parts by weight of polyether-modified silicone, 2 - 4 parts by weight of quaternary ammonium salt-modified triazole, and 15 - 19 parts by weight of deionized water.

[0008] Preferably, the preparation method of the quaternary ammonium salt-modified triazole is as follows: S1 Add organic tertiary amine and 1,3-propane sultone to an acetone solvent for dissolution, then dropwise add a sodium hydroxide solution with a mass fraction of 2 - 4%, react at 70 - 80°C, concentrate under reduced pressure to remove the solvent after the reaction, and recrystallize the crude product in ethanol to obtain intermediate 1; The reaction equation is as follows: (Ⅰ) Under the action of NaOH, 1,3 - propane sultone undergoes a nucleophilic ring - opening reaction with organic tertiary amine to form quaternary ammonium salt sulfonate.

[0009] S2. Add intermediate 1 and sodium azide to N,N - dimethylformamide solvent, stir to dissolve, react at 60 - 75 °C. After the reaction, add the reaction solution to n - hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain intermediate 2; The reaction equation is as follows: (Ⅱ); Intermediate 1 reacts with sodium azide, and the sulfonate group is replaced by an azide group to form the corresponding azide; S3. Add 3 - 4 parts by weight of 1 - methylpropargylamine and 2.4 - 2.6 parts by weight of intermediate 2 to anhydrous N,N - dimethylformamide, then continue to add 0.1 - 0.2 parts by weight of N,N,N',N'',N'' - pentamethyldiethylenetriamine and 0.1 - 0.12 parts by weight of cuprous bromide. Protect with nitrogen, react at 50 - 65 °C. After completion, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran to remove the copper salt in the system, then concentrate by rotary evaporation and dialyze with water for 2 - 4 days to remove N,N - dimethylformamide to obtain quaternary ammonium salt - modified triazole; The reaction equation is as follows: (Ⅲ); Cuprous bromide (CuBr) coordinates with N,N,N',N'',N'' - pentamethyldiethylenetriamine to form an active Cu(I) catalyst. Under the catalysis of Cu(I), intermediate 2 (containing an azide group) and 1 - methylpropargylamine undergo a Cu(I) - catalyzed Huisgen cycloaddition reaction to form a 1,2,3 - triazole ring.

[0010] Preferably, in S1, the molar ratio of bis(2 - chloroethyl)methylamine to 1,3 - propane sultone is 1:1.2 - 1.4.

[0011] Preferably, in S1, R1, R2, and R3 of the organic tertiary amine are one or more of alkyl groups, aromatic groups, isoalkyl groups, and alcohol groups.

[0012] Preferably, the organic tertiary amine in S1 is one of trimethylamine, triethylamine, and N,N - dimethylethanolamine.

[0013] Preferably, the reaction time in S1 is 4 - 6 h.

[0014] Preferably, in S2, the molar ratio of intermediate 1 to sodium azide is 1.1 - 1.23:1.35 - 1.47.

[0015] Preferably, the reaction time in S2 is 10 - 12 h.

[0016] Preferably, the reaction time in S3 is 5 - 6 h.

[0017] Preferably, the preparation method of the antibacterial water-based gravure ink is as follows: Add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water into a stirrer, stir for 15 - 20 min, and obtain the antibacterial water-based gravure ink after completion.

[0018] Beneficial technical effects In the present invention, acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water are added into a stirrer, stirred for 15 - 20 min, and the antibacterial water-based gravure ink is obtained after completion. The cationic bactericidal effect of the quaternary ammonium salt and the metal chelating ability of triazole cooperate to destroy the microbial cell membrane, and the quaternary ammonium salt is connected to the triazole ring through a covalent bond to avoid the migration and loss of traditional physically mixed antibacterial agents. Nano-zinc oxide acts as a photocatalytic bactericide, especially under ultraviolet light, providing long-term protection. Specific embodiments

[0019] Acrylic resin Soluryl-60L, manufacturer: Hanwha, South Korea; Nano-zinc oxide, particle size 50 nm, manufacturer: Fujian Ruisen New Materials Co., Ltd.; Silicone defoamer, TEGO AIREX 902W, manufacturer: Evonik Degussa; Hydroxyethyl cellulose, methoxy content: 28% - 32%, manufacturer: Jinzhou Xincheng Cellulose Co., Ltd.; Polyether-modified silicone BJ-46B, manufacturer: Nanjing Dahai New Materials Technology Co., Ltd.; Trimethylamine: content 99%, manufacturer: Shandong Yuxuan Chemical Products Co., Ltd.; Triethylamine: content 99%, manufacturer: Shandong Yuxuan Chemical Products Co., Ltd.; N,N-Dimethylethanolamine, content 99%, manufacturer: Shandong Zhuo'an Chemical Co., Ltd.; 1,3-Propane sultone, content 99%, manufacturer: Guangdong Fangxin Biotechnology Co., Ltd.; Sodium azide, content 99.5%, manufacturer: Qingdao Xuejie Auxiliary Co., Ltd.; Methylpropargylamine, content 98%, manufacturer: Shanghai Yuanye Bio-Technology Co., Ltd.; N,N,N',N'',N''-Pentamethyldiethylenetriamine, content 98%, manufacturer: Shanghai Yuanye Bio-Technology Co., Ltd.; Copper(I) bromide, content 98%, manufacturer: Shandong Maina New Materials Co., Ltd.

[0020] Example 1 Antibacterial water-based gravure ink, comprising the following weight components: 35 parts by weight of acrylic resin, 0.4 parts by weight of nano-zinc oxide, 0.3 parts by weight of silicone defoamer, 0.5 parts by weight of hydroxyethyl cellulose, 1 part by weight of polyether-modified silicone, 2 parts by weight of quaternary ammonium salt-modified triazole, 15 parts by weight of deionized water.

[0021] The preparation method of the quaternary ammonium salt-modified triazole is as follows: S1. Add 6 g of trimethylamine and 15 g of 1,3-propanesultone to 60 mL of acetone solvent for dissolution, then dropwise add a 2% sodium hydroxide solution, react at 70 °C for 4 h, after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product in ethanol to obtain Intermediate 1; The reaction equation is as follows: ; S2. Add 12 g of Intermediate 1 and 5.4 g of sodium azide to 40 mL of N,N-dimethylformamide solvent, stir for dissolution, react at 60 °C for 10 h, after the reaction, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain Intermediate 2; The reaction equation is as follows: ; S3. Add 3 g of 1-methylpropargylamine and 8 g of Intermediate 2 to 30 mL of anhydrous N,N-dimethylformamide, then continue to add 0.3 g of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.3 g of copper(I) bromide, protect with nitrogen, react at 50 °C for 5 h, after the reaction, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran as the eluent to remove the copper salt in the system, then concentrate by rotary evaporation and dialyze with water for 2 days to remove N,N-dimethylformamide to obtain the quaternary ammonium salt-modified triazole; The reaction equation is as follows: .

[0022] The preparation method of the antibacterial water-based gravure ink is: add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water to a stirrer, stir for 15 min, and obtain the antibacterial water-based gravure ink after completion.

[0023] Example 2 The antibacterial water-based gravure ink comprises the following components by weight: 50 parts by weight of acrylic resin, 0.6 part by weight of nano zinc oxide, 0.5 part by weight of silicone defoamer, 0.6 part by weight of hydroxyethyl cellulose, 2 parts by weight of polyether modified silicone, 4 parts by weight of quaternary ammonium salt modified triazole, and 19 parts by weight of deionized water.

[0024] The preparation method of the quaternary ammonium salt modified triazole is as follows: S1. 6 g of triethylamine and 10.2 g of 1,3 - propane sultone are added to 40 mL of acetone solvent for dissolution, and then a sodium hydroxide solution with a mass fraction of 4% is added dropwise. The reaction is carried out at 80 °C for 6 h. After the reaction, the solvent is removed by reduced pressure concentration. The crude product is recrystallized from ethanol to obtain intermediate 1; The reaction equation is as follows: ; S2. 12 g of intermediate 1 and 5.55 g of sodium azide are added to 35 mL of N,N - dimethylformamide solvent, stirred and dissolved. The reaction is carried out at 75 °C for 12 h. After the reaction, the reaction solution is added to n - hexane for dissolution, washed with saturated sodium chloride, the organic phase is dried with anhydrous sodium sulfate, filtered, and the solvent is removed under vacuum to obtain intermediate 2; The reaction equation is as follows: ; S3. 3 g of 1 - methylpropargylamine and 12.5 g of intermediate 2 are added to 40 mL of anhydrous N,N - dimethylformamide, and then 0.3 g of N,N,N',N'',N'' - pentamethyldiethylenetriamine and 0.18 g of copper bromide are added continuously. Nitrogen is introduced for protection, and the reaction is carried out at 65 °C for 6 h. After completion, the reaction solution is passed through an alumina chromatography column, eluted with tetrahydrofuran as the eluent to remove the copper salt in the system, and then concentrated by rotary evaporation and dialyzed with water for 4 days to remove N,N - dimethylformamide to obtain the quaternary ammonium salt modified triazole; The reaction equation is as follows: .

[0025] The preparation method of the antibacterial water-based gravure ink is as follows: The acrylic resin, nano zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether modified silicone, quaternary ammonium salt modified triazole, and deionized water are added to a stirrer and stirred for 18 min to obtain the antibacterial water-based gravure ink.

[0026] Example 3 Antibacterial water-based gravure ink, comprising the following components by weight: 40 parts by weight of acrylic resin, 0.5 part by weight of nano-zinc oxide, 0.4 part by weight of silicone defoamer, 0.55 part by weight of hydroxyethyl cellulose, 1 part by weight of polyether-modified silicone, 3 parts by weight of quaternary ammonium salt-modified triazole, and 17 parts by weight of deionized water.

[0027] The preparation method of the quaternary ammonium salt-modified triazole is as follows: S1. Add 8 g of N,N-dimethylethanolamine and 13.2 g of 1,3-propanesultone to 60 mL of acetone solvent for dissolution, then dropwise add a 3% sodium hydroxide solution, react at 75 °C for 5 h, concentrate under reduced pressure to remove the solvent after the reaction, and recrystallize the crude product in ethanol to obtain intermediate 1; The reaction equation is as follows: ; S2. Add 12 g of intermediate 1 and 5.55 g of sodium azide to 50 mL of N,N-dimethylformamide solvent, stir for dissolution, react at 65 °C for 11 h, after the reaction is completed, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain intermediate 2; The reaction equation is as follows: ; S3. Add 6.2 g of 1-methylpropargylamine and 12 g of intermediate 2 to 35 mL of anhydrous N,N-dimethylformamide, then continue to add 0.45 g of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.33 g of copper bromide, protect with nitrogen, react at 55 °C for 6 h, after completion, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran as the eluent to remove the copper salt in the system, then concentrate by rotary evaporation and dialyze with water for 3 days to remove N,N-dimethylformamide to obtain the quaternary ammonium salt-modified triazole; The reaction equation is as follows: .

[0028] The preparation method of the antibacterial water-based gravure ink is as follows: Add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water to a stirrer, stir for 17 min, and obtain the antibacterial water-based gravure ink after completion.

[0029] Example 4 Antibacterial water-based gravure ink, comprising the following components by weight: 35 parts by weight of acrylic resin, 0.4 parts by weight of nano-zinc oxide, 0.3 parts by weight of silicone defoamer, 0.5 parts by weight of hydroxyethyl cellulose, 1 part by weight of polyether-modified silicone, 2 parts by weight of quaternary ammonium salt-modified triazole, 15 parts by weight of deionized water.

[0030] The preparation method of the quaternary ammonium salt-modified triazole is as follows: S1. Add 6 g of trimethylamine and 17.6 g of 1,3-propanesultone to 60 mL of acetone solvent for dissolution, then dropwise add a sodium hydroxide solution with a mass fraction of 2%, react at 70 °C for 4 h, after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product in ethanol to obtain intermediate 1; S2. Add 12 g of intermediate 1 and 8.6 g of sodium azide to 40 mL of N,N-dimethylformamide solvent, stir for dissolution, react at 75 °C for 12 h, after the reaction, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain intermediate 2; S3. Add 4 g of 1-methylpropargylamine and 8 g of intermediate 2 to 40 mL of anhydrous N,N-dimethylformamide, then continue to add 0.2 g of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.12 g of cuprous bromide, pass in nitrogen for protection, react at 65 °C for 6 h, after completion, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran as the eluent to remove the copper salt in the system, then concentrate by rotary evaporation and dialyze with water for 4 days to remove N,N-dimethylformamide to obtain the quaternary ammonium salt-modified triazole.

[0031] The preparation method of the antibacterial water-based gravure ink is as follows: Add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water to a stirrer, stir for 17 min, and obtain the antibacterial water-based gravure ink after completion.

[0032] Example 5 Antibacterial water-based gravure ink, comprising the following components by weight: 50 parts by weight of acrylic resin, 0.6 parts by weight of nano-zinc oxide, 0.5 parts by weight of silicone defoamer, 0.6 parts by weight of hydroxyethyl cellulose, 2 parts by weight of polyether-modified silicone, 4 parts by weight of quaternary ammonium salt-modified triazole, 19 parts by weight of deionized water.

[0033] The preparation method of the quaternary ammonium salt-modified triazole is as follows: S1. Dissolve 8 g of N,N-dimethylethanolamine and 15.3 g of 1,3-propanesultone in 60 mL of acetone solvent, then dropwise add a sodium hydroxide solution with a mass fraction of 4%, react at 80 °C for 6 h, after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product from ethanol to obtain Intermediate 1; S2. Add 12 g of Intermediate 1 and 6.03 g of sodium azide to 50 mL of N,N-dimethylformamide solvent, stir to dissolve, react at 65 °C for 11 h, after the reaction ends, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain Intermediate 2; S3. Add 4.95 g of 1-methylpropargylamine and 12 g of Intermediate 2 to 30 mL of anhydrous N,N-dimethylformamide, then continue to add 0.3 g of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.3 g of cuprous bromide, protect with nitrogen, react at 50 °C for 5 h, after the reaction ends, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran as the eluent to remove the copper salt in the system, then concentrate by rotary evaporation and dialyze with water for 2 days to remove N,N-dimethylformamide to obtain the quaternary ammonium salt modified triazole.

[0034] The preparation method of the antibacterial water-based gravure ink is as follows: Add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt modified triazole, and deionized water to a stirrer, stir for 15 min, and obtain the antibacterial water-based gravure ink after the end.

[0035] Example 6 The antibacterial water-based gravure ink comprises the following weight components: 35 parts by weight of acrylic resin, 0.4 part by weight of nano-zinc oxide, 0.3 part by weight of silicone defoamer, 0.5 part by weight of hydroxyethyl cellulose, 1 part by weight of polyether-modified silicone, 2 parts by weight of quaternary ammonium salt modified triazole, and 15 parts by weight of deionized water.

[0036] The preparation method of the quaternary ammonium salt modified triazole is as follows: S1. Dissolve 6 g of triethylamine and 8.7 g of 1,3-propanesultone in 40 mL of acetone solvent, then dropwise add a sodium hydroxide solution with a mass fraction of 4%, react at 80 °C for 6 h, after the reaction, concentrate under reduced pressure to remove the solvent, and recrystallize the crude product from ethanol to obtain Intermediate 1; S2. Add 12 g of intermediate 1 and 6.03 g of sodium azide to 26 mL of N,N-dimethylformamide solvent, stir to dissolve, react at 65 °C for 11 h. After the reaction, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent under vacuum to obtain intermediate 2; S3. Add 3.5 g of 1-methylpropargylamine and 12.5 g of intermediate 2 to 35 mL of anhydrous N,N-dimethylformamide, then continue to add 0.15 g of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.11 g of cuprous bromide, introduce nitrogen for protection, react at 55 °C for 6 h. After completion, pass the reaction solution through an alumina chromatography column, elute with tetrahydrofuran as the eluent to remove the copper salts in the system, then concentrate by rotary evaporation and dialyze with water for 3 days to remove N,N-dimethylformamide to obtain the quaternary ammonium salt-modified triazole.

[0037] The preparation method of the antibacterial water-based gravure ink is as follows: Add acrylic resin, nano-zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether-modified silicone, quaternary ammonium salt-modified triazole, and deionized water to a stirrer, stir for 17 min, and obtain the antibacterial water-based gravure ink after completion.

[0038] Comparative Example 1 Compared with Example 6, the difference in this comparative example is that the quaternary ammonium salt-modified triazole is not added.

[0039] Comparative Example 2 Compared with Example 6, the difference in this comparative example is that the quaternary ammonium salt-modified triazole is not added, and an equal amount of cetyl dimethyl allyl ammonium chloride is used instead.

[0040] Comparative Example 3 Compared with Example 6, the difference in this comparative example is that the quaternary ammonium salt-modified triazole is not added, and an equal amount of nano-zinc oxide is used instead.

[0041] Antibacterial property: Test according to the standard GB / T21866-2008 "Determination Method and Antibacterial Effect of Antibacterial Coatings (Paint Films)"; Table 1: Antibacterial property test.

[0042] As can be seen from Table 1, the antibacterial rates of Examples 1-6 are better than those of Comparative Examples 1-3, indicating that the antibacterial water-based gravure ink prepared by the present invention has good antibacterial effect.

[0043] Test of storage stability Test Method 1 The inks prepared in Examples 1-6 and Comparative Examples 1-3 were stored in a constant temperature environment at 60 °C, and the viscosity of the inks after storage was measured.

[0044] The viscosity change rate of the ink = (viscosity of the aqueous composition after storage) / (viscosity of the aqueous composition before storage) * 100%.

[0045] The storage stability was evaluated according to the following evaluation criteria.

[0046] A: The viscosity change rate of the ink after 4 weeks of storage is above 90% and below 110%.

[0047] B: The viscosity change rate of the ink after 2 weeks of storage is above 90% and below 110%, but the viscosity change rate after more than 2 weeks is less than 90% or more than 110%.

[0048] C: The viscosity change rate of the ink after 1 week of storage is above 90% and below 110%, but the viscosity change rate after more than 1 week is less than 90% or more than 110%.

[0049] D: Through storage for less than 1 week, the viscosity change rate of the ink is less than 90% or more than 110%.

[0050] If the evaluation result is B or above, the storage stability is sufficient.

[0051] Test Method 2 Measured by the centrifuge method. At room temperature, the inks prepared in Examples 1-6 and Comparative Examples 1-3 were placed in centrifuge tubes, and the rotation speed was 3000 r / min. After centrifugation for 15 min, observe whether there is precipitation in the inks in the centrifuge tubes. If there is no precipitation, it indicates that the ink has a storage stability of 6 months. The test results are shown in Table 2.

[0052] Table 2 As can be seen from Table 2, the storage stability of Examples 1-6 is better than that of Comparative Examples 1-3.

[0053] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor limit the invention to the specific embodiments described. Obviously, according to the content of this specification, many modifications and changes can be made. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention.

Claims

1. Antibacterial water-based gravure ink, characterized in that: The invention comprises the following components by weight: 35-50 parts by weight of acrylic resin, 0.4-0.6 parts by weight of nano zinc oxide, 0.3-0.5 parts by weight of organic silicon defoamer, 0.5-0.6 parts by weight of hydroxyethyl cellulose, 1-2 parts by weight of polyether modified siloxane, 2-4 parts by weight of quaternary ammonium salt modified triazole and 15-19 parts by weight of deionized water.

2. The antibacterial water-based gravure ink according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt modified triazole is: S1: adding organic tertiary ammonium and 1,3-propane sultone to acetone solvent for dissolution, then dropping 2-4% sodium hydroxide solution by mass, reacting at 70-80°C, concentrating under reduced pressure to remove the solvent after the reaction, recrystallizing the crude product in ethanol, and washing with ether / acetone mixed solvent to improve the purity, to obtain intermediate 1; The reaction equation is as follows: （Ⅰ） S2. Add intermediate 1 and sodium azide to N,N-dimethylformamide solvent, stir to dissolve, react at 60-75°C, and after the reaction, add the reaction solution to n-hexane for dissolution, wash with saturated sodium chloride, dry the organic phase with anhydrous sodium sulfate, filter, and remove the solvent in vacuo to obtain intermediate 2; The reaction equation is as follows: （Ⅱ）； S3. 3-4 parts by weight of 1-methylpropargylamine and 2.4-2.6 parts by weight of intermediate 2 are added to anhydrous N,N-dimethylformamide, and then 0.1-0.2 parts by weight of N,N,N',N'',N''-pentamethyldiethylenetriamine and 0.1-0.12 parts by weight of cuprous bromide are added, nitrogen is introduced for protection, and the reaction is carried out at 50-65° C. After completion, the reaction solution is passed through an alumina chromatography column and washed with tetrahydrofuran as an eluent to remove copper salts in the system, and then concentrated by rotary evaporation, and dialyzed with water for 2-4 days to remove N,N-dimethylformamide to obtain a quaternary ammonium salt-modified triazole; The reaction equation is as follows: （Ⅲ）。 3. The antibacterial water-based gravure ink according to claim 2, characterized in that: The molar ratio of the organic tertiary amine to 1,3-propane sultone in S1 is 1:1.2-1.

4.

4. The antibacterial water-based gravure ink according to claim 3, characterized in that: R1, R2, and R3 of the organic tertiary amine in S1 are one or more of an alkyl group, an aromatic group, an isomeric alkyl group, and an alcohol group.

5. The antibacterial water-based gravure ink according to claim 4, characterized in that: The organic tertiary amine in S1 is one of trimethylamine, triethylamine and N,N-dimethylethanolamine.

6. The antibacterial water-based gravure ink according to claim 2, characterized in that: The reaction time in S1 is 4-6h.

7. The antibacterial water-based gravure ink according to claim 2, characterized in that: The molar ratio of the intermediate 1 to sodium azide in S2 is 1:1.35-1.

47.

8. The antibacterial water-based gravure ink according to claim 2, characterized in that: The reaction time in S2 is 10-12h.

9. The antibacterial water-based gravure ink according to claim 2, characterized in that: The reaction time in S3 is 5-6h.

10. A method for preparing the antibacterial water-based gravure ink according to any one of claims 1 to 9, characterized in that: The preparation method of the antibacterial water-based gravure ink comprises the following steps: adding acrylic resin, nano zinc oxide, silicone defoamer, hydroxyethyl cellulose, polyether modified siloxane, quaternary ammonium salt modified triazole and deionized water into a stirrer, stirring for 15-20 minutes, and obtaining the antibacterial water-based gravure ink.

Images