Environment-friendly antibacterial ink as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of ink, and particularly relates to environment-friendly antibacterial ink as well as a preparation method and application thereof. The environment-friendly antibacterial ink comprises the following components in parts by weight: 100 parts of water-based acrylic resin; 3 to 7 parts of Ti < 3 > C < 2 > T < x > (at) MnCe-MOF; 2 to 4 parts of PHMG coated CuO; 1-3 parts of a dispersant; 2-4 parts of a defoaming agent; and 120 to 140 parts of water. By obtaining the composite antibacterial agent materials Ti3C2Tx-coated MnCe-MOF and PHMG-coated CuO and utilizing the interaction among the components, the antibacterial property of the ink is remarkably improved, meanwhile, the mechanical property is also improved, and the ink is environmentally friendly and good in application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of inks, and more specifically, relates to an environmentally friendly antibacterial ink and a preparation method and application thereof. Background Art

[0002] Inks can be divided into solvent-based inks and water-based inks according to the different solvents. The solvents of solvent-based inks are mainly organic solvents. During the printing and drying process, organic solvents will evaporate in large quantities, causing harm to the environment. The solvent of water-based inks is mainly water, which has the advantages of safety, non-toxicity, environmental protection and low cost compared to organic solvents. Therefore, the research and development of high-performance water-based inks is the main direction of current ink development.

[0003] Antibacterial materials are functional materials that can resist bacterial adhesion for a certain period of time, or control bacterial growth, reproduction and other physiological activities, or kill bacteria. They have antibacterial and bactericidal properties. By adding materials to inks, antibacterial properties can be given to inks.

[0004] CN105694585A discloses a water-based antibacterial ink for antibacterial wallpaper, comprising the following raw materials by mass fraction: 20-40 parts of acrylic resin, 30-40 parts of ethanol, 5-10 parts of pigment, 0.1-4 parts of polyether siloxane copolymer, 1-5 parts of sodium pyrophosphate, 0.5-5 parts of polypropylene glycol, 0.1-3 parts of thickener, 0.1-0.2 parts of antibacterial agent, and the balance of deionized water. The water-based antibacterial ink of the present invention has the excellent characteristics of long-term antibacterial, good stability, and non-toxicity, and greatly inhibits the spread of infectious diseases and epidemics.

[0005] CN109233439A discloses an ink, an antibacterial resin for ink and a preparation method thereof. The antibacterial resin for ink comprises 40-60 parts by weight of acrylic resin and 2.1-6.6 parts by weight of silver; wherein the silver and the acrylic resin are connected by chemical bonds. The preparation method of the antibacterial resin for ink comprises first dissolving the acrylic resin in ethanol to obtain a first mixture, then dissolving the silver in ethanol to obtain a second mixture, mixing the first mixture with the second mixture and filtering to obtain the antibacterial resin for ink. The ink comprises 30-40 parts by weight of calcium carbonate, 5-8 parts by weight of titanium dioxide, 55-65 parts by weight of ethanol, 1-1.5 parts by weight of a plasticizer and 5-8 parts by weight of the antibacterial resin for ink. The antibacterial resin for ink prepared by the above preparation method has a better and more stable antibacterial effect and does not affect the color and appearance of the ink layer.

[0006] CN100589698A discloses an antibacterial ink and a method for making the same. The antibacterial ink contains a composite antibacterial agent in an ink base material at a weight percentage of 5-20%. The composite antibacterial agent is a mixture of an inorganic-organic composite antibacterial agent and a rosin-modified phenolic resin; the inorganic-organic composite antibacterial agent contains an inorganic antibacterial agent and an organic antibacterial agent; the inorganic antibacterial agent is a phosphate or glass powder loaded with silver ions, zinc ions or silver-zinc composite ions. The antibacterial ink of the present invention uses a composite antibacterial agent to give the ink a broad-spectrum, long-lasting and efficient antibacterial property. The product is not easy to change color, and there is no wear on processing equipment such as a three-roller machine during the ink production process, so it is suitable for ink production. The obtained ink does not produce an unpleasant odor, and is proven to be non-toxic and non-irritating by acute oral toxicity tests on mice and acute skin irritation tests on rabbits.

[0007] CN102399471A discloses a tipping paper gravure antibacterial ink, which is made of the following raw materials in weight ratio: pigment 15-35; resin 10-25; solvent 30-60; antibacterial agent A 0.5-3; antibacterial agent B 0.2-1. The resin is selected from a mixture of one of polyvinyl butyral, nitrocellulose, polyurethane and one of modified rosin ester and polyketone resin; the solvent is selected from one or more of ethyl acetate, n-propyl acetate, isopropyl acetate, ethanol, isopropanol, and n-propanol; the antibacterial agent A is nano-grade modified titanium dioxide; the antibacterial agent B is selected from one of sulfadimethoxine, sulfadimethoxine, trimethoprim, and dimethoxine. The tipping paper gravure antibacterial ink of the present invention has a reasonable formula, can realize gravure printing on tipping paper, and has antibacterial and antibacterial effects.

[0008] The present invention prepares Ti3C2T x @MnCe-MOF and PHMG@CuO, by adding the two together into the ink, significantly improved the antibacterial properties of the ink, while also improving the mechanical properties. Summary of the invention

[0009] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the prior art and provide an environmentally friendly antibacterial ink and its preparation method and application. The environmentally friendly antibacterial ink comprises the following components by weight: water-based acrylic resin: 100 parts; Ti3C2T x @MnCe-MOF 3-7 parts; PHMG@CuO 2-4 parts; dispersant 1-3 parts; defoamer 2-4 parts; water 120-140 parts. The present invention obtains the composite antibacterial material Ti3C2T x @MnCe-MOF and PHMG@CuO, by utilizing the interaction between the above components, significantly improve the antibacterial properties of the ink, while also improving the mechanical properties. Moreover, the ink is environmentally friendly and has good application prospects.

[0010] The purpose of the invention is to provide an environmentally friendly antibacterial ink.

[0011] Another object of the present invention is to provide a method for preparing an environmentally friendly antibacterial ink.

[0012] Another object of the present invention is to provide an application of environmentally friendly antibacterial ink.

[0013] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0014] An environmentally friendly antibacterial ink, which comprises the following components in parts by weight:

[0015] Water-based acrylic resin: 100 parts;

[0016] Ti3C2T x @MnCe-MOF 3-7 parts;

[0017] PHMG@CuO 2-4 parts;

[0018] 1 to 3 parts of dispersant;

[0019] 2 to 4 parts of defoaming agent;

[0020] 120-140 parts of water.

[0021] The water-based acrylic resin is E0503 water-based acrylic resin with a solid content of 40%; the dispersant is TEGO Dispers 651; and the defoamer is TEGO Foamex 825.

[0022] In the present invention, the preferred technical solution is that the Ti3C2T x The preparation method of @MnCe-MOF includes the following steps:

[0023] (1) Etch the Ti3AlC2 precursor with concentrated HF solution to obtain Ti3C2T x Dispersion, separation, washing, drying to Ti3C2T x ;

[0024] (2) Ultrasonic dispersion of the Ti3C2Tx, cerium salt and manganese salt obtained in step (1) in deionized water, ultrasonication, then addition of 2-methylimidazole, stirring, and then hydrothermal reaction to obtain Ti3C2Tx x @MnCe-MOF;

[0025] Preferably, in step (1), the drying is performed at 80-120° C. for 14-20 hours.

[0026] Further preferably, in step (2), the ratio of Ti3C2Tx, cerium salt, manganese salt and 2-methylimidazole is 30g:1-3mmol:0.5-1.5mmol:8-12mmol; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese acetate.

[0027] More preferably, in step (2), the ultrasonic time is 20 to 40 min, the stirring time is 20 to 40 min, and the hydrothermal reaction conditions are hydrothermal reaction at 110 to 130° C. for 16 to 24 h.

[0028] In the present invention, a further preferred technical solution is that the preparation method of PHMG@CuO comprises the following steps:

[0029] The copper oxide and the silane coupling agent are ultrasonically dispersed in ethanol water, and then stirred at 40-60° C. for 1-3 h, filtered, washed, and dried at 60-90° C. to constant weight to obtain silane-modified copper oxide. The silane-modified copper oxide and polyhexamethylene guanidine are ultrasonically dispersed in deionized water, stirred at 40-60° C. for 10-18 h, filtered, washed, and dried at 60-90° C. to constant weight to obtain PHMG@CuO.

[0030] Preferably, the volume ratio of the ethanol to water is 4:1; the silane coupling agent is one of KH-560 and KH-570; and the mass ratio of the copper oxide to the silane coupling agent is 1:0.2-0.4.

[0031] Further preferably, the mass ratio of the silane-modified copper oxide to polyhexamethylene guanidine is 1:2-3.

[0032] Based on the above-mentioned method for preparing an environmentally friendly antibacterial ink, the preparation method comprises the following steps:

[0033] Water-based acrylic resin, Ti3C2T x @MnCe-MOF, PHMG@CuO, dispersant, defoamer and water were mixed evenly, and then ball-milled at 1500 rpm to 2500 rpm for 1 to 3 h at room temperature to obtain an environmentally friendly antibacterial ink.

[0034] Based on the above, an environmentally friendly antibacterial ink is used in food packaging.

[0035] The present invention has the following beneficial effects:

[0036] MXenes can destroy the cell wall of bacteria, thus killing them. Moreover, MXenes can react with the biological molecules in the bacterial cell membrane and cytoplasm, destroy the cell microstructure, hinder the intake and metabolism of bacterial nutrients, thereby inhibiting bacterial growth and even causing bacterial death. MXenes are made to adsorb manganese and cerium through ultrasound, and then react with 2-methylimidazole to prepare Ti3C2T x @MnCe-MOF has further improved the antibacterial properties. By grafting polyhexamethylene guanidine (PHMG) on the surface of nano-CuO, it not only improves the dispersibility of CuO in the ink, but also makes the above materials have better antibacterial properties as a whole. The prepared environmentally friendly ink has excellent antibacterial properties and good mechanical properties. DETAILED DESCRIPTION

[0037] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0038] The water-based acrylic resin is E0503 water-based acrylic resin, and the solid content is 40%; the dispersant is TEGODispers 651; and the defoamer is TEGO Foamex 825.

[0039] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0040] Example 1

[0041] An environmentally friendly antibacterial ink, which comprises the following components in parts by weight:

[0042] Water-based acrylic resin: 100 parts;

[0043] Ti3C2T x @MnCe-MOF 5 parts;

[0044] PHMG@CuO 3 parts;

[0045] 2 parts of dispersant;

[0046] 3 parts of defoaming agent;

[0047] 130 parts water;

[0048] The Ti3C2T x The preparation method of @MnCe-MOF includes the following steps:

[0049] (1) Weigh 100 g Ti3AlC2 and add it to 100 mL 45 wt% HF solution, stir for 24 h, filter, wash, and dry at 100 °C for 18 h to obtain Ti3C2T x ;

[0050] (2) 30 g of Ti3C2Tx obtained in step (1), 2 mmol of cerium nitrate and 1 mmol of manganese chloride were ultrasonically dispersed in 200 mL of deionized water, ultrasonicated for 30 min, and then 10 mmol of 2-methylimidazole was added, stirred for 30 min, and then hydrothermally reacted at 120 ° C for 20 h to obtain Ti3C2Tx. x @MnCe-MOF.

[0051] The preparation method of PHMG@CuO comprises the following steps:

[0052] 10 g of copper oxide and 3 g of KH-560 were ultrasonically dispersed in 200 mL of ethanol water (the volume ratio of ethanol to water was 4:1), then stirred and reacted at 50°C for 2 h, filtered, washed, and dried at 80°C to constant weight to obtain silane-modified copper oxide; then 10 g of silane-modified copper oxide and 25 g of polyhexamethylene guanidine were ultrasonically dispersed in 200 mL of deionized water, stirred and reacted at 50°C for 14 h, filtered, washed, and dried at 80°C to constant weight to obtain PHMG@CuO, where the molecular weight of the polyhexamethylene guanidine was 3605.

[0053] The preparation method of the environmentally friendly antibacterial ink is as follows:

[0054] Water-based acrylic resin, Ti3C2T x @MnCe-MOF, PHMG@CuO, dispersant, defoamer and water were mixed evenly and then ball-milled at 2000 rpm for 2 h at room temperature to obtain the environmentally friendly antibacterial ink.

[0055] Example 2

[0056] An environmentally friendly antibacterial ink, which comprises the following components in parts by weight:

[0057] Water-based acrylic resin: 100 parts;

[0058] Ti3C2T x @MnCe-MOF 7 parts;

[0059] PHMG@CuO 2 parts;

[0060] 3 parts of dispersant;

[0061] 2 parts of defoaming agent;

[0062] 140 parts water;

[0063] The Ti3C2T x The preparation method of @MnCe-MOF includes the following steps:

[0064] (1) Weigh 100 g Ti3AlC2 and add it to 100 mL 45 wt% HF solution, stir for 24 h, filter, wash, and dry at 100 °C for 18 h to obtain Ti3C2T x ;

[0065] (2) 30 g of Ti3C2Tx obtained in step (1), 3 mmol of cerium chloride and 0.5 mmol of manganese acetate were ultrasonically dispersed in 200 mL of deionized water for 40 min, and then 12 mmol of 2-methylimidazole was added, stirred for 20 min, and then hydrothermally reacted at 130 ° C for 16 h to obtain Ti3C2Tx. x @MnCe-MOF.

[0066] The preparation method of PHMG@CuO comprises the following steps:

[0067] 10 g of copper oxide and 4 g of KH-570 were ultrasonically dispersed in 200 mL of ethanol water (the volume ratio of ethanol to water was 4:1), then stirred and reacted at 60° C. for 1 h, filtered, washed, and dried at 90° C. to constant weight to obtain silane-modified copper oxide; then 10 g of silane-modified copper oxide and 30 g of polyhexamethylene guanidine were ultrasonically dispersed in 200 mL of deionized water, stirred and reacted at 60° C. for 10 h, filtered, washed, and dried at 90° C. to constant weight to obtain PHMG@CuO, where the molecular weight of the polyhexamethylene guanidine was 3605.

[0068] The preparation method of the environmentally friendly antibacterial ink is the same as that of Example 1.

[0069] Example 3

[0070] An environmentally friendly antibacterial ink, which comprises the following components in parts by weight:

[0071] Water-based acrylic resin: 100 parts;

[0072] Ti3C2T x @MnCe-MOF 3 parts;

[0073] PHMG@CuO 4 parts;

[0074] 1 part of dispersant;

[0075] 4 parts of defoamer;

[0076] 120 parts water;

[0077] The Ti3C2T x The preparation method of @MnCe-MOF includes the following steps:

[0078] (1) Weigh 100 g Ti3AlC2 and add it to 100 mL 45 wt% HF solution, stir for 24 h, filter, wash, and dry at 100 °C for 18 h to obtain Ti3C2T x ;

[0079] (2) 30 g of Ti3C2Tx obtained in step (1), 1 mmol of cerium acetate and 1.5 mmol of manganese nitrate were ultrasonically dispersed in 200 mL of deionized water, ultrasonicated for 20 min, then 2-methylimidazole was added, stirred for 40 min, and then hydrothermally reacted at 110 ° C for 24 h to obtain Ti3C2Tx. x @MnCe-MOF.

[0080] The preparation method of PHMG@CuO comprises the following steps:

[0081] 10 g of copper oxide and 2 g of KH-560 were ultrasonically dispersed in 200 mL of ethanol water (the volume ratio of ethanol to water was 4:1), and then stirred at 40°C for 3 h, filtered, washed, and dried at 60°C to constant weight to obtain silane-modified copper oxide; then 10 g of silane-modified copper oxide and 20 g of polyhexamethylene guanidine were ultrasonically dispersed in deionized water, stirred at 40°C for 18 h, filtered, washed, and dried at 60°C to constant weight to obtain PHMG@CuO, and the molecular weight of the polyhexamethylene guanidine was 3605.

[0082] The preparation method of the environmentally friendly antibacterial ink is the same as that of Example 1.

[0083] Comparative Example 1

[0084] The difference between Comparative Example 1 and Example 1 is that the same amount of Ti3C2T x @Ce-MOF replaces Ti3C2T x @MnCe-MOF, the rest will not be elaborated.

[0085] Among them, the Ti3C2T x The preparation method of @Ce-MOF includes the following steps:

[0086] (1) Weigh 100 g Ti3AlC2 and add it to 100 mL 45 wt% HF solution, stir for 24 h, filter, wash, and dry at 100 °C for 18 h to obtain Ti3C2T x ;

[0087] (2) 30 g of Ti3C2Tx obtained in step (1) and 3 mmol of cerium nitrate were ultrasonically dispersed in 200 mL of deionized water, ultrasonicated for 30 min, and then 10 mmol of 2-methylimidazole was added, stirred for 30 min, and then hydrothermally reacted at 120 ° C for 20 h to obtain Ti3C2Tx. x @Ce-MOF.

[0088] Comparative Example 2

[0089] The difference between Comparative Example 2 and Example 1 is that the same amount of Ti3C2T x Replacement of Ti3C2T x @MnCe-MOF, the rest will not be elaborated.

[0090] Among them, the Ti3C2T x The preparation method comprises the following steps:

[0091] Weigh 100g Ti3AlC2 and add it to 100mL 45wt% HF solution, stir for 24h, filter, wash, and dry at 100℃ for 18h to obtain Ti3C2T x .

[0092] Comparative Example 3

[0093] The difference between Comparative Example 3 and Example 1 is that an equal amount of CuO is used to replace PHMG@CuO. The rest is not described in detail.

[0094] Comparative Example 4

[0095] The difference between Comparative Example 4 and Example 1 is that: Ti3C2T x @MnCe-MOF 9 parts; PHMG@CuO 0 parts; the rest are not mentioned here.

[0096] The performance of Examples 1-3 and Comparative Examples 1-4 was tested, and the specific test results are shown in Table 1.

[0097] Among them, surface tension test: surface tension tester;

[0098] Adhesion: tested according to GB / T7706-2008;

[0099] Antibacterial properties are tested according to GB15979-2002.

[0100] Table 1:

[0101]

[0102] It can be seen from Table 1 that the environmentally friendly antibacterial ink prepared by the present invention is prepared by adding Ti3C2T x@MnCe-MOF and PHMG@CuO, by utilizing the interaction between the above components, the antibacterial properties of the ink are significantly improved. The antibacterial rate against Escherichia coli can reach up to 99.95%, and the antibacterial rate against Staphylococcus aureus can reach up to 99.98%. At the same time, the environmentally friendly antibacterial ink prepared by the present invention also has excellent mechanical properties, excellent performance and good application prospects.

[0103] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An environmentally friendly antibacterial ink, characterized in that: The environmentally friendly antibacterial ink comprises the following components by weight: Water-based acrylic resin: 100 parts; Ti3C2T x @MnCe-MOF 3-7 parts; PHMG@CuO 2-4 parts; 1 to 3 parts of dispersant; 2 to 4 parts of defoaming agent; 120-140 parts of water.

2. The environmentally friendly antibacterial ink according to claim 1, characterized in that: The Ti3C2T x The preparation method of @MnCe-MOF includes the following steps: (1) Etch the Ti3AlC2 precursor with concentrated HF solution to obtain Ti3C2T x Dispersion, separation, washing, drying to Ti3C2T x ; (2) Ultrasonic dispersion of the Ti3C2Tx, cerium salt and manganese salt obtained in step (1) in deionized water, ultrasonication, then addition of 2-methylimidazole, stirring, and then hydrothermal reaction to obtain Ti3C2Tx x @MnCe-MOF.

3. The environmentally friendly antibacterial ink according to claim 2, characterized in that: In step (1), the drying is performed at 80 to 120° C. for 14 to 20 hours.

4. The environmentally friendly antibacterial ink according to claim 2, characterized in that: In step (2), the ratio of Ti3C2Tx, cerium salt, manganese salt and 2-methylimidazole is 30g:1-3mmol:0.5-1.5mmol:8-12mmol; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium acetate; the manganese salt is at least one of manganese nitrate, manganese chloride and manganese acetate.

5. The environmentally friendly antibacterial ink according to claim 2, characterized in that: In step (2), the ultrasonic time is 20 to 40 minutes, the stirring time is 20 to 40 minutes, and the hydrothermal reaction conditions are hydrothermal reaction at 110 to 130° C. for 16 to 24 hours.

6. The environmentally friendly antibacterial ink according to claim 1, characterized in that: The preparation method of PHMG@CuO comprises the following steps: The copper oxide and the silane coupling agent are ultrasonically dispersed in ethanol water, and then stirred at 40-60° C. for 1-3 h, filtered, washed, and dried at 60-90° C. to constant weight to obtain silane-modified copper oxide. The silane-modified copper oxide and polyhexamethylene guanidine are ultrasonically dispersed in deionized water, stirred at 40-60° C. for 10-18 h, filtered, washed, and dried at 60-90° C. to constant weight to obtain PHMG@CuO.

7. The environmentally friendly antibacterial ink according to claim 6, characterized in that: The volume ratio of the ethanol to the water is 4:1; the silane coupling agent is one of KH-560 and KH-570; and the mass ratio of the copper oxide to the silane coupling agent is 1:0.2-0.

4.

8. The environmentally friendly antibacterial ink according to claim 6, characterized in that: The mass ratio of the silane-modified copper oxide to polyhexamethylene guanidine is 1:2-3.

9. The method for preparing an environmentally friendly antibacterial ink according to any one of claims 1 to 8 is characterized in that: The preparation method comprises the following steps: Water-based acrylic resin, Ti3C2T x @MnCe-MOF, PHMG@CuO, dispersant, defoamer and water were mixed evenly, and then ball-milled at 1500 rpm to 2500 rpm for 1 to 3 h at room temperature to obtain an environmentally friendly antibacterial ink.

10. Use of the environmentally friendly antibacterial ink according to any one of claims 1 to 8 in food packaging.

Images