A solvent-free antibacterial ink and its preparation method

Abstract

The present application discloses a solvent-free, dual-repellent antibacterial ink and a preparation method thereof. Through the synergistic effect of a homemade low-surface-energy photosensitive resin, micro-nano silica, and homemade antibacterial filler, the ink film has excellent water- and oil-proof properties and self-cleaning properties, which can greatly reduce the adhesion of water and organic solvents on the coating surface, thereby further preventing the growth of bacteria. At the same time, it has an excellent antibacterial rate, and ultimately effectively solves the problem that current packaging coatings based on UV antibacterial inks are prone to failure during long-term use. In addition, the preparation raw materials are simple, the reaction conditions are mild, and no expensive and highly toxic fluorinated surfactants or long-chain silane coupling agents are used. The production cost is low and it is easy to scale up production. The ink can be applied not only to the field of packaging technology, but also to the field of metal protection and glass protection surfaces.

Description

Technical Field

[0001] The present disclosure relates to the technical field of UV inks, and in particular to a UV-curable antibacterial ink. Background Art

[0002] In recent years, metal container packaging has shifted toward environmental friendliness, functionality, fast curing speeds, and high efficiency, with inks being a primary application. Research into environmentally friendly inks focuses on developing solvent-free inks. Functional inks include inks with antibacterial, water- and oil-resistant properties to meet the specific performance requirements of electronics, optics, and sensors. UV-curable inks, which contain no volatile organic compounds and offer fast curing speeds, low energy consumption, and high efficiency, hold great promise.

[0003] Conventional antibacterial inks are divided into four categories: antibacterial UV inks, antibacterial water-based inks, antibacterial water-based UV inks, and antibacterial alcohol-based inks. However, these four types of antibacterial inks have poor stability and are only effective in the short term, but lack long-term effectiveness. They quickly lose effectiveness, especially in high humidity environments and when contaminated by oily pollutants, which greatly shortens their service life. In addition, conventional antibacterial agents such as quaternary ammonium salts, TiO2, nano-Ag, and ZnO have strong photosensitive reactions and are very easy to change color when exposed to light or stored for a long time. Moreover, the performance of antibacterial materials prepared by direct addition is significantly reduced, and Ag changes when exposed to water. + It is easy to precipitate, resulting in a short antibacterial effectiveness period. Organic antibacterial agents such as quaternary ammonium salts will cause secondary pollution and other side effects, which makes it difficult to have application value in UV curing systems. Summary of the Invention

[0004] In view of this, the present disclosure provides a solvent-free ambiphobic antibacterial ink and a preparation method thereof, which solves the problems that the current packaging coating based on UV antibacterial ink is easy to fail in long-term use and the conventional antibacterial agents used have photosensitivity reactions that cause discoloration.

[0005] To achieve the above-mentioned object of the invention, in a first aspect, the solvent-free ambiphobic antibacterial ink disclosed herein comprises the following raw materials in parts by mass:

[0006] 2-25 parts of acrylic resin, 5-40 parts of epoxy resin, 5-25 parts of diluent, 1-15 parts of low surface energy photosensitive resin, 3-4 parts of fluorine-containing additives, 5-15 parts of micro-nano silica, 0.5-5 parts of antibacterial filler, 0.5-5.0 parts of defoaming agent, 0.5-5.0 parts of wetting and dispersing agent, 0.1-5.0 parts of leveling agent, and 0.5-10 parts of photoinitiator.

[0007] In the present disclosure and possible embodiments, the method for preparing the low surface energy photosensitive resin includes:

[0008] After free radical copolymerization of a sulfonyl chain transfer agent, a fluoromonomer containing para-methacrylic acid and poly(ethylene glycol) methyl ether acrylate, glycidyl methacrylate is added to the copolymerization product to introduce a photosensitive group at the tail end of the sulfonyl chain transfer agent to obtain the low surface energy photosensitive resin.

[0009] In the present disclosure and possible embodiments, the synthesis route of the low surface energy photosensitive resin is:

[0010]

[0011] In the present disclosure and possible embodiments, the method for preparing the antibacterial filler includes:

[0012] 5-10 parts of nano-zinc oxide are dispersed in 90 parts of anhydrous ethanol, 1-2 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride are added, 1-2 parts of dopamine are self-assembled on the surface of the nano-zinc oxide to form a polydopamine functional interface, and then a cerium nitrate solution is added to perform an in-situ reduction reaction. After the in-situ reduction reaction is completed, 10-20 parts of calcined flaky microparticles are added to the system in an autoclave at 0.2 MPa, 100°C, and N2, and the reaction is carried out for 12 hours to obtain the antibacterial filler.

[0013] In the present disclosure and possible embodiments, the flaky micron particles are selected from a mixture of one or more of boron nitride, talc, hydrotalcite, montmorillonite, mica powder and kaolin, and have a particle size D≤300 mesh.

[0014] In the present disclosure and possible embodiments, the micro-nano silicon dioxide is a composite of micron SiO2 and nano-SiO2, the particle size of the micron SiO2 is in the range of 5-20 μm, the particle size of the nano-SiO2 is in the range of 7-50 nm, and the mass ratio of the micron SiO2 to the nano-SiO2 is 7-9:1-3.

[0015] In the present disclosure and possible embodiments, the acrylic resin is a mixture of one or more of acrylic polyurethane resin, pure acrylic resin and acrylic epoxy resin; the epoxy resin is a UV-curable difunctional epoxy resin; and the diluent is an acrylic monomer and an epoxy monomer.

[0016] In the present disclosure and possible embodiments, the epoxy resin is a UV-curable difunctional epoxy resin that is a mixture of one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, bis((3,4-epoxycyclohexyl)methyl)adipate and (3,4,3',4'-diepoxy)dicyclohexane.

[0017] In the present disclosure and possible embodiments, the acrylic monomer is one or more of trimethylolpropane triacrylate, tripropylene glycol diacrylate, and 1,6-hexanediol diacrylate;

[0018] The epoxy monomer is a mixture of one or more of pentaerythritol glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and 3-ethyl-3-hydroxymethyloxetane.

[0019] In a second aspect, a method for preparing the solvent-free ambiphobic antibacterial ink according to any one of the first aspects comprises:

[0020] After all the liquid raw materials are mixed and dispersed for 10-30 minutes, all the solid raw materials except the antibacterial filler are added to the liquid raw material mixture and continue to disperse and stir for 30-50 minutes; finally, the antibacterial filler is added and stirred and dispersed for 10-20 minutes. After the dispersion is completed, the mixture is placed in a black container away from light to obtain the solvent-free ambiphobic antibacterial ink; the particle size D of the ink is controlled to be ≤10 μm, and the viscosity is controlled to be 100-800 cps.

[0021] The present invention has the beneficial effects:

[0022] The solvent-free amphiphobic antibacterial ink disclosed in the present invention, through the self-made new low surface photosensitive resin, makes the ink film have better water and oil resistance and self-cleaning properties than commercially available low surface energy resins, which can greatly reduce the adhesion of water and organic solvents on the coating surface, thereby further preventing the breeding of bacteria, and ultimately effectively solving the problem that the current packaging coating based on UV antibacterial ink is easy to lose effectiveness in long-term use; and the self-made antibacterial filler, because it does not use traditional antibacterial agents that are easy to change color and has been modified, is not only not easy to change color, but also has an excellent antibacterial rate; through the use of micro-nano silica, on the one hand, it provides an amphiphobic nano-microstructure, and on the other hand, it improves the wear resistance and hardness of the coating, assisting At the same time, it extends the life of the coating; therefore, the present invention utilizes the synergistic effect of a homemade low-surface-energy photosensitive resin, a homemade antibacterial filler and nano-silica, so that the ink of this patent has multiple properties that are significantly outstanding compared to conventional antibacterial UV inks; in addition, the preparation raw materials are simple, the reaction conditions are mild, and no expensive and highly toxic fluorinated surfactants or long-chain silane coupling agents are used, which reduces production costs, avoids the problem of discoloration of raw materials caused by antibacterial agents, and facilitates scale-up production; moreover, the ink of the present invention can be applied not only to the field of packaging technology, but also to the field of metal protection and glass protection surfaces, and can achieve efficient energy utilization through its effective antibacterial and dirt adhesion reduction properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The above and other objects, features and advantages of the present disclosure will become more apparent through the following description of the embodiments of the present disclosure with reference to the accompanying drawings, in which:

[0024] Figure 1-1 This is the test trace effect of the ink highlighter pen of Examples 1-5 of the present disclosure and the comparative example;

[0025] Figure 1-2 This is the effect of the ink of Examples 1-5 of the present disclosure and the comparative example after wiping off the fluorescent pen test marks;

[0026] Figure 2 These are the antibacterial test results of inks of Examples 1-5 and the comparative example of the present disclosure. DETAILED DESCRIPTION

[0027] The present disclosure is described below based on specific embodiments, but it is worth noting that the present disclosure is not limited to these specific embodiments. In the detailed description of the present disclosure below, some specific details are described in detail. However, for the parts not described in detail, those skilled in the art can also fully understand the present disclosure.

[0028] At the same time, unless the context clearly requires otherwise, words such as "include", "comprising" and the like throughout the specification and claims should be interpreted as inclusive rather than exclusive or exhaustive; that is, as "including but not limited to".

[0029] Unless otherwise specified, the raw materials or reagents used in the examples of the present disclosure can be purchased or synthesized using conventional methods with reference to relevant literature.

[0030] In various embodiments of the present disclosure, the method for preparing the solvent-free ambiphobic antibacterial ink comprises the following steps:

[0031] 1. Preparation of low surface energy photosensitive resin:

[0032] At 75°C, azobisisobutyl cyanide (AIBN) is used as an initiator to cause a free radical copolymerization of a sulfide chain transfer agent (CTA), a fluoromonomer containing para-methacrylic acid, and poly(ethylene glycol) methyl ether acrylate. Glycidyl methacrylate is then added to the copolymer to introduce a photosensitive group at the end of the CTA, ultimately yielding a hydrophobic and oleophobic photosensitive resin with low surface energy. The specific synthetic route is:

[0033]

[0034] 2. Preparation of micro-nano silica:

[0035] Micron-sized and nano-sized SiO2 are compounded in a mass ratio of 7-9:1-3 to obtain micro-nano silicon dioxide; wherein the particle size range of the micron-sized SiO2 is 5-20um, and the particle size range of the nano-sized SiO2 is 7-50nm.

[0036] 3. Preparation of antibacterial fillers:

[0037] 5-10 parts of nano-zinc oxide are dispersed in 90 parts of anhydrous ethanol, 1-2 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride are added, and 1-2 parts of dopamine are used to self-assemble on the surface of the nano-zinc oxide to form a PDA (polydopamine) functional interface. Then, in a closed environment at 80°C, a cerium nitrate solution (mass concentration of 0.2%) is added for an in-situ reduction reaction, and CeO2 is further adsorbed through the PDA functional port by reacting with 5-10 parts of cerium nitrate. Thereafter, the system is transferred to a 0.2MPa, 100°C, N2 autoclave, 10-20 parts of calcined flaky microparticles are added, and a hydrothermal reaction is carried out for 12 hours to obtain an antibacterial filler.

[0038] In a specific embodiment, the calcined flaky micron particles are selected from a mixture of one or more of boron nitride, talc, hydrotalcite, montmorillonite, mica powder and kaolin, and have a particle size D≤300 mesh.

[0039] 4. Preparation of solvent-free dual-repellent antibacterial ink:

[0040] (1) The raw material composition of the solvent-free dual-repellent antibacterial ink is as follows:

[0041] Acrylic resin 2-25%, epoxy resin 5-40%, diluent 5-25%, low surface energy photosensitive resin 1-15%, fluorine-containing additive 3-4 parts, micro-nano silica 5-15%, antibacterial filler 0.5-5%, defoaming agent 0.5-5.0%, wetting and dispersing agent 0.5-5.0%, leveling agent 0.1-5.0%, photoinitiator 0.5-10%.

[0042] In a specific embodiment, the acrylic resin is a mixture of one or more of polyurethane acrylate resin (Agisyn 248), pure acrylic resin (Agisyn 262), and acrylic epoxy resin (Lancolu, L-6111).

[0043] In a specific embodiment, the epoxy resin is a UV-curable difunctional epoxy resin, specifically a mixture of one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, bis((3,4-epoxycyclohexyl)methyl)adipate, and (3,4,3',4'-diepoxy)dicyclohexane.

[0044] In one specific embodiment, the diluent comprises an acrylic monomer and an epoxy monomer. The acrylic monomer is one or more of trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), and 1,6-hexanediol diacrylate (HDDA). The epoxy monomer is a mixture of one or more of pentaerythritol glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 3-ethyl-3-hydroxymethyloxetane.

[0045] In a specific embodiment, the fluorine-containing additive is DSP-859F from Zhongshan Jieshida Fine Chemicals; SiO2 with micron and nanoparticle sizes is purchased from Pioneer Nanomaterials (20nm:5um=9:2); the defoaming agent is BYKJET-9151; the wetting and dispersing agent is BYKJET-9151; the leveling agent is BYK-UV3510; and the photoinitiator is BASF IGM from Germany.

[0046] (2) After all the liquid raw materials in the raw material composition are placed in a stirring tank and stirred and dispersed for 10-30 minutes, all the solid raw materials except the antibacterial filler are added to the above liquid and dispersed and stirred for 30-50 minutes; finally, the antibacterial filler is added and dispersed for 10-20 minutes. After the dispersion is completed, the mixture is placed in a black barrel in the dark to obtain a solvent-free amphiphobic antibacterial ink with a particle size D≤10 μm and a viscosity of 100-800 cps.

[0047] The following are specific embodiments of the present disclosure.

[0048] Example 1

[0049] 1. Preparation of low surface energy photosensitive resin:

[0050] 0.1 parts of CAT and 50 parts of butyl acetate were added to a reaction kettle. A mixture of 10 parts of heptadecafluorodecyl methacrylate and 0.01 parts of AIBN was added dropwise at 75°C. After 1.5 hours of reaction, 10 parts of poly(ethylene glycol) methyl ether acrylate (z=19) was added and the reaction continued for 4 hours. After the reaction, 2 drops of triethylamine were added, the temperature was raised to 80°C, and 0.1 parts of glycidyl methacrylate was added dropwise until the carboxyl absorption peak disappeared as detected by infrared spectroscopy. After the reaction, the solvent was removed by rotary evaporation, and the viscous liquid was collected to obtain a low-surface-energy photosensitive resin.

[0051] 2. Preparation of antibacterial fillers:

[0052] 5 parts of nano-zinc oxide were dispersed in 90 parts of anhydrous ethanol, 1 part of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and stirred at 50°C for 4 hours, 1 part of dopamine was added to the above solution to self-assemble into a PDA functional interface, and then in a closed environment at 80°C, 5 parts of cerium nitrate solution with a mass concentration of 2% was added for in situ reduction reaction. After that, the system was transferred to a 0.2MPa, 100°C, N2 autoclave, 10 parts of calcined boron nitride were added, and the reaction was carried out for 12 hours to obtain an antibacterial filler.

[0053] 3. Preparation of solvent-free amphiphilic antibacterial ink:

[0054] (1) Ink raw material composition:

[0055] 15 parts of difunctional acrylic polyurethane resin, 30 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 5 parts of TPGDA, 16 parts of 3-ethyl-3-hydroxymethyloxetane, 10 parts of low surface energy photosensitive resin, 3 parts of fluorine-containing additives, 7.5 parts of micro-nano silica, 3 parts of antibacterial filler, 0.5 parts of defoaming agent, 2 parts of wetting and dispersing agent, 0.1 parts of leveling agent, and 7.9 parts of photoinitiator.

[0056] (2) Preparation process:

[0057] After all the liquids were placed in a stirring tank and stirred and dispersed for 15 minutes, all the solids except the antibacterial filler were added and continued to be dispersed and stirred for 35 minutes. Finally, the antibacterial filler was added and stirred and dispersed for 20 minutes. After the dispersion was completed, the mixture was placed in a black container in the dark to obtain the solvent-free ambiphobic antibacterial ink of Example 1.

[0058] Example 2

[0059] 1. Preparation of low surface energy photosensitive resin:

[0060] 0.2 parts of CAT and 50 parts of butyl acetate were added to a reaction kettle. A mixture of 15 parts of heptadecafluorodecyl methacrylate and 0.015 parts of AIBN was added dropwise at 75°C. After 1.5 hours of reaction, 10 parts of ethylene glycol methyl ether acrylate (z=17) was added and the reaction continued for 4 hours. After the reaction, 2 drops of triethylamine were added, the temperature was raised to 80°C, and 0.2 parts of glycidyl methacrylate was added dropwise until the carboxyl absorption peak disappeared as detected by infrared detection. After the reaction, the solvent was removed by rotary evaporation and the viscous liquid was collected to obtain a hydrophobic and oleophobic photosensitive resin with low surface energy.

[0061] 2. Preparation of antibacterial fillers:

[0062] 5 parts of nano-zinc oxide were dispersed in 90 parts of anhydrous ethanol, 1.5 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were added and stirred at 50°C for 4 hours, 2 parts of dopamine were added to the above solution to self-assemble into a PDA functional interface, and then in a closed environment at 80°C, 5 parts of a 2% mass concentration of cerium nitrate solution were added for in situ reduction reaction. After that, it was transferred to a 0.2MPa, 100°C, N2 autoclave, 10 parts of calcined hydrotalcite were added, and the reaction was carried out for 12 hours to obtain an antibacterial filler.

[0063] 3. Preparation of solvent-free amphiphilic antibacterial ink:

[0064] (1) Ink raw material composition:

[0065] 25 parts of pure acrylic resin and acrylic epoxy resin, 10 parts of bis((3,4-epoxycyclohexyl)methyl)adipate, 10 parts of TPGDA and pentaerythritol glycidyl ether (1:1), 3 parts of fluorine-containing additives, 15 parts of low surface photosensitive resin, 10 parts of micro-nano silica, 2 parts of antibacterial filler, 5 parts of defoaming agent, 5 parts of wetting and dispersing agent, 5 parts of leveling agent, and 10 parts of photoinitiator.

[0066] (2) Preparation process:

[0067] After all the liquids were placed in a stirring tank and stirred and dispersed for 15 minutes, all the solids except the antibacterial filler were added and continued to be dispersed and stirred for 50 minutes. Finally, the antibacterial filler was added and stirred and dispersed for 10 minutes. After the dispersion was completed, the mixture was placed in a black container in the dark to obtain the solvent-free amphiphobic antibacterial ink of Example 2.

[0068] Example 3

[0069] 1. Preparation of low surface energy photosensitive resin:

[0070] 0.2 parts of CAT and 50 parts of butyl acetate were added to a reaction kettle. A mixture of 10 parts of heptadecafluorodecyl methacrylate and 0.01 parts of AIBN was added dropwise at 75°C. After 1.5 hours of reaction, 15 parts of ethylene glycol methyl ether acrylate (z=19) was added and the reaction continued for 4 hours. After the reaction, 2 drops of triethylamine were added, the temperature was raised to 80°C, and 0.2 parts of glycidyl methacrylate was added dropwise until the carboxyl absorption peak disappeared as detected by infrared detection. After the reaction, the solvent was removed by rotary evaporation and the viscous liquid was collected to obtain a hydrophobic and oleophobic photosensitive resin with low surface energy.

[0071] 2. Preparation of antibacterial fillers:

[0072] 7 parts of nano zinc oxide were dispersed in 90 parts of anhydrous ethanol, 2 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were added and stirred at 50°C for 4 hours, 2 parts of dopamine were added to the above solution to self-assemble into a PDA functional interface, and then in a closed environment at 80°C, 10 parts of a 2% cerium nitrate solution were added for in-situ reduction reaction, and then transferred to a 0.2MPa, 100°C, N2 autoclave, 14 parts of calcined talc were added, and the reaction was carried out for 12 hours to obtain an antibacterial filler.

[0073] 3. Preparation of solvent-free amphiphilic antibacterial ink:

[0074] (1) Ink raw material composition:

[0075] 5 parts of acrylic polyurethane resin and pure acrylic resin, 40 parts of bis((3,4-epoxycyclohexyl)methyl)adipate and (3,4,3',4'-diepoxy)dicyclohexane film-forming agent, 10 parts of HDDA, 15 parts of neopentyl glycol diglycidyl ether, 4 parts of fluorine-containing additives, 5 parts of low surface photosensitive resin, 10 parts of micro-nano silica, 0.5 parts of antibacterial filler, 1.0 parts of defoaming agent, 1.0 parts of wetting and dispersing agent, 0.5 parts of leveling agent, and 8 parts of photoinitiator.

[0076] (2) Preparation process:

[0077] After all the liquids were placed in a stirring tank and stirred and dispersed for 20 minutes, all the solids except the antibacterial filler were added and continued to disperse and stir for 50 minutes. Finally, the antibacterial filler was added and stirred and dispersed for 10 minutes. After the dispersion was completed, the mixture was placed in a black container in the dark to obtain the solvent-free ambiphobic antibacterial ink of Example 3.

[0078] Example 4

[0079] 1. Preparation of low surface energy photosensitive resin:

[0080] 0.15 parts of CAT and 50 parts of butyl acetate were added to a reaction kettle. A mixture of 10 parts of heptadecafluorodecyl methacrylate and 0.01 parts of AIBN was added dropwise at 75°C. After 1.5 hours of reaction, 20 parts of ethylene glycol methyl ether acrylate (z=17) was added and the reaction continued for 4 hours. After the reaction, 2 drops of triethylamine were added, the temperature was raised to 80°C, and 0.15 parts of glycidyl methacrylate was added dropwise until the carboxyl absorption peak disappeared as detected by infrared detection. After the reaction, the solvent was removed by rotary evaporation, and the viscous liquid was collected to obtain a hydrophobic and oleophobic photosensitive resin with low surface energy.

[0081] 2. Preparation of antibacterial fillers:

[0082] 5 parts of nano-zinc oxide were dispersed in 90 parts of anhydrous ethanol, 1 part of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and stirred at 50°C for 4 hours, 1.5 parts of dopamine were added to the above solution to self-assemble into a PDA functional interface, and then in a closed environment at 80°C, 10 parts of a 2% cerium nitrate solution were added for in-situ reduction reaction, and then it was transferred to a 0.2MPa, 100°C, N2 autoclave, 10 parts of calcined mica powder were added, and the reaction was carried out for 12 hours to obtain an antibacterial filler.

[0083] 3. Preparation of solvent-free amphiphilic antibacterial ink:

[0084] (1) Ink raw material composition:

[0085] 5 parts of pure acrylic resin, 10 parts of acrylic polyurethane resin, 30 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 5 parts of TMPTA, 20 parts of 3-ethyl-3-hydroxymethyloxetane, 4 parts of fluorine-containing additives, 9 parts of low surface photosensitive resin, 11.5 parts of micro-nano silica, 5 parts of antibacterial filler, 2 parts of defoaming agent, 2 parts of wetting and dispersing agent, 0.5 parts of leveling agent, and 7 parts of photoinitiator.

[0086] (2) Preparation process:

[0087] After all the liquids were placed in a stirring tank and stirred and dispersed for 10 minutes, all the solids except the antibacterial filler were added and continued to disperse and stir for 50 minutes. Finally, the antibacterial filler was added and stirred and dispersed for 20 minutes. After the dispersion was completed, the mixture was placed in a black container in the dark to obtain the solvent-free ambiphobic antibacterial ink of Example 4.

[0088] Example 5

[0089] 1. Preparation of low surface energy photosensitive resin:

[0090] 0.2 parts of CAT and 50 parts of butyl acetate were added to a reaction kettle. A mixture of 15 parts of heptadecafluorodecyl methacrylate and 0.01 parts of AIBN was added dropwise at 75°C. After 1.5 hours of reaction, 15 parts of ethylene glycol methyl ether acrylate (z=19) was added and the reaction continued for 4 hours. After the reaction, 2 drops of triethylamine were added, the temperature was raised to 80°C, and 0.2 parts of glycidyl methacrylate was added dropwise until the carboxyl absorption peak disappeared as detected by infrared detection. After the reaction, the solvent was removed by rotary evaporation and the viscous liquid was collected to obtain a hydrophobic and oleophobic photosensitive resin with low surface energy.

[0091] 2. Preparation of antibacterial fillers:

[0092] 10 parts of nano-zinc oxide were dispersed in 90 parts of anhydrous ethanol, 1 part of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added and stirred at 50°C for 4 hours, 2 parts of dopamine were added to the above solution to self-assemble into a PDA functional interface, and then in a closed environment at 80°C, 10 parts of a 2% mass concentration of cerium nitrate solution were added for in situ reduction reaction, and then it was transferred to a 0.2MPa, 100°C, N2 autoclave, 20 parts of calcined kaolin were added, and the reaction was carried out for 12 hours to obtain an antibacterial filler.

[0093] 3. Preparation of solvent-free amphiphilic antibacterial ink:

[0094] (1) Ink raw material composition:

[0095] 15 parts of acrylic epoxy resin, 25 parts of (3,4,3',4'-diepoxy)dicyclohexane, 5 parts of TMPTA, 5 parts of TPGDA, 15 parts of 3-ethyl-3-hydroxymethyloxetane, 12 parts of low surface photosensitive resin, 3 parts of fluorine-containing additives, 2 parts of antibacterial filler, 8.5 parts of micro-nano silica, 1.0 part of defoaming agent, 1.0 part of wetting and dispersing agent, 0.5 part of leveling agent, and 7 parts of photoinitiator.

[0096] (2) Preparation process:

[0097] After all the liquids were placed in a stirring tank and stirred and dispersed for 15 minutes, all the solids except the antibacterial filler were added and continued to disperse and stir for 30 minutes. Finally, the antibacterial filler was added and stirred and dispersed for 20 minutes. After the dispersion was completed, the mixture was placed in a black container in the dark to obtain the solvent-free ambiphobic antibacterial ink of Example 5.

[0098] Performance testing:

[0099] In order to compare and illustrate the performance of the inks in Examples 1-5, UV flexographic varnish UV-5100 produced by Zhongshan Kairui High-tech Applied Materials Co., Ltd. was selected as a comparative example.

[0100] 1. The ink properties and properties after coating of the embodiments and comparative examples were measured. The results are shown in Table 1:

[0101] Table 1: Performance of inks after coating in Examples and Comparative Examples

[0102] Viscosity cPs / 25℃ odor Appearance Glossiness finger touch Resistant tape Highlighter-resistant Example 1 459 No obvious odor Light yellow opaque 20 Curing Curing Curing Example 2 399 No obvious odor Milky white opaque 17 Curing Curing Curing Example 3 389 No obvious odor White opaque 19 Curing Curing Curing Example 4 425 No obvious odor White opaque 22 Curing Curing Curing Example 5 401 No obvious odor White opaque 18 Curing Curing Curing Comparative Example 125 Resin smell transparent 94 Curing Curing Curing

[0103] As can be seen from Table 1, in Examples 1-5, the main cross-linked resin is an epoxy UV resin, which reduces the odor of the varnish and avoids the odor of the ink based on acrylic resin. In the comparative example, no relevant micro-nanoparticles are added, and the coating shows transparency but has a resin odor.

[0104] 2. Determination of contact angle:

[0105] Referring to GB / T 30447-2013 "Nanofilm Contact Angle Measurement Method", the instrument used was Shanghai Zhongchen JC2000D1 dynamic contact angle measuring instrument. Each sample was scraped with a 5μm offset applicator. Each droplet was 5μl, the sliding angle was 30ul, and three parallel experiments were set. The experimental results are shown in Tables 2 and 3:

[0106] Table 2 Comparison of contact angles between the low surface energy photosensitive resin of the embodiment and the commercially available low surface energy resin

[0107]

[0108]

[0109] It can be seen from the data in Table 2 that the low surface energy photosensitive resins of Examples 1-5 have significantly improved amphiphobic properties compared to commercially available low surface energy resins.

[0110] Table 3 Contact angle test of ink of embodiment and comparative example

[0111] Water contact angle WCA Oil contact angle OCA Slip angle WSA Example 1 106-110 88-91 30-35 Example 2 108-112 86-89 33-37 Example 3 107-113 89-92 35-40 Example 4 109-112 87-90 38-42 Example 5 110-114 89-94 20-35 Comparative Example 45-50 30-45 /

[0112] Note: Deionized water was used for the water contact angle test and rapeseed oil was used for the oil contact angle test.

[0113] It can be seen from the data in Table 2 that the samples of Examples 1-5 have excellent hydrophobicity and oleophobicity, that is, WCA>90°, OCA>90°, SA<60°; and are significantly better than the samples of the comparative example.

[0114] The solvent-free antibacterial ink film of the present invention has excellent water contact angle and oil contact angle, which cannot be achieved by the products currently sold on the market. The good waterproof and oil-proof and self-cleaning properties can greatly reduce the adhesion of water and organic solvents on the coating surface, thereby further preventing the growth of bacteria and effectively solving the problem that the current packaging coating based on UV antibacterial ink is prone to failure during long-term use.

[0115] 3. Fluorescent pen resistance test:

[0116] When conducting a fluorescent pen resistance test, after the fluorescent pen is applied, the oily fluorescent ink on the coating surface gradually shrinks into small droplets. The smaller the droplets, the more obvious the effect. That is, gently wipe off the ink on the surface. The fewer the remaining traces, the better the effect.

[0117] Depend on Figure 1-1 、 1-2 The test results show that the fluorescent pen marks of the comparative example could not be erased; the fluorescent pen marks of Examples 1-5 could all be erased. In addition, after being applied with the fluorescent pen, the coating surface shrank to a certain extent and shrunk into a small droplet state.

[0118] 4. Antibacterial test:

[0119] Test basis: JIS Z 2801:2012 "Testing and evaluating the antimicrobial properties of antimicrobial products"; test bacteria: Escherichia coli ATCC 8739; Staphylococcus aureus ATCC 6538p; test samples are 6 pieces per group, and the test sample size is 4*4cm; test results are shown in Tables 3.1-3.7 and Figure 2 :

[0120] Table 3.1 Blank Example

[0121]

[0122] Table 3.2 Antibacterial test results of Example 1

[0123]

[0124] Table 3.3 Antibacterial test results of Example 2

[0125]

[0126]

[0127] Table 3.4 Antibacterial test results of Example 3

[0128]

[0129] Table 3.5 Antibacterial test results of Example 4

[0130]

[0131]

[0132] Table 3.6 Antibacterial test results of Example 5

[0133]

[0134] Table 3.7 Comparative Example Antibacterial Test Results

[0135]

[0136]

[0137] It can be seen from the data in the above tables that the antibacterial rates of the inks of Examples 1-5 against Escherichia coli and Staphylococcus aureus are all above 95%, while the comparative example has no antibacterial effect.

[0138] Figure 2The antibacterial test graph shows that after 24 hours, Escherichia coli and Staphylococcus aureus multiplied very densely in the blank control, as did the comparative example, while no obvious colonies appeared in Examples 1-5, indicating that the inks of Examples 1-5 have better antibacterial properties.

[0139] The following conclusions can be drawn from the performance tests of the above comparative examples and embodiments:

[0140] The solvent-free antibacterial ink of the present invention has good antibacterial properties, waterproof and oil-proof effects, and anti-ink adhesion performance. Its comprehensive performance cannot be achieved by other products on the market, filling the gap in the high hydrophobicity and oleophobicity of UV antibacterial, waterproof and oil-proof coatings in the current market; the solvent-free antibacterial, waterproof and oil-proof ink can be used not only in the field of packaging technology, but also in the field of metal protection and glass protection surfaces. Through its effective antibacterial and dirt adhesion reduction performance, efficient energy utilization is achieved.

[0141] The above-described embodiments are merely examples of implementation methods of the present disclosure, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art may make various modifications, equivalent substitutions, and improvements without departing from the scope of the present disclosure, and these modifications are all within the scope of protection of the present disclosure. Therefore, the scope of protection of the present invention shall be based on the appended claims.

Claims

1. A solvent-free, dual-repellent antibacterial ink, characterized in that: Calculated by mass, its raw material composition is: 2-25 parts of acrylic resin, 5-40 parts of epoxy resin, 5-25 parts of diluent, 1-15 parts of low surface energy photosensitive resin, 3-4 parts of fluorine-containing additive, 5-15 parts of micro-nano silica, 0.5-5 parts of antibacterial filler, 0.5-5.0 parts of defoaming agent, 0.5-5.0 parts of wetting and dispersing agent, 0.1-5.0 parts of leveling agent, and 0.5-10 parts of photoinitiator; The method for preparing the low surface energy photosensitive resin comprises: After free radical copolymerization of a sulfonyl chain transfer agent, a fluoromonomer containing para-methacrylic acid, and poly(ethylene glycol) methyl ether acrylate, glycidyl methacrylate is added to the copolymerization product to introduce a photosensitive group at the tail end of the sulfonyl chain transfer agent to obtain the low surface energy photosensitive resin; The preparation method of the antibacterial filler comprises: 5-10 parts of nano-zinc oxide are dispersed in 90 parts of anhydrous ethanol, 1-2 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride are added, 1-2 parts of dopamine are self-assembled on the surface of the nano-zinc oxide to form a polydopamine functional interface, and then a cerium nitrate solution is added to perform an in-situ reduction reaction; after the in-situ reduction reaction is completed, the system is placed in an autoclave at 0.2 MPa, 100°C, and N2, and 10-20 parts of calcined flaky microparticles are added, and the reaction is carried out for 12 hours to obtain the antibacterial filler; The epoxy resin is a UV-curable bifunctional epoxy resin.

2. The solvent-free antibacterial ink according to claim 1, characterized in that: The flaky micron particles are selected from a mixture of one or more of boron nitride, talc, hydrotalcite, montmorillonite, mica powder and kaolin, and have a particle size D≤300 meshes.

3. The solvent-free ambiphobic antibacterial ink according to claim 1 or 2, characterized in that: The micro-nano silicon dioxide is a composite of micron SiO2 and nano-SiO2, the particle size of the micron SiO2 is in the range of 5-20 um, the particle size of the nano-SiO2 is in the range of 7-50 nm, and the mass ratio of the micron SiO2 to the nano-SiO2 is 7-9:1-3.

4. The solvent-free, dual-repellent antibacterial ink according to claim 3, characterized in that: The acrylic resin is a mixture of one or more of acrylic polyurethane resin, pure acrylic resin and acrylic epoxy resin; the diluent is an acrylic monomer and an epoxy monomer.

5. The solvent-free, dual-repellent antibacterial ink according to claim 4, characterized in that: The epoxy resin is a mixture of one or more of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, bis((3,4-epoxycyclohexyl)methyl)adipate and (3,4,3',4'-diepoxy)dicyclohexane.

6. The solvent-free ambiphobic antibacterial ink according to claim 5, characterized in that: The acrylic monomer is one or more of trimethylolpropane triacrylate, tripropylene glycol diacrylate and 1,6-hexanediol diacrylate; The epoxy monomer is a mixture of one or more of pentaerythritol glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and 3-ethyl-3-hydroxymethyloxetane.

7. A method for preparing the solvent-free ambiphobic antibacterial ink according to any one of claims 1 to 6, characterized in that: include: After all the liquid raw materials are mixed and dispersed for 10-30 minutes, all the solid raw materials except the antibacterial filler are added to the liquid raw material mixture and continue to disperse and stir for 30-50 minutes; finally, the antibacterial filler is added and stirred and dispersed for 10-20 minutes. After the dispersion is completed, it is placed in a black container in the dark to obtain the solvent-free double-repellent antibacterial ink; the particle size D of the ink is controlled to be ≤10um, and the viscosity is 100-800 cps.

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