Durable antibacterial cooking-resistant ink as well as preparation method and application thereof

Abstract

The invention relates to the field of ink preparation, and particularly discloses durable antibacterial cooking-resistant ink as well as a preparation method and application thereof. The ink comprises the following components in parts by weight: 20-30 parts of waterborne acrylic resin, 20-30 parts of waterborne polyurethane resin, 10-20 parts of modified carbon black, 3-8 parts of an antibacterial component, 1-2 parts of a wetting dispersant, 1-2 parts of a defoaming agent and 25-35 parts of water, the water-based acrylic resin is prepared from the following raw materials: 30 to 40 parts of acrylic acid, 15 to 20 parts of butyl acrylate, 10 to 20 parts of methyl methacrylate, 5 to 10 parts of phenyl-containing monomer, 20 to 30 parts of hydroxyl-containing monomer, 0.5 to 2 parts of initiator and 20 to 40 parts of solvent. The phenyl-containing monomer comprises styrene and allyl benzyl ether; the hydroxyl group-containing monomer is prepared from hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The printing ink prepared by the invention has steaming and boiling resistance and lasting antibacterial property.

Description

Technical Field

[0001] The present application relates to the field of ink preparation, and more specifically, to a durable antibacterial and retort-resistant ink and a preparation method and application thereof. Background Art

[0002] Traditional inks with a lot of organic solvents have the disadvantages of strong odor and heavy pollution. With the development requirements of green, energy-saving and environmental protection, the development of water-based inks is becoming more and more urgent, and it is an irreversible trend for water-based inks to replace traditional inks.

[0003] However, water-based inks face many problems, including low adhesion, poor weather resistance, and poor abrasion resistance. Especially in the packaging of food and medicine, the penetration of ink after boiling seriously affects food safety. Therefore, the requirements for water-based inks that can resist long-term bacteria and boiling are increasing. However, the presence of ink pigments and the addition of too many antibacterial particles can easily lead to weak boiling resistance of inks. Existing antibacterial agents cannot achieve long-term antibacterial effects. Therefore, how to develop a water-based ink that is long-lasting and resistant to bacteria and boiling is a problem that needs to be solved. Summary of the invention

[0004] In order to solve the problem of poor boiling resistance and antibacterial durability of water-based ink, the present application provides a durable antibacterial and boiling-resistant ink and a preparation method and application thereof.

[0005] In a first aspect, the present application provides a durable antibacterial and cooking-resistant ink, the ink comprising the following components in parts by weight: 20-30 parts of aqueous acrylic resin, 20-30 parts of aqueous polyurethane resin, 10-20 parts of modified carbon black, 3-8 parts of antibacterial component, 1-2 parts of wetting and dispersing agent, 1-2 parts of defoaming agent, and 25-35 parts of water; Preferably, the ink comprises the following components in parts by weight: 25 parts of water-based acrylic resin, 25 parts of water-based polyurethane resin, 18 parts of modified carbon black, 6 parts of antibacterial component, 1 part of wetting and dispersing agent, 1.5 parts of defoaming agent, and 35 parts of water; The raw materials for preparing the water-based acrylic resin include: 30-40 parts of acrylic acid, 15-20 parts of butyl acrylate, 10-20 parts of methyl methacrylate, 5-10 parts of phenyl-containing monomers, 20-30 parts of hydroxyl-containing monomers, 0.5-2 parts of initiators, and 20-40 parts of solvents; Preferably, the raw materials for preparing acrylic resin include: 35 parts of acrylic acid, 16 parts of butyl acrylate, 14 parts of methyl methacrylate, 9 parts of phenyl-containing monomer, 24 parts of hydroxyl-containing monomer, 0.5 parts of initiator, and 30 parts of solvent; The phenyl-containing monomers include: styrene, allyl benzyl ether; The hydroxyl-containing monomers include: hydroxyethyl acrylate and 4-hydroxybutyl acrylate.

[0006] The inventor uses water-based acrylic resin and water-based polyurethane resin as the main resins, and the prepared ink has the characteristics of water-based acrylic resin and water-based polyurethane resin, and has excellent acid and alkali resistance, weather resistance, bonding and other properties. The modified carbon black gives the ink the required color, and the antibacterial component can improve the antibacterial effect of the ink. Under the demand for further improving boiling resistance and wear resistance, the applicant hopes to prepare a water-based acrylic resin with water resistance, high temperature resistance, weather resistance, and good compatibility in the aqueous system as a film-forming substance. By adopting the above scheme, the prepared acrylic resin unexpectedly has excellent water boiling resistance, and the wear resistance and weather resistance are also good. This may be due to the fact that the present application selects phenyl-containing monomers and hydroxyl-containing monomers in the preparation of the resin, and the phenyl-containing monomers select styrene and allyl benzyl ether, and the hydroxyl-containing monomers select hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The introduction of phenyl groups can improve the wear resistance, water resistance and high temperature resistance of the resin, and the introduction of hydroxyl-containing monomers into the polymer chain further improves the water solubility of the resin.

[0007] Through experiments, it was found that the phenyl-containing monomers and hydroxyl-containing monomers of the present application have better boiling resistance when the above-mentioned specific monomers are selected. The inventors believe that styrene and allyl benzyl ether introduce phenyl groups of different chain lengths into the polymer side chains, which may help to arrange and distribute the phenyl groups in the resin system, thereby giving full play to the water resistance and wear resistance of the benzene ring. Hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more conducive to improving the water solubility of the finally prepared acrylic resin based on similar side chain lengths, thereby improving the system compatibility effect and improving the ink performance.

[0008] Preferably, the mass ratio of styrene to allyl benzyl ether is (1-3):1; more preferably 2:1. The mass ratio of hydroxyethyl acrylate to 4-hydroxybutyl acrylate is 5:(2-4); more preferably 5:3.

[0009] Under the above ratio, better arrangement and distribution of the side chain groups are beneficial to the water resistance and water solubility of the finally prepared resin.

[0010] Preferably, the initiator is selected from one or more of azobisisobutyronitrile, dibenzoyl peroxide and azobisisovaleronitrile.

[0011] Preferably, the solvent is selected from one or more of ethyl acetate, toluene, cyclohexanone and isopropanol.

[0012] The water-based acrylic resin of the present application can be prepared by conventional addition polymerization methods. Preferably, the preparation steps of the water-based acrylic resin include: adding 1 / 2 mass acrylic acid, 1 / 2 mass butyl acrylate, 1 / 2 mass methyl methacrylate monomer and 1 / 2 mass initiator to 1 / 2 solvent and stirring evenly, heating to 80-90°C under nitrogen protection for 0.5-1h, adding phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass initiator and 1 / 4 solvent, heating to 100-120°C for 2-4h; continuing to add the remaining monomers, initiator and solvent, and keeping the temperature for 2-4h. After stopping the reaction, cooling, washing and filtering to obtain the product.

[0013] The preparation process is simple in steps and does not require high equipment. The reaction is controlled by feeding in stages, supplementing the initiator, etc. to obtain a water-based acrylic resin with better performance. The water solubility of the resin is improved by simultaneously adding phenyl-containing monomers and hydroxyl-containing monomers to control the reaction.

[0014] Preferably, the modified carbon black is quaternary ammonium salt chitosan modified carbon black, and the preparation steps thereof include: firstly performing an acid treatment on the carbon black, and then grafting the quaternary ammonium salt chitosan with a silane coupling agent as a bridging agent.

[0015] The agglomeration and sedimentation of carbon black are important factors affecting the cooking resistance. Carbon black is modified by quaternary ammonium chitosan. On the one hand, quaternary ammonium chitosan carries a positive charge, which enhances the electrostatic repulsion of carbon black particles after grafting on the carbon black surface, thereby facilitating the dispersion of carbon black in the ink and preventing agglomeration. In addition, the excellent water solubility of quaternary ammonium chitosan can improve the compatibility of carbon black in the system. On the other hand, quaternary ammonium chitosan has good antibacterial properties and can greatly reduce the addition of antibacterial components. It can improve the antibacterial effect together with the antibacterial components, thereby maintaining the long-lasting antibacterial properties of the ink.

[0016] Preferably, the preparation of quaternary ammonium salt chitosan modified carbon black comprises the following steps: 1) Add carbon black into nitric acid aqueous solution and stir to acidify to obtain acidified carbon black; 2) preparing a mixed solution of a silane coupling agent; then adding the acidified carbon black obtained in 1) into the mixed solution, and performing a reflux reaction to obtain silane-modified carbon black; 3) preparing a quaternary ammonium salt chitosan aqueous solution, adding the above-obtained silane-modified carbon black into the aqueous solution, and then adding sodium hydroxide to react to obtain the quaternary ammonium salt chitosan-modified carbon black.

[0017] Nitric acid treatment increases the hydroxyl activity of carbon black, and silane-modified carbon black is obtained by dehydration modification with a silane coupling agent. Carbon black modified with an epoxy silane coupling agent provides a quaternary ammonium salt chitosan grafting site for grafting. The modification of carbon black is achieved through a simple three-step process.

[0018] Preferably, the method for preparing the antibacterial component comprises: preparing a silver-loaded graphene oxide dispersion to obtain a liquid A, preparing a silver-loaded hydrotalcite dispersion to obtain a liquid B, and mixing the liquid A and the liquid B, ultrasonically treating, and filtering to obtain the antibacterial component.

[0019] Preferably, the preparation method of the antibacterial component comprises: 1) Add graphene oxide to water to prepare graphene oxide dispersion, add silver nitrate aqueous solution to the graphene oxide dispersion, ultrasonically disperse, and then centrifuge to obtain silver-loaded graphene oxide; ultrasonically disperse the silver-loaded graphene oxide in 1L of water to obtain silver-loaded graphene oxide dispersion, i.e., solution A. 2) Add hydrotalcite into the silver nitrate aqueous solution and stir to obtain a silver-loaded hydrotalcite dispersion to obtain solution B; 3) Mix liquid A and liquid B, and perform ultrasonic treatment at 500W and 20KHz. After the treatment, filter, wash with water, and dry to obtain the antibacterial component.

[0020] Silver ions are a spectrum of antibacterial agents that achieve antibacterial effects by destroying cell activity, but silver ions are lost quickly and are prone to agglomeration. Conventional wall material coatings and porous material loading can reduce agglomeration to a certain extent and achieve a sustained release effect, but too fast a sustained release cannot achieve a more lasting antibacterial effect, and too slow a sustained release can easily lead to insufficient antibacterial performance. The antibacterial component prepared in this application unexpectedly has an adaptive sustained release effect, which may be because this application loads silver ions on graphene oxide and hydrotalcite to prevent silver ion agglomeration, and then mixes and ultrasonically treats liquid A and liquid B to form a loose but complex loading structure based on different charge assembly and hydrogen bonding. This loading structure has a more complex sustained release path than the layered structure of hydrotalcite and graphene oxide, which effectively improves the sustained release effect of silver ions and prolongs the antibacterial time.

[0021] Preferably, the mass ratio of the modified carbon black to the antibacterial component is 3:1.

[0022] Both quaternary ammonium salts and silver ions have good antibacterial properties. Better antibacterial effects can be achieved through the combined use of organic antibacterial agents and inorganic antibacterial agents. The inventors can further complement each other by using quaternary ammonium chitosan modified carbon black and sustained-release loaded silver ions together to achieve a lasting antibacterial effect. The experimental results show that the modified carbon black and the antibacterial component have better initial antibacterial properties when the mass ratio is 3:1. This may be because at this ratio, the two are better dispersed in the ink and the two different antibacterial agents achieve a better coordinated bactericidal effect.

[0023] On the other hand, the present application provides a method for preparing the above-mentioned durable antibacterial and boiling-resistant ink, comprising the following steps: mixing the components in a uniform ratio to obtain the ink.

[0024] On the other hand, the present application also provides an application of the above-mentioned durable antibacterial and boiling-resistant ink, characterized in that it is applied to printing on BOPP film, and the BOPP film is treated with plasma before printing.

[0025] Polar groups are introduced into the BOPP film after plasma treatment. The modified carbon black of the present application is positively charged, and its adhesion can be further improved through the interaction with the substrate, thereby preventing the precipitation of carbon black and improving the cooking resistance.

[0026] In summary, this application has at least the following beneficial effects: 1. The present application prepares acrylic resin by using phenyl-containing monomers and hydroxyl-containing monomers, and improves the water resistance and abrasion resistance of the obtained acrylic resin by specifically selecting the phenyl-containing monomers and hydroxyl-containing monomers and adjusting the ratio, so as to improve the boiling resistance effect.

[0027] 2. The present application improves the dispersion of carbon black and prevents the precipitation of carbon black by modifying carbon black with quaternary ammonium chitosan, thereby improving the cooking resistance of the system. At the same time, the quaternary ammonium chitosan further gives the ink good antibacterial properties.

[0028] 3. The present application prepares a sustained-release structure by mixing silver-loaded graphene oxide and silver-loaded hydrotalcite, which can effectively prolong the antibacterial property of the ink.

[0029] 4. The present application uses quaternary ammonium salt chitosan to modify carbon black and antibacterial components to achieve antibacterial effects together, and adjusts the ratio of the two to optimize the antibacterial effect and achieve long-lasting antibacterial effects. DETAILED DESCRIPTION

[0030] The present application is further described in detail below in conjunction with the examples. The waterborne polyurethane resin is ADM-F206 from Shandong Aodemei Polymer Materials Co., Ltd.; the carbon black is Cabot 250R; the quaternary ammonium salt chitosan is from Qiuhe Biotechnology, model QHSW202101; and the hydrotalcite is aluminum-magnesium type DHT-4A hydrotalcite.

[0031] Unless otherwise specified, the experimental reagents in the examples or comparative examples are all conventional commercial brands or obtained through conventional preparation processes.

[0032] Preparation Example 1: Preparation of quaternary ammonium salt chitosan modified carbon black: 1) Add 20g of carbon black into 500mL of 20% nitric acid aqueous solution, stir and acidify for 8h, filter, wash with water 3 times, and dry in an oven at 60℃ to obtain acidified carbon black; 2) Prepare 1L of ethanol / water mixed solution (ethanol / water volume ratio 2 / 1), add silane coupling agent KH560 to the mixed solution and stir for 30 minutes, the amount of KH560 added is 2.5wt% of the mixed solution; then add the acidified carbon black obtained in 1) to the mixed solution, reflux and stir at 75°C for 2h, centrifuge after the reaction, wash with water 3 times, and dry in an oven at 60°C to obtain silane-modified carbon black; 3) Prepare a quaternary ammonium chitosan aqueous solution with a mass concentration of 3%, add the above-obtained silane-modified carbon black to the above solution, then add sodium hydroxide and stir, heat to 100°C for reaction for 6 hours, and remove the solvent after the reaction to obtain quaternary ammonium chitosan-modified carbon black. The mass ratio of quaternary ammonium chitosan to silane-modified carbon black is 1:3; the mass of sodium hydroxide is 4% of the mass of the quaternary ammonium chitosan aqueous solution.

[0033] Preparation Example 2: Preparation of antimicrobial components: 1) 10 g of graphene oxide was added to water and stirred to prepare a 5 g / L graphene oxide dispersion, and a 0.1 mol / L silver nitrate aqueous solution was added dropwise to the graphene oxide dispersion, wherein the volume ratio of the graphene oxide dispersion to the silver nitrate aqueous solution was 1:1, ultrasonically dispersed for 1 h, and then centrifuged and washed with water to obtain silver-loaded graphene oxide; the silver-loaded graphene oxide was ultrasonically dispersed in 1 L of water to obtain a silver-loaded graphene oxide dispersion, i.e., liquid A. 2) Add 50g of hydrotalcite into 1L of 3% silver nitrate aqueous solution, stir at 35℃ for 1h to obtain silver-loaded hydrotalcite dispersion, i.e., solution B; 3) Liquid A and liquid B were mixed in a volume ratio of 1:3, and ultrasonically treated at 500 W and 20 kHz for 6 h. After the treatment, the mixture was filtered, washed with water for 3 times, and dried at 60°C to obtain the antibacterial component.

[0034] Preparation Example 3: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a mixed monomer of styrene and allyl benzyl ether in a mass ratio of 2:1; the hydroxyl monomer is a mixed monomer of hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a mass ratio of 5:3; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0035] Preparation Example 4: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a mixed monomer of styrene and allyl benzyl ether in a mass ratio of 0.5:1; the hydroxyl monomer is a mixed monomer of hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a mass ratio of 5:3; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0036] Preparation Example 5: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a mixed monomer of styrene and allyl benzyl ether in a mass ratio of 4:1; the hydroxyl monomer is a mixed monomer of hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a mass ratio of 5:3; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0037] Preparation Example 6: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a styrene monomer; the hydroxyl monomer is a mixed monomer of hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a mass ratio of 5:3; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0038] Preparation Example 7: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is allyl benzyl ether; the hydroxyl monomer is a mixed monomer of hydroxyethyl acrylate and 4-hydroxybutyl acrylate in a mass ratio of 5:3; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0039] Preparation Example 8: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a mixed monomer of styrene and allyl benzyl ether in a mass ratio of 4:1; the hydroxyl monomer is hydroxyethyl acrylate monomer; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0040] Preparation Example 9: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 9g phenyl-containing monomer, 24g hydroxyl-containing monomer, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; wherein the phenyl-containing monomer is a mixed monomer of styrene and allyl benzyl ether in a mass ratio of 4:1; the hydroxyl monomer is 4-hydroxybutyl acrylate monomer; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator to 1 / 2 mass of solvent and stir evenly, heat to 85°C under nitrogen protection and react for 0.5h, add phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass of initiator and 1 / 4 solvent, heat to 110°C and continue reflux reaction for 3h; continue to add remaining monomers, initiator and solvent, keep warm and react for 3h. After stopping the reaction, remove the solvent to obtain the product.

[0041] Preparation Example 10: Preparation of waterborne acrylic resin: Prepare the raw materials: 35g acrylic acid, 16g butyl acrylate, 14g methyl methacrylate, 0.5g azobisisobutyronitrile as initiator, and 30g isopropanol as solvent; Add 1 / 2 mass of acrylic acid, 1 / 2 mass of butyl acrylate, 1 / 2 mass of methyl methacrylate monomer and 1 / 2 mass of initiator into 1 / 2 solvent and stir evenly. Heat to 85°C and react for 0.5h under nitrogen protection. Add remaining monomers, initiator and solvent, heat to 110°C and continue reflux reaction for 4h. Stop the reaction and remove the solvent to obtain the product. Example

[0042] Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 3, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink. Example

[0043] Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 3, 25g of water-based polyurethane resin, 18g of modified carbon black in Preparation Example 1, 6g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink. Example

[0044] Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 3, 25g of water-based polyurethane resin, 16g of modified carbon black in Preparation Example 1, 8g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink. Example

[0045] Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 4, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink. Example

[0046] Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 5, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0047] Comparative Example 1 Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 6, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0048] Comparative Example 2 Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 7, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0049] Comparative Example 3 Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 8, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0050] Comparative Example 4 Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 9, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0051] Comparative Example 5 Raw materials for preparing ink: 25g of water-based acrylic resin in Preparation Example 10, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0052] Comparative Example 6 Ink preparation raw materials: 25g of water-based acrylic resin in Preparation Example 3, 25g of water-based polyurethane resin, 20g of modified carbon black in Preparation Example 1, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 39g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add modified carbon black and wetting dispersant at 800r / min and stir for 30min to obtain ink.

[0053] Comparative Example 7 Preparation of ink raw materials: 25g of water-based acrylic resin in Preparation Example 3, 25g of water-based polyurethane resin, 20g of carbon black, 4g of antibacterial component in Preparation Example 2, 1g of DISPERBYK2012 wetting and dispersing agent, 1.5g of BYK024 defoaming agent, and 35g of water; Specific process steps: add water-based acrylic resin, water-based polyurethane resin and defoaming agent into water according to the proportion and stir at 500r / min for 20min, then add carbon black, antibacterial component and wetting dispersant and stir at 800r / min for 30min to obtain ink.

[0054] Performance testing: The inks of Examples 1-5 and Comparative Examples 1-7 were tested for performance: Retort resistance: The ink is printed on the BOPP film, and the film is boiled in 100°C boiling water to observe whether the ink layer of the film falls off or bubbles. If the ink layer falls off slightly, partially, or completely, it is recorded as falling off. If there are a few bubbles in the ink layer, it is recorded as slight bubbling. If there are obvious bubbles or severe bubbles, it is recorded as bubbling.

[0055] Antibacterial property: Escherichia coli and Staphylococcus aureus were used to determine the antibacterial rate according to GB / T21866-2008. The antibacterial rate after 8 months of testing was the same as the standard. The results of the boiling resistance test are shown in Table 1 below: The results of the persistent antibacterial test are shown in Table 2: It can be seen from Examples 1-5 and Comparative Examples 1-7 of the present application that the ink prepared in the present application can achieve long-lasting high-temperature cooking resistance and long-lasting antibacterial properties. It can be seen from Examples 1-3 that after 120 minutes of boiling water boiling, the ink layer is still intact, does not fall off, and does not bubble; when the mass ratio of modified carbon black to antibacterial component is 3:1, the antibacterial property is the best, which may be due to the two components acting together based on different antibacterial modes, improving the antibacterial effect, and the increase in antibacterial components is conducive to maintaining the long-lasting antibacterial property of the ink. Within the above range, the antibacterial property can be maintained relatively good and long-lasting.

[0056] In combination with Example 1 and Example 4-5, when preparing acrylic resin, the boiling resistance is better when the mass ratio of styrene to allyl benzyl ether is 2:1. This may be because within the above range, the more appropriate distribution of benzene rings improves the water resistance of the system. In combination with Example 1 and Comparative Examples 1-2, it can be seen that the co-polymerization of styrene and allyl benzyl ether to prepare acrylic resin is beneficial to improving the boiling resistance of ink and has little effect on antibacterial properties. The scheme of the present application achieves long-lasting boiling resistance and long-lasting antibacterial effects.

[0057] Combining Example 5 and Comparative Examples 3-4, it can be seen that Example 5 has significantly better resistance to boiling. This may be because, when styrene and allyl benzyl ether are used to prepare acrylic resin, hydroxyl comonomers with different side chain lengths work together with styrene and allyl benzyl ether monomers to improve the distribution of groups and the compatibility of the system, which is beneficial to improving the resistance to boiling of the ink. In addition, the use of hydroxyl comonomers with different side chain lengths improves the compatibility of the system, resulting in a slightly better antibacterial effect.

[0058] Combining Example 1 and Comparative Example 5, it can be seen that when the phenyl-containing monomer and the hydroxyl-containing monomer are not added to the acrylic resin, the boiling resistance is poor; it can be seen from Example 1 and Comparative Example 6 that when the antibacterial component is not added, not only the antibacterial property is poor, but also the antibacterial rate is as low as below 90% after 8 months, and effective and lasting antibacterial cannot be achieved. Combining Example 1 and Comparative Example 7, it can be seen that the antibacterial effect of adding the antibacterial component alone without modifying the carbon black is also poor. The modification of carbon black and the joint action of the antibacterial component not only achieve an excellent antibacterial rate but also a lasting antibacterial effect. In addition, it can be seen from Comparative Example 7 that the modified carbon black has a greater effect on the boiling resistance of the ink. Combining Example 1, Comparative Example 5 and Comparative Example 7, it can be seen that the present application greatly improves the boiling resistance of the ink by modifying the carbon black and preparing a specific boiling-resistant resin to work together.

[0059] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A durable antibacterial and boiling-resistant ink, characterized in that: The ink comprises the following components in parts by weight: 20-30 parts of water-based acrylic resin, 20-30 parts of water-based polyurethane resin, 10-20 parts of modified carbon black, 3-8 parts of antibacterial component, 1-2 parts of wetting dispersant, 1-2 parts of defoaming agent, and 25-35 parts of water; The raw materials for preparing the water-based acrylic resin include: 30-40 parts of acrylic acid, 15-20 parts of butyl acrylate, 10-20 parts of methyl methacrylate, 5-10 parts of phenyl-containing monomers, 20-30 parts of hydroxyl-containing monomers, 0.5-2 parts of initiators, and 20-40 parts of solvents; The phenyl-containing monomers include: styrene, allyl benzyl ether; The hydroxyl-containing monomers include: hydroxyethyl acrylate and 4-hydroxybutyl acrylate.

2. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The mass ratio of styrene to allyl benzyl ether is 1-3:1; the mass ratio of hydroxyethyl acrylate to 4-hydroxybutyl acrylate is 5:2-4.

3. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The initiator is selected from one or more of azobisisobutyronitrile, dibenzoyl peroxide and azobisisovaleronitrile.

4. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The solvent is selected from one or more of ethyl acetate, toluene, cyclohexanone and isopropanol.

5. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The preparation steps of the water-based acrylic resin include: adding 1 / 2 mass acrylic acid, 1 / 2 mass butyl acrylate, 1 / 2 mass methyl methacrylate monomer and 1 / 2 mass initiator to 1 / 2 solvent and stirring evenly, heating to 80-90° C. and reacting for 0.5-1h under nitrogen protection, adding phenyl-containing monomer, hydroxyl-containing monomer, 1 / 4 mass initiator and 1 / 4 solvent, heating to 100-120° C. and reacting for 2-4h; continuing to add the remaining monomers, initiator and solvent, and keeping the temperature for reaction for 2-4h. After stopping the reaction, cooling and removing the solvent to obtain the product.

6. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The modified carbon black is quaternary ammonium salt chitosan modified carbon black, and the preparation steps thereof include: firstly performing an acid treatment on the carbon black, and then grafting the quaternary ammonium salt chitosan with a silane coupling agent as a bridging agent.

7. The durable antibacterial and boiling-resistant ink according to claim 1, characterized in that: The preparation method of the antibacterial component comprises: preparing a silver-loaded graphene oxide dispersion to obtain a liquid A, preparing a silver-loaded hydrotalcite dispersion to obtain a liquid B, and mixing the liquid A and the liquid B, ultrasonically treating, and filtering to obtain the antibacterial component.

8. The durable antibacterial and boiling-resistant ink according to claim 7, characterized in that: The mass ratio of the modified carbon black to the antibacterial component is 3:

1.

9. A method for preparing the durable antibacterial and boiling-resistant ink according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to a proportion.

10. An application of the durable antibacterial and boiling-resistant ink according to any one of claims 1 to 8, characterized in that: Applied to the printing of BOPP film, the BOPP film is treated by plasma before printing.