CN119039833B

CN119039833B - Permeable code-spraying ink for materials difficult to adhere and preparation method thereof

Info

Publication number: CN119039833B
Application number: CN202411515111.6A
Authority: CN
Inventors: 刘金德; 潘龙
Original assignee: Fortuna Imatek Chemical Co ltd
Current assignee: Gu'an Liangchuang Jiayi Inkjet Technology Co ltd
Priority date: 2024-10-29
Filing date: 2024-10-29
Publication date: 2025-01-21
Anticipated expiration: 2044-10-29
Also published as: CN119039833A

Abstract

The invention belongs to the technical field of code-spraying ink, and provides permeable code-spraying ink for materials difficult to adhere and a preparation method thereof, the penetrating code-spraying ink comprises silane modified epoxy acrylic resin, rosin modified acrylic resin, pigment, dispersing agent, leveling agent, defoamer, wetting agent, n-butyl alcohol and deionized water. The permeable code-spraying ink provided by the invention consists of a resin binder, pigment, an auxiliary agent and a solvent, wherein silane modified epoxy acrylic resin and rosin modified acrylic resin are used as compound binders of the code-spraying ink, n-butanol and deionized water are used as compound solvents of the code-spraying ink, so that the permeability and wettability of the code-spraying ink to a substrate difficult to adhere are effectively improved, and the bonding strength and adhesive force between the cured film layer and the substrate difficult to adhere are higher.

Description

Permeable code-spraying ink for materials difficult to adhere and preparation method thereof

Technical Field

The invention belongs to the technical field of code-spraying ink, and relates to permeable code-spraying ink for materials difficult to adhere and a preparation method thereof.

Background

Along with the continuous improvement of the living standard of people, the product quality awareness of modern people is stronger and higher, the labeling requirement on product information is higher and higher, especially, the safety problem of products such as foods, medicines, cosmetics and the like is higher and higher, the label of the products such as foods, medicines, cosmetics and the like is required to be marked with the explanation of protecting the rights and interests of consumers such as production date, batch number, quality control and self-protection awareness of enterprises and automation management level are also continuously improved, the quality control and tracking of the products by using the code spraying technology, the sales channel management and storage management and other businesses are also more and more common, and the code spraying technology can obviously improve the image of the enterprises and the products, promote the sales of the products, improve the working efficiency, increase the economic benefit of the enterprises due to the advantages of flexible, high efficiency, low cost and the like in the aspect of bar code printing, so the application field is increasingly diversified, and the development of the code spraying ink as a main consumable material has wide market prospect.

In the use process of the code-spraying ink, the ink is continuously ink-jet printed on various substrate media to form marks such as patterns, codes, letters, dates and the like. In this process, the code-spraying ink is required to be continuously, uniformly, clearly and firmly printed on the medium. Therefore, the viscosity, the volatility, the adhesion property, the acidity and the alkalinity of the ink are all required to be high.

However, the existing code-spraying ink has poor adhesion on the substrate such as PVC and PE, and needs to be additionally pretreated when in use, such as corona and polarization treatment measures, and good adhesion can be realized by improving the surface energy of the substrate, so that the treatment process is complicated, and therefore, the improvement of the existing code-spraying ink is needed to improve the adhesion between the existing code-spraying ink and the substrate.

Disclosure of Invention

Aiming at the defects existing in the prior art, the invention aims to provide the permeable code-spraying ink for materials difficult to adhere and the preparation method thereof, the permeable code-spraying ink provided by the invention consists of a resin binder, pigment, an auxiliary agent and a solvent, the silane modified epoxy acrylic resin and the rosin modified acrylic resin are used as the compound connecting material of the code-spraying ink, and the n-butyl alcohol and the deionized water are used as the compound solvent of the code-spraying ink, so that the permeability and wettability of the code-spraying ink to the substrate difficult to adhere are effectively improved, and the bonding strength and the adhesive force between the cured film layer and the substrate difficult to adhere are higher.

To achieve the purpose, the invention adopts the following technical scheme:

In a first aspect, the invention provides a permeable code-spraying ink for materials difficult to adhere to, wherein the permeable code-spraying ink comprises silane modified epoxy acrylic resin, rosin modified acrylic resin, pigment, dispersing agent, leveling agent, defoamer, wetting agent, n-butyl alcohol and deionized water.

The permeable code-spraying ink comprises the following components in parts by weight:

28-30 parts of silane modified epoxy acrylic resin;

20-22 parts of rosin modified acrylic resin;

12-15 parts of pigment;

0.1-0.3 parts of a dispersing agent;

0.1-0.3 part of leveling agent;

0.1-0.3 part of defoaming agent;

0.1-0.3 parts of wetting agent;

20-23 parts of n-butanol;

13-15 parts of deionized water.

Wherein the weight part of the silane modified epoxy acrylic resin can be 28 parts, 28.2 parts, 28.4 parts, 28.6 parts, 28.8 parts, 29 parts, 29.2 parts, 29.4 parts, 29.6 parts, 29.8 parts or 30 parts, the weight part of the rosin modified acrylic resin can be 20 parts, 20.2 parts, 20.4 parts, 20.6 parts, 20.8 parts, 21 parts, 21.2 parts, 21.4 parts, 21.6 parts, 21.8 parts or 22 parts, the weight part of the pigment can be 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts or 15 parts, the weight part of the dispersing agent can be 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts or 0.3 parts, the leveling agent may be 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part, the defoamer may be 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part, the wetting agent may be 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part, the n-butanol may be 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts or 23 parts, and the deionized water may be 13 parts, 13.2 parts, 13.4 parts, 13.6 parts, 13.8 parts, 14 parts, 14.2 parts, 14.4 parts, 14.6 parts, 14.8 parts or 15 parts, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

The permeable code-spraying ink provided by the invention consists of a resin binder, pigment, an auxiliary agent and a solvent, wherein silane modified epoxy acrylic resin and rosin modified acrylic resin are used as compound binders of the code-spraying ink, n-butanol and deionized water are used as compound solvents of the code-spraying ink, so that the permeability and wettability of the code-spraying ink to a substrate difficult to adhere are effectively improved, and the bonding strength and adhesive force between the cured film layer and the substrate difficult to adhere are higher.

In the aspect of resin binder, after the silane modified epoxy acrylic resin and the rosin modified acrylic resin are compounded, the dispersibility of the pigment in the code-spraying ink and the fluidity and wettability of the code-spraying ink can be effectively improved, so that a uniform and firm film layer can be formed on the surface of a substrate after the code-spraying ink is solidified.

In the aspect of the composite solvent, the n-butyl alcohol and the deionized water are used as the composite solvent and are mainly used for dissolving resin, regulating the viscosity and the drying speed of ink, and meanwhile, the composite solvent can be matched with a resin binder to a certain extent, so that the adhesive force between the code-spraying ink and a substrate is improved; on the other hand, because the solubility parameters of the n-butanol and the substrate made of plastic materials are similar, the addition of the n-butanol can swell the substrate, so that components such as the resin binder can be facilitated to permeate into the molecular structure of the surface of the substrate, and the branched chains on the molecules of the resin binder and the molecular chains on the surface of the substrate are physically entangled, so that firm interface combination is formed.

The invention also adds other auxiliary agents such as dispersing agent, leveling agent, defoaming agent and wetting agent into the code-spraying ink, wherein, the dispersing agent can be adsorbed on the surface of the pigment, the generated charge repulsion and steric hindrance can avoid flocculation and precipitation of the pigment, the wetting agent can reduce the surface tension of the substance and increase the floatability of the pigment in the resin binder, and the system forms a uniform dispersed phase through the compounding of the dispersing agent and the wetting agent. The permeable code-spraying ink provided by the invention has good quick-drying property and stability, and has good adhesive force between a film layer formed by solidifying the code-spraying ink on the surface of a substrate (such as polyvinyl chloride, polyethylene, polypropylene and other nonpolar polymer materials) which has low surface energy and is difficult to adhere to the substrate.

The polymer resin is used as the binder of the code-spraying ink, and can influence the glossiness, quick-drying property, water resistance, viscosity, rheological property, printing performance and the like of the code-spraying ink to a great extent. Acrylic resins are often used as resin binders for code-spraying inks because of their good gloss and high transparency, but they also have disadvantages of poor pigment dispersibility and storage stability, slow curing speed, and the like. In order to simultaneously improve the curing speed, the storage stability and the adhesive force between the ink and a substrate difficult to adhere, the invention adopts different modification schemes aiming at the characteristics of low surface energy and non-polarity of the substrate difficult to adhere, designs silane modified epoxy acrylic resin and rosin modified acrylic resin with different functional groups and branched structures, increases active functional groups on the molecular chain of the modified resin binder, the modified resin binder prepared by different modification methods can form different colloid centers with pigments and assistants, and the modified resin binder is easier to disperse due to different polarities among different colloid centers compared with a single colloid center formed by a single resin binder, so that stable and uniform code-spraying ink is formed.

The silane modified epoxy acrylic resin and the rosin modified acrylic resin adopted by the invention have a synergistic effect, and are specifically characterized in that in general, the complete peeling between the film layer and the substrate does not occur on the contact surface of the film layer and the substrate, and often occurs in the film layer, so that the disappearance of the adhesive force between the film layer and the substrate is caused by the destruction of the cohesive force of the film layer. In addition, because the epoxy functional group in the silane modified epoxy acrylic resin has strong cohesive force, the silane modified epoxy acrylic resin and the rosin modified acrylic resin have synergistic effect, so that the strong cohesive force of the film itself is endowed, the adhesive force between the film and the substrate is improved, the cohesive force damage of the internal stress is greatly reduced, and the excellent bonding performance between the film and the substrate can be maintained.

The quick-drying property of the code-spraying ink refers to the drying speed of the code-spraying ink, the drying process of the film layer is finished through volatilization, particularly on the surface of a substrate which is difficult to attach, the drying mechanism is that the solvent in the code-spraying ink volatilizes and escapes from the film layer after code spraying, a small part of the solvent is soaked and permeated on the surface of the substrate, then gradually diffuses from the resin binder molecules of the bottom layer to the top layer, finally, the resin binder and pigment remained on the surface of the substrate are completely volatilized, and the resin binder and pigment are dried and film-formed and attached on the surface of the substrate.

Therefore, the molecular structure and the dosage of the resin binder have great influence on the quick-drying property of the code-spraying ink, and therefore, the dosage of the resin binder is particularly limited, and because the molecular structures of the silane modified epoxy acrylic resin and the rosin modified acrylic resin adopted by the invention are complex, when the dosages of the silane modified epoxy acrylic resin and the rosin modified acrylic resin exceed the upper limit of the range defined by the invention, the solvent molecules can cause overlarge resistance to pass through a film layer in the volatilizing process, the volatility of the solvent is poor, and finally the quick-drying property of the code-spraying ink is influenced.

The invention particularly limits the use amount of the pigment to 12-15 parts, the use amount of the pigment can directly influence the storage stability of the code-spraying ink, the storage stability of the code-spraying ink is in a change trend of increasing and then decreasing along with the increase of the use amount of the pigment, when the use amount of the pigment is lower than 12 parts, insufficient pigment molecules and resin binder molecules form a containing system with sufficient number, so that the storage stability of the code-spraying ink is poor, and when the use amount of the pigment exceeds 15 parts, the stability of the code-spraying ink is rapidly reduced because the pigment is too much and cannot be fully dissolved.

The invention particularly limits the use amount of the dispersing agent to 0.1-0.3 part, the use amount of the dispersing agent can directly influence the drying speed of the code-spraying ink, and the drying speed of the code-spraying ink is improved as the use amount of the dispersing agent increases, because the dispersing agent belongs to a surfactant, and is dispersed in a water phase after being added, and is adsorbed on the surface of pigment particles to form a layer of protective film under the action of the surface tension of the pigment particles, the pigment particles cannot be aggregated into large particles to be precipitated under the action of a resistance effect and electrostatic repulsion, in the process, the water adsorbed on the surface of the pigment particles is repelled by the adsorption of the dispersing agent, so that the water is more easily separated from a system in the subsequent drying process, and the drying speed of the code-spraying ink is improved, but when the use amount of the dispersing agent exceeds 0.3 part, the surface of the pigment particles reaches a saturated state, and the redundant dispersing agent is dispersed in a dispersing medium, so that the water which is easily separated from the system becomes difficult to separate under the action of hydration, and the drying speed of the code-spraying ink is reduced.

The invention particularly limits the dosage of deionized water to 13-15 parts, the water content in the code-spraying ink mainly affects the glossiness of the film layer, when the dosage of deionized water is lower than 13 parts, the viscosity of the code-spraying ink is overlarge, the solid content is overlarge, the surface of the film layer is rough, the glossiness is poor, and when the dosage of deionized water exceeds 15 parts, the concentration and the viscosity of the code-spraying ink are affected, the drying speed is too slow, and a flat film layer cannot be formed, so that the glossiness of the film layer is reduced.

In a second aspect, the present invention provides a method for preparing the permeable code-spraying ink for materials difficult to adhere according to the first aspect, where the preparation method includes:

The method comprises the steps of uniformly mixing silane modified epoxy acrylic resin, rosin modified acrylic resin and pigment to obtain a first solution, adding a dispersing agent, a leveling agent, a defoaming agent and a wetting agent into the first solution, uniformly mixing to obtain a second solution, adding n-butyl alcohol and deionized water into the second solution, uniformly mixing, and grinding to obtain the permeable code-spraying ink.

In a preferred embodiment of the present invention, the particle size after grinding is not more than 20. Mu.m, for example, 10. Mu.m, 11. Mu.m, 12. Mu.m, 13. Mu.m, 14. Mu.m, 15. Mu.m, 16. Mu.m, 17. Mu.m, 18. Mu.m, 19. Mu.m, or 20. Mu.m, but the particle size after grinding is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are applicable.

As a preferable technical scheme of the invention, the silane modified epoxy acrylic resin is prepared by the following method:

The method comprises the steps of (1) uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol to obtain a modified solution, injecting epoxy resin and N-butanol into a reaction kettle, mixing, stirring and heating to obtain a first resin solution, adding the modified solution into the reaction kettle under the conditions of stirring and heating, mixing and reacting with the first resin solution in the kettle, and cooling and discharging when the acid value of a reaction product is less than or equal to 5mg/KOH to obtain the modified epoxy resin;

Adding a first composite solvent into another reaction kettle, heating the first composite solvent, adding the modified epoxy resin, the acrylic acid monomer and the first initiator obtained in the step (1) into the reaction kettle under the condition of stirring, and mixing and reacting with the first composite solvent in the kettle to obtain a first intermediate product;

And (3) heating the temperature in the reaction kettle to a first temperature, adding organic siloxane and a second initiator into the reaction kettle under the stirring condition, mixing and reacting with the first intermediate product in the reaction kettle, and adding a pH regulator into the reaction product after the reaction is finished to obtain the silane modified epoxy acrylic resin.

The epoxy resin contains aliphatic hydroxyl groups and ether bonds which are high in polarity and difficult to hydrolyze, the formed film has strong adhesive force and good chemical resistance, rigid phenyl groups and flexible hydroxyl groups on the main chain of the epoxy resin molecule are alternately arranged, the formed film has good temperature resistance, thermal stability and mechanical property, and meanwhile, the epoxy resin modified acrylic resin has strong cohesive force and is difficult to crack, the internal structure of the film can be effectively regulated through the epoxy resin modified acrylic resin, the internal stress of the film is improved, the peeling between the film and a substrate is prevented, and the adhesive force between the film and the substrate is improved. The organic siloxane has excellent heat resistance, weather resistance, oxidation resistance, radiation resistance and other properties, and has low surface energy, hydrophobicity and stain resistance.

The preparation method comprises the steps of firstly introducing unsaturated acid methyl acrylic acid into a molecular chain of epoxy resin by using N, N-dimethylethanolamine as a catalyst, enabling two ends of the molecular chain of the epoxy resin to be connected with unsaturated double bonds, synthesizing an epoxy grafted acrylic acid copolymer by utilizing a graft copolymerization reaction between the epoxy resin and an acrylic acid monomer under the action of an initiator, curing the prepared epoxy grafted acrylic acid copolymer under ultraviolet light or electron radiation by introducing the double bonds, and then adding organic siloxane, wherein a silane chain segment is connected onto the molecular chain of the copolymer by virtue of a ring-opening reaction between an amino functional group on the molecular chain of the organic siloxane and an epoxy functional group on the molecular chain of the epoxy grafted acrylic acid copolymer, so as to obtain the silane modified epoxy acrylic acid resin.

The silane modified epoxy acrylic resin provided by the invention not only has excellent adhesiveness, higher strength and chemical resistance of the epoxy resin, but also keeps good glossiness, plumpness and weather resistance of the acrylic resin, and in addition, the excellent hydrophobicity, impact resistance and high temperature resistance of the silane modified epoxy acrylic resin are endowed by introducing Si-O bond and C-Si bond of the organosiloxane into a molecular chain.

In the preferred embodiment of the present invention, in the step (1), the mass ratio of N, N-dimethylethanolamine, methacrylic acid and N-butanol is 1 (30-35): (30-35), for example, may be 1:30:30, 1:30.5:30.5, 1:31:31, 1:31.5:31.5, 1:32:32, 1:32.5:32.5, 1:33:33, 1:33.5:33.5, 1:34:34, 1:34.5:34.5 or 1:35, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.

In some alternative examples, the epoxy is epoxy E44 or epoxy E51.

In some optional examples, the mass ratio of the epoxy resin to the n-butanol is 1 (0.2-0.3), for example, may be 1:0.2, 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29 or 1:0.3, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the heating temperature of the epoxy resin and the n-butanol is 70-80 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the stirring time of the epoxy resin and the n-butanol is 1-2h, for example, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2.0h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

In some alternative examples, the mass ratio of the methacrylic acid in the modifying solution to the epoxy resin in the first resin solution is 1 (3-5), for example, may be 1:3.0, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4.0, 1:4.2, 1:4.4, 1:4.6, 1:4.8 or 1:5.0, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction temperature of the modifying solution and the first resin solution is 110 to 120 ℃, for example, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ or 120 ℃, but the present invention is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, heating is stopped when the acid value of the reaction product is less than or equal to 5mg/KOH, and discharging is performed when the temperature in the kettle is cooled to 20-30 ℃, wherein the temperature can be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃,28 ℃, 29 ℃ or 30 ℃, but the method is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.

As a preferred embodiment of the present invention, in the step (2), the first compound solvent is composed of an alcohol solvent and an ether solvent.

In some alternative examples, the mass ratio of the alcohol solvent to the ether solvent is 1 (0.5-0.7), for example, may be 1:0.5, 1:0.52, 1:0.54, 1:0.56, 1:0.58, 1:0.6, 1:0.62, 1:0.64, 1:0.66, 1:0.68 or 1:0.7, but not limited to the recited values, and other non-recited values within the range are equally applicable.

In some alternative examples, the alcohol solvent is any one or a combination of at least two of ethylene glycol, propylene glycol, isopropanol, n-butanol, or isobutanol.

In some alternative examples, the ether solvent is any one or a combination of at least two of propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether, or dipropylene glycol butyl ether.

In some alternative examples, the heating temperature of the first compound solvent in the kettle is 70-80 ℃, for example, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but the heating temperature is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.

The invention particularly limits the heating temperature of the first composite solvent in the kettle to 70-80 ℃, the modified epoxy resin, the acrylic acid monomer and the first initiator react at the temperature to obtain the epoxy grafted acrylic acid copolymer, and the grafting conversion rate of the acrylic acid monomer is increased along with the increase of the reaction temperature, but when the reaction temperature exceeds 80 ℃, the heat is mainly used for solvent evaporation, and no obvious promotion effect is caused on the reaction.

In some alternative examples, the modified epoxy resin, the acrylic monomer and the first initiator are injected into the reaction kettle at a constant speed within 0.5-1 h, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of the first composite solvent, the modified epoxy resin, the acrylic monomer and the first initiator is 1 (0.05-0.06): (1.1-1.2): (0.04-0.05), for example, 1:0.05:1.1:0.04、1:0.051:1.11:0.041、1:0.052:1.12:0.042、1:0.053:1.13:0.043、1:0.054:1.14:0.044、1:0.055:1.15:0.045、1:0.056:1.16:0.046、1:0.057:1.17:0.047、1:0.058:1.18:0.048、1:0.059:1.19:0.049 or 1:0.06:1.2:0.05, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction time of the first composite solvent, the modified epoxy resin, the acrylic monomer and the first initiator is 2 to 3 hours, for example, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the acrylic monomer consists of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate, and N-methylolacrylamide.

In some alternative examples, the mass ratio of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide is 1 (0.8-0.9): (0.07-0.08): (0.3-0.4): (0.07-0.08), and may be 1:0.8:0.07:0.3:0.07、1:0.81:0.071:0.31:0.071、1:0.82:0.072:0.32:0.072、1:0.83:0.073:0.33:0.073、1:0.84:0.074:0.34:0.074、1:0.85:0.075:0.35:0.075、1:0.86:0.076:0.36:0.076、1:0.87:0.077:0.37:0.077、1:0.88:0.078:0.38:0.078、1:0.89:0.079:0.39:0.079 or 1:0.9:0.08:0.4:0.08, for example, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

The invention is particularly limited to methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide, wherein the mass ratio of (0.8-0.9), (0.07-0.08), (0.3-0.4), (0.07-0.08) is 1, the methyl methacrylate is taken as a hard monomer, excellent mechanical strength, impact resistance and wear resistance are provided for a film layer, and the ethyl acrylate is taken as a soft monomer, and excellent flexibility, adhesive force and film forming property are provided for the film layer. The acrylic acid is used as a functional monomer, the hardness of the film layer is reduced along with the increase of the use amount of the acrylic acid, and the adhesive force is improved, because the carboxyl content is correspondingly increased along with the increase of the use amount of the acrylic acid, the free movement of a high molecular chain is hindered, and the molecular grid structure replaces intermolecular acting force, so that the rigidity of the epoxy grafted acrylic copolymer is improved, but the adhesive force is reduced. The invention controls the mass ratio of different acrylic monomers, so that the prepared film has excellent film forming property and adhesive force, and also has higher strength and hardness.

In a preferred embodiment of the present invention, in the step (3), the first temperature is 90 to 100 ℃, for example, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃, but the present invention is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.

In some alternative examples, the organosiloxane and the second initiator are injected into the reaction kettle at a constant speed within 0.5-1 h, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of the acrylic monomer, the organosiloxane, and the second initiator when mixed is 10 (0.5-0.6): (0.1-0.12), such as 10:0.5:0.1、10:0.51:0.102、10:0.52:0.104、10:0.53:0.106、10:0.54:0.108、10:0.55:0.11、10:0.56:0.112、10:0.57:0.114、10:0.58:0.116、10:0.59:0.118 or 10:0.6:0.12, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

The invention particularly limits the mass ratio of (0.5-0.6): (0.1-0.12) of the acrylic monomer, the organosiloxane and the second initiator to 10 when being mixed, and particularly limits the dosage of the organosiloxane, wherein the dosage of the organosiloxane can influence the water resistance, hardness, stability, adhesion force between the substrate and other properties of the code-spraying ink. Specifically:

in terms of water resistance, when the amount of organosiloxane is too low, the improvement of the water resistance of the code-spraying ink is limited;

in terms of stability, when the dosage of the organosiloxane is too high, the alkoxy in the molecular chain segment of the connected resin binder can generate hydrolytic polycondensation and crosslinking during storage, so that the free space of the molecular chain of the resin binder is greatly reduced, the viscosity of the code-spraying ink is improved, the particle size of emulsion liquid drops is increased, the system is unstable, and the precipitation layering phenomenon is easy to occur.

In terms of hardness and adhesive force, with the increase of the usage amount of the organosiloxane, si-O-Si bonds formed between the interface of the film layer and the substrate are increased, the adhesive force between the film layer and the substrate is enhanced under the action of chemical bonds, and meanwhile, alkoxy grafted on a molecular chain of the resin binder is subjected to intermolecular chain condensation in the film layer, so that a compact crosslinked structure is formed inside the film layer, and the water resistance and hardness of the film layer are further improved. Meanwhile, the organosiloxane is easy to hydrolyze in water and is self-polymerized, so that the organosiloxane is difficult to copolymerize with epoxy resin, and in the film forming process, resin connecting feed liquid drops obtained by self-polymerization cannot continuously form a film due to large difference of glass transition temperature, and the film layer is cracked, so that the adhesive force between the film layer and a substrate is greatly reduced.

In some alternative examples, the reaction time of the first intermediate product, the organosiloxane and the second initiator is 3-4 h, for example, 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4.0h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

The organosiloxane is any one or a combination of at least two of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triisopropoxy silane or vinyl triacetoxy silane.

The first initiator and the second initiator are each independently selected from azobisisobutyronitrile or benzoyl peroxide.

In some alternative examples, the pH adjuster is added to the reaction product after the reaction is finished to adjust the pH to 8-9, for example, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9 or 9.0, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

The pH regulator is any one or the combination of at least two of N, N-dimethylethanolamine, triethylamine or triethanolamine.

As a preferable technical scheme of the invention, the rosin modified acrylic resin is prepared by the following method:

Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle, mixing and stirring in nitrogen atmosphere, heating to obtain a raw material solution, adding maleic anhydride into the reaction kettle, mixing and reacting with the raw material solution in the kettle to obtain a second intermediate product, continuously adding diethylenetriamine into the reaction kettle, mixing and reacting with the second intermediate product in the kettle to obtain a third intermediate product, continuously adding pentaerythritol and zinc oxide into the reaction kettle, mixing and reacting with the third intermediate product in the kettle, and cooling and discharging after the reaction is finished to obtain the maleated rosin modified polyurethane resin;

And (II) adding a second composite solvent into another reaction kettle, heating the second composite solvent, adding the maleic rosin modified polyurethane resin obtained in the step (I) into the reaction kettle under the condition of stirring, mixing with the second composite solvent in the kettle to obtain a second resin solution, heating the temperature in the kettle to a second temperature, adding methyl methacrylate, acrylic acid, styrene and a third initiator into the reaction kettle under the condition of stirring, mixing with the second resin solution in the kettle to react to obtain a fourth intermediate product, heating the temperature in the kettle to a third temperature, adding the fourth initiator and butanone into the reaction kettle under the condition of stirring, mixing with the fourth intermediate product in the kettle to react, and obtaining the rosin modified acrylic resin after the reaction is finished.

The rosin molecule contains more hydrophobic functional groups, so that the glossiness and the water resistance of the code-spraying ink can be improved, but the rosin has the defects of brittleness, easiness in crystallization, easiness in oxidation, corrosion resistance, relatively high acid value and the like, so that the unmodified rosin raw material is difficult to meet the use requirement of the code-spraying ink.

The invention firstly carries out D-A addition reaction on rosin through maleic anhydride, in the addition reaction process of maleic anhydride and rosin, the generation of side reaction caused by local overheating of rosin raw materials in the heating process can be prevented by adding antioxidant para-hydroxyanisole and a small amount of deionized water, meanwhile, in the early stage of the D-A addition reaction, the para-hydroxyanisole and the deionized water can protect the rosin raw materials from being oxidized, the D-A addition reaction is promoted to be fully carried out, polyamide resin with good water solubility is synthesized, and the maleic rosin synthesized through the D-A addition reaction has greatly improved softening point of resin connecting materials due to the generation of compound with condensed multi-alicyclic structure, so that the film layer after code spraying has better gloss and higher heat resistance;

Then, the polyamide is subjected to esterification reaction with pentaerythritol under the action of a zinc oxide catalyst to generate water-soluble maleic rosin modified polyurethane resin, and the esterification reaction between the maleic rosin and the pentaerythritol can not only reduce the acid value of the rosin and improve the thermal stability of the rosin, but also strengthen the acid and alkali corrosion resistance of the rosin;

Finally, through graft copolymerization reaction between acrylic monomers and the maleic rosin modified polyurethane resin, rosin modified acrylic resin is synthesized, carboxyl in acrylic acid is a strong polar group, chemical bonding is easy to occur, and the adhesive force between a film layer and a substrate is improved.

The rosin modified acrylic resin provided by the invention has complex branched chain functional groups of the maleic rosin, under the swelling corrosion action of a composite solvent on a substrate, the branched chain functional groups of the maleic rosin on the rosin modified acrylic resin easily enter spiral gaps of molecules on the surface of the substrate, and the branched chain functional groups which have entered the spiral gaps are hindered to be removed along with the further movement of the rosin modified acrylic resin molecules, so that a molecular-scale physical anchoring effect is formed, the distance between a resin binder molecule and the substrate molecules is further shortened by the anchoring effect, and when the distance between the resin binder molecule and the substrate molecules is shortened from 1X 10 ^-3 mu m to 0.3X 10 ^-3 mu m, the molecular acting force between the resin binder molecule and the substrate molecules is increased by 10 times, so that the adhesive force between a film layer and the substrate is greatly improved.

In the step (I), the mass ratio of the rosin to the para-hydroxyanisole to the deionized water is (8-10): (0.12-0.15): 1, for example, 8:0.12:1、8.2:0.125:1、8.4:0.13:1、8.6:0.135:1、8.8:0.14:1、9:0.145:1、9.2:0.15:1、9.4:0.12:1、9.6:0.13:1、9.8:0.14:1 or 10:0.15:1, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the heating temperature of the rosin, the para-hydroxyanisole and the deionized water is 175-180 ℃, such as 175 ℃, 175.5 ℃, 176 ℃, 176.5 ℃, 177 ℃, 177.5 ℃, 178 ℃, 178.5 ℃, 179 ℃, 179.5 ℃ or 180 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the heating time of the rosin, the para-hydroxyanisole and the deionized water is 0.5-1.5 h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of the rosin to the maleic anhydride is 1 (0.2-0.25), for example, 1:0.2, 1:0.205, 1:0.21, 1:0.215, 1:0.22, 1:0.225, 1:0.23, 1:0.235, 1:0.24, 1:0.245 or 1:0.25, but not limited to the recited values, and other non-recited values within the range are equally applicable.

In some alternative examples, the reaction temperature of the raw material solution and the maleic anhydride is 200-210 ℃, for example, 200 ℃, 201 ℃, 202 ℃, 203 ℃, 204 ℃, 205 ℃, 206 ℃, 207 ℃, 208 ℃, 209 ℃ or 210 ℃, but not limited to the recited values, and other non-recited values in the range of the values are equally applicable.

The effective reaction component in the rosin is abietic acid type resin acid, and the maleic anhydride and the abietic acid type resin acid in the rosin are easy to generate D-A addition reaction to generate the maleic rosin with a tricarboxyl structure. However, at normal temperature, the abietic acid type resin acid content in rosin is very low, and at high temperature, resin acids of other structures in rosin are converted into abietic acid type resin acids. Thus, the high temperature favors the D-A addition reaction of maleic anhydride with rosin. However, there are two factors that limit the reaction temperature not to be too high:

(1) Rosin is used as a substance which is relatively active at high temperature, and can not be oxidized under the completely anaerobic reaction condition, so that the color of a reaction product is deepened, the chromaticity of the finally obtained code-spraying ink is seriously influenced, and (2) maleic anhydride is unstable at high temperature, and sublimation phenomenon occurs when the reaction temperature exceeds 210 ℃, so that the waste of reaction raw materials and the reduction of reaction yield are caused. In view of the above two factors, the present invention is particularly limited to a reaction temperature of 200 to 210 ℃ between the raw material solution and maleic anhydride.

In some alternative examples, the reaction time between the raw material solution and the maleic anhydride is 2-3 h, for example, 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

In some alternative examples, the mass ratio of the rosin to the diethylenetriamine is 1 (0.4-0.6), for example, 1:0.4, 1:0.42, 1:0.44, 1:0.46, 1:0.48, 1:0.5, 1:0.52, 1:0.54, 1:0.56, 1:0.58 or 1:0.6, but not limited to the recited values, other non-recited values within the range are equally applicable.

In some alternative examples, the reaction temperature of the second intermediate product and the diethylenetriamine is 150 to 160 ℃, for example, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃, 156 ℃, 157 ℃, 158 ℃, 159 ℃ or 160 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction time between the second intermediate product and the diethylenetriamine is 0.5-1.5 h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of rosin, pentaerythritol, and zinc oxide is 1 (0.08-0.12): (0.14-0.16), such as 1:0.08:0.14、1:0.085:0.142、1:0.09:0.144、1:0.095:0.146、1:0.1:0.148、1:0.105:0.15、1:0.11:0.152、1:0.115:0.154、1:0.12:0.156、1:0.1:0.158 or 1:0.11:0.16, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction temperature of the third intermediate product, pentaerythritol and zinc oxide is 260-265 ℃, such as 260 ℃, 260.5 ℃, 261 ℃, 261.5 ℃, 262 ℃, 262.5 ℃, 263 ℃, 263.5 ℃, 264 ℃, 264.5 ℃ or 265 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction time of the third intermediate product, pentaerythritol and zinc oxide is 0.5 to 1.5h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, heating is stopped after the reaction is finished, and the material is discharged when the temperature in the kettle is cooled to 20-30 ℃, for example, 20 ℃,21 ℃,22 ℃,23 ℃,24 ℃,25 ℃,26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but the material is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.

In a preferred embodiment of the present invention, in the step (II), the second compound solvent is composed of isopropanol, ethylene glycol diethyl ether and ethanol.

In some alternative examples, the mass ratio of isopropyl alcohol, ethylene glycol diethyl ether and ethanol is 1 (0.3-0.35): (0.7-0.8), for example, 1:0.3:0.7、1:0.305:0.71、1:0.31:0.72、1:0.315:0.73、1:0.32:0.74、1:0.325:0.75、1:0.33:0.76、1:0.335:0.77、1:0.4:0.78、1:0.45:0.79 or 1:0.5:0.8, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the heating temperature of the second compound solvent in the kettle is 40-50 ℃, for example, 40 ℃, 41 ℃,42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ or 50 ℃, but not limited to the recited values, and other non-recited values in the range of the values are equally applicable.

In some optional examples, the mass ratio of the maleated rosin modified polyurethane resin to the second compound solvent is 1 (1.5-1.6), for example, may be 1:1.5, 1:1.51, 1:1.52, 1:1.53, 1:1.54, 1:1.55, 1:1.56, 1:1.57, 1:1.58, 1:1.59 or 1:1.6, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the second temperature is 70 to 80 ℃, such as 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, or 80 ℃, but the second temperature is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the methyl methacrylate, acrylic acid, styrene and the third initiator are injected into the reaction kettle at a constant speed within 0.5-1 h, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of the maleated rosin modified polyurethane resin, the methyl methacrylate, the acrylic acid, the styrene and the third initiator is 10 (2.5-2.6): (1.5-1.6): (1.4-1.5): (0.015-0.025), for example, 10:2.5:1.5:1.4:0.015、10:2.51:1.51:1.41:0.016、10:2.52:1.52:1.42:0.017、10:2.53:1.53:1.43:0.018、10:2.54:1.54:1.44:0.019、10:2.55:1.55:1.45:0.02、10:2.56:1.56:1.46:0.021、10:2.57:1.57:1.47:0.022、10:2.58:1.58:1.48:0.023、10:2.59:1.59:1.49:0.024 or 10:2.6:1.6:1.5:0.025, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

In some alternative examples, the reaction time of the second resin solution, methyl methacrylate, acrylic acid, styrene and the third initiator is 1 to 2 hours, for example, 1.0 hours, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2.0 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.

In some alternative examples, the third temperature is 85 to 95 ℃, such as 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃,90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃ or 95 ℃, but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.

In some alternative examples, the fourth initiator and butanone are injected into the reaction kettle at a constant speed within 0.5-1 h, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the mass ratio of the maleated rosin modified polyurethane resin, the fourth initiator and the butanone is 10 (1.3-1.4): (0.001-0.002), for example, 10:1.3:0.001、10:1.31:0.0011、10:1.32:0.0012、10:1.33:0.0013、10:1.34:0.0014、10:1.35:0.0015、10:1.36:0.0016、10:1.37:0.0017、10:1.38:0.0018、10:1.39:0.0019 or 10:1.4:0.002, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the reaction time of the fourth intermediate product, the fourth initiator and the methyl ethyl ketone is 3-4 h, for example, 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4.0h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.

In some alternative examples, the third initiator and the fourth initiator are each independently selected from azobisisobutyronitrile or benzoyl peroxide.

Compared with the prior art, the invention has the beneficial effects that:

Drawings

FIG. 1 is a flow chart of a method for preparing the permeable code-spraying ink according to embodiments 1-5 of the present invention;

FIG. 2 is an infrared spectrum of a silane modified epoxy acrylic resin prepared in example 1 of the present invention;

FIG. 3 is an infrared spectrum of a rosin raw material and a maleated rosin modified polyurethane resin prepared in example 1 of the present invention;

FIG. 4 is an infrared spectrum of the rosin-modified acrylic resin prepared in example 1 of the present invention;

FIG. 5 is a nuclear magnetic resonance spectrum of the maleated rosin-modified polyurethane resin prepared in example 1 of the present invention;

FIG. 6 is a nuclear magnetic resonance spectrum of the rosin-modified acrylic resin prepared in example 1 of the present invention;

FIG. 7 is a graph showing the particle size distribution of the permeable code-jet ink prepared in comparative example 1 of the present invention;

FIG. 8 is a graph showing the particle size distribution of the permeable code-jet ink prepared in comparative example 2 of the present invention;

FIG. 9 is a graph showing the particle size distribution of the permeation type code-spraying ink prepared in example 1 of the present invention.

Detailed Description

The technical scheme of the application is described in detail below with reference to specific embodiments and attached drawings. The examples described herein are specific embodiments of the present application for illustrating the concepts of the application, and are intended to be illustrative and exemplary and are not to be construed as limiting the scope of the embodiments and the application. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.

The chemical reagents adopted in the embodiment and the comparative example are all commercial products, and the information of the specification, the model, the manufacturer and the like is as follows:

N, N-dimethylethanolamine of 99% purity, available from Gu Xu chemical Co., ltd;

methacrylic acid, 99.5% pure, purchased from Shandong Jinyue New Material Co., ltd;

n-butanol with purity of 99.9% was purchased from Jinan chemical industry Co., ltd;

epoxy E44, industrial grade, available from Wuhan energy Kernel pharmaceutical chemical Co., ltd;

epoxy E51, industrial grade, available from Wuhan energy Kernel pharmaceutical chemical Co., ltd;

ethylene glycol B25695-5ml, available from Shanghai Yuan Ye Biotechnology Co., ltd;

Isopropyl alcohol with purity of 99.5% is purchased from Jinan Shanhai chemical technology Co., ltd;

Dipropylene glycol methyl ether with purity of 99.5% is purchased from Shandong Xin Heng chemical Co., ltd;

Ethylene glycol butyl ether B65648-250mg, available from Shanghai Seiyaku Biotechnology Co., ltd;

dipropylene glycol butyl ether with purity of 99.9% was purchased from Jinan Jinri and chemical industry Co., ltd;

benzoyl peroxide, 99% pure, was purchased from ataxia, yofeng chemical company, inc;

azobisisobutyronitrile, 99% pure, purchased from Shandong Jinyue New Material Co., ltd;

triethylamine with 99% purity was purchased from ataxia poly-mex chemical company, inc;

triethanolamine, an industrial grade, purchased from Nantong Runfeng petrochemical Co., ltd;

methyl methacrylate with purity of 99.5%, purchased from Jinan century to chemical industry Co., ltd;

ethyl acrylate with 99.9% purity, purchased from Shandong chemical industry Co., ltd;

acrylic acid with a purity of 99.9% was purchased from the company of chemical industry, inc. of the south China century;

hydroxyethyl acrylate with purity of 99.9 percent, which is purchased from Shandonglang chemical industry Co., ltd;

N-methylolacrylamide S71476-25g, available from Shanghai Seiya Biotechnology Co., ltd;

Vinyl trimethoxy silane with purity of 99.5% and purchased from Wohan Xinxin Jiali biotechnology Co., ltd;

vinyl triethoxysilane, 99% pure, purchased from the biological technology limited of kanli, marchan Xinxin;

vinyl triisopropoxysilane S95559-25g available from Shanghai Seiyaka Biotechnology Co., ltd;

Rosin M81442, available from Shanghai Michelson Biochemical Co., ltd;

The purity of the p-hydroxyanisole is 99.5%, and the p-hydroxyanisole is purchased from Jinan century to chemical industry Co., ltd;

maleic anhydride with 99% purity was purchased from ataxia south kernel chemical company, ltd;

diethylenetriamine with purity of 99.5% is purchased from Jinan chemical industry Co., ltd;

Zinc oxide (S24314-500 g, available from Shanghai Yuan Yes Biotechnology Co., ltd.;

ethylene glycol ethyl ether with purity of 99.5%, which is purchased from Jinan Jinri and chemical industry limited company;

ethanol, 99% pure, purchased from Nanjing chemical agents Co., ltd;

Styrene, 99% pure, purchased from Shandong new materials Co., ltd;

Methyl ethyl ketone, 99% pure, fu Chemicals, inc.

Example 1

The embodiment provides a preparation method of permeable code-spraying ink for materials difficult to adhere, as shown in fig. 1, which specifically comprises the following steps:

(1) Uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol according to the mass ratio of 1:30:30 to obtain a modified solution, injecting epoxy resin E44 and N-butanol into a reaction kettle according to the mass ratio of 1:0.2, mixing and stirring for 2 hours at 70 ℃ to obtain a first resin solution, adding the modified solution into the reaction kettle under the heating condition of stirring and 110 ℃, mixing and reacting with the first resin solution in the kettle, wherein the mass ratio of the methacrylic acid in the modified solution to the epoxy resin in the first resin solution is 1:3, stopping heating when the acid value of a reaction product is less than or equal to 5mg/KOH, and discharging when the temperature in the kettle is reduced to 20 ℃ to obtain the modified epoxy resin;

(2) Adding a first composite solvent (composed of ethylene glycol and ethylene glycol butyl ether with the mass ratio of 1:0.5) into another reaction kettle, heating the first composite solvent to 70 ℃, adding the modified epoxy resin, the acrylic acid monomer and benzoyl peroxide obtained in the step (1) into the reaction kettle at a constant speed within 0.5h under the stirring condition, mixing and reacting for 3h with the first composite solvent in the kettle, wherein the mass ratio of the first composite solvent to the modified epoxy resin to the acrylic acid monomer to the benzoyl peroxide is 1:0.05:1.1:0.04, and the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide with the mass ratio of 1:0.8:0.07:0.3:0.07, so as to obtain a first intermediate product after the reaction is finished;

Heating the temperature in the reaction kettle to 90 ℃, adding vinyltrimethoxysilane and benzoyl peroxide into the reaction kettle at a constant speed within 0.5h under the stirring condition, mixing and reacting for 4h with a first intermediate product in the reaction kettle, wherein the mass ratio of the acrylic acid monomer to the vinyltrimethoxysilane to the benzoyl peroxide is 10:0.5:0.1, and adding N, N-dimethylethanolamine into the reaction product after the reaction is finished to adjust the pH value to 8, so as to obtain silane modified epoxy acrylic resin;

(3) Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle according to the mass ratio of 8:0.12:1, and mixing and stirring for 1.5 hours under the nitrogen atmosphere at 175 ℃ to obtain a raw material solution;

Adding maleic anhydride into a reaction kettle, wherein the mass ratio of rosin to maleic anhydride is 1:0.2, and mixing the maleic anhydride with a raw material solution in the kettle at 200 ℃ for 3 hours to obtain a second intermediate product;

continuously adding diethylenetriamine into a reaction kettle, wherein the mass ratio of rosin to diethylenetriamine is 1:0.4, and mixing the diethylenetriamine with a second intermediate product in the kettle to react for 1.5 hours at 150 ℃ to obtain a third intermediate product;

Continuously adding pentaerythritol and zinc oxide into a reaction kettle, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide is 1:0.08:0.14, mixing the pentaerythritol, the zinc oxide and a third intermediate product in the kettle at 260 ℃ for reaction for 1.5 hours, stopping heating after the reaction is finished, and discharging when the temperature in the kettle is reduced to 20 ℃ to obtain the maleated rosin modified polyurethane resin;

(4) Adding a second composite solvent (consisting of isopropanol, ethylene glycol diethyl ether and ethanol with the mass ratio of 1:0.3:0.7) into another reaction kettle, heating the second composite solvent to 40 ℃, adding the maleated rosin modified polyurethane resin obtained in the step (3) into the reaction kettle under the stirring condition, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleated rosin modified polyurethane resin to the second composite solvent is 1:1.5;

Heating the temperature in the kettle to 70 ℃, adding methyl methacrylate, acrylic acid, styrene and benzoyl peroxide into the reaction kettle at a constant speed within 0.5h under the stirring condition, mixing and reacting with a second resin solution in the kettle for 2h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the methyl methacrylate to the acrylic acid to the styrene to the benzoyl peroxide is 10:2.5:1.5:1.4:0.015, and obtaining a fourth intermediate product after the reaction is finished;

And heating the temperature in the kettle to 85 ℃, adding benzoyl peroxide and methyl ethyl ketone into the reaction kettle at a constant speed within 0.5h under the stirring condition, mixing and reacting with a fourth intermediate product in the kettle for 4h, wherein the mass ratio of the maleic rosin modified polyurethane resin to the benzoyl peroxide to the methyl ethyl ketone is 10:1.3:0.001, and obtaining the rosin modified acrylic resin after the reaction is finished.

(5) Uniformly mixing 28 parts by weight of silane modified epoxy acrylic resin obtained in the step (2), 22 parts by weight of rosin modified acrylic resin obtained in the step (4) and 15 parts by weight of pigment carbon black to obtain a first solution, adding 0.1 part by weight of dispersant BYK-180, 0.3 part by weight of flatting agent BYK-3560, 0.2 part by weight of defoamer BYK-015 and 0.3 part by weight of wetting agent BYK-2070 into the first solution, uniformly mixing to obtain a second solution, adding 20 parts by weight of n-butanol and 14.1 parts by weight of deionized water into the second solution, uniformly mixing, and grinding until the average particle size is 18 mu m to obtain the permeable code-spraying ink.

FIG. 2 is an infrared spectrum of the silane-modified epoxy acrylic resin prepared in this example, as can be seen from the figure, the association peak of carboxyl group and-OH on the epoxy skeleton at 3446cm ^-1, the stretching vibration peak of methyl group and methylene group at 2953cm ^-1 and 2873cm ^-1, the stretching vibration peak of-C=O at 1734cm ^-1, the shearing vibration peak of methyl group at 1456cm ^-1 and 1386cm ^-1, the non-inverted stretching peak of Si-O-C at 1166cm ^-1, the absorption peak of-Si (CH ₃)₂ O-at 842cm ^-1, and the stretching vibration peaks of-C=C-and-CH ₂ -are not seen in the figure, which indicates that the double bond in the organosiloxane participates in copolymerization.

Fig. 3 is an infrared spectrum of a rosin raw material and a maleic rosin-modified polyurethane resin prepared in this example, and it can be seen that in the infrared spectrum of the rosin raw material, there is a telescopic vibration absorption peak of c=c at 1687cm ^-1. In the infrared spectrum curve of the maleic rosin modified polyurethane resin, only one absorption peak is left at 1687cm ^-1, meanwhile, the telescopic vibration absorption peak of an anhydride carbonyl group appears at 1839cm ^-1, and the C-O-C telescopic vibration absorption peak of anhydride appears at 1095cm ^-1, which indicates that the maleic rosin modified polyurethane resin contains anhydride functional groups, the rosin and the maleic anhydride undergo an addition reaction, and in addition, the telescopic vibration absorption peak of hydroxyl appears at 3651cm ^-1, which indicates that the hydroxyl exists in the product, and the hydroxyl comes from pentaerythritol introduced after the esterification reaction.

FIG. 4 is an infrared spectrum of the rosin-modified acrylic resin prepared in this example, and it can be seen that the vibration absorption peak of C=O of amide group at 1643cm ^-1, the bending absorption peak of N-H at 1552cm ^-1, the stretching vibration absorption peak of secondary amide N-H at 3062cm ^-1, the absorption peak of-OH at 3296cm ^-1, the stretching vibration peak of primary amine C-N at 1198cm ^-1, and the characteristic band of ester group at 1736cm ^-1 show that the acrylic monomer reacts with the maleated rosin-modified urethane resin.

Fig. 5 and 6 show nuclear magnetic resonance spectra of the maleated rosin modified polyurethane resin and the maleated rosin modified acrylic resin prepared in this example, respectively, and comparing the nuclear magnetic resonance spectra of the maleated rosin modified acrylic resin, the chemical shift of the proton on-CONH at δ=7.2 ppm is smaller than that of the maleated rosin modified polyurethane resin, the chemical shift of the proton on-CH ₂ CO-at δ=2.5 ppm is larger than that of the maleated rosin modified polyurethane resin, and simultaneously, the chemical shift of the proton on-COOCH ₃ occurs at δ=3.3 ppm, and no peak exists at δ=5 to 6ppm, which indicates that the c=c double bond of the acrylic monomer is not present in the maleated rosin modified acrylic resin, and further indicates that the acrylic monomer reacts with the maleated rosin modified polyurethane resin.

Example 2

(1) Uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol according to the mass ratio of 1:31:31 to obtain a modified solution, injecting epoxy resin E44 and N-butanol into a reaction kettle according to the mass ratio of 1:0.22, mixing and stirring for 1.8 hours at 72 ℃ to obtain a first resin solution, adding the modified solution into the reaction kettle under the heating conditions of stirring and 112 ℃, mixing and reacting with the first resin solution in the kettle, wherein the mass ratio of methacrylic acid in the modified solution to epoxy resin in the first resin solution is 1:3.5, stopping heating when the acid value of a reaction product is less than or equal to 5mg/KOH, and discharging when the temperature in the kettle is reduced to 22 ℃ to obtain the modified epoxy resin;

(2) Adding a first composite solvent (composed of ethylene glycol and ethylene glycol butyl ether with the mass ratio of 1:0.55) into another reaction kettle, heating the first composite solvent to 72 ℃, adding the modified epoxy resin, the acrylic acid monomer and benzoyl peroxide obtained in the step (1) into the reaction kettle at a constant speed within 0.6h under the stirring condition, mixing and reacting for 2.8h with the first composite solvent in the kettle, wherein the mass ratio of the first composite solvent to the modified epoxy resin to the acrylic acid monomer to the benzoyl peroxide is 1:0.052:1.12:0.042, and the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylol acrylamide with the mass ratio of 1:0.82:0.072:0.32:0.072, so as to obtain a first intermediate product after the reaction is finished;

Heating the temperature in the reaction kettle to 92 ℃, adding vinyltrimethoxysilane and benzoyl peroxide into the reaction kettle at a constant speed within 0.6h under the stirring condition, mixing and reacting with a first intermediate product in the reaction kettle for 3.8h, wherein the mass ratio of acrylic acid monomer to vinyltrimethoxysilane to benzoyl peroxide is 10:0.52:0.105, and adding N, N-dimethylethanolamine into the reaction product after the reaction is finished to adjust the pH value to 8.2, so as to obtain silane modified epoxy acrylic resin;

(3) Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle according to the mass ratio of 8.5:0.13:1, and mixing and stirring for 1.2h under the nitrogen atmosphere at 176 ℃ to obtain a raw material solution;

adding maleic anhydride into a reaction kettle, wherein the mass ratio of rosin to maleic anhydride is 1:0.21, and mixing the maleic anhydride with a raw material solution in the kettle at 202 ℃ for 2.8 hours to obtain a second intermediate product;

Continuously adding diethylenetriamine into a reaction kettle, wherein the mass ratio of rosin to diethylenetriamine is 1:0.45, and mixing the diethylenetriamine with a second intermediate product in the kettle at 152 ℃ for reaction for 1.2 hours to obtain a third intermediate product;

Continuously adding pentaerythritol and zinc oxide into a reaction kettle, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide is 1:0.09:0.145, mixing the pentaerythritol, the zinc oxide and a third intermediate product in the kettle at 261 ℃ for reaction for 1.2 hours, stopping heating after the reaction is finished, and discharging when the temperature in the kettle is reduced to 22 ℃ to obtain the maleated rosin modified polyurethane resin;

(4) Adding a second composite solvent (consisting of isopropanol, ethylene glycol diethyl ether and ethanol with the mass ratio of 1:0.31:0.72) into another reaction kettle, heating the second composite solvent to 42 ℃, adding the maleated rosin modified polyurethane resin obtained in the step (3) into the reaction kettle under the stirring condition, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleated rosin modified polyurethane resin to the second composite solvent is 1:1.52;

Heating the temperature in the kettle to 72 ℃, adding methyl methacrylate, acrylic acid, styrene and benzoyl peroxide into the reaction kettle at a constant speed within 0.6h under the stirring condition, mixing and reacting with a second resin solution in the kettle for 1.8h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the methyl methacrylate to the acrylic acid to the styrene to the benzoyl peroxide is 10:2.52:1.52:1.42:0.018, and obtaining a fourth intermediate product after the reaction is finished;

Heating the temperature in the kettle to 88 ℃, adding benzoyl peroxide and methyl ethyl ketone into the reaction kettle at a constant speed within 0.6h under the stirring condition, mixing and reacting with a fourth intermediate product in the kettle for 3.8h, wherein the mass ratio of the maleic rosin modified polyurethane resin to the benzoyl peroxide to the methyl ethyl ketone is 10:1.32:0.0012, and obtaining the rosin modified acrylic resin after the reaction is finished.

(5) Uniformly mixing 28 parts by weight of silane modified epoxy acrylic resin obtained in the step (2), 22 parts by weight of rosin modified acrylic resin obtained in the step (4) and 14.2 parts by weight of pigment carbon black to obtain a first solution, adding 0.2 part by weight of dispersant BYK-180, 0.1 part by weight of flatting agent BYK-3560, 0.3 part by weight of defoamer BYK-015 and 0.2 part by weight of wetting agent BYK-2070 into the first solution, uniformly mixing to obtain a second solution, adding 21 parts by weight of n-butanol and 14 parts by weight of deionized water into the second solution, uniformly mixing, and grinding until the average particle size is 18.5 mu m to obtain the permeable code-spraying ink.

Example 3

(1) Uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol according to the mass ratio of 1:32:32 to obtain a modified solution, injecting epoxy resin E44 and N-butanol into a reaction kettle according to the mass ratio of 1:0.25, mixing and stirring for 1.5 hours at 75 ℃ to obtain a first resin solution, adding the modified solution into the reaction kettle under the heating conditions of stirring and 115 ℃ to react with the first resin solution in the kettle in a mixing manner, stopping heating when the acid value of a reaction product is less than or equal to 5mg/KOH, and discharging when the temperature in the kettle is reduced to 25 ℃ to obtain the modified epoxy resin;

(2) Adding a first composite solvent (composed of N-butyl alcohol and dipropylene glycol butyl ether with the mass ratio of 1:0.6) into another reaction kettle, heating the first composite solvent to 75 ℃, adding the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile obtained in the step (1) into the reaction kettle at a constant speed within 0.7h under the stirring condition, mixing and reacting for 2.5h with the first composite solvent in the kettle, wherein the mass ratio of the first composite solvent to the modified epoxy resin to the acrylic acid monomer to the azodiisobutyronitrile is 1:0.055:1.15:0.045, and the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide with the mass ratio of 1:0.85:0.075:0.35:0.075, so as to obtain a first intermediate product after the reaction is finished;

Heating the temperature in the reaction kettle to 95 ℃, adding vinyl triethoxysilane and azodiisobutyronitrile into the reaction kettle at a constant speed within 0.7h under the stirring condition, mixing and reacting with a first intermediate product in the reaction kettle for 3.5h, wherein the mass ratio of acrylic acid monomer to vinyl triethoxysilane to azodiisobutyronitrile is 10:0.55:0.11, and adding triethylamine into the reaction product after the reaction is finished to adjust the pH value to 8.5, so as to obtain silane modified epoxy acrylic resin;

(3) Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle according to the mass ratio of 9:0.14:1, and mixing and stirring for 1h under the nitrogen atmosphere at 178 ℃ to obtain a raw material solution;

Adding maleic anhydride into a reaction kettle, wherein the mass ratio of rosin to maleic anhydride is 1:0.22, and mixing the maleic anhydride with a raw material solution in the kettle at 205 ℃ for 2.5 hours to obtain a second intermediate product;

Continuously adding diethylenetriamine into a reaction kettle, wherein the mass ratio of rosin to diethylenetriamine is 1:0.5, and mixing the diethylenetriamine with a second intermediate product in the kettle for reaction for 1h at 155 ℃ to obtain a third intermediate product;

Continuously adding pentaerythritol and zinc oxide into a reaction kettle, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide is 1:0.1:0.15, mixing the pentaerythritol, the zinc oxide and a third intermediate product in the kettle at 262 ℃ for reaction for 1h, stopping heating after the reaction is finished, and discharging when the temperature in the kettle is reduced to 25 ℃ to obtain the maleated rosin modified polyurethane resin;

(4) Adding a second composite solvent (consisting of isopropanol, ethylene glycol diethyl ether and ethanol with the mass ratio of 1:0.32:0.75) into another reaction kettle, heating the second composite solvent to 45 ℃, adding the maleated rosin modified polyurethane resin obtained in the step (3) into the reaction kettle under the stirring condition, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleated rosin modified polyurethane resin to the second composite solvent is 1:1.55;

Heating the temperature in the kettle to 75 ℃, adding methyl methacrylate, acrylic acid, styrene and azodiisobutyronitrile into the reaction kettle at a constant speed within 0.7h under the stirring condition, mixing and reacting with the second resin solution in the kettle for 1.5h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the methyl methacrylate to the acrylic acid to the styrene to the azodiisobutyronitrile is 10:2.55:1.55:1.45:0.02, and obtaining a fourth intermediate product after the reaction is finished;

heating the temperature in the kettle to 90 ℃, adding azodiisobutyronitrile and methyl ethyl ketone into the reaction kettle at a constant speed within 0.7h under the stirring condition, mixing and reacting with a fourth intermediate product in the kettle for 3.5h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the azodiisobutyronitrile to the methyl ethyl ketone is 10:1.35:0.0015, and obtaining the rosin modified acrylic resin after the reaction is finished.

(5) Uniformly mixing 29 parts by weight of silane modified epoxy acrylic resin obtained in the step (2), 21 parts by weight of rosin modified acrylic resin obtained in the step (4) and 14 parts by weight of pigment carbon black to obtain a first solution, adding 0.2 part by weight of dispersant BYK-180, 0.2 part by weight of flatting agent BYK-3560, 0.2 part by weight of defoamer BYK-015 and 0.2 part by weight of wetting agent BYK-2070 into the first solution, uniformly mixing to obtain a second solution, adding 22 parts by weight of n-butanol and 13.2 parts by weight of deionized water into the second solution, uniformly mixing, and grinding until the average particle size is 19 mu m to obtain the permeable code-spraying ink.

Example 4

(1) Uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol according to the mass ratio of 1:33:33 to obtain a modified solution, injecting epoxy resin E51 and N-butanol into a reaction kettle according to the mass ratio of 1:0.28, mixing and stirring for 1.2h at 78 ℃ to obtain a first resin solution, adding the modified solution into the reaction kettle under the heating conditions of stirring and 118 ℃ to react with the first resin solution in the kettle in a mixing manner, stopping heating when the acid value of a reaction product is less than or equal to 5mg/KOH, and discharging when the temperature in the kettle is reduced to 28 ℃ to obtain the modified epoxy resin;

(2) Adding a first composite solvent (composed of isopropyl alcohol and dipropylene glycol methyl ether with the mass ratio of 1:0.65) into another reaction kettle, heating the first composite solvent to 78 ℃, adding the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile obtained in the step (1) into the reaction kettle at a constant speed within 0.8h under the stirring condition, mixing the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile with the first composite solvent in the kettle for 2.2h, and reacting the first composite solvent, the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile with the mass ratio of 1:0.058:1.18:0.048, wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide with the mass ratio of 1:0.88:0.078, and obtaining a first intermediate product after the reaction is finished;

Heating the temperature in the kettle to 98 ℃, adding vinyl triisopropoxy silane and azobisisobutyronitrile into the reaction kettle at a constant speed within 0.8h under the stirring condition, mixing and reacting with a first intermediate product in the kettle for 3.2h, wherein the mass ratio of acrylic acid monomer to vinyl triisopropoxy silane to azobisisobutyronitrile is 10:0.58:0.115, and adding triethanolamine into the reaction product after the reaction is finished to adjust the pH value to 8.8 to obtain silane modified epoxy acrylic resin;

(3) Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle according to the mass ratio of 9.5:0.14:1, and mixing and stirring for 0.8h under the nitrogen atmosphere at the temperature of 179 ℃ to obtain a raw material solution;

Adding maleic anhydride into a reaction kettle, wherein the mass ratio of rosin to maleic anhydride is 1:0.23, and mixing the maleic anhydride with a raw material solution in the kettle at 208 ℃ for 2.2 hours to obtain a second intermediate product;

continuously adding diethylenetriamine into a reaction kettle, wherein the mass ratio of rosin to diethylenetriamine is 1:0.55, and mixing and reacting the diethylenetriamine with a second intermediate product in the kettle for 0.8h at 158 ℃ to obtain a third intermediate product;

continuously adding pentaerythritol and zinc oxide into a reaction kettle, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide is 1:0.11:0.155, mixing the pentaerythritol, the zinc oxide and a third intermediate product in the kettle at 263 ℃ for reaction for 0.8h, stopping heating after the reaction is finished, and discharging when the temperature in the kettle is reduced to 28 ℃ to obtain the maleated rosin modified polyurethane resin;

(4) Adding a second composite solvent (consisting of isopropanol, ethylene glycol diethyl ether and ethanol with the mass ratio of 1:0.33:0.78) into another reaction kettle, heating the second composite solvent to 48 ℃, adding the maleated rosin modified polyurethane resin obtained in the step (3) into the reaction kettle under the stirring condition, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleated rosin modified polyurethane resin to the second composite solvent is 1:1.58;

Heating the temperature in the kettle to 78 ℃, adding methyl methacrylate, acrylic acid, styrene and azodiisobutyronitrile into the reaction kettle at a constant speed within 0.8h under the stirring condition, mixing and reacting with the second resin solution in the kettle for 1.2h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the methyl methacrylate to the acrylic acid to the styrene to the azodiisobutyronitrile is 10:2.58:1.58:1.48:0.022, and obtaining a fourth intermediate product after the reaction is finished;

Heating the temperature in the kettle to 92 ℃, adding azodiisobutyronitrile and methyl ethyl ketone into the reaction kettle at a constant speed within 0.8h under the stirring condition, mixing and reacting with a fourth intermediate product in the kettle for 3.2h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the azodiisobutyronitrile to the methyl ethyl ketone is 10:1.38:0.0018, and obtaining the rosin modified acrylic resin after the reaction is finished.

(5) Uniformly mixing 28.3 parts by weight of silane modified epoxy acrylic resin obtained in the step (2), 20 parts by weight of rosin modified acrylic resin obtained in the step (4) and 15 parts by weight of pigment carbon black to obtain a first solution, adding 0.3 part by weight of dispersant BYK-180, 0.2 part by weight of flatting agent BYK-3560, 0.1 part by weight of defoamer BYK-015 and 0.1 part by weight of wetting agent BYK-2070 into the first solution, uniformly mixing to obtain a second solution, adding 23 parts by weight of n-butanol and 13 parts by weight of deionized water into the second solution, and uniformly mixing and grinding until the average particle size is 19.5 mu m to obtain the permeable code-spraying ink.

Example 5

(1) Uniformly mixing N, N-dimethylethanolamine, methacrylic acid and N-butanol according to the mass ratio of 1:35:35 to obtain a modified solution, injecting epoxy resin E51 and N-butanol into a reaction kettle according to the mass ratio of 1:0.3, mixing and stirring for 1h at 80 ℃ to obtain a first resin solution, adding the modified solution into the reaction kettle under the heating conditions of stirring and 120 ℃, mixing and reacting with the first resin solution in the kettle, wherein the mass ratio of methacrylic acid in the modified solution to epoxy resin in the first resin solution is 1:5, stopping heating when the acid value of a reaction product is less than or equal to 5mg/KOH, and discharging when the temperature in the kettle is reduced to 30 ℃ to obtain the modified epoxy resin;

(2) Adding a first composite solvent (composed of isopropyl alcohol and dipropylene glycol methyl ether with the mass ratio of 1:0.7) into another reaction kettle, heating the first composite solvent to 80 ℃, adding the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile obtained in the step (1) into the reaction kettle at a constant speed within 1h under the stirring condition, mixing and reacting for 2h with the first composite solvent in the kettle, wherein the mass ratio of the first composite solvent, the modified epoxy resin, the acrylic acid monomer and the azodiisobutyronitrile is 1:0.06:1.2:0.05, and the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-methylolacrylamide with the mass ratio of 1:0.9:0.08:0.4:0.08, so as to obtain a first intermediate product after the reaction is finished;

heating the temperature in the kettle to 100 ℃, adding vinyl triisopropoxy silane and azodiisobutyronitrile into the reaction kettle at a constant speed within 1h under the stirring condition, mixing and reacting for 3h with a first intermediate product in the kettle, wherein the mass ratio of acrylic acid monomer to vinyl triisopropoxy silane to azodiisobutyronitrile is 10:0.6:0.12, and adding triethanolamine into the reaction product after the reaction is finished to adjust the pH value to 9 to obtain silane modified epoxy acrylic resin;

(3) Adding rosin, para-hydroxyanisole and deionized water into a reaction kettle according to the mass ratio of 10:0.15:1, and mixing and stirring for 0.5h under the nitrogen atmosphere at 180 ℃ to obtain a raw material solution;

Adding maleic anhydride into a reaction kettle, wherein the mass ratio of rosin to maleic anhydride is 1:0.25, and mixing the maleic anhydride with a raw material solution in the kettle at 210 ℃ for 2 hours to obtain a second intermediate product;

Continuously adding diethylenetriamine into a reaction kettle, wherein the mass ratio of rosin to diethylenetriamine is 1:0.6, and mixing the diethylenetriamine with a second intermediate product in the kettle to react for 0.5h at 160 ℃ to obtain a third intermediate product;

Continuously adding pentaerythritol and zinc oxide into a reaction kettle, wherein the mass ratio of the rosin to the pentaerythritol to the zinc oxide is 1:0.12:0.16, mixing the pentaerythritol, the zinc oxide and a third intermediate product in the kettle at 265 ℃ for reaction for 0.5h, stopping heating after the reaction is finished, and discharging when the temperature in the kettle is reduced to 30 ℃ to obtain the maleated rosin modified polyurethane resin;

(4) Adding a second composite solvent (consisting of isopropanol, ethylene glycol diethyl ether and ethanol with the mass ratio of 1:0.35:0.8) into another reaction kettle, heating the second composite solvent to 50 ℃, adding the maleated rosin modified polyurethane resin obtained in the step (3) into the reaction kettle under the stirring condition, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleated rosin modified polyurethane resin to the second composite solvent is 1:1.6;

Heating the temperature in the kettle to 80 ℃, adding methyl methacrylate, acrylic acid, styrene and azodiisobutyronitrile into the reaction kettle at a constant speed in 1h under the stirring condition, mixing and reacting with a second resin solution in the kettle for 1h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the methyl methacrylate to the acrylic acid to the styrene to the azodiisobutyronitrile is 10:2.6:1.6:1.5:0.025, and obtaining a fourth intermediate product after the reaction is finished;

Heating the temperature in the kettle to 95 ℃, adding azodiisobutyronitrile and methyl ethyl ketone into the reaction kettle at a constant speed within 1h under the stirring condition, mixing and reacting with a fourth intermediate product in the kettle for 3h, wherein the mass ratio of the maleated rosin modified polyurethane resin to the azodiisobutyronitrile to the methyl ethyl ketone is 10:1.4:0.002, and obtaining the rosin modified acrylic resin after the reaction is finished.

(5) Uniformly mixing 30 parts by weight of silane modified epoxy acrylic resin obtained in the step (2), 20 parts by weight of rosin modified acrylic resin obtained in the step (4) and 12 parts by weight of pigment carbon black to obtain a first solution, adding 0.1 part by weight of dispersant BYK-180, 0.1 part by weight of flatting agent BYK-3560, 0.1 part by weight of defoamer BYK-015 and 0.1 part by weight of wetting agent BYK-2070 into the first solution, uniformly mixing to obtain a second solution, adding 22.6 parts by weight of n-butanol and 15 parts by weight of deionized water into the second solution, and uniformly mixing and grinding until the average particle size is 20 mu m to obtain the permeable code-spraying ink.

Comparative example 1

The comparative example provides a method for preparing a permeable code-spraying ink for materials difficult to adhere, which is different from the method in the embodiment 1 in that in the step (2), the mass ratio of the acrylic monomer, the vinyl trimethoxy silane and the benzoyl peroxide is adjusted to be 10:0.4:0.1 when the acrylic monomer, the vinyl trimethoxy silane and the benzoyl peroxide are mixed, and other process parameters and operation steps are identical to those in the embodiment 1.

Comparative example 2

The comparative example provides a method for preparing a permeable code-spraying ink for materials difficult to adhere, which is different from the method in the embodiment 1 in that in the step (2), the mass ratio of the acrylic monomer, the vinyl trimethoxy silane and the benzoyl peroxide is adjusted to be 10:0.7:0.1 when the acrylic monomer, the vinyl trimethoxy silane and the benzoyl peroxide are mixed, and other process parameters and operation steps are identical to those in the embodiment 1.

Fig. 7, 8 and 9 are particle size distribution diagrams of the penetrating inkjet inks prepared in comparative example 1, comparative example 2 and example 1, respectively, and it can be seen from comparison that the particle size of the penetrating inkjet ink is in a bimodal distribution (as shown in fig. 7), and the particle size distribution of the inkjet ink is changed from the bimodal distribution to the unimodal distribution (as shown in fig. 8 and 9) gradually with increasing usage of the organosiloxane, because si—o bonds in the molecular structure are hydrolyzed and crosslinked after the modification system is dispersed by adding water, and part of small particles are grown, so that the particle size distribution gradually tends to be uniform, and the particle size distribution is changed from the bimodal distribution to the unimodal distribution. When the amount is too high (as in comparative example 2), the particle size increases rapidly due to more Si-O bond hydrolysis and crosslinking (as shown in FIG. 8), the system is unstable, and precipitation delamination tends to occur.

Comparative example 3

The comparative example provides a method for preparing permeable code-spraying ink for materials difficult to adhere, which is different from the method in the embodiment 1 in that in the step (3), the reaction temperature of the raw material solution and the maleic anhydride is adjusted to 180 ℃, and other process parameters and operation steps are identical to those in the embodiment 1.

Comparative example 4

The comparative example provides a method for preparing permeable code-spraying ink for materials difficult to adhere to, which is different from the method in the embodiment 1 in that in the step (3), the reaction temperature of the raw material solution and the maleic anhydride is adjusted to be 230 ℃, and other process parameters and operation steps are identical to those in the embodiment 1.

Comparative example 5

The comparative example provides a preparation method of permeable code-spraying ink for materials difficult to adhere, which is different from the preparation method in the example 1 in that the dosage of silane-modified epoxy acrylic resin is adjusted to 25 parts, the dosage of other components is amplified in equal proportion, the relative mass ratio among the other components except the silane-modified epoxy acrylic resin is ensured to be unchanged, and the weight parts of the components are as follows:

25 parts of silane modified epoxy acrylic resin;

22.917 parts of rosin modified acrylic resin;

15.625 parts of pigment carbon black;

0.1042 part of dispersant BYK-180;

0.3125 parts of flatting agent BYK-3560;

0.2083 parts of defoaming agent BYK-015;

0.3125 parts of wetting agent BYK-2070;

20.833 parts of n-butanol;

14.6875 parts of deionized water.

Other process parameters and operating steps were exactly the same as in example 1.

Comparative example 6

The comparative example provides a preparation method of permeable code-spraying ink for materials difficult to adhere, which is different from the preparation method in the embodiment 1 in that the dosage of silane-modified epoxy acrylic resin is adjusted to 35 parts, the dosage of other components is reduced in equal proportion, the relative mass ratio among other components except the silane-modified epoxy acrylic resin is ensured to be unchanged, and the weight parts of the components are as follows:

35 parts of silane modified epoxy acrylic resin;

19.86 parts of rosin modified acrylic resin;

13.54 parts of pigment carbon black;

0.09 part of dispersant BYK-180;

0.271 parts of flatting agent BYK-3560;

0.181 parts of defoaming agent BYK-015;

0.271 parts of wetting agent BYK-2070;

18.06 parts of n-butanol;

12.73 parts of deionized water.

Comparative example 7

The comparative example provides a method for preparing permeable code-spraying ink for materials difficult to adhere, which is different from the method in the example 1 in that the dosage of rosin-modified acrylic resin is adjusted to 18 parts, the dosage of other components is amplified in equal proportion, and the relative mass ratio among other components except the rosin-modified acrylic resin is ensured to be unchanged, and the method specifically comprises the following steps:

29.44 parts of silane modified epoxy acrylic resin;

18 parts of rosin modified acrylic resin;

15.77 parts of pigment;

0.105 parts of dispersing agent;

0.315 part of leveling agent;

0.21 parts of defoamer;

0.315 parts of wetting agent;

21.03 parts of n-butanol;

14.82 parts of deionized water.

Comparative example 8

The comparative example provides a method for preparing penetrating code-spraying ink for materials difficult to adhere, which is different from example 1 in that the dosage of rosin-modified acrylic resin is adjusted to 25 parts, the dosage of other components is reduced in equal proportion, and the relative mass ratio among other components except the rosin-modified acrylic resin is ensured to be unchanged, and specifically comprises the following steps:

26.92 parts of silane modified epoxy acrylic resin;

25 parts of rosin modified acrylic resin;

14.42 parts of pigment;

0.096 parts of dispersant;

0.288 parts of leveling agent;

0.192 parts of defoamer;

0.288 parts of wetting agent;

19.23 parts of n-butanol;

13.56 parts of deionized water.

The adhesive force, quick-drying property and stability of the penetrating inkjet inks provided in examples 1 to 5 and comparative examples 1 to 8 were tested as follows:

(1) Adhesion test

Referring to the test method provided in GB/T5210-2006 "pull-apart adhesion test", the adhesion of the film to the substrate was determined using the pull-apart method:

Coating the penetrating code-spraying inks provided in examples 1-5 and comparative examples 1-8 on a flat and clean polyethylene substrate, forming a film layer after the film is completely dried, adhering a test column of a GLS002 adhesion tester to the film layer through an adhesive, drying and standing for 24 hours, pulling the test column after 24 hours, tearing the film layer from the polyethylene substrate, reading the adhesion (N/mm ²) displayed on the adhesion tester, testing 3 times for each group of examples/comparative examples, and taking an average value.

(2) Quick-drying test

Taking a proper amount of code-spraying ink sample by a 5-mu L capillary, placing the sample in an open surface dish at room temperature, recording the total solidification time of the code-spraying ink sample, namely t ₁(s), taking an ether solution with the same mass, placing the sample in the open surface dish at room temperature, recording the total volatilization time of the ether solution, namely t ₀(s), and calculating the quick-drying rate E of the code-spraying ink by adopting the following steps:

the smaller the E value, the shorter the volatilization time, and the better the quick-drying property.

(3) Stability test

The desk type centrifuge is used for carrying out forced solid-liquid separation on the code-spraying ink, the stability of the code-spraying ink is judged by the change of the absorbance of the code-spraying ink, and the specific operation steps are as follows:

Taking 0.5mL of the permeable code-spraying ink provided in examples 1-5 and comparative examples 1-8, diluting the permeable code-spraying ink in a 500mL volumetric flask by adopting deionized water, injecting the diluted code-spraying ink into a cuvette of an ultraviolet-visible spectrophotometer, and measuring absorbance A ₀ at a proper wavelength.

The osmotic code-spraying inks provided in examples 1 to 5 and comparative examples 1 to 8 were poured into a centrifuge tube, centrifuged at 5000r/min for 20min, and the upper liquid layer of the centrifuge tube was taken out to 0.5mL, diluted with deionized water in a 500mL volumetric flask, and the absorbance A ₁ was measured.

The absorbance ratio a of the inkjet ink before and after centrifugation was calculated using the following:

,

the larger the value of a is, the larger the color difference of the code-spraying ink before and after centrifugal separation is, and the poorer the stability of the code-spraying ink is.

TABLE 1 Performance test results of the penetrating inkjet inks provided in examples 1-5 and comparative examples 1-8

From the test data provided in table 1, it can be seen that the inkjet inks prepared in examples 1 to 5 of the present invention have excellent adhesion, quick-drying property and stability.

As can be seen from the test data of example 1, comparative example 1 and comparative example 2, the adhesive force, quick drying rate and absorbance ratio of the code-spraying ink prepared in comparative example 1 and comparative example 2 are lower than those of example 1, because the amount of vinyltrimethoxysilane in comparative example 1 is too low to effectively exert the hydrophobicity thereof and the hydrophobic modification effect on the resin binder is weak, while the amount of vinyltrimethoxysilane in comparative example 2 is too high, the alkoxy groups in the molecular chain segments of the resin binder undergo hydrolytic polycondensation and crosslinking, and finally the properties of the code-spraying ink are affected.

As can be seen from the test data of example 1, comparative example 3 and comparative example 4, the adhesive force, the quick drying rate and the absorbance ratio of the code-spraying ink prepared in comparative example 3 and comparative example 4 are lower than those of example 1, because the reaction temperature of the raw material solution and the maleic anhydride in comparative example 3 is too low, the D-A addition reaction of the rosin in the raw material solution and the maleic anhydride is not thoroughly carried out, the yield of the maleic rosin is low, the reaction temperature of the raw material solution and the maleic anhydride in comparative example 4 is too high, and the maleic anhydride sublimates in a large amount, so that the reaction yield is low, and the performances of the code-spraying ink are finally affected.

As can be seen from the test data of example 1, comparative example 5 and comparative example 6, the adhesion, the quick-drying rate and the absorbance ratio of the code-spraying ink prepared in comparative example 5 and comparative example 6 are all lower than those of example 1, because the amount of silane-modified epoxy acrylic resin in comparative example 5 is too low, the amount of silane-modified epoxy acrylic resin in comparative example 6 is too high, and the amount of rosin-modified acrylic resin is relatively low, which ultimately affects various properties of the code-spraying ink.

As can be seen from the test data of example 1, comparative example 7 and comparative example 8, the adhesion, quick-drying rate and absorbance ratio of the code-spraying ink prepared in comparative example 7 and comparative example 8 are all lower than those of example 1, because the amount of rosin-modified acrylic resin in comparative example 7 is too low, the amount of rosin-modified acrylic resin in comparative example 8 is too high, and the amount of silane-modified epoxy acrylic resin is relatively low, which ultimately affects various properties of the code-spraying ink.

The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims

1. A penetrating inkjet ink for hard-to-attach materials, characterized in that the penetrating inkjet ink comprises silane-modified epoxy acrylic resin, rosin-modified acrylic resin, pigment, dispersant, leveling agent, defoamer, wetting agent, n-butanol and deionized water;

The weight parts of each component in the penetration type inkjet ink are as follows:

Silane modified epoxy acrylic resin 28-30 parts;

Rosin modified acrylic resin 20-22 parts;

Pigment 12~15 parts;

Dispersant 0.1~0.3 parts;

Leveling agent 0.1~0.3 parts;

Defoaming agent 0.1~0.3 parts;

Wetting agent 0.1~0.3 parts;

20-23 parts of n-butanol;

Deionized water 13~15 parts;

The silane-modified epoxy acrylic resin is prepared by the following method:

Step (1), N, N-dimethylethanolamine, methacrylic acid and n-butanol are mixed uniformly to obtain a modified solution; epoxy resin and n-butanol are injected into a reaction kettle, mixed, stirred and heated to obtain a first resin solution; under stirring and heating conditions, the modified solution is added to the reaction kettle, mixed and reacted with the first resin solution in the kettle, and when the acid value of the reaction product is ≤5 mg/KOH, the temperature is reduced and the material is discharged to obtain a modified epoxy resin;

Step (2), adding a first composite solvent into another reaction kettle and heating the first composite solvent, adding the modified epoxy resin, acrylic acid monomer and a first initiator obtained in step (1) into the reaction kettle under stirring conditions, mixing and reacting with the first composite solvent in the kettle to obtain a first intermediate product; wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide, and the mass ratio of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide is 1:(0.8-0.9):(0.07-0.08):(0.3-0.4):(0.07-0.08);

Step (3), raising the temperature in the kettle to a first temperature, adding an organosiloxane and a second initiator to the reaction kettle under stirring conditions, and mixing and reacting with the first intermediate product in the kettle, wherein the mass ratio of the acrylic monomer, the organosiloxane and the second initiator when mixed is 10:(0.5-0.6):(0.1-0.12), and adding a pH adjuster to the reaction product after the reaction is completed to obtain the silane-modified epoxy acrylic resin;

The rosin-modified acrylic resin is prepared by the following method:

Step (I), adding rosin, p-hydroxyanisole and deionized water into a reaction kettle, mixing, stirring and heating in a nitrogen atmosphere to obtain a raw material solution; adding maleic anhydride into the reaction kettle, mixing and reacting with the raw material solution in the kettle to obtain a second intermediate product; continuing to add diethylenetriamine into the reaction kettle, mixing and reacting with the second intermediate product in the kettle to obtain a third intermediate product; continuing to add pentaerythritol and zinc oxide into the reaction kettle, mixing and reacting with the third intermediate product in the kettle, cooling and discharging after the reaction is completed to obtain a maleic rosin modified polyurethane resin;

Step (II) adds a second composite solvent to another reaction kettle and heats the second composite solvent, adds the maleic rosin modified polyurethane resin obtained in step (I) to the reaction kettle under stirring conditions, and mixes with the second composite solvent in the kettle to obtain a second resin solution; raises the temperature in the kettle to a second temperature, adds methyl methacrylate, acrylic acid, styrene and a third initiator to the reaction kettle under stirring conditions, and mixes with the second resin solution in the kettle to obtain a fourth intermediate product; raises the temperature in the kettle to a third temperature, adds a fourth initiator and butanone to the reaction kettle under stirring conditions, and mixes with the fourth intermediate product in the kettle to obtain the rosin modified acrylic resin after the reaction is completed.

2. A method for preparing the penetrating inkjet ink for hard-to-adhere materials according to claim 1, characterized in that the preparation method comprises:

Silane-modified epoxy acrylic resin, rosin-modified acrylic resin and pigment are mixed evenly to obtain a first solution; a dispersant, a leveling agent, a defoaming agent and a wetting agent are added to the first solution, and the mixture is mixed evenly to obtain a second solution; n-butanol and deionized water are added to the second solution, and the mixture is mixed evenly and then ground to obtain the penetration-type inkjet ink for difficult-to-attach materials.

3. The method for preparing a penetrating inkjet ink for difficult-to-adhere materials according to claim 2, characterized in that in step (1), the mass ratio of N,N-dimethylethanolamine, methacrylic acid and n-butanol is 1:(30-35):(30-35);

The epoxy resin is epoxy resin E44 or epoxy resin E51;

The mass ratio of the epoxy resin to n-butanol is 1:(0.2-0.3);

The heating temperature of the epoxy resin and n-butanol is 70-80° C.;

The stirring time of the epoxy resin and n-butanol is 1 to 2 hours;

The mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution is 1:(3-5);

The reaction temperature of the modified solution and the first resin solution is 110-120°C;

When the acid value of the reaction product is ≤5mg/KOH, stop heating and discharge the material when the temperature in the kettle cools to 20~30℃.

4. The method for preparing a penetrating inkjet coding ink for difficult-to-adhere materials according to claim 2, characterized in that in step (2), the first composite solvent is composed of an alcohol solvent and an ether solvent;

The mass ratio of the alcohol solvent to the ether solvent is 1:(0.5-0.7);

The alcohol solvent is any one of ethylene glycol, propylene glycol, isopropanol, n-butanol or isobutanol, or a combination of at least two thereof;

The ether solvent is any one of propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol butyl ether, dipropylene glycol methyl ether or dipropylene glycol butyl ether, or a combination of at least two thereof;

The heating temperature of the first composite solvent in the kettle is 70-80°C;

The modified epoxy resin, acrylic monomer and first initiator are uniformly injected into the reaction kettle within 0.5 to 1 hour;

The mass ratio of the first composite solvent, the modified epoxy resin, the acrylic monomer and the first initiator is 1:(0.05-0.06):(1.1-1.2):(0.04-0.05);

The reaction time of the first composite solvent, the modified epoxy resin, the acrylic monomer and the first initiator is 2 to 3 hours.

5. The method for preparing a penetrating inkjet ink for difficult-to-adhere materials according to claim 2, characterized in that in step (3), the first temperature is 90-100°C;

The organosiloxane and the second initiator are uniformly injected into the reaction kettle within 0.5 to 1 hour;

The reaction time of the first intermediate product, the organosiloxane and the second initiator is 3 to 4 hours;

The organosiloxane is any one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane or vinyltriacetoxysilane, or a combination of at least two thereof;

The first initiator and the second initiator are independently selected from azobisisobutyronitrile or benzoyl peroxide;

After the reaction is completed, a pH regulator is added to the reaction product to adjust its pH value to 8-9;

The pH regulator is any one of N,N-dimethylethanolamine, triethylamine or triethanolamine, or a combination of at least two thereof.

6. The method for preparing a penetrating inkjet ink for difficult-to-adhere materials according to claim 2, characterized in that in step (I), the mass ratio of the rosin, p-hydroxyanisole and deionized water is (8-10):(0.12-0.15):1;

The heating temperature of the rosin, p-hydroxyanisole and deionized water is 175-180° C.;

The heating time of the rosin, p-hydroxyanisole and deionized water is 0.5 to 1.5 h;

The mass ratio of the rosin to the maleic anhydride is 1:(0.2-0.25);

The reaction temperature of the raw material solution and the maleic anhydride is 200-210° C.;

The reaction time of the raw material solution and the maleic anhydride is 2 to 3 hours;

The mass ratio of the rosin to the diethylenetriamine is 1:(0.4-0.6);

The reaction temperature of the second intermediate product and the diethylenetriamine is 150-160° C.;

The reaction time of the second intermediate product and the diethylenetriamine is 0.5 to 1.5 hours;

The mass ratio of the rosin, pentaerythritol and zinc oxide is 1:(0.08-0.12):(0.14-0.16);

The reaction temperature of the third intermediate product, pentaerythritol and zinc oxide is 260-265° C.;

The reaction time of the third intermediate product, pentaerythritol and zinc oxide is 0.5 to 1.5 hours;

After the reaction is completed, stop heating and discharge the material when the temperature in the kettle cools to 20~30℃.

7. The method for preparing a penetrating inkjet ink for difficult-to-adhere materials according to claim 2, characterized in that in step (II), the second composite solvent consists of isopropyl alcohol, ethylene glycol ethyl ether and ethanol;

The mass ratio of the isopropanol, ethylene glycol ethyl ether and ethanol is 1:(0.3-0.35):(0.7-0.8);

The heating temperature of the second composite solvent in the kettle is 40-50°C;

The mass ratio of the maleic rosin modified polyurethane resin to the second composite solvent is 1:(1.5-1.6);

The second temperature is 70-80°C;

The methyl methacrylate, acrylic acid, styrene and the third initiator are uniformly injected into the reaction kettle within 0.5 to 1 hour;

The mass ratio of the maleic rosin modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and the third initiator is 10:(2.5-2.6):(1.5-1.6):(1.4-1.5):(0.015-0.025);

The reaction time of the second resin solution, methyl methacrylate, acrylic acid, styrene and the third initiator is 1 to 2 hours;

The third temperature is 85-95°C;

The fourth initiator and butanone are uniformly injected into the reactor within 0.5 to 1 hour;

The mass ratio of the maleic rosin modified polyurethane resin, the fourth initiator and butanone is 10:(1.3-1.4):(0.001-0.002);

The reaction time of the fourth intermediate product, the fourth initiator and butanone is 3 to 4 hours;

The third initiator and the fourth initiator are independently selected from azobisisobutyronitrile or benzoyl peroxide.