A kind of penetrating inkjet ink for difficult-to-adhere materials and its preparation method

Abstract

The present invention belongs to the technical field of inkjet coding, and provides a permeable inkjet coding ink for difficult-to-attach materials and a preparation method thereof, wherein the permeable inkjet coding ink comprises a silane-modified epoxy acrylic resin, a rosin-modified acrylic resin, a pigment, a dispersant, a leveling agent, a defoamer, a wetting agent, n-butanol and deionized water. The permeable inkjet coding ink provided by the present invention is composed of a resin binder, a pigment, an auxiliary agent and a solvent, and silane-modified epoxy acrylic resin and rosin-modified acrylic resin are used as composite binders of the inkjet coding ink, and n-butanol and deionized water are used as composite solvents of the inkjet coding ink, which effectively improves the permeability and wettability of the inkjet coding ink to difficult-to-attach substrates, so that the bonding strength and adhesion between the cured film layer and the difficult-to-attach substrate are higher.

Description

Technical Field

[0001] The invention belongs to the technical field of inkjet coding inks, and relates to a penetrating inkjet coding ink for difficult-to-adhere materials and a preparation method thereof. Background Art

[0002] With the continuous improvement of people's living standards, modern people's awareness of product quality is getting stronger and stronger, and the requirements for the labeling of product information are getting higher and higher, especially the safety issues of food, medicine, cosmetics and other products. Legislation stipulates that the labels of food, medicine, cosmetics and other products must be marked with product production date, batch number, shelf life and other instructions to protect consumer rights. The company's own quality management and self-protection awareness and automation management level are also constantly improving. The use of inkjet coding technology to control and track product quality, strengthen sales channel management and warehousing management is becoming more and more common. The inkjet coding technology can significantly improve the image of the company and its products, promote product sales, improve work efficiency and increase the economic benefits of the company due to its advantages such as flexibility, high efficiency and low cost in barcode printing. Therefore, its application areas are becoming increasingly diversified, and the development of inkjet coding inks as its main consumables has broad market prospects.

[0003] In the process of using inkjet ink, the ink is continuously printed on various substrate media to form graphics, codes, letters, dates and other marks. In this process, the inkjet ink is required to be able to be printed on the media continuously, evenly, clearly and firmly. Therefore, there are high requirements for the viscosity, volatility, adhesion, acidity and alkalinity, and conductivity of the ink.

[0004] However, the existing inkjet inks have poor adhesion on substrates such as PVC and PE. When used, the substrates need to be pre-treated, such as corona, polarization and other treatment measures. Good adhesion can only be achieved by increasing the surface energy of the substrate. The treatment process is relatively complicated. Therefore, it is urgent to improve the existing inkjet inks to improve their adhesion to the substrate. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a permeable inkjet ink for difficult-to-adhere materials and a preparation method thereof. The permeable inkjet ink provided by the present invention is composed of a resin binder, a pigment, an additive and a solvent. Silane-modified epoxy acrylic resin and rosin-modified acrylic resin are used as composite binders of the inkjet ink, and n-butanol and deionized water are used as composite solvents of the inkjet ink, which effectively improves the permeability and wettability of the inkjet ink to difficult-to-adhere substrates, so that the bonding strength and adhesion between the cured film layer and the difficult-to-adhere substrate are higher.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a penetrating inkjet ink for difficult-to-adhere materials, wherein the penetrating inkjet ink comprises silane-modified epoxy acrylic resin, rosin-modified acrylic resin, pigment, dispersant, leveling agent, defoaming agent, wetting agent, n-butanol and deionized water.

[0008] The weight parts of each component in the penetration type inkjet ink are as follows:

[0009] Silane modified epoxy acrylic resin 28-30 parts;

[0010] 20-22 parts of rosin modified acrylic resin;

[0011] Pigment 12~15 parts;

[0012] Dispersant 0.1~0.3 parts;

[0013] Leveling agent 0.1~0.3 parts;

[0014] Defoaming agent 0.1~0.3 parts;

[0015] Wetting agent 0.1~0.3 parts;

[0016] 20-23 parts of n-butanol;

[0017] 13~15 parts of deionized water.

[0018] Wherein, the weight portion of 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 portion of 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 portion of pigment can be 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts or 15 parts, the weight portion of dispersant can be 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts or 0.3 parts, and the weight portion of leveling agent can be The weight parts of the defoaming agent can be 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part, the weight parts of the wetting agent can be 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part, the weight parts of the n-butanol can be 20 parts, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts or 23 parts, and the weight parts of the deionized water can 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 are not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0019] The permeable inkjet ink provided by the present invention is composed of a resin binder, a pigment, an additive and a solvent. Silane-modified epoxy acrylic resin and rosin-modified acrylic resin are used as the composite binder of the inkjet ink, and n-butanol and deionized water are used as the composite solvent of the inkjet ink. The permeability and wettability of the inkjet ink to difficult-to-adhere substrates are effectively improved, so that the bonding strength and adhesion between the cured film layer and the difficult-to-adhere substrate are higher.

[0020] In terms of resin binders, the present invention can effectively improve the dispersibility of pigments in inkjet inks as well as the fluidity and wettability of inkjet inks after compounding silane-modified epoxy acrylic resins and rosin-modified acrylic resins, so that the inkjet inks can form a uniform and firm film layer on the surface of the substrate after curing.

[0021] In terms of composite solvent, the present invention uses n-butanol and deionized water as composite solvents, which are mainly used to dissolve resin, adjust ink viscosity and drying speed, and can cooperate with resin binders to a certain extent to improve the adhesion between inkjet ink and substrate. This is because, on the one hand, the addition of n-butanol can improve the dispersion performance of the pigment and enhance the solubility of the resin binder, so that the resin polymer chain can be fully and evenly expanded in the water phase, accelerate the penetration of the ink, and form a dense film layer after the solvent evaporates and dries; on the other hand, since the solubility parameters of n-butanol and the plastic substrate are similar, the addition of n-butanol can swell the substrate, which helps the resin binder and other components to penetrate into the molecular structure of the substrate surface, and the side chains on the resin binder molecules are physically entangled with the molecular chains on the substrate surface, thereby forming a strong interface bond.

[0022] The present invention also adds other additives to the inkjet ink, such as dispersants, leveling agents, defoamers and wetting agents, wherein the dispersant can be adsorbed on the surface of the pigment, and the generated charge repulsion and steric hindrance can prevent the pigment from flocculating and settling, while the wetting agent can reduce the surface tension of the substance and increase the floatability of the pigment in the resin binder; through the compounding of the dispersant and the wetting agent, the system forms a uniform dispersed phase. The permeable inkjet ink provided by the present invention has good quick-drying and stability, and the film layer formed by curing after the inkjet ink is sprayed on the surface of a difficult-to-attach substrate with low surface energy (such as non-polar polymer materials such as polyvinyl chloride, polyethylene, polypropylene, etc.) has good adhesion to the substrate.

[0023] As a binder of inkjet ink, polymer resin can greatly affect the gloss, quick-drying, water resistance, viscosity, rheology and printing performance of inkjet ink. Since acrylic resin has the advantages of good gloss and high transparency, it is often used as a resin binder of inkjet ink, but it also has the disadvantages of poor dispersibility and storage stability to pigments and slow curing speed. In order to simultaneously improve the curing speed, storage stability and adhesion between inkjet ink and difficult-to-attach substrates, the present invention adopts different modification schemes for the low surface energy and non-polar characteristics of difficult-to-attach substrates, and designs silane-modified epoxy acrylic resin and rosin-modified acrylic resin with different functional groups and branched structures. The active functional groups on the molecular chain of the modified resin binder increase, and can form more stable colloid bundles with pigments and additives. The modified resin binder prepared by different modification methods can form different colloid centers with pigments and additives. Compared with the single colloid center formed by a single resin binder, a variety of different colloid centers are easier to disperse due to different polarities, forming a stable and uniform inkjet ink.

[0024] The silane-modified epoxy acrylic resin and the rosin-modified acrylic resin used in the present invention have a synergistic effect, which is specifically embodied in that: generally speaking, the complete peeling between the film layer and the substrate does not occur on the contact surface between the film layer and the substrate, but often occurs inside the film layer, so the disappearance of the adhesion between the film layer and the substrate is caused by the destruction of the cohesion of the film layer itself. In the process of internal stress migrating from the substrate to the film layer, since the rosin-modified acrylic resin molecules provided by the present invention have a very strong physical anchoring effect on the substrate molecules, it is beneficial to reduce the damage of the internal stress to the cohesion of the film layer itself; in addition, since the epoxy functional group in the silane-modified epoxy acrylic resin has a very strong cohesion, therefore, through the synergistic effect between the silane-modified epoxy acrylic resin and the rosin-modified acrylic resin, the film layer itself is given a strong cohesion, and the adhesion between the film layer and the substrate is improved, and at the same time, the damage of the internal stress to the cohesion is greatly reduced, so that the film layer and the substrate can maintain excellent bonding performance.

[0025] The quick-drying property of inkjet ink refers to the speed at which the inkjet ink dries. The drying process of the film layer is completed by volatilization, especially on the surface of difficult-to-attach substrates. The drying mechanism is that the solvent in the inkjet ink evaporates from the film layer after inkjet printing. A small amount of solvent first infiltrates and penetrates the surface of the substrate, and then gradually diffuses from the resin binder molecules at the bottom layer to the top layer, and finally completely evaporates. The resin binder and pigment remaining on the surface of the substrate dry into a film and adhere to the surface of the substrate.

[0026] Therefore, the molecular structure and dosage of the resin binder have a great influence on the quick-drying property of the inkjet ink. For this reason, the present invention particularly limits the dosage of the resin binder. Since the molecular structures of the silane-modified epoxy acrylic resin and the rosin-modified acrylic resin used in the present invention are complex, when the dosage of the silane-modified epoxy acrylic resin and the rosin-modified acrylic resin exceeds the upper limit of the range defined by the present invention, it will cause the resistance of the solvent molecules to pass through the film layer during the volatilization process to be too large, and the volatility of the solvent is poor, which ultimately affects the quick-drying property of the inkjet ink.

[0027] The present invention particularly limits the amount of pigment to 12-15 parts. The amount of pigment will directly affect the storage stability of the inkjet ink. As the amount of pigment increases, the storage stability of the inkjet ink shows a trend of first increasing and then decreasing. When the amount of pigment is less than 12 parts, there are not enough pigment molecules and resin binder molecules to form a sufficient number of inclusion systems, resulting in poor storage stability of the inkjet ink; when the amount of pigment exceeds 15 parts, the pigment cannot be fully dissolved due to excessive amounts, and thus its stability drops sharply.

[0028] The present invention specifically limits the dosage of the dispersant to 0.1-0.3 parts. The dosage of the dispersant will directly affect the drying speed of the inkjet ink. As the dosage of the dispersant increases, the drying speed of the inkjet ink shows a trend of first increasing and then decreasing. This is because the dispersant is a surfactant. After being added, it is dispersed in the aqueous phase and adsorbed on the surface of the pigment particles under the action of the surface tension of the pigment particles to form a protective film. Under the action of steric effect and electrostatic repulsion, the pigment particles cannot be aggregated into large particles and precipitated. In this process, the adsorption of the dispersant also repels the water originally adsorbed on the surface of the pigment particles, so that the water enters the dispersion medium and is easier to separate from the system in the subsequent drying process, thereby improving the drying speed of the inkjet ink; however, when the dosage of the dispersant exceeds 0.3 parts, the surface of the pigment particles reaches a saturated state, and the excess dispersant will be dispersed in the dispersion medium. Under the action of hydration, the water that was originally easy to separate from the system becomes difficult to separate, resulting in a decrease in the drying speed of the inkjet ink.

[0029] The present invention specifically limits the amount of deionized water to 13-15 parts. The water content in the inkjet ink mainly affects the glossiness of the film layer. When the amount of deionized water is less than 13 parts, the viscosity of the inkjet ink will be too high and the solid content will be too high, resulting in a rough surface and poor glossiness of the film layer. When the amount of deionized water exceeds 15 parts, the concentration and viscosity of the inkjet ink will be affected, resulting in a too slow drying speed and an inability to form a smooth film layer, thereby reducing the glossiness of the film layer.

[0030] In a second aspect, the present invention provides a method for preparing the permeable inkjet coding ink for hard-to-attach materials according to the first aspect, the preparation method comprising:

[0031] 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.

[0032] As a preferred technical solution of the present invention, the particle size after grinding is ≤20μm, for example, it can be 10μm, 11μm, 12μm, 13μm, 14μm, 15μm, 16μm, 17μm, 18μm, 19μm or 20μm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] As a preferred technical solution of the present invention, the silane-modified epoxy acrylic resin is prepared by the following method:

[0034] 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;

[0035] Step (2), adding a first composite solvent into another reaction kettle and heating the first composite solvent, adding the modified epoxy resin, acrylic monomer and 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;

[0036] Step (3), raising the temperature in the kettle to a first temperature, adding an organic siloxane and a second initiator to the reaction kettle under stirring conditions, mixing and reacting the organic siloxane and the first intermediate product in the kettle, and adding a pH regulator to the reaction product after the reaction is completed to obtain the silane-modified epoxy acrylic resin.

[0037] Epoxy resin contains highly polar aliphatic hydroxyl groups and ether bonds that are not easily hydrolyzed. The film formed has strong adhesion and good chemical resistance. The rigid phenyl groups and flexible hydroxyl groups on the main chain of epoxy resin molecules are arranged alternately. The film formed has good temperature resistance, thermal stability and mechanical properties. It also has strong cohesion and is not easy to crack. The epoxy resin modified acrylic resin can effectively adjust the internal structure of the film, improve the internal stress of the film, prevent the peeling between the film and the substrate, and improve the adhesion between the film and the substrate. Organic siloxane has excellent heat resistance, weather resistance, oxidation resistance and radiation resistance, and has low surface energy, water repellency and anti-fouling properties.

[0038] The invention firstly uses N,N-dimethylethanolamine as a catalyst to introduce unsaturated acid methacrylic acid into the molecular chain of epoxy resin, so that the two ends of the epoxy resin molecular chain are connected with unsaturated double bonds. Under the action of an initiator, the epoxy graft acrylic copolymer is synthesized by graft copolymerization reaction between the epoxy resin and acrylic monomers. The introduction of double bonds enables the prepared epoxy graft acrylic copolymer to be cured under ultraviolet light or electron radiation. Subsequently, organic siloxane is added, and the silane chain segment is connected to the molecular chain of the copolymer by means of a ring-opening reaction between amino functional groups on the organic siloxane molecular chain and epoxy functional groups on the molecular chain of the epoxy graft acrylic copolymer, so as to obtain a silane-modified epoxy acrylic resin.

[0039] The silane-modified epoxy acrylic resin provided by the present invention not only has the excellent adhesion, high strength and chemical resistance of epoxy resin, but also retains the good gloss, fullness and weather resistance of acrylic resin. In addition, by introducing Si-O bonds and C-Si bonds of organic siloxane into the molecular chain, the silane-modified epoxy acrylic resin is endowed with excellent hydrophobicity, impact resistance and high temperature resistance.

[0040] As a preferred technical solution of the present invention, in step (1), the mass ratio of N,N-dimethylethanolamine, methacrylic acid and n-butanol is 1:(30-35):(30-35), for example, it can 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 1:35:35, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] In some optional examples, the epoxy resin is epoxy resin E44 or epoxy resin E51.

[0042] In some optional examples, the mass ratio of the epoxy resin to n-butanol is 1:(0.2~0.3), for example, it can 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 listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] In some optional examples, the heating temperature of the epoxy resin and n-butanol is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] In some optional examples, the stirring time of the epoxy resin and n-butanol is 1 to 2 hours, for example, 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2.0 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] In some optional examples, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution is 1:(3~5), for example, it can 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 listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] In some optional examples, the reaction temperature of the modified solution and the first resin solution is 110-120°C, for example, it can be 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C or 120°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] In some optional examples, when the acid value of the reaction product is ≤5 mg / KOH, heating is stopped, and the material is discharged when the temperature in the autoclave is cooled to 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0048] As a preferred technical solution of the present invention, in step (2), the first composite solvent consists of an alcohol solvent and an ether solvent.

[0049] In some optional examples, the mass ratio of the alcohol solvent to the ether solvent is 1:(0.5~0.7), for example, it can 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] In some optional examples, the alcohol solvent is any one of ethylene glycol, propylene glycol, isopropanol, n-butanol or isobutanol, or a combination of at least two thereof.

[0051] In some optional examples, 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.

[0052] In some optional examples, the heating temperature of the first composite solvent in the kettle is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0053] The present invention specifically limits the heating temperature of the first composite solvent in the kettle to 70-80°C, and the modified epoxy resin, acrylic monomer and the first initiator react at this temperature to obtain an epoxy grafted acrylic copolymer. As the reaction temperature increases, the grafting conversion rate of the acrylic monomer increases, but when the reaction temperature exceeds 80°C, the heat will be mainly used for solvent evaporation, and will have no obvious promoting effect on the reaction.

[0054] In some optional examples, the modified epoxy resin, the acrylic monomer and the first initiator are uniformly injected into the reactor within 0.5 to 1 hour, for example, 0.5 hours, 0.55 hours, 0.6 hours, 0.65 hours, 0.7 hours, 0.75 hours, 0.8 hours, 0.85 hours, 0.9 hours, 0.95 hours or 1 hour, but are not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0055] In some optional 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, it can be 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 are not limited to the listed values, other values ​​not listed within the numerical range are also applicable.

[0056] In some optional 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0057] In some optional examples, the acrylic monomers consist of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide.

[0058] In some optional examples, 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), for example, it can 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, but are not limited to the listed values, other values ​​not listed within the numerical range are also applicable.

[0059] The present invention specifically defines the mass ratio of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide as 1: (0.8-0.9): (0.07-0.08): (0.3-0.4): (0.07-0.08), wherein methyl methacrylate, as a hard monomer, gives the film layer excellent mechanical strength, impact resistance and wear resistance; ethyl acrylate, as a soft monomer, gives the film layer excellent flexibility, adhesion and film-forming properties. Acrylic acid, as a functional monomer, decreases the hardness of the film layer and increases the adhesion as the amount of acrylic acid increases. This is because, as the amount of acrylic acid increases, the carboxyl content also increases accordingly, hindering the free movement of the polymer chain, and the molecular grid structure replaces the intermolecular force, so that the rigidity of the epoxy grafted acrylic copolymer is increased, but the adhesion is reduced. The present invention controls the mass ratio of different acrylic monomers so that the prepared film layer has both excellent film-forming properties and adhesion and high strength and hardness.

[0060] As a preferred technical solution of the present invention, in step (3), the first temperature is 90-100°C, for example, it can be 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0061] In some optional examples, the organosiloxane and the second initiator are uniformly injected into the reactor within 0.5 to 1 hour, for example, 0.5 hours, 0.55 hours, 0.6 hours, 0.65 hours, 0.7 hours, 0.75 hours, 0.8 hours, 0.85 hours, 0.9 hours, 0.95 hours or 1 hour, but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0062] In some optional 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), for example, it can be 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 listed values, and other unlisted values ​​within the numerical range are also applicable.

[0063] The present invention specifically limits the mass ratio of acrylic monomer, organosiloxane and second initiator to 10:(0.5-0.6):(0.1-0.12) when mixed, especially the amount of organosiloxane, which will affect the water resistance, hardness, stability and adhesion between the inkjet ink and the substrate. Specifically:

[0064] In terms of water resistance, when the dosage of organosiloxane is too low, the improvement of water resistance of inkjet ink is limited;

[0065] In terms of stability, when the dosage of organosiloxane is too high, the alkoxy groups connected to the molecular chain segments of the resin binder will undergo hydrolysis, condensation and cross-linking during storage, resulting in a significant reduction in the free space of the resin binder molecular chain, increasing the viscosity of the inkjet ink, increasing the particle size of the emulsion droplets, making the system unstable, and prone to precipitation and stratification.

[0066] In terms of hardness and adhesion, as the amount of organosiloxane increases, the Si-O-Si bonds formed between the film layer and the substrate interface increase, and under the action of chemical bonding, the adhesion between the film layer and the substrate is enhanced; at the same time, the alkoxy groups grafted on the molecular chains of the resin connecting material also undergo molecular chain condensation in the film layer, so that a dense cross-linked structure is formed inside the film layer, thereby improving the water resistance and hardness of the film layer. When the amount of organosiloxane exceeds the upper limit of the range defined in the present invention, the content of the Si-O-Si flexible segment formed between the film layer and the substrate interface is too high, which will lead to a decrease in the hardness of the film layer; at the same time, organosiloxane is easily hydrolyzed and self-polymerized in water, and it is difficult to copolymerize with epoxy resin. During the film forming process, the resin connecting material droplets obtained by self-polymerization cannot form a film continuously due to the large difference in glass transition temperature, which will cause the film layer to crack, resulting in a significant decrease in the adhesion between the film layer and the substrate.

[0067] In some optional examples, the reaction time of the first intermediate product, the organosiloxane and the second initiator is 3 to 4 hours, for example, 3.0 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0068] The organosiloxane is any one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane or vinyltriacetoxysilane, or a combination of at least two thereof.

[0069] The first initiator and the second initiator are independently selected from azobisisobutyronitrile or benzoyl peroxide.

[0070] In some optional embodiments, after the reaction is completed, a pH adjuster is added to the reaction product to adjust its pH value 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0071] The pH regulator is any one of N,N-dimethylethanolamine, triethylamine or triethanolamine, or a combination of at least two thereof.

[0072] As a preferred technical solution of the present invention, the rosin-modified acrylic resin is prepared by the following method:

[0073] 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;

[0074] 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.

[0075] Since rosin molecules contain more hydrophobic functional groups, the gloss and water resistance of inkjet ink can be improved. However, rosin itself has the disadvantages of being brittle, easy to crystallize, easy to oxidize, not corrosion-resistant, and having a relatively high acid value. Therefore, unmodified rosin raw materials are difficult to meet the requirements of inkjet ink.

[0076] The invention firstly performs DA addition reaction on rosin through maleic anhydride. During the addition reaction of maleic anhydride and rosin, antioxidant p-hydroxyanisole and a small amount of deionized water are added to prevent the occurrence of side reactions caused by local overheating of the rosin raw material during the heating process. Meanwhile, in the early stage of the DA addition reaction, p-hydroxyanisole and deionized water can protect the rosin raw material from being oxidized, promote the DA addition reaction to fully proceed, and synthesize a polyamide resin with good water solubility. The maleic rosin synthesized through the DA addition reaction has a compound with a condensed multi-alicyclic structure, which greatly improves the softening point of the resin connecting material, so that the film layer after coding has better gloss and higher heat resistance.

[0077] Subsequently, the maleic rosin is reacted with diethylenetriamine to generate a polyamide resin. Since diethylenetriamine has a high boiling point and less volatilization loss during the reaction process, diethylenetriamine is used as a raw material to synthesize the polyamide resin. Subsequently, the polyamide is esterified with pentaerythritol under the action of a zinc oxide catalyst to generate a water-soluble maleic rosin-modified polyurethane resin. The esterification reaction between the maleic rosin and pentaerythritol can not only reduce the acid value of the rosin and improve its thermal stability, but also enhance the ability of the rosin to resist acid and alkali corrosion.

[0078] Finally, rosin-modified acrylic resin was synthesized through the graft copolymerization reaction between acrylic monomers and maleic rosin-modified polyurethane resin. The carboxyl group in acrylic acid is a strong polar group and is easy to chemically bond, which is beneficial to improve the adhesion between the film layer and the substrate.

[0079] The rosin-modified acrylic resin provided by the present invention has complex maleic rosin side chain functional groups. Under the swelling and corrosion effect of the composite solvent on the substrate, the maleic rosin side chain functional groups on the rosin-modified acrylic resin are easy to enter the spiral gap of the molecules on the surface of the substrate. With the further movement of the rosin-modified acrylic resin molecules, the side chain functional groups that have entered the spiral gap are hindered from escaping, thereby forming a physical anchoring effect at the molecular scale. This anchoring effect further shortens the distance between the resin binder molecules and the substrate molecules. When the distance between the resin binder molecules and the substrate molecules is reduced from 1×10 -3 μm shortened to 0.3×10 -3 When the film thickness is 0.1 μm, the molecular force between the resin binder molecules and the substrate molecules will increase 10 times, thereby greatly improving the adhesion between the film layer and the substrate.

[0080] As a preferred technical solution of the present invention, in step (I), the mass ratio of rosin, p-hydroxyanisole and deionized water is (8-10):(0.12-0.15):1, for example, it can be 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 it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0081] In some optional examples, the heating temperature of the rosin, p-hydroxyanisole and deionized water is 175-180°C, for example, it can be 175°C, 175.5°C, 176°C, 176.5°C, 177°C, 177.5°C, 178°C, 178.5°C, 179°C, 179.5°C or 180°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0082] In some optional examples, the heating time of the rosin, p-hydroxyanisole and deionized water is 0.5 to 1.5 h, for example, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h or 1.5 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0083] In some optional examples, the mass ratio of the rosin to the maleic anhydride is 1:(0.2~0.25), for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0084] In some optional examples, the reaction temperature of the raw material solution and the maleic anhydride is 200-210°C, for example, it can be 200°C, 201°C, 202°C, 203°C, 204°C, 205°C, 206°C, 207°C, 208°C, 209°C or 210°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0085] The effective reaction component in rosin is abietic resin acid. Maleic anhydride and abietic resin acid in rosin are prone to DA addition reaction to generate maleic rosin with tricarboxyl structure. However, at room temperature, the content of abietic resin acid in rosin is very low. At high temperature, resin acids with other structures in rosin will transform into abietic resin acid. Therefore, high temperature is conducive to the DA addition reaction of maleic anhydride and rosin. However, there are two factors that limit the reaction temperature from being too high:

[0086] (1) As a substance that is relatively active at high temperatures, rosin will oxidize under reaction conditions that cannot be completely oxygen-free, resulting in a darker color of the reaction product, which seriously affects the color of the final inkjet ink; (2) Maleic anhydride is not stable at high temperatures. When the reaction temperature exceeds 210°C, it will sublimate, resulting in a waste of reaction raw materials and a reduction in reaction yield. Taking the above two factors into consideration, the present invention specifically limits the reaction temperature of the raw material solution and maleic anhydride to 200-210°C.

[0087] In some optional examples, the reaction time of the raw material solution and the maleic anhydride is 2 to 3 hours, for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0088] In some optional examples, the mass ratio of the rosin to the diethylenetriamine is 1:(0.4~0.6), for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0089] In some optional examples, the reaction temperature of the second intermediate product and the diethylenetriamine is 150-160°C, for example, it can be 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C or 160°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0090] In some optional examples, the reaction time of the second intermediate product and the diethylenetriamine is 0.5~1.5h, for example, it can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0091] In some optional examples, the mass ratio of the rosin, pentaerythritol and zinc oxide is 1:(0.08-0.12):(0.14-0.16), for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0092] In some optional examples, the reaction temperature of the third intermediate product, pentaerythritol and zinc oxide is 260-265°C, for example, it can be 260°C, 260.5°C, 261°C, 261.5°C, 262°C, 262.5°C, 263°C, 263.5°C, 264°C, 264.5°C or 265°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0093] In some optional examples, the reaction time of the third intermediate product, pentaerythritol and zinc oxide is 0.5~1.5h, for example, it can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0094] In some optional embodiments, heating is stopped after the reaction is completed, and the material is discharged when the temperature in the autoclave is cooled to 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0095] As a preferred technical solution of the present invention, in step (II), the second composite solvent consists of isopropanol, ethylene glycol ethyl ether and ethanol.

[0096] In some optional examples, the mass ratio of isopropanol, ethylene glycol ethyl ether and ethanol is 1:(0.3~0.35):(0.7~0.8), for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0097] In some optional examples, the heating temperature of the second composite solvent in the kettle is 40-50°C, for example, it can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0098] In some optional examples, the mass ratio of the maleic rosin modified polyurethane resin to the second composite solvent is 1:(1.5~1.6), for example, it can 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 listed values, and other unlisted values ​​within the numerical range are also applicable.

[0099] In some optional instances, the second temperature is 70-80°C, for example, it may be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0100] In some optional examples, the methyl methacrylate, acrylic acid, styrene and the third initiator are uniformly injected into the reactor within 0.5 to 1 hour, for example, it can be 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0101] In some optional examples, 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), for example, it can be 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 are not limited to the listed values, other values ​​not listed within the numerical range are also applicable.

[0102] In some optional 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, it can be 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2.0 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0103] In some optional instances, the third temperature is 85-95°C, for example, it can be 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C or 95°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0104] In some optional examples, the fourth initiator and butanone are uniformly injected into the reactor within 0.5 to 1 hour, for example, 0.5 hours, 0.55 hours, 0.6 hours, 0.65 hours, 0.7 hours, 0.75 hours, 0.8 hours, 0.85 hours, 0.9 hours, 0.95 hours or 1 hour, but are not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0105] In some optional examples, 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), for example, it can be 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 is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0106] In some optional examples, the reaction time of the fourth intermediate product, the fourth initiator and methyl ethyl ketone is 3 to 4 hours, for example, it can be 3.0 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4.0 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0107] In some optional examples, the third initiator and the fourth initiator are independently selected from azobisisobutyronitrile or benzoyl peroxide.

[0108] Compared with the prior art, the present invention has the following beneficial effects:

[0109] The permeable inkjet ink provided by the present invention is composed of a resin binder, a pigment, an additive and a solvent. Silane-modified epoxy acrylic resin and rosin-modified acrylic resin are used as the composite binder of the inkjet ink, and n-butanol and deionized water are used as the composite solvent of the inkjet ink. The permeability and wettability of the inkjet ink to difficult-to-adhere substrates are effectively improved, so that the bonding strength and adhesion between the cured film layer and the difficult-to-adhere substrate are higher. BRIEF DESCRIPTION OF THE DRAWINGS

[0110] Figure 1 A flow chart of a method for preparing a permeable inkjet coding ink provided in Examples 1-5 of the present invention;

[0111] Figure 2 This is the infrared spectrum of the silane-modified epoxy acrylic resin prepared in Example 1 of the present invention;

[0112] Figure 3 The infrared spectra of the rosin raw material and the maleic rosin modified polyurethane resin prepared in Example 1 of the present invention;

[0113] Figure 4 This is the infrared spectrum of the rosin-modified acrylic resin prepared in Example 1 of the present invention;

[0114] Figure 5 This is the nuclear magnetic resonance spectrum of the maleic rosin modified polyurethane resin prepared in Example 1 of the present invention;

[0115] Figure 6 This is the nuclear magnetic resonance spectrum of the rosin-modified acrylic resin prepared in Example 1 of the present invention;

[0116] Figure 7 This is a particle size distribution diagram of the penetration-type inkjet ink prepared in Comparative Example 1 of the present invention;

[0117] Figure 8 This is a particle size distribution diagram of the penetration-type inkjet ink prepared in Comparative Example 2 of the present invention;

[0118] Fig. 9 This is a particle size distribution diagram of the penetration-type inkjet ink prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0119] The technical solution of the present invention is described in detail below in conjunction with specific embodiments and their accompanying drawings. The embodiments recorded herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be construed as limitations on the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments recorded herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments recorded herein.

[0120] The chemical reagents used in the examples and comparative examples of the present invention are all commercially available products, and their specifications, models, manufacturers and other information are as follows:

[0121] N,N-dimethylethanolamine: purity 99%, purchased from Changzhou Guxu Chemical Co., Ltd.;

[0122] Methacrylic acid: purity 99.5%, purchased from Shandong Jinyueyuan New Materials Co., Ltd.;

[0123] n-Butanol: purity 99.9%, purchased from Jinan Chuangshi Chemical Co., Ltd.;

[0124] Epoxy resin E44: industrial grade, purchased from Wuhan Nengren Pharmaceutical Chemical Co., Ltd.;

[0125] Epoxy resin E51: industrial grade, purchased from Wuhan Nengren Pharmaceutical Chemical Co., Ltd.;

[0126] Ethylene glycol: B25695-5ml, purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0127] Isopropanol: purity 99.5%, purchased from Jinan Shanhai Chemical Technology Co., Ltd.;

[0128] Dipropylene glycol methyl ether: purity 99.5%, purchased from Shandong Xinheng Chemical Co., Ltd.;

[0129] Ethylene glycol butyl ether: B65648-250 mg, purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0130] Dipropylene glycol butyl ether: purity 99.9%, purchased from Jinan Jinrihe Chemical Co., Ltd.;

[0131] Benzoyl peroxide: purity 99%, purchased from Jinan Huifengda Chemical Co., Ltd.;

[0132] Azobisisobutyronitrile: purity 99%, purchased from Shandong Jinyueyuan New Materials Co., Ltd.;

[0133] Triethylamine: purity 99%, purchased from Jinan Jumeihui Chemical Co., Ltd.;

[0134] Triethanolamine: industrial grade, purchased from Nantong Runfeng Petrochemical Co., Ltd.;

[0135] Methyl methacrylate: purity 99.5%, purchased from Jinan Century Tongda Chemical Co., Ltd.;

[0136] Ethyl acrylate: purity 99.9%, purchased from Shandong Langcheng Chemical Co., Ltd.;

[0137] Acrylic acid: purity 99.9%, purchased from Jinan Century Tongda Chemical Co., Ltd.;

[0138] Hydroxyethyl acrylate: purity 99.9%, purchased from Shandong Langcheng Chemical Co., Ltd.;

[0139] N-Hydroxymethyl acrylamide: S71476-25g, purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0140] Vinyltrimethoxysilane: purity 99.5%, purchased from Wuhan Xinxinjiali Biotechnology Co., Ltd.;

[0141] Vinyltriethoxysilane: purity 99%, purchased from Wuhan Xinxinjiali Biotechnology Co., Ltd.;

[0142] Vinyl triisopropoxysilane: S95559-25g, purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0143] Rosin: M81442, purchased from Shanghai Myril Biochemical Technology Co., Ltd.;

[0144] p-Hydroxyanisole: purity 99.5%, purchased from Jinan Century Tongda Chemical Co., Ltd.;

[0145] Maleic anhydride: purity 99%, purchased from Jinan Renyuan Chemical Co., Ltd.;

[0146] Diethylenetriamine: purity 99.5%, purchased from Jinan Chuangshi Chemical Co., Ltd.;

[0147] Zinc oxide: S24314-500g, purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0148] Ethylene glycol ether: purity 99.5%, purchased from Jinan Jinrihe Chemical Co., Ltd.;

[0149] Ethanol: purity 99%, purchased from Nanjing Chemical Reagent Co., Ltd.;

[0150] Styrene: purity 99%, purchased from Shandong Zhengxing New Materials Co., Ltd.;

[0151] Methyl ethyl ketone: purity 99%, Fuchen (Tianjin) Chemical Reagent Co., Ltd.

[0152] Example 1

[0153] This embodiment provides a method for preparing a penetrating inkjet ink for hard-to-attach materials, such as Figure 1 As shown, the preparation method specifically comprises the following steps:

[0154] (1) N,N-dimethylethanolamine, methacrylic acid and n-butanol were mixed uniformly in a mass ratio of 1:30:30 to obtain a modified solution; epoxy resin E44 and n-butanol were injected into a reactor in a mass ratio of 1:0.2, and mixed and stirred at 70°C for 2 hours to obtain a first resin solution; under stirring and heating conditions of 110°C, the modified solution was added to the reactor and mixed with the first resin solution in the reactor for reaction, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution was 1:3, and when the acid value of the reaction product was ≤5 mg / KOH, the heating was stopped, and the material was discharged when the temperature in the reactor dropped to 20°C to obtain a modified epoxy resin;

[0155] (2) Add a first composite solvent (composed of ethylene glycol and ethylene glycol butyl ether in a mass ratio of 1:0.5) to another reaction kettle and heat the first composite solvent to 70° C. Under stirring conditions, uniformly add the modified epoxy resin, acrylic acid monomer and benzoyl peroxide obtained in step (1) to the reaction kettle within 0.5 h, and mix and react with the first composite solvent in the kettle for 3 h. The mass ratio of the first composite solvent, modified epoxy resin, acrylic acid monomer and benzoyl peroxide is 1:0.05:1.1:0.04, wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide in a mass ratio of 1:0.8:0.07:0.3:0.07. After the reaction is completed, a first intermediate product is obtained;

[0156] The temperature in the kettle was raised to 90° C., and under stirring conditions, vinyl trimethoxysilane and benzoyl peroxide were uniformly added to the reaction kettle within 0.5 h, and mixed with the first intermediate product in the kettle for reaction for 4 h, and the mass ratio of acrylic monomer, vinyl trimethoxysilane and benzoyl peroxide was 10:0.5:0.1. After the reaction was completed, N,N-dimethylethanolamine was added to the reaction product to adjust its pH value to 8, to obtain a silane-modified epoxy acrylic resin;

[0157] (3) adding rosin, p-hydroxyanisole and deionized water into a reaction kettle in a mass ratio of 8:0.12:1, mixing and stirring for 1.5 h at 175° C. in a nitrogen atmosphere to obtain a raw material solution;

[0158] Add maleic anhydride to the reaction kettle, the mass ratio of rosin to maleic anhydride is 1:0.2, and mix the maleic anhydride and the raw material solution in the kettle at 200° C. for 3 hours to obtain a second intermediate product;

[0159] Continue to add diethylenetriamine to the reactor, the mass ratio of rosin to diethylenetriamine is 1:0.4, diethylenetriamine and the second intermediate product in the reactor are mixed and reacted at 150° C. for 1.5 hours to obtain a third intermediate product;

[0160] Continue to add pentaerythritol and zinc oxide into the reaction kettle, the mass ratio of rosin, pentaerythritol and zinc oxide is 1:0.08:0.14, the pentaerythritol, zinc oxide and the third intermediate product in the kettle are mixed and reacted at 260° C. for 1.5 hours, and the heating is stopped after the reaction is completed. When the temperature in the kettle drops to 20° C., the material is discharged to obtain a maleic rosin modified polyurethane resin;

[0161] (4) adding a second composite solvent (composed of isopropanol, ethylene glycol ethyl ether and ethanol in a mass ratio of 1:0.3:0.7) into another reaction kettle and heating the second composite solvent to 40° C., adding the maleated rosin-modified polyurethane resin obtained in step (3) into the reaction kettle under stirring, 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;

[0162] The temperature in the kettle was raised to 70°C. Under stirring conditions, methyl methacrylate, acrylic acid, styrene and benzoyl peroxide were uniformly added to the reactor within 0.5h, and mixed with the second resin solution in the kettle for reaction for 2h. The mass ratio of maleic rosin-modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and benzoyl peroxide was 10:2.5:1.5:1.4:0.015. After the reaction, a fourth intermediate product was obtained.

[0163] The temperature in the kettle was raised to 85°C. Under stirring conditions, benzoyl peroxide and methyl ethyl ketone were uniformly added into the reactor within 0.5 h, and mixed with the fourth intermediate product in the kettle for reaction for 4 h. The mass ratio of maleic rosin modified polyurethane resin, benzoyl peroxide and methyl ethyl ketone was 10:1.3:0.001. After the reaction, rosin modified acrylic resin was obtained.

[0164] (5) 28 parts by weight of the silane-modified epoxy acrylic resin obtained in step (2), 22 parts by weight of the rosin-modified acrylic resin obtained in step (4) and 15 parts by weight of the pigment carbon black are mixed uniformly to obtain a first solution; 0.1 parts by weight of a dispersant BYK-180, 0.3 parts by weight of a leveling agent BYK-3560, 0.2 parts by weight of a defoaming agent BYK-015 and 0.3 parts by weight of a wetting agent BYK-2070 are added to the first solution, and the mixture is mixed uniformly to obtain a second solution; 20 parts by weight of n-butanol and 14.1 parts by weight of deionized water are added to the second solution, the mixture is mixed uniformly and then ground to an average particle size of 18 μm to obtain the penetration-type inkjet ink.

[0165] Figure 2 This is the infrared spectrum of the silane-modified epoxy acrylic resin prepared in this example. As can be seen from the figure, 3446cm -1 The peak at 2953 cm is the combined peak of carboxyl and -OH on the epoxy skeleton. -1 and 2873cm -1 The stretching vibration peaks of methyl and methylene are at 1734 cm -1 The -C=O stretching vibration peak is 1456cm -1 and 1386cm -1 The peak at 1166 cm is the shear vibration peak of the methyl group. -1 The non-antisymmetric stretching peak of Si-OC is at 842 cm -1 The absorption peak of -Si(CH3)2O- is located at the center, and there are no stretching vibration peaks of -C=C- and -CH2-, which indicates that the double bonds in the organosiloxane participate in the copolymerization reaction.

[0166] Figure 3 The infrared spectra of the rosin raw material and the maleic rosin modified polyurethane resin prepared in this embodiment are shown in FIG. 1 . By comparison, it can be seen that in the infrared spectrum curve of the rosin raw material, 1687 cm -1 The position is the stretching vibration absorption peak of C=C. In the infrared spectrum curve of maleic rosin modified polyurethane resin, 1687cm -1 There is only one absorption peak left at 1839cm -1 The stretching vibration absorption peak of the anhydride carbonyl group appeared at 1095 cm -1The COC stretching vibration absorption peak of anhydride appeared at 3651cm, which indicated that the maleic rosin-modified polyurethane resin contained anhydride functional groups and that rosin and maleic anhydride had an addition reaction. -1 The stretching vibration absorption peak of hydroxyl group appears at , which indicates the presence of hydroxyl group in the product, which comes from pentaerythritol introduced after the esterification reaction.

[0167] Figure 4 This is the infrared spectrum of the rosin-modified acrylic resin prepared in this example. As can be seen from the figure, 1643 cm -1 The C=O vibration absorption peak of the amide group is 1552 cm -1 The bending absorption peak of NH is at 3062cm -1 The stretching vibration absorption peak of secondary amide NH is 3296 cm -1 The absorption peak of -OH is 1198 cm -1 The stretching vibration peak of primary amine CN is 1736 cm -1 The characteristic band of ester group appeared at the position, which indicated that the acrylic monomer reacted with the maleic rosin modified polyurethane resin.

[0168] Figure 5 and Figure 6 They are the nuclear magnetic resonance spectra of the maleated rosin-modified polyurethane resin and the rosin-modified acrylic resin prepared in this embodiment, respectively. By comparison, it can be seen that in the nuclear magnetic resonance spectrum curve of the rosin-modified acrylic resin, δ=7.2ppm is the chemical shift of the proton on -CONH, which is smaller than the chemical shift of the maleated rosin-modified polyurethane resin; δ=2.5ppm is the chemical shift of the proton on -CH2CO-, which is larger than the chemical shift of the maleated rosin-modified polyurethane resin; at the same time, the chemical shift of the proton on -COOCH3 appears at δ=3.3ppm, and there is no peak at δ=5-6ppm, indicating that the C=C double bond of the acrylic monomer does not exist in the rosin-modified acrylic resin, further indicating that the acrylic monomer reacts with the maleated rosin-modified polyurethane resin.

[0169] Example 2

[0170] This embodiment provides a method for preparing a penetrating inkjet ink for hard-to-attach materials, such as Figure 1 As shown, the preparation method specifically comprises the following steps:

[0171] (1) N,N-dimethylethanolamine, methacrylic acid and n-butanol were mixed uniformly in a mass ratio of 1:31:31 to obtain a modified solution; epoxy resin E44 and n-butanol were injected into a reactor in a mass ratio of 1:0.22, and mixed and stirred at 72°C for 1.8 hours to obtain a first resin solution; under stirring and heating conditions of 112°C, the modified solution was added to the reactor and mixed with the first resin solution in the reactor for reaction, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution was 1:3.5, and when the acid value of the reaction product was ≤5 mg / KOH, the heating was stopped, and the material was discharged when the temperature in the reactor dropped to 22°C to obtain a modified epoxy resin;

[0172] (2) Add a first composite solvent (composed of ethylene glycol and ethylene glycol butyl ether in a mass ratio of 1:0.55) to another reaction kettle and heat the first composite solvent to 72° C. Under stirring conditions, uniformly add the modified epoxy resin, acrylic acid monomer and benzoyl peroxide obtained in step (1) to the reaction kettle within 0.6 h, and mix and react with the first composite solvent in the kettle for 2.8 h. The mass ratio of the first composite solvent, the modified epoxy resin, the acrylic acid monomer and the benzoyl peroxide is 1:0.052:1.12:0.042, wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide in a mass ratio of 1:0.82:0.072:0.32:0.072. After the reaction is completed, a first intermediate product is obtained;

[0173] The temperature in the kettle was raised to 92° C., and under stirring conditions, vinyl trimethoxysilane and benzoyl peroxide were uniformly added to the reactor within 0.6 h, and mixed with the first intermediate product in the kettle for reaction for 3.8 h, and the mass ratio of acrylic monomer, vinyl trimethoxysilane and benzoyl peroxide was 10:0.52:0.105. After the reaction was completed, N,N-dimethylethanolamine was added to the reaction product to adjust its pH value to 8.2, to obtain a silane-modified epoxy acrylic resin;

[0174] (3) adding rosin, p-hydroxyanisole and deionized water into a reaction kettle in a mass ratio of 8.5:0.13:1, mixing and stirring for 1.2 h at 176° C. in a nitrogen atmosphere to obtain a raw material solution;

[0175] Add maleic anhydride to the reaction kettle, the mass ratio of rosin to maleic anhydride is 1:0.21, and mix the maleic anhydride and the raw material solution in the kettle for reaction at 202° C. for 2.8 hours to obtain the second intermediate product;

[0176] Continue to add diethylenetriamine to the reactor, the mass ratio of rosin to diethylenetriamine is 1:0.45, diethylenetriamine and the second intermediate product in the reactor are mixed and reacted at 152° C. for 1.2 hours to obtain a third intermediate product;

[0177] Continue to add pentaerythritol and zinc oxide into the reactor, the mass ratio of rosin, pentaerythritol and zinc oxide is 1:0.09:0.145, the pentaerythritol, zinc oxide and the third intermediate product in the reactor are mixed and reacted at 261° C. for 1.2 hours, and the heating is stopped after the reaction is completed. When the temperature in the reactor drops to 22° C., the material is discharged to obtain a maleic rosin modified polyurethane resin;

[0178] (4) adding a second composite solvent (composed of isopropanol, ethylene glycol ethyl ether and ethanol in a mass ratio of 1:0.31:0.72) to another reaction kettle and heating the second composite solvent to 42° C., adding the maleated rosin-modified polyurethane resin obtained in step (3) to the reaction kettle under stirring, 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;

[0179] The temperature in the kettle was raised to 72°C. Under stirring conditions, methyl methacrylate, acrylic acid, styrene and benzoyl peroxide were uniformly added to the reactor within 0.6h, and mixed with the second resin solution in the kettle for reaction for 1.8h. The mass ratio of maleic rosin modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and benzoyl peroxide was 10:2.52:1.52:1.42:0.018. After the reaction, a fourth intermediate product was obtained;

[0180] The temperature in the kettle was raised to 88°C. Under stirring conditions, benzoyl peroxide and methyl ethyl ketone were uniformly added into the reactor within 0.6h, and mixed with the fourth intermediate product in the kettle for reaction for 3.8h. The mass ratio of maleic rosin modified polyurethane resin, benzoyl peroxide and methyl ethyl ketone was 10:1.32:0.0012. After the reaction, rosin modified acrylic resin was obtained.

[0181] (5) 28 parts by weight of the silane-modified epoxy acrylic resin obtained in step (2), 22 parts by weight of the rosin-modified acrylic resin obtained in step (4) and 14.2 parts by weight of the pigment carbon black are mixed uniformly to obtain a first solution; 0.2 parts by weight of a dispersant BYK-180, 0.1 parts by weight of a leveling agent BYK-3560, 0.3 parts by weight of a defoaming agent BYK-015 and 0.2 parts by weight of a wetting agent BYK-2070 are added to the first solution, and the mixture is mixed uniformly to obtain a second solution; 21 parts by weight of n-butanol and 14 parts by weight of deionized water are added to the second solution, the mixture is mixed uniformly and then ground to an average particle size of 18.5 μm to obtain the penetration-type inkjet ink.

[0182] Example 3

[0183] This embodiment provides a method for preparing a penetrating inkjet ink for hard-to-attach materials, such as Figure 1As shown, the preparation method specifically comprises the following steps:

[0184] (1) N,N-dimethylethanolamine, methacrylic acid and n-butanol were mixed uniformly in a mass ratio of 1:32:32 to obtain a modified solution; epoxy resin E44 and n-butanol were injected into a reactor in a mass ratio of 1:0.25, and mixed and stirred at 75°C for 1.5 hours to obtain a first resin solution; under stirring and heating conditions of 115°C, the modified solution was added to the reactor and mixed with the first resin solution in the reactor for reaction, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution was 1:4, and when the acid value of the reaction product was ≤5 mg / KOH, the heating was stopped, and when the temperature in the reactor dropped to 25°C, the material was discharged to obtain a modified epoxy resin;

[0185] (2) Add a first composite solvent (composed of n-butanol and dipropylene glycol butyl ether in a mass ratio of 1:0.6) to another reaction kettle and heat the first composite solvent to 75° C. Under stirring conditions, uniformly add the modified epoxy resin, acrylic acid monomer and azobisisobutyronitrile obtained in step (1) to the reaction kettle within 0.7 h, and mix and react with the first composite solvent in the kettle for 2.5 h. The mass ratio of the first composite solvent, modified epoxy resin, acrylic acid monomer and azobisisobutyronitrile is 1:0.055:1.15:0.045, wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide in a mass ratio of 1:0.85:0.075:0.35:0.075. After the reaction is completed, a first intermediate product is obtained;

[0186] The temperature in the kettle was raised to 95° C., and under stirring conditions, vinyl triethoxysilane and azobisisobutyronitrile were uniformly added to the reactor within 0.7 h, and mixed with the first intermediate product in the kettle for reaction for 3.5 h, and the mass ratio of acrylic acid monomer, vinyl triethoxysilane and azobisisobutyronitrile was 10:0.55:0.11. After the reaction was completed, triethylamine was added to the reaction product to adjust its pH value to 8.5, to obtain a silane-modified epoxy acrylic resin;

[0187] (3) adding rosin, p-hydroxyanisole and deionized water into a reaction kettle in a mass ratio of 9:0.14:1, mixing and stirring for 1 h at 178° C. under a nitrogen atmosphere to obtain a raw material solution;

[0188] Add maleic anhydride to the reaction kettle, the mass ratio of rosin to maleic anhydride is 1:0.22, and mix the maleic anhydride and the raw material solution in the kettle for reaction at 205° C. for 2.5 hours to obtain the second intermediate product;

[0189] Continue to add diethylenetriamine to the reactor, the mass ratio of rosin to diethylenetriamine is 1:0.5, diethylenetriamine and the second intermediate product in the reactor are mixed and reacted at 155° C. for 1 hour to obtain a third intermediate product;

[0190] Continue to add pentaerythritol and zinc oxide into the reaction kettle, the mass ratio of rosin, pentaerythritol and zinc oxide is 1:0.1:0.15, the pentaerythritol, zinc oxide and the third intermediate product in the kettle are mixed and reacted at 262° C. for 1 hour, and the heating is stopped after the reaction is completed. When the temperature in the kettle drops to 25° C., the material is discharged to obtain a maleic rosin modified polyurethane resin;

[0191] (4) adding a second composite solvent (composed of isopropanol, ethylene glycol ethyl ether and ethanol in a mass ratio of 1:0.32:0.75) to another reaction kettle and heating the second composite solvent to 45° C., adding the maleic rosin-modified polyurethane resin obtained in step (3) to the reaction kettle under stirring, and mixing with the second composite solvent in the kettle to obtain a second resin solution, wherein the mass ratio of the maleic rosin-modified polyurethane resin to the second composite solvent is 1:1.55;

[0192] The temperature in the kettle was raised to 75°C. Under stirring conditions, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile were uniformly added to the reactor within 0.7h, and mixed with the second resin solution in the kettle for reaction for 1.5h. The mass ratio of maleic rosin-modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile was 10:2.55:1.55:1.45:0.02. After the reaction was completed, a fourth intermediate product was obtained;

[0193] The temperature in the kettle was raised to 90°C. Under stirring conditions, azobisisobutyronitrile and methyl ethyl ketone were uniformly added into the reactor within 0.7h, and mixed with the fourth intermediate product in the kettle for reaction for 3.5h. The mass ratio of maleic rosin-modified polyurethane resin, azobisisobutyronitrile and methyl ethyl ketone was 10:1.35:0.0015. After the reaction, rosin-modified acrylic resin was obtained.

[0194] (5) 29 parts by weight of the silane-modified epoxy acrylic resin obtained in step (2), 21 parts by weight of the rosin-modified acrylic resin obtained in step (4) and 14 parts by weight of the pigment carbon black are mixed uniformly to obtain a first solution; 0.2 parts by weight of a dispersant BYK-180, 0.2 parts by weight of a leveling agent BYK-3560, 0.2 parts by weight of a defoaming agent BYK-015 and 0.2 parts by weight of a wetting agent BYK-2070 are added to the first solution, and the mixture is mixed uniformly to obtain a second solution; 22 parts by weight of n-butanol and 13.2 parts by weight of deionized water are added to the second solution, the mixture is mixed uniformly and then ground to an average particle size of 19 μm to obtain the penetration-type inkjet ink.

[0195] Example 4

[0196] This embodiment provides a method for preparing a penetrating inkjet ink for hard-to-attach materials, such as Figure 1 As shown, the preparation method specifically comprises the following steps:

[0197] (1) N,N-dimethylethanolamine, methacrylic acid and n-butanol were mixed uniformly in a mass ratio of 1:33:33 to obtain a modified solution; epoxy resin E51 and n-butanol were injected into a reactor in a mass ratio of 1:0.28, and mixed and stirred at 78°C for 1.2 hours to obtain a first resin solution; under stirring and heating conditions of 118°C, the modified solution was added to the reactor and mixed with the first resin solution in the reactor for reaction, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution was 1:4.5, and when the acid value of the reaction product was ≤5 mg / KOH, the heating was stopped, and the material was discharged when the temperature in the reactor dropped to 28°C to obtain a modified epoxy resin;

[0198] (2) Add a first composite solvent (composed of isopropanol and dipropylene glycol methyl ether in a mass ratio of 1:0.65) to another reaction kettle and heat the first composite solvent to 78° C. Under stirring conditions, uniformly add the modified epoxy resin, acrylic acid monomer and azobisisobutyronitrile obtained in step (1) to the reaction kettle within 0.8 h, and mix and react with the first composite solvent in the kettle for 2.2 h. The mass ratio of the first composite solvent, the modified epoxy resin, the acrylic acid monomer and the azobisisobutyronitrile is 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-hydroxymethyl acrylamide in a mass ratio of 1:0.88:0.078:0.38:0.078. After the reaction is completed, a first intermediate product is obtained;

[0199] The temperature in the kettle was raised to 98° C., and under stirring conditions, vinyl triisopropoxy silane and azobisisobutyronitrile were uniformly added to the reactor within 0.8 h, and mixed with the first intermediate product in the kettle for reaction for 3.2 h, and the mass ratio of acrylic monomer, vinyl triisopropoxy silane and azobisisobutyronitrile was 10:0.58:0.115. After the reaction was completed, triethanolamine was added to the reaction product to adjust its pH value to 8.8, to obtain a silane-modified epoxy acrylic resin;

[0200] (3) adding rosin, p-hydroxyanisole and deionized water into a reaction kettle in a mass ratio of 9.5:0.14:1, mixing and stirring for 0.8 h at 179° C. in a nitrogen atmosphere to obtain a raw material solution;

[0201] Add maleic anhydride to the reaction kettle, the mass ratio of rosin to maleic anhydride is 1:0.23, and mix the maleic anhydride and the raw material solution in the kettle for reaction at 208° C. for 2.2 hours to obtain the second intermediate product;

[0202] Continue to add diethylenetriamine to the reactor, the mass ratio of rosin to diethylenetriamine is 1:0.55, diethylenetriamine and the second intermediate product in the reactor are mixed and reacted at 158° C. for 0.8 h to obtain a third intermediate product;

[0203] Continue to add pentaerythritol and zinc oxide into the reactor, the mass ratio of rosin, pentaerythritol and zinc oxide is 1:0.11:0.155, the pentaerythritol, zinc oxide and the third intermediate product in the reactor are mixed and reacted at 263° C. for 0.8 h, and the heating is stopped after the reaction is completed. When the temperature in the reactor drops to 28° C., the material is discharged to obtain a maleic rosin modified polyurethane resin;

[0204] (4) adding a second composite solvent (composed of isopropanol, ethylene glycol ethyl ether and ethanol in a mass ratio of 1:0.33:0.78) to another reaction kettle and heating the second composite solvent to 48° C., adding the maleated rosin-modified polyurethane resin obtained in step (3) to the reaction kettle under stirring, 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;

[0205] The temperature in the kettle was raised to 78°C. Under stirring conditions, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile were uniformly added to the reactor within 0.8h, and mixed with the second resin solution in the kettle for reaction for 1.2h. The mass ratio of maleic rosin-modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile was 10:2.58:1.58:1.48:0.022. After the reaction, a fourth intermediate product was obtained.

[0206] The temperature in the kettle was raised to 92°C. Under stirring conditions, azobisisobutyronitrile and methyl ethyl ketone were uniformly added into the reactor within 0.8 h, and mixed with the fourth intermediate product in the kettle for reaction for 3.2 h. The mass ratio of maleic rosin-modified polyurethane resin, azobisisobutyronitrile and methyl ethyl ketone was 10:1.38:0.0018. After the reaction, rosin-modified acrylic resin was obtained.

[0207] (5) 28.3 parts by weight of the silane-modified epoxy acrylic resin obtained in step (2), 20 parts by weight of the rosin-modified acrylic resin obtained in step (4) and 15 parts by weight of the pigment carbon black are mixed uniformly to obtain a first solution; 0.3 parts by weight of a dispersant BYK-180, 0.2 parts by weight of a leveling agent BYK-3560, 0.1 parts by weight of a defoaming agent BYK-015 and 0.1 parts by weight of a wetting agent BYK-2070 are added to the first solution, and the mixture is mixed uniformly to obtain a second solution; 23 parts by weight of n-butanol and 13 parts by weight of deionized water are added to the second solution, the mixture is mixed uniformly and then ground to an average particle size of 19.5 μm to obtain the penetration-type inkjet ink.

[0208] Example 5

[0209] This embodiment provides a method for preparing a penetrating inkjet ink for hard-to-attach materials, such as Figure 1 As shown, the preparation method specifically comprises the following steps:

[0210] (1) N,N-dimethylethanolamine, methacrylic acid and n-butanol were mixed uniformly in a mass ratio of 1:35:35 to obtain a modified solution; epoxy resin E51 and n-butanol were injected into a reactor in a mass ratio of 1:0.3, and mixed and stirred at 80°C for 1 hour to obtain a first resin solution; under stirring and heating at 120°C, the modified solution was added to the reactor and mixed with the first resin solution in the reactor for reaction, the mass ratio of methacrylic acid in the modified solution to the epoxy resin in the first resin solution was 1:5, and when the acid value of the reaction product was ≤5 mg / KOH, the heating was stopped, and when the temperature in the reactor dropped to 30°C, the material was discharged to obtain a modified epoxy resin;

[0211] (2) Add a first composite solvent (composed of isopropanol and dipropylene glycol methyl ether in a mass ratio of 1:0.7) to another reaction kettle and heat the first composite solvent to 80° C. Under stirring conditions, uniformly add the modified epoxy resin, acrylic acid monomer and azobisisobutyronitrile obtained in step (1) to the reaction kettle within 1 hour, and mix and react with the first composite solvent in the kettle for 2 hours. The mass ratio of the first composite solvent, modified epoxy resin, acrylic acid monomer and azobisisobutyronitrile is 1:0.06:1.2:0.05, wherein the acrylic acid monomer is composed of methyl methacrylate, ethyl acrylate, acrylic acid, hydroxyethyl acrylate and N-hydroxymethyl acrylamide in a mass ratio of 1:0.9:0.08:0.4:0.08. After the reaction is completed, a first intermediate product is obtained;

[0212] The temperature in the kettle was raised to 100° C., and under stirring conditions, vinyl triisopropoxy silane and azobisisobutyronitrile were uniformly added to the reaction kettle within 1 hour, and mixed with the first intermediate product in the kettle for reaction for 3 hours, and the mass ratio of acrylic monomer, vinyl triisopropoxy silane and azobisisobutyronitrile was 10:0.6:0.12. After the reaction was completed, triethanolamine was added to the reaction product to adjust its pH value to 9, to obtain a silane-modified epoxy acrylic resin;

[0213] (3) adding rosin, p-hydroxyanisole and deionized water into a reaction kettle in a mass ratio of 10:0.15:1, mixing and stirring for 0.5 h at 180° C. in a nitrogen atmosphere to obtain a raw material solution;

[0214] Add maleic anhydride to the reaction kettle, the mass ratio of rosin to maleic anhydride is 1:0.25, and mix the maleic anhydride and the raw material solution in the kettle for reaction at 210° C. for 2 hours to obtain the second intermediate product;

[0215] Continue to add diethylenetriamine to the reactor, the mass ratio of rosin to diethylenetriamine is 1:0.6, diethylenetriamine and the second intermediate product in the reactor are mixed and reacted at 160° C. for 0.5 h to obtain a third intermediate product;

[0216] Continue to add pentaerythritol and zinc oxide into the reactor, the mass ratio of rosin, pentaerythritol and zinc oxide is 1:0.12:0.16, the pentaerythritol, zinc oxide and the third intermediate product in the reactor are mixed and reacted at 265° C. for 0.5 h, and the heating is stopped after the reaction is completed. When the temperature in the reactor drops to 30° C., the material is discharged to obtain a maleic rosin modified polyurethane resin;

[0217] (4) adding a second composite solvent (composed of isopropanol, ethylene glycol ethyl ether and ethanol in a mass ratio of 1:0.35:0.8) into another reaction kettle and heating the second composite solvent to 50° C., adding the maleated rosin-modified polyurethane resin obtained in step (3) into the reaction kettle under stirring, 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;

[0218] The temperature in the kettle was raised to 80° C., and under stirring conditions, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile were uniformly added to the reaction kettle within 1 hour, and mixed with the second resin solution in the kettle for reaction for 1 hour. The mass ratio of maleic rosin-modified polyurethane resin, methyl methacrylate, acrylic acid, styrene and azobisisobutyronitrile was 10:2.6:1.6:1.5:0.025. After the reaction was completed, a fourth intermediate product was obtained;

[0219] The temperature in the kettle was raised to 95°C. Under stirring conditions, azobisisobutyronitrile and methyl ethyl ketone were uniformly added into the reactor within 1 hour, and mixed with the fourth intermediate product in the kettle for reaction for 3 hours. The mass ratio of maleic rosin-modified polyurethane resin, azobisisobutyronitrile and methyl ethyl ketone was 10:1.4:0.002. After the reaction, rosin-modified acrylic resin was obtained.

[0220] (5) 30 parts by weight of the silane-modified epoxy acrylic resin obtained in step (2), 20 parts by weight of the rosin-modified acrylic resin obtained in step (4) and 12 parts by weight of the pigment carbon black are mixed uniformly to obtain a first solution; 0.1 parts by weight of a dispersant BYK-180, 0.1 parts by weight of a leveling agent BYK-3560, 0.1 parts by weight of a defoaming agent BYK-015 and 0.1 parts by weight of a wetting agent BYK-2070 are added to the first solution, and the mixture is mixed uniformly to obtain a second solution; 22.6 parts by weight of n-butanol and 15 parts by weight of deionized water are added to the second solution, the mixture is mixed uniformly and then ground to an average particle size of 20 μm to obtain the penetration-type inkjet ink.

[0221] Comparative Example 1

[0222] This comparative example provides a method for preparing a penetrating inkjet coding ink for difficult-to-attach materials. The difference from Example 1 is that in step (2), the mass ratio of acrylic acid monomer, vinyltrimethoxysilane and benzoyl peroxide during mixing is adjusted to 10:0.4:0.1, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0223] Comparative Example 2

[0224] This comparative example provides a method for preparing a penetrating inkjet coding ink for difficult-to-attach materials. The difference from Example 1 is that in step (2), the mass ratio of acrylic acid monomer, vinyltrimethoxysilane and benzoyl peroxide during mixing is adjusted to 10:0.7:0.1, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0225] Figure 7 , Figure 8 and Fig. 9 The particle size distribution diagrams of the penetrating inkjet ink prepared in Comparative Example 1, Comparative Example 2 and Example 1 are shown in Figure 1. By comparison, it can be seen that the particle size of the penetrating inkjet ink is bimodal (e.g. Figure 7 As shown in Figure 2, with the increase of the amount of organosiloxane used, the particle size distribution of the inkjet ink gradually changes from a bimodal distribution to a unimodal distribution (as shown in Figure 2). Figure 8 and Fig. 9As shown in Figure 2, this is because after the modified system is dispersed in water, the Si-O bonds in the molecular structure are hydrolyzed and cross-linked, and some small particles grow up, so the particle size distribution gradually tends to be uniform, changing from a bimodal distribution to a unimodal distribution. When the dosage is too high (such as in Comparative Example 2), more Si-O bonds are hydrolyzed and cross-linked, resulting in a rapid increase in particle size (such as Figure 8 As shown in the figure), the system is unstable and precipitation and stratification are prone to occur.

[0226] Comparative Example 3

[0227] This comparative example provides a method for preparing a penetrating inkjet coding ink for difficult-to-adhere materials. The difference from Example 1 is that in step (3), the reaction temperature of the raw material solution and maleic anhydride is adjusted to 180°C, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0228] Comparative Example 4

[0229] This comparative example provides a method for preparing a penetrating inkjet coding ink for difficult-to-adhere materials. The difference from Example 1 is that in step (3), the reaction temperature of the raw material solution and maleic anhydride is adjusted to 230°C, and the other process parameters and operating steps are exactly the same as those in Example 1.

[0230] Comparative Example 5

[0231] This comparative example provides a method for preparing a penetrating inkjet coding ink for difficult-to-attach materials. The difference from Example 1 is that the amount of silane-modified epoxy acrylic resin is adjusted to 25 parts, and the amounts of other components are enlarged in equal proportions to ensure that the relative mass ratios of the other components except the silane-modified epoxy acrylic resin remain unchanged. The specific weight parts of each component are as follows:

[0232] Silane modified epoxy acrylic resin 25 parts;

[0233] Rosin modified acrylic resin 22.917 parts;

[0234] Pigment carbon black 15.625 parts;

[0235] Dispersant BYK-180 0.1042 parts;

[0236] Leveling agent BYK-3560 0.3125 parts;

[0237] Defoamer BYK-015 0.2083 parts;

[0238] Wetting agent BYK-2070 0.3125 parts;

[0239] 20.833 parts of n-butanol;

[0240] 14.6875 parts of deionized water.

[0241] Other process parameters and operation steps are exactly the same as those in Example 1.

[0242] Comparative Example 6

[0243] This comparative example provides a method for preparing a penetrating inkjet ink for difficult-to-attach materials. The difference from Example 1 is that the amount of silane-modified epoxy acrylic resin is adjusted to 35 parts, and the amounts of other components are reduced in proportion to ensure that the relative mass ratios of the other components except the silane-modified epoxy acrylic resin remain unchanged. The specific weight parts of each component are as follows:

[0244] Silane modified epoxy acrylic resin 35 parts;

[0245] 19.86 parts of rosin-modified acrylic resin;

[0246] Pigment carbon black 13.54 parts;

[0247] Dispersant BYK-180 0.09 parts;

[0248] Leveling agent BYK-3560 0.271 parts;

[0249] Defoamer BYK-015 0.181 parts;

[0250] Wetting agent BYK-2070 0.271 parts;

[0251] 18.06 parts of n-butanol;

[0252] 12.73 parts of deionized water.

[0253] Other process parameters and operation steps are exactly the same as those in Example 1.

[0254] Comparative Example 7

[0255] This comparative example provides a method for preparing a penetrating inkjet ink for difficult-to-attach materials. The difference from Example 1 is that the amount of rosin-modified acrylic resin is adjusted to 18 parts, and the amounts of other components are enlarged in equal proportions to ensure that the relative mass ratios of the other components except the rosin-modified acrylic resin remain unchanged, as follows:

[0256] Silane-modified epoxy acrylic resin 29.44 parts;

[0257] 18 parts of rosin modified acrylic resin;

[0258] Pigment 15.77 parts;

[0259] Dispersant 0.105 parts;

[0260] 0.315 parts of leveling agent;

[0261] Defoaming agent 0.21 parts;

[0262] Wetting agent 0.315 parts;

[0263] 21.03 parts of n-butanol;

[0264] 14.82 parts of deionized water.

[0265] Other process parameters and operation steps are exactly the same as those in Example 1.

[0266] Comparative Example 8

[0267] This comparative example provides a method for preparing a penetrating inkjet ink for difficult-to-attach materials. The difference from Example 1 is that the amount of rosin-modified acrylic resin is adjusted to 25 parts, and the amounts of other components are reduced in equal proportions to ensure that the relative mass ratios of the other components except the rosin-modified acrylic resin remain unchanged, as follows:

[0268] Silane-modified epoxy acrylic resin 26.92 parts;

[0269] 25 parts of rosin modified acrylic resin;

[0270] Pigment 14.42 parts;

[0271] Dispersant 0.096 parts;

[0272] 0.288 parts of leveling agent;

[0273] Defoaming agent 0.192 parts;

[0274] Wetting agent 0.288 parts;

[0275] 19.23 parts of n-butanol;

[0276] 13.56 parts of deionized water.

[0277] Other process parameters and operation steps are exactly the same as those in Example 1.

[0278] The adhesion, quick-drying and stability of the penetrating inkjet coding ink provided in Examples 1-5 and Comparative Examples 1-8 were tested, and the specific test steps are as follows:

[0279] (1) Adhesion test

[0280] Refer to the test method provided in GB / T 5210-2006 "Pull-off Adhesion Test" and use the pull-off method to measure the adhesion between the film layer and the substrate:

[0281] The permeable inkjet coding ink provided in Examples 1-5 and Comparative Examples 1-8 was coated on a flat and clean polyethylene substrate. After the coating was completely dried to form a film layer, the test column of the GLS002 adhesion tester was bonded to the film layer through an adhesive and dried and left to stand for 24 hours. After 24 hours, the test column was pulled to tear off the film layer from the polyethylene substrate, and the adhesion (N / mm 2 ), each group of embodiments / comparative examples was tested 3 times and the average value was taken.

[0282] (2) Quick-drying test

[0283] Take an appropriate amount of inkjet ink sample with a 5μL capillary, place it in an open watch glass at room temperature, record the time for the inkjet ink sample to solidify completely, and record it as t1 (s); then take an equal amount of ether solution, place it in an open watch glass at room temperature, and record the time for its complete evaporation, and record it as t0 (s); use the following formula to calculate the quick-drying rate E of the inkjet ink:

[0284]

[0285] The smaller the E value, the shorter the volatilization time and the better the quick-drying property.

[0286] (3) Stability test

[0287] Use a desktop centrifuge to force solid-liquid separation of the inkjet ink, and judge the stability of the inkjet ink by the change in the absorbance of the inkjet ink. The specific steps are as follows:

[0288] Take 0.5 mL of the permeable inkjet ink provided in Examples 1-5 and Comparative Examples 1-8, dilute it in a 500 mL volumetric flask with deionized water, inject the diluted inkjet ink into the cuvette of a UV-visible spectrophotometer, and measure the absorbance A0 at a suitable wavelength.

[0289] The penetrating inkjet coding ink provided in Examples 1-5 and Comparative Examples 1-8 was injected into a centrifuge tube, centrifuged at 5000 r / min for 20 min, 0.5 mL of the upper liquid in the centrifuge tube was taken, diluted with deionized water in a 500 mL volumetric flask, and the absorbance A1 was measured.

[0290] The absorbance ratio a of the inkjet ink before and after centrifugation is calculated using the following formula:

[0291] ,

[0292] The larger the a value is, the greater the color difference of the coding ink before and after centrifugal separation is, and the worse the stability of the coding ink is.

[0293] Table 1 Performance test results of the penetration-type inkjet ink provided by Examples 1-5 and Comparative Examples 1-8

[0294]

[0295] It can be seen from the test data provided in Table 1 that the inkjet ink prepared in Examples 1-5 of the present invention has excellent adhesion, quick drying and stability.

[0296] It can be seen from the test data of Example 1, Comparative Example 1 and Comparative Example 2 that the adhesion, quick-drying rate and absorbance ratio of the inkjet inks prepared in Comparative Example 1 and Comparative Example 2 are lower than those in Example 1. This is because the amount of vinyltrimethoxysilane used in Comparative Example 1 is too low, and its hydrophobicity cannot be effectively exerted, and the hydrophobic modification effect on the resin binder is weak; while the amount of vinyltrimethoxysilane used in Comparative Example 2 is too high, and the alkoxy groups in the molecular chain segments of the resin binder will undergo hydrolysis, condensation and cross-linking, which ultimately affects the various properties of the inkjet ink.

[0297] It can be seen from the test data of Example 1, Comparative Example 3 and Comparative Example 4 that the adhesion, quick drying rate and absorbance ratio of the inkjet ink prepared in Comparative Example 3 and Comparative Example 4 are lower than those in Example 1. This is because the reaction temperature of the raw material solution and maleic anhydride in Comparative Example 3 is too low, resulting in incomplete DA addition reaction of rosin in the raw material solution and maleic anhydride, and the amount of maleic rosin generated is low; the reaction temperature of the raw material solution and maleic anhydride in Comparative Example 4 is too high, and maleic anhydride sublimates in large quantities, resulting in a low reaction yield, which ultimately affects the various properties of the inkjet ink.

[0298] It can be seen from the test data of Example 1, Comparative Example 5 and Comparative Example 6 that the adhesion, quick drying rate and absorbance ratio of the inkjet ink prepared in Comparative Example 5 and Comparative Example 6 are lower than those in Example 1. This is 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 too low, which ultimately affects the various properties of the inkjet ink.

[0299] It can be seen from the test data of Example 1, Comparative Example 7 and Comparative Example 8 that the adhesion, quick drying rate and absorbance ratio of the inkjet ink prepared in Comparative Example 7 and Comparative Example 8 are lower than those in Example 1. This is 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 too low, which ultimately affects the various properties of the inkjet ink.

[0300] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

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; 20-22 parts of rosin modified acrylic resin; 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; 13-15 parts of deionized water; 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 a penetrating inkjet ink for hard-to-attach 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 ink for difficult-to-adhere materials according to claim 2, characterized in that: In step (2), the first composite solvent consists 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 the 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 the penetrating inkjet ink for difficult-to-adhere materials according to claim 2, characterized in that: In step (I), the mass ratio of 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 isopropanol, 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.

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