A high adhesion printing ink and a method for its preparation

Abstract

This invention relates to the field of printing ink technology, specifically to a high-adhesion printing ink and its preparation method, which is made from the following raw materials in parts by weight: 20-25 parts of bisphenol A type epoxy resin, 18-22 parts of pigment, 1.5-2.5 parts of dispersant, 3-5 parts of first functional additive, 2-3 parts of second functional additive, 3-4 parts of triethylenetetramine, and 3-5 parts of phenyl glycidyl ether. In this invention, the second functional additive enhances the surface activity of halloysite by pretreatment with hydrochloric acid solution, and the silane coupling agent KH560 modifies and optimizes its compatibility and chemical bonding ability in the resin system. This not only significantly improves the bonding strength between the ink and the substrate surface and enhances the adhesion stability, but also optimizes the structural integrity of the ink film after formation, effectively resists the erosion of the film layer by the external environment, and extends the service life of printed products.

Description

Technical Field

[0001] This invention relates to the field of printing ink technology, specifically to a high-adhesion printing ink and its preparation method. Background Technology

[0002] Ink is a key material used in printing and coating processes to achieve image and text reproduction, information transmission and surface decoration. Its main function is to form a firm and clear imprint on the surface of the substrate through a controlled deposition method, so as to achieve the purposes of visual communication, identification protection, decoration and beautification and functional coating.

[0003] In the prior art, traditional inks, after drying and curing, often exhibit poor adhesion and easy wear and peeling, especially on non-absorbent or low surface energy substrates, due to weak interfacial bonding and insufficient cohesive strength. This seriously affects the service life and appearance integrity of printed materials. Based on this, the present invention provides a high-adhesion printing ink and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide a high-adhesion printing ink and its preparation method. The ink prepared by this invention not only has good interfacial bonding performance, but also excellent adhesion stability, effectively improving the performance of printing ink.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a high-adhesion printing ink, made from the following raw materials in parts by weight: 20-25 parts of bisphenol A epoxy resin, 18-22 parts of pigment, 1.5-2.5 parts of dispersant, 3-5 parts of first functional additive, 2-3 parts of second functional additive, 3-4 parts of triethylenetetramine, and 3-5 parts of phenyl glycidyl ether; The pigment is carbon black, and the dispersing agent is sodium dodecylbenzene sulfonate; The raw materials for the first functional additive include asphaltene, n-heptane, dilute phosphoric acid solution, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt; The second functional additive raw materials include halloysite, hydrochloric acid solution, silane coupling agent KH560, polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives.

[0006] Preferably, the preparation method of the first functional additive includes the following steps: Step 1: Mix 75% ethanol solution, asphaltene, and n-heptane in a mass ratio of (1.2-1.4):1:(2.2-2.8), stir at 32-38℃ for 70-80 min, let stand for 1.5-2 h, filter to obtain solid filter residue, add 5-6% dilute phosphoric acid solution to solid filter residue, stir at 48-52℃ for 30-35 min, filter, wash 2-3 times, dry at 72-78℃ for 1.5-2 h, pulverize and pass through a 160-200 mesh sieve to obtain the first additive powder; Step 2: Mix the first additive powder, toluene, and petroleum ether, and stir at 42-48℃ for 35-40 min. Then, add 1% glutaraldehyde solution, 30% hydrogen peroxide solution, and chitosan quaternary ammonium salt in sequence, and stir continuously for 15-20 min. Raise the temperature to 62-68℃, sonicate for 70-80 min, cool, filter and collect the solid, and dry at 82-88℃ for 2.5-3 h to obtain the first functional additive.

[0007] Preferably, the mass ratio of the dilute phosphoric acid solution to the solid filter residue is (2-5):1.

[0008] Preferably, the mass ratio of the first additive powder, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution and chitosan quaternary ammonium salt is 1:(4-8):(4-8):(0.05-0.1):0.1:(0.2-0.5).

[0009] Preferably, the preparation method of the second functional additive includes the following steps: Step 1: Mix halloysite powder with a 6-7% hydrochloric acid solution at a mass ratio of 1:(20-40), stir at 42-48℃ for 70-80 minutes, filter to collect the precipitate, add silane coupling agent KH560 to the precipitate, stir at 35-40℃ for 30-35 minutes, dry and pulverize, and pass through a 400-500 mesh sieve to obtain the second additive powder, wherein the mass ratio of precipitate to silane coupling agent KH560 is 100:(0.5-2); Step 2: Mix the second additive powder, deionized water, and polyethylene glycol 600, heat to 52-58℃ and stir for 25-30 minutes to obtain the first mixture. Add 1-butyl-3-methylimidazolium tetrafluoroborate and additives to the first mixture, and stir at normal temperature and pressure for 100-110 minutes. Filter to obtain solid particles, wash with anhydrous ethanol 2-3 times, and dry at 78-82℃ for 2.2-2.8 hours to obtain the second functional additive.

[0010] Preferably, the mass ratio of the second additive powder, deionized water and polyethylene glycol 600 is 1:(5-20):(0.2-2), and the mass ratio of the first mixture, 1-butyl-3-methylimidazolium tetrafluoroborate and additive is 100:(5-15):(1-10).

[0011] Preferably, the preparation method of the additive includes the following steps: mixing black walnut shell oil with anhydrous ethanol at a mass ratio of 1:(3-5), stirring at 30-35℃ for 20 min, allowing to stand for 1 h to separate into layers, taking the upper oil phase to obtain the treatment liquid, mixing the treatment liquid with epoxy acrylate, stirring at 72-78℃ for 35-40 min, cooling to room temperature to obtain the additive.

[0012] Preferably, the mass ratio of the treatment solution to epoxy acrylate is 1:(0.18-0.24).

[0013] A preferred method for preparing a high-adhesion printing ink includes the following steps: S1: Weigh out triethylenetetramine, first functional additive, second functional additive, dispersant, bisphenol A epoxy resin and phenyl glycidyl ether by weight, put them into a mixer, and mix for 20-30 minutes at 50-60℃ and 500-600r / min to obtain a preliminary mixture. S2: Weigh the pigment by weight, mix it with the initial mixture, add it to a sand mill, and grind it to obtain a pigment slurry; S3: Add the pigment paste to the disperser and disperse it at 800 r / min for 10 min and 1500 r / min for 20 min in sequence. Degas the resulting material at -0.098 MPa and 40℃ for 30 min, and then filter it through a 400 mesh filter to obtain a high-adhesion printing ink.

[0014] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, the second functional additive enhances the surface activity of halloysite by pretreating it with hydrochloric acid solution. The silane coupling agent KH560 modifies and optimizes its compatibility and chemical bonding ability in the resin system. The synergistic effect of polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate and additives not only significantly improves the bonding strength between the ink and the substrate surface and enhances the adhesion stability, but also optimizes the structural integrity of the ink film after it is formed, effectively resists the erosion of the film layer by the external environment, and extends the service life of printed products.

[0015] 2. In this invention, the first functional additive uses asphaltene as raw material. After purification by mixing ethanol solution and n-heptane, it is modified with dilute phosphoric acid solution to introduce active functional groups. Subsequently, it is mixed with toluene and petroleum ether, and glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt are added in sequence. The mixture is then subjected to heating and ultrasonic treatment to promote the reaction and fusion of the components. The oxidizing effect of hydrogen peroxide can increase the active sites, and the chitosan quaternary ammonium salt can enhance the polar interaction with the substrate, optimize the dispersion uniformity of pigment and resin components, and avoid uneven adhesion caused by local agglomeration. At the same time, through the dual effects of physical adsorption and chemical bonding, the adhesion between the ink film layer and the substrate is greatly enhanced, effectively preventing the film layer from peeling and flaking after printing.

[0016] 3. In this invention, the additive is composed of black walnut shell oil treated with anhydrous ethanol and then compounded with epoxy acrylate. It has both good compatibility and strong adhesion properties. It can form a synergistic effect with halloysite modified component and 1-butyl-3-methylimidazolium tetrafluoroborate in the second functional additive, improve the flexibility and adhesion of ink film, significantly improve the adhesion and durability of ink to substrate, and optimize the flexibility of film layer. Attached Figure Description

[0017] Figure 1 The present invention provides a flowchart of a high-adhesion printing ink and its preparation method. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] It should be noted that the raw materials used in the following embodiments are all commercially available.

[0020] Example 1: A high-adhesion printing ink is made from the following raw materials in parts by weight: 20 parts of bisphenol A type epoxy resin, 18 parts of pigment, 1.5 parts of dispersant, 3 parts of primary functional additive, 2 parts of secondary functional additive, 3 parts of triethylenetetramine, and 3 parts of phenyl glycidyl ether. The pigment is carbon black, and the dispersing agent is sodium dodecylbenzene sulfonate; The raw materials for the first functional additive include asphaltene, n-heptane, dilute phosphoric acid solution, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt; The second functional additive raw materials include halloysite, hydrochloric acid solution, silane coupling agent KH560, polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives.

[0021] The preparation method of the first functional additive includes the following steps: Step 1: Mix 75% ethanol solution, asphaltene, and n-heptane in a mass ratio of 1.2:1:2.2, stir at 32℃ for 70 min, let stand for 1.5 h, filter to obtain solid filter residue, add 5% dilute phosphoric acid solution to solid filter residue, stir at 48℃ for 30 min, filter, wash twice, dry at 72℃ for 1.5 h, pulverize and pass through a 160 mesh sieve to obtain the first additive powder; Step 2: Mix the first additive powder, toluene and petroleum ether, stir at 42°C for 35 min, then add 1% glutaraldehyde solution, 30% hydrogen peroxide solution and chitosan quaternary ammonium salt in sequence, stir continuously for 15 min, heat to 62°C, sonicate for 70 min, cool and filter to collect the solid, dry at 82°C for 2.5 h to obtain the first functional additive.

[0022] The mass ratio of dilute phosphoric acid solution to solid filter residue is 2:1.

[0023] The mass ratio of the first additive powder, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt is 1:4:4:0.05:0.1:0.2.

[0024] The preparation method of the second functional additive includes the following steps: Step 1: Mix halloysite powder with a 6% hydrochloric acid solution at a mass ratio of 1:20, stir at 42℃ for 70 min, filter to collect the precipitate, add silane coupling agent KH560 to the precipitate, stir at 35℃ for 30 min, dry and pulverize, and pass through a 400-mesh sieve to obtain the second additive powder. The mass ratio of precipitate to silane coupling agent KH560 is 100:0.5. Step 2: Mix the second additive powder, deionized water and polyethylene glycol 600, heat to 52℃ and stir for 25 min to obtain the first mixture. Add 1-butyl-3-methylimidazolium tetrafluoroborate and additives to the first mixture, and stir at normal temperature and pressure for 100 min. Filter to obtain solid particles, wash twice with anhydrous ethanol, and dry at 78℃ for 2.2 h to obtain the second functional additive.

[0025] The mass ratio of the second additive powder, deionized water, and polyethylene glycol 600 is 1:5:0.2, and the mass ratio of the first mixture, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives is 100:5:1.

[0026] The preparation method of the additive includes the following steps: black walnut shell oil and anhydrous ethanol are mixed at a mass ratio of 1:3, stirred at 30°C for 20 min, allowed to stand for 1 h to separate into layers, the upper oil phase is taken to obtain the treatment liquid, the treatment liquid is mixed with epoxy acrylate, stirred at 72°C for 35 min, and cooled to room temperature to obtain the additive.

[0027] The mass ratio of the treatment solution to epoxy acrylate is 1:0.18.

[0028] A method for preparing high-adhesion printing ink includes the following steps: S1: Weigh out triethylenetetramine, first functional additive, second functional additive, dispersant, bisphenol A epoxy resin and phenyl glycidyl ether by weight, put them into a mixer, and mix for 20 min at 50℃ and 500 r / min to obtain a preliminary mixture. S2: Weigh the pigment by weight, mix it with the initial mixture, add it to a sand mill, and grind it to obtain a pigment slurry; S3: Add the pigment paste to the disperser and disperse it at 800 r / min for 10 min and 1500 r / min for 20 min in sequence. Degas the resulting material at -0.098 MPa and 40℃ for 30 min, and then filter it through a 400 mesh filter to obtain a high-adhesion printing ink.

[0029] Example 2: A high-adhesion printing ink is made from the following raw materials in parts by weight: 23 parts of bisphenol A type epoxy resin, 20 parts of pigment, 2 parts of dispersant, 4 parts of primary functional agent, 2.5 parts of secondary functional agent, 3.5 parts of triethylenetetramine, and 4 parts of phenyl glycidyl ether. The pigment is carbon black, and the dispersing agent is sodium dodecylbenzene sulfonate; The raw materials for the first functional additive include asphaltene, n-heptane, dilute phosphoric acid solution, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt; The second functional additive raw materials include halloysite, hydrochloric acid solution, silane coupling agent KH560, polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives.

[0030] The preparation method of the first functional additive includes the following steps: Step 1: Mix 75% ethanol solution, asphaltene, and n-heptane in a mass ratio of 1.3:1:2.6, stir at 35°C for 75 min, let stand for 1.8 h, filter to obtain solid filter residue, add 5% dilute phosphoric acid solution to the solid filter residue, stir at 50°C for 33 min, filter, wash twice, dry at 75°C for 1.8 h, pulverize and pass through an 180-mesh sieve to obtain the first additive powder; Step 2: Mix the first additive powder, toluene and petroleum ether, stir at 45°C for 38 min, add 1% glutaraldehyde solution, 30% hydrogen peroxide solution and chitosan quaternary ammonium salt in sequence, stir continuously for 18 min, heat to 65°C, sonicate for 75 min, cool and filter to collect the solid, dry at 85°C for 2.8 h to obtain the first functional additive.

[0031] The mass ratio of dilute phosphoric acid solution to solid filter residue is 3:1.

[0032] The mass ratio of the first additive powder, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt is 1:6:6:0.08:0.1:0.3.

[0033] The preparation method of the second functional additive includes the following steps: Step 1: Mix halloysite powder with a 7% hydrochloric acid solution at a mass ratio of 1:30, stir at 45°C for 75 min, filter to collect the precipitate, add silane coupling agent KH560 to the precipitate, stir at 38°C for 32 min, dry and pulverize, and pass through a 450-mesh sieve to obtain the second additive powder. The mass ratio of precipitate to silane coupling agent KH560 is 100:1. Step 2: Mix the second additive powder, deionized water and polyethylene glycol 600, heat to 55℃ and stir for 28 min to obtain the first mixture. Add 1-butyl-3-methylimidazolium tetrafluoroborate and additives to the first mixture, and stir at normal temperature and pressure for 105 min. Filter to obtain solid particles, wash three times with anhydrous ethanol, and dry at 80℃ for 2.5 h to obtain the second functional additive.

[0034] The mass ratio of the second additive powder, deionized water, and polyethylene glycol 600 is 1:12:1, and the mass ratio of the first mixture, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives is 100:10:5.

[0035] The preparation method of the additive includes the following steps: black walnut shell oil and anhydrous ethanol are mixed at a mass ratio of 1:4, stirred at 33°C for 20 min, allowed to stand for 1 h to separate into layers, the upper oil phase is taken to obtain the treatment liquid, the treatment liquid is mixed with epoxy acrylate, stirred at 75°C for 38 min, and cooled to room temperature to obtain the additive.

[0036] The mass ratio of the treatment solution to epoxy acrylate is 1:0.2.

[0037] A method for preparing high-adhesion printing ink includes the following steps: S1: Weigh out triethylenetetramine, first functional additive, second functional additive, dispersant, bisphenol A epoxy resin and phenyl glycidyl ether by weight, put them into a mixer, and mix for 25 minutes at 55℃ and 550r / min to obtain the initial mixture. S2: Weigh the pigment by weight, mix it with the initial mixture, add it to a sand mill, and grind it to obtain a pigment slurry; S3: Add the pigment paste to the disperser and disperse it at 800 r / min for 10 min and 1500 r / min for 20 min in sequence. Degas the resulting material at -0.098 MPa and 40℃ for 30 min, and then filter it through a 400 mesh filter to obtain a high-adhesion printing ink.

[0038] Example 3: A high-adhesion printing ink is made from the following raw materials in parts by weight: 25 parts of bisphenol A type epoxy resin, 22 parts of pigment, 2.5 parts of dispersant, 5 parts of primary functional additive, 3 parts of secondary functional additive, 4 parts of triethylenetetramine, and 5 parts of phenyl glycidyl ether. The pigment is carbon black, and the dispersing agent is sodium dodecylbenzene sulfonate; The raw materials for the first functional additive include asphaltene, n-heptane, dilute phosphoric acid solution, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt; The second functional additive raw materials include halloysite, hydrochloric acid solution, silane coupling agent KH560, polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives.

[0039] The preparation method of the first functional additive includes the following steps: Step 1: Mix 75% ethanol solution, asphaltene, and n-heptane in a mass ratio of 1.4:1:2.8, stir at 38℃ for 80 min, let stand for 2 h, filter to obtain solid filter residue, add 6% dilute phosphoric acid solution to solid filter residue, stir at 52℃ for 35 min, filter, wash 3 times, dry at 78℃ for 2 h, and pass through a 200 mesh sieve to obtain the first additive powder; Step 2: Mix the first additive powder, toluene and petroleum ether, stir at 48°C for 40 min, add 1% glutaraldehyde solution, 30% hydrogen peroxide solution and chitosan quaternary ammonium salt in sequence, stir continuously for 20 min, heat to 68°C, sonicate for 80 min, cool and filter to collect the solid, dry at 88°C for 3 h to obtain the first functional additive.

[0040] The mass ratio of dilute phosphoric acid solution to solid filter residue is 5:1.

[0041] The mass ratio of the first additive powder, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt is 1:8:8:0.1:0.1:0.5.

[0042] The preparation method of the second functional additive includes the following steps: Step 1: Mix halloysite powder with a 7% hydrochloric acid solution at a mass ratio of 1:40, stir at 48℃ for 80 min, filter to collect the precipitate, add silane coupling agent KH560 to the precipitate, stir at 40℃ for 35 min, dry and pulverize, and pass through a 500-mesh sieve to obtain the second additive powder. The mass ratio of precipitate to silane coupling agent KH560 is 100:2. Step 2: Mix the second additive powder, deionized water and polyethylene glycol 600, heat to 58℃ and stir for 30 min to obtain the first mixture. Add 1-butyl-3-methylimidazolium tetrafluoroborate and additives to the first mixture, and stir at normal temperature and pressure for 110 min. Filter to obtain solid particles, wash three times with anhydrous ethanol, and dry at 82℃ for 2.8 h to obtain the second functional additive.

[0043] The mass ratio of the second additive powder, deionized water, and polyethylene glycol 600 is 1:20:2, and the mass ratio of the first mixture, 1-butyl-3-methylimidazolium tetrafluoroborate, and additives is 100:15:10.

[0044] The preparation method of the additive includes the following steps: mixing black walnut shell oil and anhydrous ethanol at a mass ratio of 1:5, stirring at 35°C for 20 min, allowing to stand for 1 h to separate into layers, taking the upper oil phase to obtain the treatment liquid, mixing the treatment liquid with epoxy acrylate, stirring at 78°C for 40 min, and cooling to room temperature to obtain the additive.

[0045] The mass ratio of the treatment solution to epoxy acrylate is 1:0.24.

[0046] A method for preparing high-adhesion printing ink includes the following steps: S1: Weigh out triethylenetetramine, first functional additive, second functional additive, dispersant, bisphenol A epoxy resin and phenyl glycidyl ether by weight, put them into a mixer, and mix for 30 min at 60℃ and 600 r / min to obtain a preliminary mixture; S2: Weigh the pigment by weight, mix it with the initial mixture, add it to a sand mill, and grind it to obtain a pigment slurry; S3: Add the pigment paste to the disperser and disperse it at 800 r / min for 10 min and 1500 r / min for 20 min in sequence. Degas the resulting material at -0.098 MPa and 40℃ for 30 min, and then filter it through a 400 mesh filter to obtain a high-adhesion printing ink.

[0047] Comparative Example 1: The difference between this comparative example and Example 1 is that this comparative example does not contain the first functional additive.

[0048] Comparative Example 2 differs from Example 1 in that it does not contain a second functional additive.

[0049] Comparative Example 3 differs from Example 1 in that no additives were added when preparing the second functional agent in this comparative example.

[0050] Performance testing: The high-adhesion printing inks prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance testing, and the test data are recorded in the table below: Table 1 In the performance test, the peel strength was tested according to GB / T2792-2014 to quantitatively evaluate the adhesion between the ink coating and the substrate. The higher the value, the stronger the adhesion. The abrasion resistance was determined according to the "Ink Layer Abrasion Resistance" test method in GB / T7706-2008. The number of rubs required for the ink layer to be completely worn through was recorded. The higher the number of rubs, the better the abrasion resistance. The chemical resistance was tested according to GB / T23989-2009. The ability to resist solvent erosion was evaluated by recording the number of times the ink layer resisted wiping with a specific solvent until the substrate was exposed. The higher the value, the better the chemical resistance.

[0051] The test data clearly show that the performance of Comparative Examples 1-3 decreased significantly due to the absence of key components. Specifically, Comparative Example 1, which does not contain the second functional additive, has the lowest peel strength, proving that the halloysite coupled with silane in the second functional additive is the core for building the reinforcing network and improving interfacial bonding and cohesive strength. Comparative Example 2, which does not contain the first functional additive, has the worst abrasion resistance, indicating that the first functional additive is crucial for optimizing dispersion and forming a coating. Its absence leads to structural defects in the coating and makes it susceptible to wear. Comparative Example 3, which does not contain additives, has significantly lower ethanol wiping resistance and peel strength than the examples, indicating that additives play an important role in toughening the matrix and stabilizing interfacial compatibility. The lack of additives weakens the synergistic effect.

[0052] In summary, the high-adhesion printing ink provided by this invention exhibits multiple technical advantages. The first functional additive is mainly responsible for optimizing dispersion, introducing active sites, and constructing a cross-linked coating base. The second functional additive is mainly responsible for providing nano-reinforcement and physical barrier, significantly improving mechanical strength and durability. The additives effectively toughen and stabilize the overall structure. The three work together to achieve a comprehensive improvement in adhesion, abrasion resistance, and chemical resistance.

[0053] Comparison and analysis of test data show that the ink prepared by this invention not only has extremely high peel strength, but also exhibits excellent abrasion resistance and excellent solvent resistance. This indicates that the ink and its preparation method provided by this invention can effectively solve the common technical problems of insufficient adhesion, easy abrasion and peeling, and poor resistance to media erosion of traditional printing inks, and has broad market application prospects, making it more suitable for promotion.

[0054] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0055] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-adhesion printing ink, made from the following raw materials in parts by weight: 20-25 parts of bisphenol A type epoxy resin, 18-22 parts of pigment, 1.5-2.5 parts of dispersant, 3-5 parts of primary functional agent, 2-3 parts of secondary functional agent, 3-4 parts of triethylenetetramine, and 3-5 parts of phenyl glycidyl ether; The pigment is carbon black, and the dispersing agent is sodium dodecylbenzene sulfonate; The raw materials for the first functional additive include asphaltene, n-heptane, dilute phosphoric acid solution, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution, and chitosan quaternary ammonium salt; The second functional additive raw materials include halloysite, hydrochloric acid solution, silane coupling agent KH560, polyethylene glycol 600, 1-butyl-3-methylimidazolium tetrafluoroborate and additives; The method of preparing the additive comprises the following steps: Black walnut shell oil and anhydrous ethanol were mixed at a mass ratio of 1:(3-5), stirred at 30-35℃ for 20 min, allowed to stand for 1 h to separate into layers, and the upper oil phase was taken to obtain the treatment liquid. The treatment liquid was mixed with epoxy acrylate and stirred at 72-78℃ for 35-40 min. After cooling to room temperature, the additive was obtained.

2. The high adhesion printing ink according to claim 1, characterized in that, The preparation method of the first functional additive includes the following steps: Step 1: Mix 75% ethanol solution, asphaltene, and n-heptane, stir at 32-38℃ for 70-80 min, let stand for 1.5-2 h, filter to obtain solid filter residue, add 5-6% dilute phosphoric acid solution to solid filter residue, stir at 48-52℃ for 30-35 min, filter, wash 2-3 times, dry at 72-78℃ for 1.5-2 h, pulverize and pass through a 160-200 mesh sieve to obtain the first additive powder; Step 2: Mix the first additive powder, toluene, and petroleum ether, and stir at 42-48℃ for 35-40 min. Then, add 1% glutaraldehyde solution, 30% hydrogen peroxide solution, and chitosan quaternary ammonium salt in sequence, and stir continuously for 15-20 min. Raise the temperature to 62-68℃, sonicate for 70-80 min, cool, filter and collect the solid, and dry at 82-88℃ for 2.5-3 h to obtain the first functional additive.

3. The high adhesion printing ink according to claim 2, characterized in that, The mass ratio of the ethanol solution, asphaltene, and n-heptane is (1.2-1.4):1:(2.2-2.8), and the mass ratio of the dilute phosphoric acid solution to the solid filter residue is (2-5):

1.

4. The high adhesion printing ink according to claim 2, characterized in that, The mass ratio of the first additive powder, toluene, petroleum ether, glutaraldehyde solution, hydrogen peroxide solution and chitosan quaternary ammonium salt is 1:(4-8):(4-8):(0.05-0.1):0.1:(0.2-0.5).

5. The high adhesion printing ink according to claim 1, characterized in that, The preparation method of the second functional additive includes the following steps: Step 1: Mix halloysite powder with a 6-7% hydrochloric acid solution and stir at 42-48℃ for 70-80 minutes. Filter to obtain the precipitate, add silane coupling agent KH560 to the precipitate, stir at 35-40℃ for 30-35 minutes, dry and pulverize, and pass through a 400-500 mesh sieve to obtain the second additive powder. The mass ratio of the precipitate to the silane coupling agent KH560 is 100:(0.5-2). Step 2: Mix the second additive powder, deionized water, and polyethylene glycol 600, heat to 52-58℃ and stir for 25-30 minutes to obtain the first mixture. Add 1-butyl-3-methylimidazolium tetrafluoroborate and additives to the first mixture, and stir at normal temperature and pressure for 100-110 minutes. Filter to obtain solid particles, wash with anhydrous ethanol 2-3 times, and dry at 78-82℃ for 2.2-2.8 hours to obtain the second functional additive.

6. The high adhesion printing ink according to claim 5, characterized in that The mass ratio of the second additive powder, deionized water and polyethylene glycol 600 is 1:(5-20):(0.2-2), and the mass ratio of the first mixture, 1-butyl-3-methylimidazolium tetrafluoroborate and additives is 100:(5-15):(1-10).

7. The high-adhesion printing ink according to claim 5, characterized in that, The mass ratio of halloysite to hydrochloric acid solution is 1:(20-40).

8. The high-adhesion printing ink according to claim 1, characterized in that, The mass ratio of the treatment solution to epoxy acrylate is 1:(0.18-0.24).

9. A method for preparing a high-adhesion printing ink as described in any one of claims 1-8, characterized in that, Includes the following steps: S1: Weigh out triethylenetetramine, first functional additive, second functional additive, dispersant, bisphenol A epoxy resin and phenyl glycidyl ether by weight, put them into a mixer, and mix for 20-30 minutes at 50-60℃ and 500-600r / min to obtain a preliminary mixture. S2: Weigh the pigment by weight, mix it with the initial mixture, add it to a sand mill, and grind it to obtain a pigment slurry; S3: Add the pigment paste to the disperser and disperse it at 800 r / min for 10 min and 1500 r / min for 20 min in sequence. Degas the resulting material at -0.098 MPa and 40℃ for 30 min, and then filter it through a 400 mesh filter to obtain a high-adhesion printing ink.

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