A high-temperature resistant ink and its preparation method

Abstract

This invention belongs to the field of ink technology. This invention provides a high-temperature resistant ink and its preparation method. The high-temperature resistant ink, by weight, comprises the following components: 26-30 parts ethyl acetate, 3-6 parts n-propyl acetate, 0.1-0.3 parts dispersant, 3-6 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution, 28-34 parts polyurethane resin solution, 26-30 parts titanium dioxide, 0.3-0.8 parts aluminum silicate, 0.5-0.8 parts matte, 0.2-0.5 parts wax paste, 0.6-0.8 parts 20wt% adhesion promoter, 1.2-1.5 parts laccase-modified sodium lignin sulfonate, and 3.1-3.4 parts rosin acid-modified epoxidized soybean oil. This invention is environmentally friendly, safe, and low in cost. After being packaged at 240℃, 2s, and 0.2MPa high temperature using toothed packaging, it meets the requirements for sterilization by boiling at 121℃ for 30min. The bags are leak-proof and leak-free, fully meeting the requirements for a long shelf life of medicines.

Description

Technical Field

[0001] This invention belongs to the field of ink technology, specifically relating to a high-temperature resistant ink and its preparation method. Background Technology

[0002] Currently, the most commonly used plastic packaging film for liquid medicines by major domestic pharmaceutical packaging companies has a PET / AL / PE structure, which is the largest component in pharmaceutical packaging products. To ensure the performance and efficacy of liquid medicines over a longer shelf life, and with the continuous upgrading of packaging equipment, the emergence of a new type of pharmaceutical toothed packaging machine has raised new challenges regarding the production and manufacturing of liquid medicine packaging composite films, as well as whether the high-temperature resistance of the inks used, and the strength and hardness of the film after formation, can meet the requirements.

[0003] The existing technology has the following shortcomings: In the pharmaceutical packaging industry, most pharmaceutical packaging material manufacturers use ordinary polyurethane integrated composite inks. Pharmaceutical packaging films produced with these inks, after being filled with contents on ordinary packaging machines, can meet the requirements of a 121℃ / 30min cooking process. However, when used in new toothed packaging machines, after packaging liquid medicines at approximately 240℃, 2s, and 0.2MPa, bubbles and delamination occur. After automatic packaging by the toothed machine, the packaging still requires a 121℃ / 30min cooking process, resulting in extremely high frequencies of bag breakage and leakage. Batch quality incidents occur frequently, seriously troubling pharmaceutical packaging companies. Summary of the Invention

[0004] To address the problems existing in the background technology, this invention provides a high-temperature resistant ink and its preparation method. Using esters as diluents, it is environmentally friendly and safe, and can be used for printing on various treated substrates. The solvent can be recycled and reused, resulting in a very low overall cost and environmental friendliness, making it very friendly to the environment and human health. The synergistic effect of laccase-modified sodium lignosulfonate and rosin acid-modified epoxidized soybean oil solves the defect that while matting powder makes the ink layer matte, it also reduces the abrasion resistance of the ink layer, thereby improving the abrasion resistance of the ink layer.

[0005] To achieve the above objectives, in a first aspect, the present invention provides a high-temperature resistant ink, comprising, by weight, the following components: 26-30 parts ethyl acetate, 3-6 parts n-propyl acetate, 0.1-0.3 parts polyester dispersant, 3-6 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution, 28-34 parts 3618H high-viscosity polyurethane resin solution, 26-30 parts C1TYR588 chlorinated titanium dioxide, 0.3-0.8 parts 820A aluminum silicate, 0.5-0.8 parts matte, 0.2-0.5 parts wax paste, 0.6-0.8 parts 20wt% adhesion promoter, 1.2-1.5 parts laccase-modified sodium lignosulfonate, and 3.1-3.4 parts rosin acid-modified epoxidized soybean oil.

[0006] Furthermore, by weight, each 100 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution comprises the following components: 85 parts of n-propyl acetate and 15 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin.

[0007] The specific preparation method is as follows: First, add n-propyl acetate, turn on the disperser at a speed of 100 r / min, then add the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin. After the material is finished, increase the speed to 1500 r / min, seal and stir for 30 min until completely dissolved, with a fineness ≤3 μm and a viscosity of 45 s-48 s. The solution is then ready for use.

[0008] Furthermore, by weight, each 100 parts of matte paste comprises the following components: 78 parts of n-propyl acetate, 12 parts of 350 matte powder, and 10 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid.

[0009] The specific preparation method is as follows: First, add 70 parts of n-propyl acetate, turn on the disperser at a speed of 50 r / min, and add 12 parts of 350 matting powder at a speed of 5 kg / min; after the material is finished, increase the speed to 1000 r / min, seal and stir for 45 min until completely dissolved and the fineness is ≤10 μm; decrease the speed to 50 r / min, add 10 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and 8 parts of n-propyl acetate, increase the speed to 1000 r / min, seal and stir for 10 min, and the product is ready for use.

[0010] Furthermore, by weight, each 100 parts of wax paste comprises the following components: 75 parts of acetic acid and 25 parts of 3620 wax.

[0011] The specific preparation method is as follows: Add 75 parts of acetic acid to a ball mill for making wax slurry, turn on the disperser at a speed of 20 r / min, add 25 parts of 3620 wax at a speed of 5 kg / min, after the material is finished, increase the speed to 100 r / min, seal and stir for 45 min until a spherical network is seen under a microscope, and then it is ready for use.

[0012] Further, the preparation method of the laccase-modified sodium lignosulfonate is as follows: a sodium lignosulfonate solution with a concentration of 100 g / L is prepared by using an acetate-sodium acetate buffer solution with a pH of 4.88 and a sodium lignosulfonate solution with a mass fraction of 70%. Laccase is added, with 6 U of laccase added per gram of sodium lignosulfonate. After reacting in a parallel reactor at 65°C for different times, the solution is boiled for 10 min to inactivate the laccase. The solution is filtered, and the filtrate is freeze-dried to obtain the laccase-modified sodium lignosulfonate.

[0013] Furthermore, the preparation method of rosin acid modified epoxidized soybean oil is as follows: 30.25g of rosin acid powder and 97.54g of epoxidized soybean oil are added to a three-necked flask equipped with a mechanical stirrer. Under nitrogen protection, the temperature is raised to 110℃ to start the reaction. After the mixture in the flask becomes transparent, 3.83g of BTEAC is added and the reaction continues at 110℃ for 2 hours. The temperature is then raised to 120℃ and the reaction continues for another 6 hours. After the reaction is completed, a gel-like liquid is obtained, which is rosin acid modified epoxidized soybean oil.

[0014] Secondly, the present invention provides a method for preparing a high-temperature resistant ink, comprising the following steps: S1. Pre-dispersion: At 500 r / min, a portion of ethyl acetate and n-propyl acetate are introduced through the corresponding solvent pipeline. Polyester dispersant is added at 0.5 kg / min. The speed is increased to 800 r / min and dispersed for 5 min. At 500 r / min, a ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and a portion of 3618H high-viscosity polyurethane resin solution are added. The speed is increased to 800 r / min and dispersed for 10 min. The speed is decreased to 500 r / min. C1TYR588 chlorinated titanium dioxide and 820A aluminum silicate are added in two batches. The disperser speed is adjusted to 1300 r / min each time and dispersed for 20 min each time at a temperature of 40-45℃ to obtain a mixed slurry. S2. Sand milling: Sand milling once with two machines connected in series at a flow rate of 8-10 kg / min, temperature of 40-45℃, fineness ≤12um, and then rinsing the sand milling chamber with the remaining ethyl acetate. S3. Adjusting the dispersion: In the adjusting vessel, add the matte, wax paste, laccase-modified sodium lignosulfonate, rosin acid-modified epoxidized soybean oil, the remaining 3618H high-viscosity polyurethane resin liquid and 20wt% adhesion promoter in sequence. Seal and disperse at 800r / min for 30min at a temperature of 40-45℃ to obtain high-temperature resistant ink. Then stop the machine and send it for testing.

[0015] This application has the following beneficial effects: This invention is environmentally friendly, safe, and low-cost. It is a special ink for high-temperature resistant toothed oral liquid medicine packets. Production and use primarily utilize single esters as diluents, eliminating the need for alcohol or ether solvents. The product is environmentally friendly and meets the requirements of GB38507-2020 "Limits of Volatile Organic Compounds (VOCs) Content in Inks" standard.

[0016] This invention can be used not only for conventional pharmaceutical packaging, but its most prominent advantage is that after being packaged at 240℃, 2s, and 0.2MPa high temperature by toothed packaging, it can still meet the requirements for sterilization by boiling at 121℃ / 30min. The bags are leak-proof and have no leakage, which fully meets the requirements for a long shelf life of pharmaceuticals.

[0017] Production and use primarily rely on single esters as diluents. It exhibits good volatility balance during printing and excellent drying properties. In particular, the volatile components generated during production can be burned or recycled, significantly reducing production costs for printing companies.

[0018] The flexible interface layer established by rosin acid-modified epoxidized soybean oil absorbs frictional energy and prevents filler debinding; the cross-linked network formed by laccase-modified sodium lignosulfonate acts as a "skeleton" to improve surface hardness and resist abrasive cutting. The two work together to improve the wear resistance of the ink layer. Detailed Implementation

[0019] The present application will be further described in detail below with reference to the embodiments.

[0020] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application are all commercially available.

[0021] Example 1: A high-temperature resistant ink, comprising the following components by weight: 28 parts ethyl acetate, 4 parts n-propyl acetate, 0.2 parts polyester dispersant, 4 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid, 30 parts 3618H high viscosity polyurethane resin liquid, 28 parts C1TYR588 chlorinated titanium dioxide, 0.5 parts 820A aluminum silicate, 0.6 parts matte, 0.4 parts wax paste, 0.7 parts 20wt% adhesion promoter, 1.4 parts laccase-modified sodium lignosulfonate, and 3.2 parts rosin acid-modified epoxidized soybean oil.

[0022] By weight, every 100 parts of the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution comprises the following components: 85 parts of n-propyl acetate and 15 parts of the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin. The specific preparation method is as follows: First, add 85 parts of n-propyl acetate, turn on the disperser at a speed of 100 r / min, then add 15 parts of the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin. After the mixture is completely added, increase the speed to 1500 r / min, seal and stir for 30 min until completely dissolved, with a fineness ≤3 μm and a viscosity of 45 s-48 s. This solution is then ready for use.

[0023] By weight, each 100 parts of matte paste comprises the following components: 78 parts of n-propyl acetate, 12 parts of 350 matte powder, and 10 parts of a ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution. The specific preparation method is as follows: First, add 70 parts of n-propyl acetate, turn on the disperser at a speed of 50 r / min, and add 12 parts of 350 matte powder at a rate of 5 kg / min; after the material is added, increase the speed to 1000 r / min, seal and stir for 45 min until completely dissolved, with a fineness ≤10 μm; decrease the speed to 50 r / min, add 10 parts of the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and 8 parts of n-propyl acetate, increase the speed to 1000 r / min, seal and stir for 10 min, and the paste is ready for use.

[0024] By weight, every 100 parts of wax paste comprises the following components: 75 parts acetic acid and 25 parts 3620 wax. The specific preparation method is as follows: 75 parts acetic acid are added to a ball mill specifically for wax paste preparation. The disperser is turned on at a speed of 20 r / min, and 25 parts 3620 wax are added at a rate of 5 kg / min. After the material is added, the speed is increased to 100 r / min, and the mixture is sealed and stirred for 45 minutes until a spherical network is visible under a microscope. This is the final product and is ready for use.

[0025] By weight, every 100 parts of 20wt% adhesion promoter comprises the following components: 80 parts of ethyl acetate and 20 parts of adhesion promoter. The specific preparation method is as follows: First, add 60 parts of ethyl acetate, turn on the disperser at 100 r / min, and add the adhesion promoter at a rate of 5 kg / min. After the material is added, increase the speed to 1500 r / min, seal and stir for 90 min until completely dissolved with a fineness ≤10 μm; decrease the speed to 100 r / min, slowly add 20 parts of ethyl acetate, increase the speed to 800 r / min, seal and stir for 10 min, and the product is ready for use.

[0026] The preparation method of laccase-modified sodium lignin sulfonate is as follows: a sodium lignin sulfonate solution with a concentration of 100 g / L is prepared by using an acetate-sodium acetate buffer solution with a pH of 4.88 and a sodium lignin sulfonate solution with a mass fraction of 70%. Laccase is added, with 6 U of laccase added per gram of sodium lignin sulfonate. After reacting in a parallel reactor at 65 °C for different times, the solution is boiled for 10 min to inactivate the laccase. The solution is filtered, and the filtrate is freeze-dried to obtain laccase-modified sodium lignin sulfonate.

[0027] The preparation method of rosin acid modified epoxidized soybean oil is as follows: 30.25g of rosin acid powder and 97.54g of epoxidized soybean oil are added to a three-necked flask equipped with a mechanical stirrer. The mixture is heated to 110℃ under nitrogen protection to start the reaction. After the mixture in the flask becomes transparent, 3.83g of BTEAC is added and the reaction is continued at 110℃ for 2 hours. The temperature is then raised to 120℃ and the reaction is continued for another 6 hours. After the reaction is completed, a gel-like liquid is obtained, which is rosin acid modified epoxidized soybean oil.

[0028] A method for preparing a high-temperature resistant ink includes the following steps: S1. Pre-dispersion: By weight, 11 parts of ethyl acetate and 4 parts of n-propyl acetate are introduced through the corresponding solvent pipeline at 500 r / min. 0.2 parts of polyester dispersant are added at 0.5 kg / min. The speed is increased to 800 r / min and dispersed for 5 min. The speed is decreased to 500 r / min. 4 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and 5 parts of 3618H high-viscosity polyurethane resin solution are added. The speed is increased to 800 r / min and dispersed for 10 min. The speed is decreased to 500 r / min. 28 parts of C1TYR588 chloride-process titanium dioxide and 0.5 parts of 820A aluminum silicate are added in two equal portions. The disperser speed is adjusted to 1300 r / min each time, and the dispersion is carried out for 20 min each time at a temperature of 40-45℃ to obtain a mixed slurry.

[0029] S2. Sand milling: Sand milling once with two machines in series at a flow rate of 9 kg / min, temperature 40-45℃, fineness ≤12um, and rinse the sand milling chamber with 17 parts of ethyl acetate.

[0030] S3. Adjusting the dispersion: Add 0.6 parts of dull paste, 0.4 parts of wax paste, 1.4 parts of laccase-modified sodium lignosulfonate, 3.2 parts of rosin acid-modified epoxidized soybean oil, 25 parts of 3618H high-viscosity polyurethane resin liquid, and 0.7 parts of 20wt% adhesion promoter to the adjustment vessel in sequence. Seal and disperse at 800 r / min for 30 min at a temperature of 40-45℃ to obtain high-temperature resistant ink. Then stop the machine and send it for testing.

[0031] Example 2: The difference between this example and Example 1 is that the content of each component is different, as detailed below: A high-temperature resistant ink, by weight, comprises the following components: 26 parts ethyl acetate, 5 parts n-propyl acetate, 0.3 parts polyester dispersant, 3 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid, 32 parts 3618H high-viscosity polyurethane resin liquid, 30 parts C1TYR588 chlorinated titanium dioxide, 0.5 parts 820A aluminum silicate, 0.8 parts matte, 0.5 parts wax paste, 0.6 parts 20wt% adhesion promoter, 1.2 parts laccase-modified sodium lignosulfonate, and 3.1 parts rosin acid-modified epoxidized soybean oil.

[0032] A method for preparing a high-temperature resistant ink includes the following steps: S1. Pre-dispersion: By weight, 8 parts of ethyl acetate and 5 parts of n-propyl acetate are introduced through the corresponding solvent pipeline at 500 r / min. 0.3 parts of polyester dispersant are added at 0.5 kg / min. The dispersion is increased to 800 r / min and dispersed for 5 min. The dispersion is then reduced to 500 r / min. 3 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and 6 parts of 3618H high-viscosity polyurethane resin solution are added. The dispersion is increased to 800 r / min and dispersed for 10 min. The dispersion is then reduced to 500 r / min. 30 parts of C1TYR588 chloride-process titanium dioxide and 0.5 parts of 820A aluminum silicate are added in two equal portions. The disperser speed is adjusted to 1300 r / min each time, and the dispersion is carried out for 20 min each time at a temperature of 40-45℃ to obtain a mixed slurry.

[0033] S2. Sand milling: Sand milling once with two machines in series at a flow rate of 9 kg / min, temperature 40-45℃, fineness ≤12um, and rinse the sand milling chamber with 18 parts of ethyl acetate.

[0034] S3. Adjusting the dispersion: Add 0.8 parts of dull paste, 0.5 parts of wax paste, 1.2 parts of laccase-modified sodium lignosulfonate, 3.1 parts of rosin acid-modified epoxidized soybean oil, 26 parts of 3618H high-viscosity polyurethane resin liquid, and 0.6 parts of 20wt% adhesion promoter to the adjusting vessel in sequence. Seal and disperse at 800 r / min for 30 min at a temperature of 40-45℃ to obtain high-temperature resistant ink. Then stop the machine and send it for testing.

[0035] Comparative Example 1: The difference between this comparative example and Example 1 is that laccase-modified sodium lignin sulfonate and rosin acid-modified epoxidized soybean oil are not added.

[0036] Specifically, a high-temperature resistant ink, by weight, comprises the following components: 28 parts ethyl acetate, 4 parts n-propyl acetate, 0.2 parts polyester dispersant, 4 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid, 30 parts 3618H high-viscosity polyurethane resin liquid, 28 parts C1TYR588 chlorinated titanium dioxide, 0.5 parts 820A aluminum silicate, 0.6 parts matte, 0.4 parts wax paste, and 0.7 parts 20wt% adhesion promoter.

[0037] Comparative Example 2: The difference between this comparative example and Example 1 is that rosin acid-modified epoxidized soybean oil is not added.

[0038] Specifically, a high-temperature resistant ink, by weight, comprises the following components: 28 parts ethyl acetate, 4 parts n-propyl acetate, 0.2 parts polyester dispersant, 4 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid, 30 parts 3618H high-viscosity polyurethane resin liquid, 28 parts C1TYR588 chlorinated titanium dioxide, 0.5 parts 820A aluminum silicate, 0.6 parts matte, 0.4 parts wax paste, 0.7 parts 20wt% adhesion promoter, and 1.4 parts laccase-modified sodium lignosulfonate.

[0039] Comparative Example 3: The difference between this comparative example and Example 1 is that no laccase-modified sodium lignin sulfonate was added.

[0040] Specifically, a high-temperature resistant ink, by weight, comprises the following components: 28 parts ethyl acetate, 4 parts n-propyl acetate, 0.2 parts polyester dispersant, 4 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid, 30 parts 3618H high-viscosity polyurethane resin liquid, 28 parts C1TYR588 chlorinated titanium dioxide, 0.5 parts 820A aluminum silicate, 0.6 parts matte, 0.4 parts wax paste, 0.7 parts 20wt% adhesion promoter, and 3.2 parts rosin acid modified epoxidized soybean oil.

[0041] Test example: The execution standards are QB / T2024-2012 "Gravure Plastic Film Composite Ink" and GB38507-2020 "Limits of Volatile Organic Compounds (VOCS) Content in Inks". The test data are shown in Table 1.

[0042]

[0043] (2) The test data of the high-temperature retort pharmaceutical packaging film produced using Examples 1-2 of the present invention are as follows: Product Standard: YY0236-1996, General Rules for Composite Films for Pharmaceutical Packaging (People's Republic of China Pharmaceutical Industry Standard) A. Appearance; Free from defects such as perforations, foreign objects, odors, adhesion, ineffective coatings, separation of composite layers, obvious damage, bubbles, wrinkles, and dirt. Printed text and patterns are clear and complete, with uniform color, no obvious color difference, and precise registration.

[0044] B. Physical performance indicators; The mechanical properties meet the specifications in Table 2 (N / 15mm).

[0045]

[0046] Results analysis: Analysis of Examples 1-2 shows that the results are environmentally friendly, safe, and low-cost. This invention relates to a high-temperature resistant toothed roller packaging ink specifically for oral liquid medicine packets. Production and use primarily utilize a single ester as a diluent, eliminating the need for alcohol or ether solvents. The product is environmentally friendly, meeting the requirements of GB38507-2020 "Limits of Volatile Organic Compounds (VOCs) Content in Inks". The process is simple, highly operable, and extremely efficient. The grinding resins and additives used in the production of white and colored inks are universal, semi-finished products can be mass-produced, and finished products can be manufactured on intelligent production lines with extremely high efficiency at each stage. This invention can not only be used for conventional pharmaceutical packaging, but its most prominent advantage is that after high-temperature toothed packaging at 240℃, 2s, and 0.2MPa, it can still meet the requirements for sterilization at 121℃ / 30min, with no leaks or seepage, fully meeting the requirements for a long shelf life of medicines. The overall cost is very low. Production and use primarily utilize a single ester as a diluent, resulting in good volatility balance during printing and excellent drying. In particular, the volatile components generated during production can be burned or recycled, significantly reducing production costs for printing companies.

[0047] Comparing Comparative Example 1 and Comparative Example 2, it can be seen that when laccase-modified sodium lignosulfonate is added alone, the dynamic friction coefficient of Comparative Example 2 (0.3236) and the static friction coefficient (0.3216) are greater than those of Comparative Example 1 (0.2812) and the static friction coefficient (0.2621), respectively. That is, the wear resistance of Comparative Example 2 is lower than that of Comparative Example 1.

[0048] This is because the sodium lignosulfonate molecular chain contains a large number of polar groups (such as sulfonic acid groups and phenolic hydroxyl groups), and its hydrophilicity repels the hydrophobic resin (ternary hydroxychloroethylene-vinyl acetate-vinyl alcohol resin). Laccase-modified sodium lignosulfonate is unevenly dispersed in the resin, forming agglomerates, which actually increases the defect density at the filler-resin interface. These agglomerates become new stress concentration sources, accelerating microcrack initiation during friction or scratching, and reducing the abrasion resistance of the ink layer. The rigid network of laccase-modified sodium lignosulfonate has a high shrinkage rate during drying and film formation, and its coefficient of thermal expansion differs greatly from that of the resin matrix, resulting in high residual internal stress after curing. In abrasion resistance tests, increased brittleness makes the ink layer more prone to brittle fracture rather than plastic deformation, thus reducing abrasion resistance.

[0049] Comparing Comparative Example 1 and Comparative Example 3, it can be seen that when rosin acid is introduced alone to modify epoxidized soybean oil, the dynamic friction coefficient of Comparative Example 3 (0.2716) and the static friction coefficient (0.2583) are smaller than those of Comparative Example 1 (0.2812) and the static friction coefficient (0.2621), respectively. That is, the wear resistance of Comparative Example 3 is higher than that of Comparative Example 1.

[0050] This is because during the friction process, the long fatty chains of epoxidized soybean oil absorb kinetic energy through van der Waals forces, converting it into heat energy dissipation and avoiding rapid wear caused by energy concentration. Simultaneously, the strong interfacial bonding between rosin acid and the matting agent effectively inhibits particle detachment under friction, keeping the ink layer surface intact. After adding rosin acid to modify epoxidized soybean oil, the wear loss rate is reduced because the flexible matrix can "wrap" the hard filler, forming a "sacrificial layer" protection mechanism.

[0051] In comparison with Example 1, it can be seen that the simultaneous introduction of laccase-modified sodium lignosulfonate and rosin acid-modified epoxidized soybean oil can produce a synergistic effect, making the dynamic friction coefficient and static friction coefficient of Example 1 lower than those of Comparative Example 3, that is, the wear resistance of Example 1 is higher than that of Comparative Example 3.

[0052] This is because laccase modification endows sodium lignin sulfonate with oxidative crosslinking potential, but crosslinking is too rapid and uneven when used alone. Rosin acid-modified epoxidized soybean oil acts as a "retarder," slowly reacting its epoxy groups with the phenolic hydroxyl groups of lignin to form an interpenetrating polymer network (IPN). This network combines the rigidity of lignin (providing a wear-resistant skeleton) with the flexibility of epoxidized soybean oil (providing scratch-resistant buffer), avoiding brittleness. Furthermore, the flexible interface layer established by rosin acid-modified epoxidized soybean oil absorbs frictional energy, preventing filler debonding. The crosslinked network formed by laccase-modified sodium lignin sulfonate acts as a "skeleton," increasing surface hardness and resisting abrasive cutting. The synergistic effect of these two processes transforms the ink layer from a "vulnerable composite material" to a "high-toughness polymer structure," synergistically improving the ink layer's wear resistance.

[0053] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0054] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A high-temperature resistant ink, characterized in that, By weight, it comprises the following components: 26-30 parts ethyl acetate, 3-6 parts n-propyl acetate, 0.1-0.3 parts dispersant, 3-6 parts ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution, 28-34 parts polyurethane resin solution, 26-30 parts titanium dioxide, 0.3-0.8 parts aluminum silicate, 0.5-0.8 parts matting agent, 0.2-0.5 parts wax paste, 0.6-0.8 parts 20wt% adhesion promoter, 1.2-1.5 parts laccase-modified sodium lignosulfonate, and 3.1-3.4 parts rosin acid-modified epoxidized soybean oil.

2. The high-temperature resistant ink according to claim 1, characterized in that, By weight, every 100 parts of the ternary hydroxychloroethylene-acetic acid-ethylene alcohol resin solution comprises the following components: 85 parts of n-propyl acetate and 15 parts of ternary hydroxychloroethylene-acetic acid-ethylene alcohol resin.

3. The high-temperature resistant ink according to claim 2, characterized in that, The preparation method of the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution is as follows: first, add n-propyl acetate, turn on the disperser at a speed of 100 r / min, then add the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin, increase the speed to 1500 r / min, seal and stir until dissolved, with a fineness ≤3 μm and a viscosity of 45 s-48 s, and the solution is obtained.

4. The high-temperature resistant ink according to claim 2 or 3, characterized in that, By weight, every 100 parts of the said matte comprises the following components: 78 parts of n-propyl acetate, 12 parts of matting powder, and 10 parts of ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin liquid.

5. The high-temperature resistant ink according to claim 4, characterized in that, The preparation method of the matte paste is as follows: First, add a portion of n-propyl acetate, turn on the disperser at a speed of 50 r / min, then add the matte powder, increase the speed to 1000 r / min, seal and stir until completely dissolved, with a fineness ≤10 μm; decrease the speed to 50 r / min, then add the ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and the remaining n-propyl acetate, increase the speed to 1000 r / min, seal and stir to obtain the paste.

6. The high-temperature resistant ink according to claim 1, characterized in that, By weight, each 100 parts of wax paste comprises the following components: 75 parts acetic acid and 25 parts wax.

7. The high-temperature resistant ink according to claim 6, characterized in that, The preparation method of the wax paste is as follows: First, add acetic acid, turn on the disperser at a speed of 20 r / min, then add the wax, increase the speed to 100 r / min, and stir in a sealed manner until a spherical network can be seen under a microscope.

8. The high-temperature resistant ink according to claim 1, characterized in that, The preparation method of the laccase-modified sodium lignin sulfonate is as follows: prepare a 100 g / L sodium lignin sulfonate solution using an acetate-sodium acetate buffer solution with pH 4.88 and a 70 wt% sodium lignin sulfonate solution; add 6 U of laccase to each gram of sodium lignin sulfonate solution, react in a parallel reactor at 65 °C for 40 min, boil for 10 min, filter, and freeze-dry the filtrate to obtain the product.

9. The high-temperature resistant ink according to claim 1, characterized in that, The preparation method of the rosin acid modified epoxidized soybean oil is as follows: 30.25g of rosin acid powder and 97.54g of epoxidized soybean oil are added to a three-necked flask, and the mixture is heated to 110°C under nitrogen protection to start the reaction. After the mixture in the flask becomes transparent, 3.83g of benzyltriethylammonium chloride is added and the reaction continues for 2 hours. The temperature is then raised to 120°C and the reaction continues for another 6 hours to obtain the final product.

10. A method for preparing a high-temperature resistant ink as described in any one of claims 1-9, characterized in that, Includes the following steps: S1. Input a portion of ethyl acetate and n-propyl acetate, then add a dispersant, increase the speed to 800 r / min and disperse for 5 min, then decrease the speed to 500 r / min, add a ternary hydroxychloroethylene-ethylene acetate-ethylene alcohol resin solution and a portion of polyurethane resin solution, increase the speed to 800 r / min and disperse for 10 min, decrease the speed to 500 r / min, add titanium dioxide and aluminum silicate, adjust the disperser speed to 1300 r / min, disperse, and obtain a mixed slurry; S2. Perform a double-machine series sand milling once at a temperature of 40-45℃, with a fineness of ≤12um. Rinse the sand milling chamber with the remaining ethyl acetate and transfer it to the conditioning vessel. S3. Add the following ingredients in sequence to the adjusting vessel: matte, wax paste, laccase-modified sodium lignosulfonate, rosin acid-modified epoxidized soybean oil, the remaining polyurethane resin liquid, and 20wt% adhesion promoter. Seal and disperse at 800r / min for 30min to obtain the high-temperature resistant ink.

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