High-adhesion magnetic ink, its preparation method and application in chip production

Abstract

The present invention relates to the field of inks, specifically to a high-adhesion magnetic ink, its preparation method and application in chip production. The preparation method of the high-adhesion magnetic ink comprises the following steps: first, synthesize sodium carboxyl-terminated hyperbranched polyester, and then load nano-ferroferric oxide thereon to obtain hyperbranched polyester loaded with nano-ferroferric oxide; prepare a silicon-acrylic prepolymer using acrylate compounds, vinyltriethoxysilane, oleic acid, and linoleic acid as monomers, then synthesize a basic alkyd resin, and then compound the basic alkyd resin, the silicon-acrylic prepolymer, the hyperbranched polyester loaded with nano-ferroferric oxide, triethylamine, ethylene glycol dibutyl ether, ethanol, and water to prepare the high-adhesion magnetic ink. The ink can be cured by heating at 130 °C for 10 min, and has the advantages of strong adhesion fastness and good magnetic separation performance, and can be used to mark defective crystal grains, and then the defective crystal grains can be separated by magnetic separation technology.

Description

Technical Field

[0001] The present invention relates to the field of inks, and specifically to a high-adhesion magnetic ink, a preparation method thereof, and an application thereof in chip production. Background Art

[0002] A wafer is a silicon wafer used for fabricating silicon semiconductor integrated circuits and is used to fabricate various circuit element structures. A single wafer can be divided into thousands of identical or different die. Due to the characteristics of the material itself and operational problems during the manufacturing process, the finally fabricated wafer has normal die and defective die. To avoid the impact of defective die on the performance of the wafer during subsequent packaging, it is usually necessary to mark the defective die and then reject them.

[0003] Chinese Patent Application CN101369516A discloses a method for marking a wafer, a method for marking defective die, a method for wafer alignment, and a wafer testing machine. The defective die are marked by laser marking and then rejected. However, laser marking is likely to contaminate the wafer, and an additional dust removal device is required. When rejecting, it is also necessary to rely on a machine for discrimination, and it is difficult to directly distinguish with the naked eye. Chinese Patent CN100514629C discloses a wafer with markings, and the defective die on the wafer are marked with a thermosetting ink. The thermosetting ink will adhere to the defective die after curing and is difficult to be removed by the solvents during subsequent manufacturing processes. However, manual sorting is required after subsequent cutting, which is time-consuming and laborious. Summary of the Invention

[0004] To solve the above problems, the present invention provides a high-adhesion magnetic ink, a preparation method thereof, and an application thereof in chip production, which solves the problem that it is time-consuming and laborious to reject defective die by manual sorting after marking.

[0005] To achieve the above object, the present invention provides a method for preparing a high-adhesion magnetic ink, comprising the following steps:

[0006] Step (1), prepare hyperbranched polyester loaded with nano-ferroferric oxide, silicone-acrylic prepolymer and basic alkyd resin. Among them, the preparation of hyperbranched polyester loaded with nano-ferroferric oxide includes the following steps: heat 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide to the first set temperature under an inert gas atmosphere, react, after the reaction ends, add maleic anhydride, heat to the second set temperature, react, after the reaction ends, perform post-treatment and dry to obtain hyperbranched polyester sodium salt with carboxyl end groups (HBPE-Na); mix hyperbranched polyester sodium salt with carboxyl end groups, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate, ultrasonicate, add sodium hydroxide aqueous solution to adjust the pH value to 10, introduce air, react, after the reaction ends, separate and purify, dry to obtain hyperbranched polyester loaded with nano-ferroferric oxide (HBPE@Fe3O4); among them, the preparation of silicone-acrylic prepolymer includes the following steps: mix acrylate compounds, vinyltriethoxysilane, oleic acid, and linoleic acid, add an initiator to obtain a mixed monomer, drop the mixed monomer into xylene at a set temperature, maintain the set temperature for reaction to obtain a silicone-acrylic prepolymer; among them, the preparation of basic alkyd resin includes the following steps: uniformly mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid, heat to the third set temperature under an inert gas atmosphere, react, after the reaction ends, heat to the fourth set temperature, react, stop the reaction after measuring the acid value of the reaction system to the target acid value to obtain basic alkyd resin;

[0007] Step (2), mix the basic alkyd resin, silicone-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide, ultrasonically disperse, stir and heat to the fifth set temperature, keep the temperature for reaction, stop the reaction after measuring the acid value of the reaction system to the target acid value, cool to the sixth set temperature, add ethylene glycol dibutyl ether and triethylamine, stir and react, after the reaction ends, add water to adjust the solid content of the system to obtain a modified waterborne alkyd resin; mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether, grind and disperse to obtain a high-adhesion magnetic ink.

[0008] Preferably, in the step (1), when preparing the sodium salt of the carboxyl-terminated hyperbranched polyester, the rate of heating to the first set temperature is 20 - 25 °C / h, the first set temperature is 110 - 120 °C, and the reaction duration at the first set temperature is 2.5 - 3.5 h; the rate of heating to the second set temperature is 10 °C / h, the second set temperature is 140 - 150 °C, and the reaction duration at the second set temperature is 2 - 2.5 h; the inert gas includes nitrogen; the drying condition is vacuum drying at 110 - 120 °C for 4 - 5 h; the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, maleic anhydride is (60 - 75):(260 - 280):(110 - 130):(380 - 420):(4.5 - 8.5):(800 - 900):(25 - 35).

[0009] Preferably, in the step (1), when preparing the sodium salt of the carboxyl-terminated hyperbranched polyester, the post-treatment operation steps include: evaporating and concentrating the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution, adding a saturated sodium hydroxide ethanol solution to the concentrated solution, standing for precipitation, filtering, and drying the filter cake, wherein the mass ratio of the concentrated solution to the saturated sodium hydroxide ethanol solution is 900:100.

[0010] Preferably, in the step (1), when preparing the hyperbranched polyester loaded with nano-ferroferric oxide, the ultrasonic condition is ultrasonic treatment at a frequency of 20 - 40 kHz for 20 - 30 min; the air inlet volume is 30 - 60 L / h; the reaction condition is reaction at room temperature for 6 h; the mass ratio of the sodium salt of the carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, ferrous sulfate is 50:30:(500 - 600):(0.5 - 1):(25 - 60).

[0011] Preferably, in the step (1), when preparing the hyperbranched polyester loaded with nano-ferroferric oxide, the concentration of the sodium hydroxide aqueous solution is 6 mol / L, the separation and purification operations include rotary evaporation, washing with water, filtering, and the drying condition is vacuum drying at 90 - 100 °C for 6 - 8 h.

[0012] Preferably, in the step (1), when preparing the silicon-acrylic prepolymer, the acrylate compound includes methacrylic acid, methyl methacrylate, and n-butyl acrylate, the initiator is di-tert-butyl peroxide, the set temperature is 135-145 °C, the reaction duration at the set temperature is 1.5-2.5 h, the dropping duration of the mixed monomers is 8 h, and the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is (69-86):(50-60):(77-102):(57-95):28:(28-42):(7-9), and the mass ratio of the mixed monomers to xylene is (350-410):(320-400).

[0013] Preferably, in the step (1), when preparing the basic alkyd resin, the third set temperature is 140-160 °C, the reaction duration at the third set temperature is 30-60 min; the fourth set temperature is 220-240 °C, the reaction duration at the fourth set temperature is 4-6 h, the target acid value is 5-15 mgKOH / g, and the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is (21-27):(16-30):3:(20-30):(20-30):8:0.3; the inert gas includes nitrogen.

[0014] Preferably, in the step (2), the conditions for ultrasonic treatment are ultrasonic treatment for 10-20 min at a frequency of 20-40 kHz; the fifth set temperature is 180-190 °C, the reaction duration at the fifth set temperature is 2-4 h; the target acid value is 35-45 mgKOH / g; the sixth set temperature is 80 °C, the reaction duration at the sixth set temperature is 1 h; the adjusted solid content of the system is 30-40%.

[0015] Preferably, in the step (2), the mass ratio of the basic alkyd resin, the silicon-acrylic prepolymer, the hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:(45-55):(45-55):30:(12-18); the mass ratio of the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether is 90:5:5.

[0016] Preferably, a high-adhesion magnetic ink prepared by the method for preparing a high-adhesion magnetic ink as described above.

[0017] Preferably, an application of a high-adhesion magnetic ink as described above in chip production.

[0018] Preferably, the application of the high-adhesion magnetic ink in chip production includes its application in marking defective chips.

[0019] Further, the method of applying the above high-adhesion magnetic ink to the marking of defective grains includes the following steps: spraying the high-adhesion magnetic ink on the surface of defective grains, curing at 130 °C for 10 min, and separating the defective grains through magnetic separation technology.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: In this solution, carboxyl-terminated hyperbranched polyester sodium salt is first synthesized, and then used as a template to prepare nano-magnetite magnetic particles, so that the nano-magnetite is loaded on it. On the one hand, it ensures the dispersion of nano-magnetite in the ink. At the same time, the carboxyl groups at the ends of the hyperbranched polyester can react with the hydroxyl groups on the surface of the nano-magnetite, improving the loading stability and loading amount. The introduction of magnetite makes the ink have excellent magnetism, and under the action of a magnetic field, the marked grains can be easily separated; in this solution, acrylate compounds and vinyl silanes are pre-polymerized first to obtain a silicon-acrylic prepolymer, and then the silicon-acrylic prepolymer and hyperbranched polyester are used to modify alkyd resin together. Alkyd resin is a kind of compound with multiple hydroxyl groups and many unsaturated fatty acids. Through the reaction of the unsaturated double bonds and carboxyl groups of the silicon-acrylic prepolymer and hyperbranched polyester with the unsaturated double bonds and hydroxyl groups of the alkyd resin, while ensuring the system compatibility, the water solubility of the alkyd resin is increased; the addition of vinyl silane, on the one hand, can increase the flexibility of the system. Due to its own cross-linked structure, the hyperbranched polyester is brittle after film formation, and the elasticity of acrylate compounds at room temperature is also poor. Therefore, adding vinyl silane can improve the film-forming property of the ink. On the other hand, the silanol groups generated after the hydrolysis of vinyl silane can undergo dehydration condensation with the hydroxyl groups on the surface of the grains, improving the adhesion of the ink after film formation, so that the prepared ink has high adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is the process flow chart of the preparation of the high-adhesion magnetic ink of the present invention;

[0022] Figure 2 is the bar chart of the test results of the adhesion fastness of the high-adhesion magnetic ink prepared by the present invention on the surface of a glass sheet;

[0023] Figure 3 is the bar chart of the test results of the adhesion fastness of the high-adhesion magnetic ink prepared by the present invention on the surface of an aluminum foil;

[0024] Figure 4 is the bar chart of the test results of the magnetic separation performance of the high-adhesion magnetic ink prepared by the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the protection scope of the present invention.

[0026] Embodiment 1

[0027] This embodiment discloses a preparation method of a high-adhesion magnetic ink, comprising the following steps:

[0028] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide evenly, introduce nitrogen, and slowly heat up to 110 °C at a stirring speed of 180 r / min at a rate of 20 °C / h, react for 3 h, add maleic anhydride, heat up to 140 °C at a rate of 10 °C / h, and continue to react for 2.5 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 110 °C for 5 h to obtain a carboxyl-terminated hyperbranched polyester sodium salt; wherein, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, maleic anhydride is 60:260:110:380:4.5:800:25, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0029] (2) Mix the carboxyl-terminated hyperbranched polyester sodium salt, N,N-dimethylformamide, and water, stir and dissolve at a stirring speed of 180 r / min at room temperature, add sodium citrate and ferrous sulfate, ultrasonically treat for 30 min at a frequency of 20 kHz, dropwise add a 6 mol / L sodium hydroxide aqueous solution to adjust the pH value of the reaction solution to 10, finish dropping within 1 h, introduce air at a rate of 30 L / h, react at room temperature for 6 h. After the reaction, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 90 °C for 8 h to obtain a hyperbranched polyester loaded with nano-ferroferric oxide; wherein, the mass ratio of the carboxyl-terminated hyperbranched polyester sodium salt, N,N-dimethylformamide, water, sodium citrate, ferrous sulfate is 50:30:500:0.5:25;

[0030] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid evenly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat xylene to 135 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and finish dropping within 8 h. Keep the temperature at 135 °C and react for 2.5 h to obtain a silicon-acrylic prepolymer; Among them, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is 69:60:102:57:28:28:7; The mass ratio of the mixed monomer to xylene is 350:320;

[0031] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir evenly at a stirring speed of 300 r / min, add xylene and hypophosphorous acid, introduce nitrogen, heat to 140 °C, keep warm and react for 60 min. After the heat preservation reaction is over, heat to 220 °C and maintain the reaction at 220 °C for 6 h. Measure the acid value of the reaction system to be 5 mgKOH / g, stop the reaction, and obtain a basic alkyd resin; Among them, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 27:30:3:20:20:8:0.3;

[0032] (5) Mix the basic alkyd resin, silicon-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 20 min at a frequency of 20 kHz, stir and heat to 180 °C at a stirring speed of 300 r / min, keep warm and react for 4 h. Measure the acid value of the reaction system to be 35 mgKOH / g, stop the reaction, cool to 80 °C, add ethylene glycol dibutyl ether, stir evenly, maintain at 80 °C and add triethylamine, stir and react for 1 h. After the reaction is over, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 30%, and finish dropping within 2 h to obtain a modified waterborne alkyd resin. Among them, the mass ratio of the basic alkyd resin, silicon-acrylic prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:45:55:30:18; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to a mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain a high-adhesion magnetic ink.

[0033] Example 2

[0034] This example discloses a preparation method of a high-adhesion magnetic ink, including the following steps:

[0035] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, succinic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide evenly. Introduce nitrogen, and slowly heat the mixture to 120 °C at a rate of 20 °C / h with a stirring speed of 180 r / min. React for 2.5 h, add maleic anhydride, then heat the mixture to 150 °C at a rate of 10 °C / h and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 120 °C for 4 h to obtain sodium carboxyl-terminated hyperbranched polyester; wherein, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, succinic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is 65:265:115:390:5.5:825:30, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0036] (2) Mix sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, and water, and stir and dissolve them at a stirring speed of 180 r / min at room temperature. Add sodium citrate and ferrous sulfate, and ultrasonicate for 25 min at a frequency of 30 kHz. Dropwise add a 6 mol / L sodium hydroxide aqueous solution to adjust the pH value of the reaction solution to 10, and complete the dropwise addition within 1 h. Introduce air at a rate of 30 L / h and react at room temperature for 6 h. After the reaction, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 95 °C for 7 h to obtain hyperbranched polyester loaded with nano-ferroferric oxide; wherein, the mass ratio of sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:600:1:30;

[0037] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid evenly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat xylene to 140 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and complete the dropwise addition within 8 h. Keep the temperature at 140 °C and react for 2 h to obtain a silicon-propylene prepolymer; wherein, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is 77:60:90:76:28:28:7.5; the mass ratio of the mixed monomer to xylene is 365:340;

[0038] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until homogeneous, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, hold the temperature for reaction for 45 min. After the holding reaction is completed, heat up to 230 °C and maintain the reaction at 230 °C for 5 h. Measure the acid value of the reaction system to be 15 mg KOH / g, stop the reaction, and obtain the basic alkyd resin; wherein, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 25:27:3:25:20:8:0.3;

[0039] (5) Mix the basic alkyd resin, silicone-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 15 min at a frequency of 30 kHz, stir and heat up to 190 °C at a stirring speed of 300 r / min, hold the temperature for reaction for 3 h. Measure the acid value of the reaction system to be 45 mg KOH / g, stop the reaction, cool down to 80 °C, add ethylene glycol dibutyl ether, stir evenly, add triethylamine while maintaining 80 °C, stir and react for 1 h. After the reaction is completed, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 35%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin. Among them, the mass ratio of the basic alkyd resin, silicone-acrylic prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:50:50:30:15; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to a mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain a high-adhesion magnetic ink.

[0040] Example 3

[0041] This example discloses a preparation method of a high-adhesion magnetic ink, including the following steps:

[0042] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide evenly. Introduce nitrogen gas and slowly heat the mixture to 120 °C at a rate of 25 °C / h with a stirring speed of 180 r / min. React for 3.5 h, add maleic anhydride, then heat the mixture to 150 °C at a rate of 10 °C / h and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 120 °C for 4 h to obtain sodium salt of carboxyl-terminated hyperbranched polyester. Among them, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is 65:270:120:400:6.5:850:30, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0043] (2) Mix the sodium salt of carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, and water, and stir and dissolve them at a stirring speed of 180 r / min at room temperature. Add sodium citrate and ferrous sulfate, and ultrasonicate for 25 min at a frequency of 30 kHz. Dropwise add 6 mol / L sodium hydroxide aqueous solution to adjust the pH value of the reaction solution to 10, and finish dropping within 1 h. Introduce air at a rate of 40 L / h and react at room temperature for 6 h. After the reaction, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 95 °C for 7 h to obtain hyperbranched polyester loaded with nano-ferroferric oxide. Among them, the mass ratio of the sodium salt of carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:600:1:40;

[0044] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid evenly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer. Stir and heat xylene to 140 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and finish dropping within 8 h. Keep the temperature at 140 °C and react for 2 h to obtain a silicon-acrylic prepolymer. Among them, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is 77:60:77:95:28:28:8; the mass ratio of the mixed monomer to xylene is 375:360;

[0045] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until homogeneous, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, hold the reaction for 45 min. After the holding reaction is completed, heat up to 230 °C and maintain the reaction at 230 °C for 5 h. Measure the acid value of the reaction system to be 10 mg KOH / g, stop the reaction, and obtain the basic alkyd resin; wherein, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 24:23:3:30:20:8:0.3;

[0046] (5) Mix the basic alkyd resin, silicone-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 15 min at a frequency of 30 kHz, stir and heat up to 190 °C at a stirring speed of 300 r / min, hold the reaction for 3 h. Measure the acid value of the reaction system to be 40 mg KOH / g, stop the reaction, cool down to 80 °C, add ethylene glycol dibutyl ether, stir evenly, add triethylamine while maintaining 80 °C, stir and react for 1 h. After the reaction is completed, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 35%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin, wherein, the mass ratio of the basic alkyd resin, silicone-acrylic prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:50:50:30:15; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to a mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain the high-adhesion magnetic ink.

[0047] Example 4

[0048] This example discloses a preparation method of a high-adhesion magnetic ink, which includes the following steps:

[0049] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide evenly. Introduce nitrogen, and slowly heat the mixture to 120 °C at a rate of 25 °C / h with a stirring speed of 180 r / min. React for 3 h, add maleic anhydride, then heat the mixture to 150 °C at a rate of 10 °C / h and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 120 °C for 4 h to obtain sodium carboxyl-terminated hyperbranched polyester; among them, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is 65:275:125:410:7.5:875:30, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0050] (2) Mix sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, and water, and stir and dissolve them at a stirring speed of 180 r / min at room temperature. Add sodium citrate and ferrous sulfate, and ultrasonicate for 25 min at a frequency of 30 kHz. Dropwise add a 6 mol / L aqueous sodium hydroxide solution to adjust the pH value of the reaction solution to 10, and complete the dropping within 1 h. Introduce air at a rate of 50 L / h and react at room temperature for 6 h. After the reaction, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 95 °C for 7 h to obtain hyperbranched polyester loaded with nano-ferroferric oxide; among them, the mass ratio of sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:600:1:50;

[0051] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid evenly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat xylene to 140 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and complete the dropping within 8 h. Keep the temperature at 140 °C and react for 2 h to obtain a silicon-acrylic prepolymer; among them, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is 77:50:90:95:28:42:8.5; the mass ratio of the mixed monomer to xylene is 390:380;

[0052] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until homogeneous, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, keep the temperature for reaction for 45 min. After the holding reaction is completed, heat up to 230 °C and maintain the reaction at 230 °C for 5 h. Measure the acid value of the reaction system to be 10 mg KOH / g, stop the reaction, and obtain the basic alkyd resin; among them, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 24:23:3:25:25:8:0.3;

[0053] (5) Mix the basic alkyd resin, silicone-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 15 min at a frequency of 30 kHz, stir and heat up to 190 °C at a stirring speed of 300 r / min, keep the temperature for reaction for 3 h. Measure the acid value of the reaction system to be 40 mg KOH / g, stop the reaction, cool down to 80 °C, add ethylene glycol dibutyl ether, stir evenly, maintain at 80 °C and add triethylamine, stir and react for 1 h. After the reaction is completed, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 35%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin. Among them, the mass ratio of the basic alkyd resin, silicone-acrylic prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:50:50:30:15; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to a mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain the high-adhesion magnetic ink.

[0054] Example 5

[0055] This example discloses a preparation method of a high-adhesion magnetic ink, which includes the following steps:

[0056] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide uniformly. Introduce nitrogen, and slowly heat the mixture to 120 °C at a rate of 25 °C / h with a stirring speed of 180 r / min. React for 2.5 h, add maleic anhydride, then heat the mixture to 150 °C at a rate of 10 °C / h and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 120 °C for 4 h to obtain sodium carboxyl-terminated hyperbranched polyester; among them, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is 70:280:130:420:8.5:900:35, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0057] (2) Mix sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, and water, and stir and dissolve them at a stirring speed of 180 r / min at room temperature. Add sodium citrate and ferrous sulfate, and ultrasonicate for 20 min at a frequency of 40 kHz. Dropwise add a 6 mol / L sodium hydroxide aqueous solution to adjust the pH value of the reaction solution to 10, and finish dropping within 1 h. Introduce air at a rate of 60 L / h and react at room temperature for 6 h. After the reaction is completed, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 100 °C for 6 h to obtain hyperbranched polyester loaded with nano-ferroferric oxide; among them, the mass ratio of sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:600:1:60;

[0058] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid uniformly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat xylene to 145 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and finish dropping within 8 h. Keep the temperature at 145 °C and react for 1.5 h to obtain a silicon-acrylic prepolymer; among them, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is 86:50:102:95:28:42:9; the mass ratio of the mixed monomer to xylene is 410:400;

[0059] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until evenly mixed, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, and keep the temperature for reaction for 45 min. After the holding reaction is completed, heat up to 240 °C and maintain the reaction at 240 °C for 4 h. Stop the reaction when the acid value of the reaction system is measured to be 10 mg KOH / g to obtain the basic alkyd resin; among them, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 21:16:3:30:30:8:0.3;

[0060] (5) Mix the basic alkyd resin, silicon-acrylic prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 10 min at a frequency of 40 kHz, stir and heat up to 200 °C at a stirring speed of 300 r / min, keep the temperature for reaction for 2 h. Stop the reaction when the acid value of the reaction system is measured to be 40 mg KOH / g, cool down to 80 °C, add ethylene glycol dibutyl ether, stir evenly, maintain at 80 °C and add triethylamine, stir and react for 1 h. After the reaction is completed, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 40%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin, among which, the mass ratio of the basic alkyd resin, silicon-acrylic prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:55:45:30:12;

[0061] (6) Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to the mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain the high-adhesion magnetic ink.

[0062] Comparative Example 1

[0063] This comparative example discloses a preparation method of high-adhesion magnetic ink, including the following steps:

[0064] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, succinic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide evenly, introduce nitrogen, slowly heat up to 120 °C at a speed of 20 °C / h under a stirring speed of 180 r / min, react for 2.5 h, add maleic anhydride, heat up to 150 °C at a speed of 10 °C / h, and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, dissolve the filter cake in water, adjust the pH to 4 with 3 mol / L hydrochloric acid aqueous solution, rotary evaporate to remove water, add acetone, filter, take the filtrate, rotary evaporate to remove acetone, and vacuum dry the product at 120 °C for 4 h to obtain a carboxyl-terminated hyperbranched polyester; among them, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, succinic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, maleic anhydride is 65:265:115:390:5.5:825:30, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0065] (2) Mix sodium citrate, ferrous sulfate, and water, stir and dissolve at a stirring speed of 180 r / min at room temperature, add 6 mol / L sodium hydroxide aqueous solution dropwise to adjust the pH value of the reaction solution to 10, finish dropping within 1 h, introduce air at a speed of 30 L / h, react at room temperature for 6 h, after the reaction is completed, rotary evaporate, wash with water, filter, and vacuum dry the filter cake at 95 °C for 7 h to obtain nano-ferroferric oxide; among them, the mass ratio of water, sodium citrate, ferrous sulfate is 500:1:30;

[0066] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, and linoleic acid evenly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat up xylene to 140 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, finish dropping within 8 h, and keep the temperature at 140 °C for reaction for 2 h to obtain a silicon-acrylic prepolymer; among them, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, di-tert-butyl peroxide is 77:60:90:76:28:28:7.5; the mass ratio of the mixed monomer to xylene is 365:340;

[0067] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until homogeneous, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, hold the temperature for reaction for 45 min. After the holding reaction is completed, heat up to 230 °C and maintain the reaction at 230 °C for 5 h. Measure the acid value of the reaction system to be 15 mg KOH / g, stop the reaction, and obtain the basic alkyd resin; among them, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 25:27:3:25:20:8:0.3;

[0068] (5) Mix the basic alkyd resin, silicone-acrylic prepolymer, carboxyl-terminated hyperbranched polyester, and nano-ferroferric oxide evenly, ultrasonically disperse at a frequency of 30 kHz for 15 min, stir and heat up to 190 °C at a stirring speed of 300 r / min, hold the temperature for reaction for 3 h. Stop the reaction when the acid value of the system is measured to be 35 - 45 mg KOH / g, cool down to 80 °C, add ethylene glycol dibutyl ether, stir evenly, maintain at 80 °C and add triethylamine, stir and react for 1 h. After the reaction is completed, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 35%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin. Among them, the mass ratio of the basic alkyd resin, silicone-acrylic prepolymer, carboxyl-terminated hyperbranched polyester, nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:50:43:7:30:15; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to a mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain the high-adhesion magnetic ink.

[0069] Comparative Example 2

[0070] This comparative example discloses a preparation method of high-adhesion magnetic ink, including the following steps:

[0071] (1) Mix 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide uniformly. Introduce nitrogen, and slowly heat the mixture to 120 °C at a rate of 20 °C / h with a stirring speed of 180 r / min. React for 2.5 h, add maleic anhydride, then heat the mixture to 150 °C at a rate of 10 °C / h and continue to react for 2 h. Evaporate and concentrate the reaction solution obtained after the reaction until solids precipitate to obtain a concentrated solution. Add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and vacuum dry the filter cake at 120 °C for 4 h to obtain sodium carboxyl-terminated hyperbranched polyester; wherein, the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is 65:265:115:390:5.5:825:30, and the mass ratio of the concentrated solution to the sodium hydroxide ethanol solution is 900:100;

[0072] (2) Mix sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, and water, and stir and dissolve them at a stirring speed of 180 r / min at room temperature. Add sodium citrate and ferrous sulfate, and ultrasonicate for 25 min at a frequency of 30 kHz. Dropwise add a 6 mol / L sodium hydroxide aqueous solution to adjust the pH value of the reaction solution to 10, and complete the dropwise addition within 1 h. Introduce air at a rate of 30 L / h and react at room temperature for 6 h. After the reaction, perform rotary evaporation, wash with water, filter, and vacuum dry the filter cake at 95 °C for 7 h to obtain hyperbranched polyester loaded with nano-ferroferric oxide; wherein, the mass ratio of sodium carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:600:1:30;

[0073] (3) Mix methacrylic acid, methyl methacrylate, n-butyl acrylate, oleic acid, and linoleic acid uniformly, add di-tert-butyl peroxide, and stir evenly to obtain a mixed monomer; Stir and heat xylene to 140 °C at a stirring speed of 300 r / min, dropwise add the mixed monomer, and complete the dropwise addition within 8 h. Keep the temperature at 140 °C and react for 2 h to obtain an acrylate prepolymer; wherein, the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, oleic acid, linoleic acid, and di-tert-butyl peroxide is 77:60:90:28:28:7.5; the mass ratio of the mixed monomer to xylene is 365:340.

[0074] (4) Mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, and linoleic acid evenly, stir at a stirring speed of 300 r / min until homogeneous, add xylene and hypophosphorous acid, introduce nitrogen, heat up to 150 °C, keep the temperature for reaction for 45 min. After the heat preservation reaction ends, heat up to 230 °C and maintain the reaction at 230 °C for 5 h. Stop the reaction when the acid value of the reaction system is measured to be 15 mg KOH / g to obtain the basic alkyd resin; among them, the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is 25:27:3:25:20:8:0.3;

[0075] (5) Mix the basic alkyd resin, acrylate prepolymer, and hyperbranched polyester loaded with nano-ferroferric oxide evenly, ultrasonically disperse for 15 min at a frequency of 30 kHz, stir and heat up to 190 °C at a stirring speed of 300 r / min, keep the temperature for reaction for 3 h. Stop the reaction when the acid value of the reaction system is measured to be 45 mg KOH / g, cool down to 80 °C, add ethylene glycol dibutyl ether and n-hexyltriethoxysilane, stir evenly, maintain at 80 °C and add triethylamine, stir and react for 1 h. After the reaction ends, dropwise add deionized water at a stirring speed of 1000 r / min to adjust the solid content of the system to 35%, and finish dropping within 2 h to obtain the modified waterborne alkyd resin. Among them, the mass ratio of the basic alkyd resin, acrylate prepolymer, hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, n-hexyltriethoxysilane, and triethylamine is 100:40:50:30:10:15; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether evenly according to the mass ratio of 90:5:5, and disperse in a dispersion grinder for 60 min to obtain a high-adhesion magnetic ink.

[0076] In all of the above examples and comparative examples, 1,3,5-benzenetricarboxylic acid was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 554-95-0; 2,2-bis(hydroxymethyl)propionic acid was from Beijing J&K Scientific Ltd., with a CAS number of 4767-3-7; PEG400 (molecular weight of 400) was from Jiangsu Haian Petrochemical Factory, with a product number of PEG400; 1,4-butanedioic acid was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 110-15-6; maleic anhydride was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 203-571-6; sodium citrate was from Hubei Qifei Pharmaceutical Co., Ltd., with a CAS number of 6132-04-3; ferrous sulfate was from Jiangsu Aikon Biopharmaceutical R & D Co., Ltd., with a CAS number of 7720-78-7; vinyltriethoxysilane was from Beijing J&K Scientific Ltd., with a CAS number of 78-08-0; methacrylic acid was from Tesla Chemicals (Hubei) Co., Ltd., with a CAS number of 79-41-4; n-butyl acrylate was from Jinan Lianshun Chemical Co., Ltd., with a CAS number of 141-32-2; methyl methacrylate was from Shandong Chuangying Chemical Co., Ltd., with a CAS number of 80-62-6; oleic acid was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 463-40-1; linoleic acid was from Shanghai Rongli Science & Technology Co., Ltd.; trimethylolpropane was from Jiangsu Runfeng Synthetic Technology Co., Ltd., with a CAS number of 77-99-6; isophthalic acid was from Jiangsu Pulesi Biotechnology Co., Ltd., with a CAS number of 121-91-5; benzoic acid was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 65-85-0; n-hexyltriethoxysilane was from Shanghai Aladdin Biochemical Technology Co., Ltd., with a CAS number of 18166-37-5.

[0077] Test Example

[0078] The high-adhesion magnetic inks prepared in Examples 1-5 and Comparative Examples 1-2 were denoted as Specimens 1-7, and were respectively printed on the surfaces of a glass sheet with a thickness of 0.5 mm and an aluminum foil, and cured at 130 °C for 10 min to obtain the cured inks; the high-adhesion magnetic inks prepared in Examples 1-5 and Comparative Examples 1-2 were respectively printed on the surface of a glass sheet with dimensions of 3.2 mm × 2.4 mm × 0.5 mm, and cured at 130 °C for 10 min to obtain Samples 1-7.

[0079] Test 1: Test for ink adhesion fastness: The adhesion fastness of Specimens 1-7 was tested in accordance with GB / T 13217.7-2009 "Test Method for Adhesion Fastness of Liquid Inks", and the test results are shown in Table 1:

[0080]

[0081] As can be seen from Table 1, the high-adhesion magnetic ink of the present invention has excellent adhesion fastness. From Samples 1-5, it can be seen that as the silicone content in the ink increases, the adhesion fastness of the ink also increases. This is because there are hydroxyl groups on the surfaces of the glass sheet and aluminum foil, which can react with the silanol groups after hydrolysis of silicone to form stable chemical bonds, improving the adhesion of the ink on the surfaces of the glass sheet and aluminum foil. From Sample 2 and Sample 7, it can be seen that when the silicone is not connected to the main chain of the acrylate polymer, the silicone is prone to self-polymerization after hydrolysis, reducing the content of silanol groups in the ink that can react with the hydroxyl groups on the surfaces of the glass sheet and aluminum foil, and the adhesion fastness decreases; from Sample 2 and Sample 6, it can be seen that when nano-ferroferric oxide is directly added to the ink, nano-ferroferric oxide is prone to agglomeration in the ink, reducing the adhesion fastness of the ink.

[0082] Test 2: Test on the magnetic separation performance of the ink: Take 100 samples of 1-7 respectively, mix them with 900 glass flakes of 3.2 mm × 2.4 mm × 0.5 mm respectively, and perform separation under the action of an external magnetic field to measure their magnetic separation performance. The test results are shown in Table 2:

[0083]

[0084] As can be seen from Table 2, the high-adhesion magnetic ink of the present invention has excellent magnetic separation performance. From Samples 1-5, it can be seen that as the nano-ferroferric oxide content in the ink increases, the magnetic separation of the ink also increases. This is because the magnetic source of the ink is ferroferric oxide. The more nano-ferroferric oxide content, the more sensitive the ink is to the magnetic field and the easier it is to be separated; from Sample 2 and Sample 6, it can be seen that when nano-ferroferric oxide is mixed with the ink by physical means, the separation performance of the ink decreases. This is because nano-ferroferric oxide is a type of magnetic particle, which is extremely prone to agglomeration in the ink. At the same time, nano-ferroferric oxide itself is hydrophilic and has poor compatibility with the ink. After curing, under the action of an external magnetic field, it will cause the separation of nano-ferroferric oxide from the ink layer, resulting in a decrease in the magnetism of the ink.

[0085] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a high-adhesion magnetic ink, characterized in that, It includes the following steps: Step (1), prepare a hyperbranched polyester loaded with nano-ferroferric oxide, a silicon-acrylic prepolymer and a basic alkyd resin; Among them, the preparation of the hyperbranched polyester loaded with nano-ferroferric oxide includes the following steps: heat 1,3,5-benzenetricarboxylic acid, 2,2-dimethylolpropionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, and N,N-dimethylformamide to a first set temperature in an inert gas atmosphere, react, after the reaction ends, add maleic anhydride, heat to a second set temperature, react, after the reaction ends, perform post-treatment, and dry to obtain a sodium salt of a carboxyl-terminated hyperbranched polyester; the operating steps of the post-treatment are: evaporate and concentrate the reaction solution obtained after the reaction ends until solids precipitate to obtain a concentrated solution, add a saturated sodium hydroxide ethanol solution to the concentrated solution, let it stand for precipitation, filter, and dry the filter cake, where the mass ratio of the concentrated solution to the saturated sodium hydroxide ethanol solution is 900:100; Mix the sodium salt of the carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate, ultrasonicate, adjust the pH value to 10, introduce air, react, after the reaction ends, separate and purify, and dry to obtain a hyperbranched polyester loaded with nano-ferroferric oxide; Among them, the preparation of the silicon-acrylic prepolymer includes the following steps: mix acrylate compounds, vinyltriethoxysilane, oleic acid, and linoleic acid, add an initiator to obtain a mixed monomer, drop the mixed monomer into xylene at a set temperature, and maintain the set temperature for reaction to obtain a silicon-acrylic prepolymer; Among them, the preparation of the basic alkyd resin includes the following steps: uniformly mix trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid, heat to a third set temperature in an inert gas atmosphere, react, after the reaction ends, heat to a fourth set temperature, react, stop the reaction after measuring the acid value of the reaction system to the target acid value to obtain a basic alkyd resin; Step (2), mix and ultrasonically disperse the basic alkyd resin, the silicon-acrylic prepolymer, and the hyperbranched polyester loaded with nano-ferroferric oxide, stir and heat to a fifth set temperature, keep the temperature for reaction, stop the reaction after measuring the acid value of the reaction system to the target acid value, cool to a sixth set temperature, add ethylene glycol dibutyl ether and triethylamine, stir and react, after the reaction ends, add water to adjust the solid content of the system to obtain a modified waterborne alkyd resin; Mix the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether, and grind and disperse to obtain a high-adhesion magnetic ink.

2. The preparation method of a high-adhesion magnetic ink according to claim 1, characterized in that, In the step (1), when preparing the sodium salt of the carboxyl-terminated hyperbranched polyester, the heating rate to the first set temperature is 20 - 25 °C / h, the first set temperature is 110 - 120 °C, and the reaction duration at the first set temperature is 2.5 - 3.5 h; the heating rate to the second set temperature is 10 °C / h, the second set temperature is 140 - 150 °C, and the reaction duration at the second set temperature is 2 - 2.5 h; the mass ratio of 1,3,5-benzenetricarboxylic acid, 2,2-bis(hydroxymethyl)propionic acid, 1,4-butanedioic acid, PEG400, p-toluenesulfonic acid, N,N-dimethylformamide, and maleic anhydride is (60 - 75):(260 - 280):(110 - 130):(380 - 420):(4.5 - 8.5):(800 - 900):(25 - 35).

3. The preparation method of a high-adhesion magnetic ink according to claim 2, characterized in that, In the step (1), when preparing the hyperbranched polyester loaded with nano-ferroferric oxide, the ultrasonic conditions are ultrasonic treatment for 20 - 30 min at a frequency of 20 - 40 kHz; the air inlet volume is 30 - 60 L / h; the reaction conditions are reaction for 6 h at room temperature; the mass ratio of the sodium salt of the carboxyl-terminated hyperbranched polyester, N,N-dimethylformamide, water, sodium citrate, and ferrous sulfate is 50:30:(500 - 600):(0.5 - 1):(25 - 60).

4. The preparation method of a high-adhesion magnetic ink according to claim 3, characterized in that, In the step (1), when preparing the silicon-acrylic prepolymer, the acrylate compounds include methacrylic acid, methyl methacrylate, and n-butyl acrylate, the initiator is di-tert-butyl peroxide, the set temperature is 135 - 145 °C, the reaction duration at the set temperature is 1.5 - 2.5 h, the dropping duration of the mixed monomers is 8 h, and the mass ratio of methacrylic acid, methyl methacrylate, n-butyl acrylate, vinyltriethoxysilane, oleic acid, linoleic acid, and di-tert-butyl peroxide is (69 - 86):(50 - 60):(77 - 102):(57 - 95):28:(28 - 42):(7 - 9), and the mass ratio of the mixed monomers to xylene is (350 - 410):(320 - 400).

5. The preparation method of a high-adhesion magnetic ink according to claim 4, characterized in that, In the step (1), when preparing the basic alkyd resin, the third set temperature is 140 - 160 °C, the reaction duration at the third set temperature is 30 - 60 min; the fourth set temperature is 220 - 240 °C, the reaction duration at the fourth set temperature is 4 - 6 h, the target acid value is 5 - 15 mgKOH / g, and the mass ratio of trimethylolpropane, isophthalic acid, benzoic acid, oleic acid, linoleic acid, xylene, and hypophosphorous acid is (21 - 27):(16 - 30):3:(20 - 30):(20 - 30):8:0.

3.

6. The preparation method of a high-adhesion magnetic ink according to claim 5, characterized in that, In the step (2), the ultrasonic conditions are ultrasonic treatment for 10 - 20 min at a frequency of 20 - 40 kHz; the fifth set temperature is 180 - 190 °C, the reaction duration at the fifth set temperature is 2 - 4 h; the target acid value is 35 - 45 mgKOH / g; the sixth set temperature is 80 °C, the reaction duration at the sixth set temperature is 1 h; the adjusted solid content of the system is 30 - 40%.

7. The preparation method of a high-adhesion magnetic ink according to claim 6, characterized in that, In the step (2), the mass ratio of the basic alkyd resin, the silicon-acrylic prepolymer, the hyperbranched polyester loaded with nano-ferroferric oxide, ethylene glycol dibutyl ether, and triethylamine is 100:(45 - 55):(45 - 55):30:(12 - 18); the mass ratio of the modified waterborne alkyd resin, ethanol, and ethylene glycol dibutyl ether is 90:5:

5.

8. A high-adhesion magnetic ink prepared by using the preparation method of the high-adhesion magnetic ink according to any one of claims 1 - 7.

9. An application of the high-adhesion magnetic ink according to claim 8 in chip production.

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