An acid- and alkali-resistant explosion-proof ink and its preparation method

Abstract

The present invention discloses an acid and alkali resistant explosion-proof ink and a preparation method thereof, belonging to the technical field of modified inks. First, an acid and alkali resistant explosion-proof ink comprises the following raw materials in parts by mass: 55-65 parts of low melting point glass powder, 17.5-22.5 parts of copper chromium black agent, 17.5-22.5 parts of ink oil, 8-10 parts of acid and alkali resistant auxiliary agent, 0.5-1 part of leveling agent and 0.5-1 part of defoaming agent. The present invention provides an acid and alkali resistant explosion-proof ink and a preparation method thereof. The acid and alkali resistant explosion-proof ink prepared by the present invention is printed on glass by screen printing process, and then after curing, an ink film is formed. After testing, the glass loaded with the above ink film shows excellent explosion-proof performance. Further, the ink film formed by ink curing shows excellent acid and alkali resistance, and the service life and application scenarios of the glass loaded with the above acid and alkali resistant explosion-proof ink are extended and expanded.

Description

Technical Field

[0001] The present invention belongs to the technical field of modified inks, and particularly relates to an acid and alkali resistant explosion-proof ink and a preparation method thereof. Background Art

[0002] In the application process of the ink for tempered glass, first, the ink is printed on the glass substrate by screen printing technology, then dried at high temperature, then transferred to a high-temperature steel furnace for hot bending and sintering, and then cooled and formed to obtain the tempered glass printed with glass ink. With the rapid development of the automotive industry and the improvement of consumers' safety requirements, explosion-proof ink has emerged. As the name implies, explosion-proof ink is an ink material that can effectively prevent glass fragments from flying when the glass is impacted by external forces and protect the safety of people in the vehicle. This requires that the explosion-proof ink has excellent viscosity.

[0003] Traditional explosion-proof inks are mainly composed of low-melting-point glass powder, copper-chromium blackening agent, ink oil, leveling agent and other additives. Among them, the low-melting-point glass powder is mainly composed of powders such as silicon dioxide, zinc oxide, and aluminum oxide. For example, the invention patent with the application number CN201910326094.4 discloses a lead-free low-melting-point glass powder for automotive glass ink and a preparation method thereof, and the disclosed glass powder is mainly composed of silicon dioxide, boron oxide, bismuth oxide, zinc oxide, titanium oxide, aluminum oxide, etc. As one of the main components of glass ink, the main function of low-melting-point glass powder is to improve the bonding performance between the ink and the glass, and at the same time play a role in heat conduction, oxygen isolation and toughening. However, the low-melting-point glass powder has poor acid and alkali corrosion resistance, and the performance of traditional explosion-proof inks can no longer meet the requirements of new energy vehicle glass inks for harsh outdoor environments. The technical problem of poor acid and alkali resistance has also become the key point for the industry to overcome. Summary of the Invention

[0004] The present invention provides an acid and alkali resistant explosion-proof ink and a preparation method thereof, aiming to improve the acid and alkali resistance of the explosion-proof ink by improving the formula of the explosion-proof ink.

[0005] The object of the present invention can be achieved by the following technical solutions:

[0006] An acid and alkali resistant explosion-proof ink, comprising the following raw materials in parts by mass:

[0007] Low-melting-point glass powder 55 - 65 parts;

[0008] Copper-chromium blackening agent 17.5 - 22.5 parts;

[0009] Ink oil 17.5 - 22.5 parts;

[0010] Acid and alkali resistant additive 8 - 10 parts;

[0011] Leveling agent 0.5 - 1 part;

[0012] Defoamer: 0.5 - 1 part;

[0013] The acid and alkali resistant auxiliary agent is prepared by the following steps:

[0014] S1. Add diethylenetriamine to p-hydroxybenzoic acid, evacuate the air, then raise the temperature to 145 - 155 °C, and stir the reaction at a constant temperature for 2 - 3 h. During the reaction, continue to evacuate the air. After completion, raise the temperature of the system to 220 - 225 °C, and stir the reaction at a constant temperature for 4 - 5 h. During the reaction, continue to evacuate the air. After completion, cool to room temperature, collect the product, and after washing and drying the product, an imidazole compound is obtained. In the above steps, an imidazole compound is obtained by the ring-forming reaction of the terminal carboxyl group in p-hydroxybenzoic acid and diethylenetriamine. The reaction process is as follows:

[0015] 。

[0016] S2. Take absolute ethanol, fill it with nitrogen, add 2-bromo-5-acetylpyridine and the imidazole compound to it, raise the temperature to reflux, and keep heating and refluxing for 4 - 5 h. After completion, cool to room temperature, rotary evaporate to remove absolute ethanol, collect the product, and an intermediate is obtained. In the above steps, a pyridine ring and an amide bond are introduced into the imidazole compound by the Schiff base reaction to obtain the intermediate. The reaction process is as follows:

[0017] 。

[0018] S3. Take chloroform, fill it with nitrogen, then add [3-(trimethoxysilyl)propyl]succinic anhydride and the intermediate to it, stir at room temperature for 1 - 2 h, then add Amberlyst-15 ion exchange resin to it. After adding, continue to stir for 1 - 2 h. After completion, raise the temperature to 65 - 70 °C, and stir the reaction at a constant temperature for 4 - 5 h. After completion, cool to room temperature, filter to remove Amberlyst-15 ion exchange resin, then rotary evaporate to remove chloroform, collect the product, and after washing and drying the product, the acid and alkali resistant auxiliary agent is obtained. In the above steps, the acid and alkali resistant auxiliary agent is obtained by the ring-opening reaction of the terminal hydroxyl group of the intermediate and the acid anhydride. The reaction process is as follows:

[0019] 。

[0020] Further, the dosage ratio of p-hydroxybenzoic acid to diethylenetriamine in S1 is 1 mol: 1.0 - 1.2 mol.

[0021] Further, the dosage ratio of absolute ethanol, 2-bromo-5-acetylpyridine, and the imidazole compound in S2 is 1 L: 0.4 mol: 82.1 - 82.5 g.

[0022] Further, the dosage ratio of chloroform, [3-(trimethoxysilyl)propyl] succinic anhydride, intermediate, and Amberlyst-15 ion exchange resin in S3 is 1L: 0.3 mol: 44-45 g: 30-40 g.

[0023] Further, the low-melting glass powder comprises the following raw materials in parts by mass:

[0024] 45-55 parts of bismuth oxide, 20-25 parts of boric acid, 12-15 parts of silicon dioxide, 7-8 parts of alumina, 5.5-7.5 parts of zirconia, 4.5-5.5 parts of tin dioxide, 3-5 parts of titanium dioxide, 2-5 parts of lithium carbonate, and 2-5 parts of sodium carbonate.

[0025] Further, the low-melting glass powder is prepared by the following steps:

[0026] Weigh each raw material according to the parts by mass. Mix bismuth oxide, silicon dioxide, boric acid, alumina, zirconia, tin dioxide, titanium dioxide, lithium carbonate, and sodium carbonate and place them in a muffle furnace. Heat from room temperature to 1120°C - 1150°C at a heating rate of 15-20°C / min, then keep it at a constant temperature and calcine for 1-2 h. After calcination, cool it naturally to room temperature to obtain a glassy mixture. Crush the glassy mixture and pass it through a 500-mesh sieve to obtain the low-melting glass powder.

[0027] Further, the D 90 particle size of the copper-chromium blackening agent is 1.5-2.0 μm.

[0028] Further, the ink oil comprises the following raw materials in parts by mass:

[0029] 8-10 parts of acrylic resin, 100 parts of solvent, and 1-1.2 parts of dispersant HLN-1708.

[0030] Further, the solvent is composed of diethylene glycol butyl ether and glycerol mixed in a volume ratio of 8-10:1.

[0031] Further, the ink oil is prepared by the following steps:

[0032] Weigh each raw material according to the parts by mass. Stir and add acrylic resin and dispersant HLN-1708 to the solvent. After adding, raise the temperature of the system to 50-55°C and continue to stir at a constant temperature until the acrylic resin is completely dissolved. After that, cool it naturally to room temperature to obtain the ink oil.

[0033] Further, the leveling agent is one of leveling agent BYK-333 and leveling agent BYK-346.

[0034] Further, the defoaming agent is one of defoaming agent BYK054, defoaming agent BYK057, and defoaming agent BYK1794.

[0035] Further, the preparation method of the acid and alkali resistant explosion-proof ink comprises the following steps:

[0036] Weigh each raw material by mass parts, stir and add low melting point glass powder and acid and alkali resistant auxiliary agent into the ink oil, stir at room temperature for 1 - 2 h, then stir and add leveling agent and defoaming agent into it, stir at room temperature for 10 - 20 min. After completion, grind it through an 800 - mesh sieve to obtain the acid and alkali resistant explosion-proof ink.

[0037] Advantages of the present invention:

[0038] The present invention provides an acid and alkali resistant explosion-proof ink and its preparation method. The acid and alkali resistant explosion-proof ink prepared by the present invention is printed on glass by screen printing process, and after curing, an ink film is formed. After testing, the glass loaded with the above ink film shows excellent explosion-proof performance. Further, the ink film formed by ink curing shows excellent acid and alkali resistance. The service life and application scenarios of the glass loaded with the above acid and alkali resistant explosion-proof ink are extended and expanded. The specific principle is as follows:

[0039] The acid and alkali resistant explosion-proof ink provided by the present invention mainly includes low melting point glass powder, acid and alkali resistant auxiliary agent, ink oil and other auxiliary agents. Among them, the low melting point glass powder is Bi2O3 - SiO2 - B2O3 series low melting point glass powder, and other metal oxides are added at the same time. Bismuth oxide as the main raw material has excellent acid and alkali corrosion resistance. Among them, the acid and alkali resistant auxiliary agent prepared by the present invention contains imidazole ring, pyridine ring, amide bond and siloxane chain molecular structure. Among them, the imidazole ring and pyridine ring structures have excellent acid and alkali corrosion resistance. Specifically, the imidazole ring and pyridine ring themselves show excellent acid and alkali corrosion resistance due to the existence of the conjugated system. Further, the imidazole ring and pyridine ring contain nitrogen atoms that can provide lone pair electrons, and these lone pair electrons can form coordination bonds with metal ions of metal oxides in the low melting point glass powder, thereby forming a protective film in the low melting point glass powder to prevent the corrosion medium from contacting the metal powder in the low melting point glass powder, and further improving the acid and alkali corrosion resistance of the overall explosion-proof ink. At the same time, the siloxane chain molecular structure can further form a coordination effect with metal ions of metal oxides in the low melting point glass powder. At the same time, the silanol groups formed by hydrolysis of the siloxane chain molecular structure can improve the interaction between the acid and alkali resistant auxiliary agent and the low melting point glass powder. At the same time, when the prepared ink is in service, the existence of the siloxane chain molecular structure can improve the bonding strength between the ink and the glass. Specific embodiments

[0040] 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 shall fall within the protection scope of the present invention.

[0041] Example 1

[0042] Preparation of low-melting glass powder:

[0043] First, the low-melting glass powder comprises the following raw materials in parts by mass:

[0044] 45 parts of bismuth oxide, 20 parts of boric acid, 12 parts of silicon dioxide, 7 parts of alumina, 5.5 parts of zirconium oxide, 4.5 parts of tin dioxide, 3 parts of titanium dioxide, 2 parts of lithium carbonate, and 2 parts of sodium carbonate. Among them, bismuth oxide, silicon dioxide, boric acid, alumina, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate, and sodium carbonate are all purchased from Sinopharm Chemical Reagent Co., Ltd.

[0045] Then, the low-melting glass powder is prepared by the following steps:

[0046] Weigh each raw material according to the parts by mass. Mix bismuth oxide, silicon dioxide, boric acid, alumina, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate, and sodium carbonate and place them in a muffle furnace. Heat from room temperature to 1150 °C at a heating rate of 20 °C / min, then keep it at a constant temperature and calcine for 1 h. After the calcination is completed, cool it naturally to room temperature to obtain a glassy mixture. Crush the glassy mixture and pass it through a 500-mesh sieve to obtain the low-melting glass powder. Detected by a thermal expansion coefficient instrument (DIL 402C type, NETZSCH Germany), the thermal expansion coefficient (25 °C - 300 °C) of the prepared low-melting glass powder is 10.63×10 -6 / °C, the glass transition temperature is 427.2 °C, and the glass softening temperature is 461.4 °C.

[0047] Example 2

[0048] Preparation of low-melting glass powder:

[0049] First, the low-melting glass powder comprises the following raw materials in parts by mass:

[0050] 50 parts of bismuth oxide, 22 parts of boric acid, 14 parts of silicon dioxide, 8 parts of alumina, 7 parts of zirconium oxide, 5 parts of tin dioxide, 4 parts of titanium dioxide, 2.5 parts of lithium carbonate, and 2.5 parts of sodium carbonate. Among them, bismuth oxide, silicon dioxide, boric acid, alumina, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate, and sodium carbonate are all purchased from Sinopharm Chemical Reagent Co., Ltd.

[0051] Then, the low-melting glass powder is prepared by the following steps:

[0052] Weigh each raw material according to parts by mass. Mix bismuth oxide, silicon dioxide, boric acid, aluminum oxide, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate and sodium carbonate, and then place the mixture in a muffle furnace. Heat it from room temperature to 1140 °C at a heating rate of 15 °C / min, and then keep it at a constant temperature for calcination for 2 h. After the calcination is completed, cool it naturally to room temperature to obtain a glassy mixture. Crush the glassy mixture and sieve it through a 500-mesh sieve to obtain low-melting glass powder. The thermal expansion coefficient (25 °C - 300 °C) of the prepared low-melting glass powder is 11.74×10 -6 / °C, the glass transition temperature is 375.8 °C, and the glass softening temperature is 408.1 °C.

[0053] Example 3

[0054] Prepare low-melting glass powder:

[0055] First, the low-melting glass powder includes the following raw materials in parts by mass:

[0056] 55 parts of bismuth oxide, 25 parts of boric acid, 15 parts of silicon dioxide, 8 parts of aluminum oxide, 7.5 parts of zirconium oxide, 5.5 parts of tin dioxide, 5 parts of titanium dioxide, 5 parts of lithium carbonate, 5 parts of sodium carbonate. Among them, bismuth oxide, silicon dioxide, boric acid, aluminum oxide, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate and sodium carbonate are all purchased from Sinopharm Chemical Reagent Co., Ltd.

[0057] Then, the low-melting glass powder is prepared by the following steps:

[0058] Weigh each raw material according to parts by mass. Mix bismuth oxide, silicon dioxide, boric acid, aluminum oxide, zirconium oxide, tin dioxide, titanium dioxide, lithium carbonate and sodium carbonate, and then place the mixture in a muffle furnace. Heat it from room temperature to 1120 °C at a heating rate of 15 °C / min, and then keep it at a constant temperature for calcination for 2 h. After the calcination is completed, cool it naturally to room temperature to obtain a glassy mixture. Crush the glassy mixture and sieve it through a 500-mesh sieve to obtain low-melting glass powder. The thermal expansion coefficient (25 °C - 300 °C) of the prepared low-melting glass powder is 11.21×10 -6 / °C, the glass transition temperature is 401.3 °C, and the glass softening temperature is 440.5 °C.

[0059] Example 4

[0060] Prepare ink oil:

[0061] First, the ink oil includes the following raw materials in parts by mass:

[0062] 8 parts of acrylic resin, 100 parts of solvent, and 1 part of dispersant HLN-1708.

[0063] Among them, the acrylic resin is purchased from Shanghai Macklin Biochemical Co., Ltd., with the product number L990045. The solvent is composed of diethylene glycol butyl ether and glycerol mixed in a volume ratio of 8:1, and both diethylene glycol butyl ether and glycerol are purchased from Shanghai Macklin Biochemical Co., Ltd.

[0064] Then, the ink oil is prepared by the following steps:

[0065] Weigh each raw material according to the mass parts, add the acrylic resin and dispersant HLN-1708 to the solvent with stirring. After the addition is completed, the temperature of the system is raised to 50 °C, and continue to stir at a constant temperature until the acrylic resin is completely dissolved. After that, it is naturally cooled to room temperature to obtain the ink oil.

[0066] Example 5

[0067] Prepare ink oil:

[0068] First, the ink oil includes the following raw materials in mass parts:

[0069] 9 parts of acrylic resin, 100 parts of solvent, and 1.1 parts of dispersant HLN-1708.

[0070] Among them, the acrylic resin is purchased from Shanghai Macklin Biochemical Co., Ltd., with the product number L990045. The solvent is composed of diethylene glycol butyl ether and glycerol mixed in a volume ratio of 9:1, and both diethylene glycol butyl ether and glycerol are purchased from Shanghai Macklin Biochemical Co., Ltd.

[0071] Then, the ink oil is prepared by the following steps:

[0072] Weigh each raw material according to the mass parts, add the acrylic resin and dispersant HLN-1708 to the solvent with stirring. After the addition is completed, the temperature of the system is raised to 55 °C, and continue to stir at a constant temperature until the acrylic resin is completely dissolved. After that, it is naturally cooled to room temperature to obtain the ink oil.

[0073] Example 6

[0074] Prepare ink oil:

[0075] First, the ink oil includes the following raw materials in mass parts:

[0076] 10 parts of acrylic resin, 100 parts of solvent, and 1.2 parts of dispersant HLN-1708.

[0077] Among them, the acrylic resin was purchased from Shanghai Macklin Biochemical Co., Ltd., with the product number L990045. The solvent was composed of diethylene glycol butyl ether and glycerol mixed in a volume ratio of 10:1, and both diethylene glycol butyl ether and glycerol were purchased from Shanghai Macklin Biochemical Co., Ltd.

[0078] Then, the ink oil was prepared by the following steps:

[0079] Weigh each raw material according to parts by mass. Stir and add the acrylic resin and the dispersant HLN-1708 to the solvent. After the addition is complete, raise the temperature of the system to 55°C, continue to stir at a constant temperature until the acrylic resin is completely dissolved. After that, cool it naturally to room temperature to obtain the ink oil.

[0080] Example 7

[0081] Prepare the acid and alkali resistant additive:

[0082] S1. Stir and add 1 mol of p-hydroxybenzoic acid (99.5%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to reactor A, and then stir and add 1.0 mol of diethylenetriamine (99%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to it. Reactor A was evacuated, and then the temperature was raised to 145°C, and the reaction was carried out with constant stirring for 2 h. During the reaction, evacuation was continuously carried out. After completion, the temperature of the system was raised to 220°C, and the reaction was carried out with constant stirring for 4 h. During the reaction, evacuation was continuously carried out. After completion, it was cooled to room temperature, the product was collected, washed three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dried in a constant temperature drying oven at 40°C for 20 min. After completion, the imidazole compound was obtained.

[0083] S2. Add 1 L of absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor B, charge nitrogen for protection, and then stir and add 0.4 mol of 2-bromo-5-acetylpyridine (97%; purchased from Shanghai Macklin Biochemical Co., Ltd.) and 82.1 g of the imidazole compound to reactor B. Reactor B was heated to reflux, and the reaction was carried out with constant heating and reflux for 4 h. After completion, it was cooled to room temperature, and the absolute ethanol was removed by rotary evaporation. The product was collected to obtain the intermediate.

[0084] S3. Add 1 L of chloroform (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor C, fill it with nitrogen for protection, then add 0.3 mol of [3-(trimethoxysilyl)propyl] succinic anhydride (95%; purchased from Sinopharm Chemical Reagent Co., Ltd.) and 44 g of the intermediate to reactor C with stirring at room temperature for 1 h. Then add 30 g of Amberlyst-15 ion exchange resin (dry; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor C. After the addition, continue stirring for 1 h. After completion, heat reactor C to 65 °C and stir at a constant temperature for 4 h. After completion, cool to room temperature, filter off the Amberlyst-15 ion exchange resin, then rotary evaporate to remove chloroform, collect the product, wash the product three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dry it in a constant temperature drying oven at 40 °C for 20 min. After completion, an acid and alkali resistant auxiliary agent is obtained.

[0085] Example 8

[0086] Preparation of acid and alkali resistant auxiliary agent:

[0087] S1. Add 1 mol of p-hydroxybenzoic acid (99.5%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to reactor A with stirring, and then add 1.1 mol of diethylenetriamine (99%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to it with stirring. Reactor A is evacuated, then heated to 150 °C and stirred at a constant temperature for 3 h. During the reaction, evacuation is continued. After completion, the system is heated to 224 °C and stirred at a constant temperature for 5 h. During the reaction, evacuation is continued. After completion, cool to room temperature, collect the product, wash the product three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dry it in a constant temperature drying oven at 45 °C for 30 min. After completion, an imidazole compound is obtained.

[0088] S2. Add 1 L of absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor B, fill it with nitrogen for protection, then add 0.4 mol of 2-bromo-5-acetylpyridine (97%; purchased from Shanghai Macklin Biochemical Co., Ltd.) and 82.4 g of the imidazole compound to reactor B with stirring. Reactor B is heated to reflux, and the reaction is heated under reflux at a constant temperature for 5 h. After completion, cool to room temperature, rotary evaporate to remove absolute ethanol, collect the product, and obtain the intermediate.

[0089] S3. Add 1 L of chloroform (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor C, fill with nitrogen for protection, then add 0.3 mol of [3-(trimethoxysilyl)propyl] succinic anhydride (95%; purchased from Sinopharm Chemical Reagent Co., Ltd.) and 45 g of the intermediate to reactor C with stirring at room temperature. Stir for 2 h, then add 40 g of Amberlyst-15 ion exchange resin (dry; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor C. After the addition, continue to stir for 2 h. After completion, heat reactor C to 68 °C and stir at a constant temperature for 5 h. After completion, cool to room temperature, filter to remove Amberlyst-15 ion exchange resin, then rotary evaporate to remove chloroform, collect the product, wash the product three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dry it in a constant temperature drying oven at 45 °C for 30 min. After completion, an acid and alkali resistant aid is obtained.

[0090] Example 9

[0091] Preparation of acid and alkali resistant aid:

[0092] S1. Add 1 mol of p-hydroxybenzoic acid (99.5%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to reactor A with stirring, then add 1.2 mol of diethylenetriamine (99%; purchased from Shanghai Macklin Biochemical Co., Ltd.) to it with stirring. Evacuate reactor A, then heat it to 155 °C and stir at a constant temperature for 3 h. Keep evacuating during the reaction. After completion, heat the system to 225 °C and stir at a constant temperature for 5 h. Keep evacuating during the reaction. After completion, cool to room temperature, collect the product, wash the product three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dry it in a constant temperature drying oven at 50 °C for 30 min. After completion, an imidazole compound is obtained.

[0093] S2. Add 1 L of absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to reactor B, fill with nitrogen for protection, then add 0.4 mol of 2-bromo-5-acetylpyridine (97%; purchased from Shanghai Macklin Biochemical Co., Ltd.) and 82.5 g of the imidazole compound to reactor B with stirring. Heat reactor B to reflux, and keep heating and refluxing for 5 h. After completion, cool to room temperature, rotary evaporate to remove absolute ethanol, collect the product, and obtain the intermediate.

[0094] S3. Add 1 L of chloroform (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.) to Reactor C, charge with nitrogen for protection, then add 0.3 mol of [3-(trimethoxysilyl)propyl] succinic anhydride (95%; purchased from Sinopharm Chemical Reagent Co., Ltd.) and 45 g of the intermediate to Reactor C with stirring at room temperature for 2 h. Then add 40 g of Amberlyst-15 ion exchange resin (dry; purchased from Sinopharm Chemical Reagent Co., Ltd.) to Reactor C. After the addition, continue stirring for 2 h. After completion, heat Reactor C to 70 °C and stir at a constant temperature for 5 h. After completion, cool to room temperature, filter to remove the Amberlyst-15 ion exchange resin, then rotary evaporate to remove chloroform, collect the product, wash the product three times with absolute ethanol (AR; purchased from Sinopharm Chemical Reagent Co., Ltd.), and then dry it in a constant temperature drying oven at 50 °C for 30 min. After completion, an acid and alkali resistant aid is obtained.

[0095] Example 10

[0096] Preparation of acid and alkali resistant and explosion-proof ink:

[0097] First, the acid and alkali resistant and explosion-proof ink comprises the following raw materials in parts by mass:

[0098] 55 parts of the low melting point glass powder prepared in Example 1;

[0099] 22.5 parts of copper-chromium black agent;

[0100] 22.5 parts of the ink oil prepared in Example 4;

[0101] 8 parts of the acid and alkali resistant aid prepared in Example 7;

[0102] 0.5 part of leveling agent;

[0103] 0.5 part of defoaming agent.

[0104] Among them, the D 90 particle size of the copper-chromium black agent is 2.0 μm.

[0105] Among them, the leveling agent is leveling agent BYK-333.

[0106] Among them, the defoaming agent is defoaming agent BYK054.

[0107] Then, the preparation method of the acid and alkali resistant and explosion-proof ink comprises the following steps:

[0108] Weigh each raw material according to the parts by mass, add the low melting point glass powder prepared in Example 1 and the acid and alkali resistant aid prepared in Example 7 to the ink oil prepared in Example 4 with stirring at room temperature for 1 h, then add the leveling agent and the defoaming agent to it with stirring at room temperature for 10 min. After completion, grind it through an 800-mesh sieve to obtain the acid and alkali resistant and explosion-proof ink.

[0109] Example 11

[0110] Prepare acid and alkali resistant explosion-proof ink:

[0111] First, the acid and alkali resistant explosion-proof ink includes the following raw materials in parts by mass:

[0112] 60 parts of low melting point glass powder prepared in Example 2;

[0113] 20 parts of copper chromium blackening agent;

[0114] 20 parts of ink leveling agent prepared in Example 5;

[0115] 10 parts of acid and alkali resistant auxiliary agent prepared in Example 8;

[0116] 1 part of leveling agent;

[0117] 1 part of defoaming agent.

[0118] Among them, the D 90 particle size of the copper chromium blackening agent is 1.5 μm.

[0119] Among them, the leveling agent is leveling agent BYK-346.

[0120] Among them, the defoaming agent is defoaming agent BYK057.

[0121] Then, the preparation method of the acid and alkali resistant explosion-proof ink includes the following steps:

[0122] Weigh each raw material according to the parts by mass, stir and add the low melting point glass powder prepared in Example 2 and the acid and alkali resistant auxiliary agent prepared in Example 8 into the ink leveling agent prepared in Example 5, stir at room temperature for 2 h, then stir and add the leveling agent and the defoaming agent into it, stir at room temperature for 20 min, and after completion, grind through an 800-mesh sieve to obtain the acid and alkali resistant explosion-proof ink.

[0123] Example 12

[0124] Prepare acid and alkali resistant explosion-proof ink:

[0125] First, the acid and alkali resistant explosion-proof ink includes the following raw materials in parts by mass:

[0126] 65 parts of low melting point glass powder prepared in Example 3;

[0127] 17.5 parts of copper chromium blackening agent;

[0128] 17.5 parts of ink leveling agent prepared in Example 6;

[0129] 10 parts of acid and alkali resistant auxiliary agent prepared in Example 9;

[0130] 1 part of leveling agent;

[0131] 1 part of defoamer.

[0132] Among them, the D of the copper-chromium black agent 90 The particle size is 1.5 μm.

[0133] Among them, the leveling agent is leveling agent BYK-346.

[0134] Among them, the defoamer is BYK1794.

[0135] Then, a method for preparing acid and alkali resistant explosion-proof ink includes the following steps:

[0136] Weigh each raw material according to parts by mass, stir and add the low melting point glass powder prepared in Example 3 and the acid and alkali resistant auxiliary agent prepared in Example 9 to the ink oil prepared in Example 6, stir at room temperature for 2 h, then stir and add the leveling agent and defoamer thereto, stir at room temperature for 20 min. After completion, grind through an 800-mesh sieve to obtain the acid and alkali resistant explosion-proof ink.

[0137] Comparative Example 1

[0138] Comparative Example 1 is the control group of Example 11. Replace the acid and alkali resistant auxiliary agent prepared in Example 8 in Example 11 with the intermediate prepared in step S2 of Example 8, and keep the other raw materials, raw material dosages and preparation steps the same as those in Example 11, and finally obtain the explosion-proof ink.

[0139] Comparative Example 2

[0140] Comparative Example 2 is the control group of Example 11. Remove the acid and alkali resistant auxiliary agent prepared in Example 8 in Example 11, and keep the other raw materials, raw material dosages and preparation steps the same as those in Example 11, and finally obtain the explosion-proof ink.

[0141] Test Example 1

[0142] Perform performance tests on the acid and alkali resistant explosion-proof inks / explosion-proof inks prepared in Examples 10 to 12 and Comparative Examples 1 to 2. The performance test process is as follows, and the test results are shown in Table 1:

[0143] Preparation of ink samples: Screen print (250 mesh, pore diameter 57 μm) the acid and alkali resistant explosion-proof inks / explosion-proof inks prepared in Examples 10 to 12 and Comparative Examples 1 to 2 on both sides of a glass substrate (40 mm × 40 mm × 5 mm), control the ink layer thickness to 20 μm, and place the glass substrate printed with the ink layer in a furnace at 720 °C for heat treatment for 200 s. After completion, cool to room temperature to obtain the ink samples.

[0144] Adhesion: The adhesion grade test was carried out according to the method specified in the national standard ISO 2409 "Paints and varnishes - Cross - cut test". Specifically, a cross - cut knife (type 5152, purchased from BYK Company, Germany) was used to test the ink layer on the surface of the ink sample. The blade scratched the ink layer of the ink sample vertically at 90°, forming a cross - cut grid. Then, tape was quickly adhered and peeled off to observe the peeling of the ink layer. The adhesion grade decreases from grade 0 to grade 5 in sequence. When the grade is 0, no peeling occurs on the surface of the ink layer.

[0145] Explosion - proof performance: The maximum impact height of the ink sample was determined according to the test method specified in the national standard GB / T 39814 - 2021 "Test method for impact strength of ultra - thin glass - Drop - ball impact method". At the same time, the damage state of the ink sample at the maximum impact height was recorded in Table 1 below. Among them, the steel ball used complies with the provisions of GB / T 308.1, the mass of the steel ball is 32 g, and the diameter is 19.844 mm.

[0146] Acid - resistance: The mass of the ink sample was accurately weighed and denoted as W0. Then the ink sample was immersed in a 0.05 mol / L H2SO4 solution at 80 °C for 72 h. After immersion, it was taken out, cooled to room temperature, the liquid on the surface of the ink sample was wiped with absorbent paper, and then dried to obtain the acid - soaked ink sample. Prepare to weigh the mass of the acid - soaked ink sample and denote it as W1. Then, the acid - resistance mass loss rate (g / cm 2 ) was calculated by the following formula (1):

[0147] Acid - resistance mass loss rate=(W0 - W1) / S (1);

[0148] In formula (1), S is the surface area of the ink layer in the ink sample, with the unit of cm 2 ;

[0149] Alkali - resistance: The mass of the ink sample was accurately weighed and denoted as W0. Then the ink sample was immersed in a 0.05 mol / L NaOH solution at 80 °C for 80 h. After immersion, it was taken out, cooled to room temperature, the liquid on the surface of the ink sample was wiped with absorbent paper, and then dried to obtain the alkali - soaked ink sample. Prepare to weigh the mass of the alkali - soaked ink sample and denote it as W1. Then, the alkali - resistance mass loss rate (g / cm 2 ) was calculated by the following formula (2):

[0150] Alkali - resistance mass loss rate=(W0 - W1) / S (2);

[0151] In formula (2), S is the surface area of the ink layer in the ink sample, with the unit of cm 2 .

[0152] Table 1 Performance test results

[0153]

[0154] As can be seen from Table 1, adding the acid- and alkali-resistant auxiliary agent prepared by the present invention can significantly improve the acid- and alkali-resistant performance of the prepared explosion-proof ink.

[0155] It should be noted that in this text, terms such as "including", "comprising" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or further includes elements inherent to such a process, method, article or device.

[0156] 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 principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An acid and alkali resistant explosion-proof ink, characterized in that, It includes the following raw materials in parts by mass: Low melting point glass powder: 55 - 65 parts; Copper chromite black agent: 17.5 - 22.5 parts; Ink oil: 17.5 - 22.5 parts; Acid and alkali resistant auxiliary agent: 8 - 10 parts; Leveling agent: 0.5 - 1 part; Defoaming agent: 0.5 - 1 part; The acid and alkali resistant auxiliary agent is prepared by the following steps: S1. Add diethylenetriamine to p-hydroxybenzoic acid, evacuate, then raise the temperature to 145 - 155 °C, stir and react at a constant temperature for 2 - 3 h, continuously evacuate during the reaction. After completion, raise the temperature of the system to 220 - 225 °C, stir and react at a constant temperature for 4 - 5 h, continuously evacuate during the reaction. After completion, cool to room temperature, collect the product, and after washing and drying the product, an imidazole compound is obtained; S2. Take absolute ethanol, fill it with nitrogen, add 2-bromo-5-acetylpyridine and the imidazole compound to it, raise the temperature until reflux occurs, and keep heating and refluxing for 4 - 5 h. After completion, cool to room temperature, rotary evaporate to remove absolute ethanol, collect the product, and an intermediate is obtained; S3. Take chloroform, fill it with nitrogen, then add [3-(trimethoxysilyl)propyl] succinic anhydride and the intermediate to it, stir at room temperature for 1 - 2 h, then add Amberlyst-15 ion exchange resin. After adding, continue to stir for 1 - 2 h. After completion, raise the temperature to 65 - 70 °C, stir and react at a constant temperature for 4 - 5 h. After completion, cool to room temperature, filter to remove Amberlyst-15 ion exchange resin, then rotary evaporate to remove chloroform, collect the product, and after washing and drying the product, the acid and alkali resistant auxiliary agent is obtained; The low melting point glass powder includes the following raw materials in parts by mass: Bismuth oxide: 45 - 55 parts, boric acid: 20 - 25 parts, silicon dioxide: 12 - 15 parts, alumina: 7 - 8 parts, zirconia: 5.5 - 7.5 parts, tin dioxide: 4.5 - 5.5 parts, titanium dioxide: 3 - 5 parts, lithium carbonate: 2 - 5 parts, sodium carbonate: 2 - 5 parts.

2. The acid and alkali resistant explosion-proof ink according to claim 1, characterized in that In S1, the dosage ratio of p-hydroxybenzoic acid to diethylenetriamine is 1 mol: 1.0 - 1.2 mol; in S2, the dosage ratio of absolute ethanol, 2-bromo-5-acetylpyridine, and the imidazole compound is 1 L: 0.4 mol: 82.1 - 82.5 g; in S3, the dosage ratio of chloroform, [3-(trimethoxysilyl)propyl] succinic anhydride, the intermediate, and Amberlyst-15 ion exchange resin is 1 L: 0.3 mol: 44 - 45 g: 30 - 40 g.

3. The acid and alkali resistant explosion-proof ink according to claim 1, characterized in that, The low melting point glass powder is prepared by the following steps: Weigh each raw material according to the parts by mass. Mix bismuth oxide, silicon dioxide, boric acid, alumina, zirconia, tin dioxide, titanium dioxide, lithium carbonate, and sodium carbonate, and place them in a muffle furnace. Heat from room temperature to 1120 °C - 1150 °C at a heating rate of 15 - 20 °C / min, then calcine at a constant temperature for 1 - 2 h. After calcination, naturally cool to room temperature to obtain a glassy mixture. Crush the glassy mixture and pass it through a 500-mesh sieve to obtain the low melting point glass powder.

4. The acid- and alkali-resistant explosion-proof ink according to claim 1, characterized in that, The D of the copper-chromium black agent 90 has a particle size of 1.5 to 2.0 μm.

5. The acid- and alkali-resistant explosion-proof ink according to claim 1, characterized in that, The ink oil includes the following raw materials in parts by mass: Acrylic resin: 8 - 10 parts, solvent: 100 parts, dispersant HLN-1708: 1 - 1.2 parts.

6. The acid and alkali resistant explosion-proof ink according to claim 5, characterized in that, The solvent is prepared by mixing diethylene glycol butyl ether and glycerol in a volume ratio of 8-10:

1.

7. An acid and alkali resistant and explosion-proof ink according to claim 5, characterized in that, The ink oil is prepared by the following steps: Weigh each raw material by mass, stir and add acrylic resin and dispersant HLN-1708 into the solvent. After the addition, heat the system to 50-55 °C, continue to stir at a constant temperature until the acrylic resin is completely dissolved, and then cool it naturally to room temperature to obtain the ink oil.

8. A kind of acid and alkali resistant explosion-proof ink according to claim 1, characterized in that, The leveling agent is one of leveling agent BYK-333 and leveling agent BYK-346; the defoaming agent is one of defoaming agent BYK054, defoaming agent BYK057 and defoaming agent BYK1794.

9. The preparation method of an acid and alkali resistant explosion-proof ink according to any one of claims 1 to 8, characterized in that, It includes the following steps: Weigh each raw material by mass, stir and add low-melting glass powder and acid and alkali resistant additives into the ink oil, stir at room temperature for 1-2 h, then stir and add the leveling agent and defoaming agent into it, stir at room temperature for 10-20 min. After that, grind it through an 800-mesh sieve to obtain the acid and alkali resistant explosion-proof ink.

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