Inorganic resin coating, preparation process and application in electrogalvanized steel sheet

Abstract

The present application relates to the field of galvanized layer surface corrosion protection technology, especially inorganic resin paint, preparation process and application in electro-galvanized steel sheet. An inorganic resin paint comprises A component and B component, the mass ratio of the A component to the B component is 100:(10-40); the A component is mainly made of epoxy silane, methyl trimethoxysilane, phenyl triethoxysilane, C1-2 alcohol, deionized water and pH value regulator; the mass ratio of the C1-2 alcohol to the deionized water is (70-80):(20-30); the sum of the mass of the C1-2 alcohol and the deionized water accounts for 80-96wt% of the A component; the B component is titanium silicon compound sol, and the titanium silicon compound sol is mainly a hydrolytic copolymer formed by titanium ester and silicate. The inorganic coating formed by the present application has good compactness and strong film adhesion, and can have excellent corrosion protection and enhancement effect.

Description

Technical Field

[0001] This invention relates to the field of corrosion protection technology for galvanized coating surfaces, and in particular to inorganic resin coatings, their preparation process, and their application in electro-galvanized steel sheets. Background Technology

[0002] Metal corrosion can lead to economic losses, safety hazards, environmental pollution, and resource waste. Therefore, metal surface corrosion technology has become one of the main means of addressing the hazards of metal corrosion. Galvanizing, as a surface corrosion protection technology for steel, can improve the corrosion resistance of steel. Galvanized steel is commonly used in environments requiring protection against corrosion and rust, such as construction, automobile manufacturing, and other industrial sectors.

[0003] Galvanizing for corrosion protection is divided into hot-dip galvanizing and electro-galvanizing. Electro-galvanizing is simple to operate and has a high zinc utilization rate, with a zinc layer thickness of 5–15 μm. Hot-dip galvanizing, on the other hand, produces a zinc layer thickness ≥30 μm, resulting in a denser and more effective coating. Hot-dip galvanizing offers superior corrosion protection compared to electro-galvanizing, but it consumes a significant amount of zinc. Research on the corrosion resistance mechanism of galvanized steel reveals that under normal atmospheric corrosion conditions, the protective film on the galvanized surface mainly consists of zinc oxide, zinc hydroxide, and basic zinc carbonate, which slows down the corrosion of the underlying zinc layer. When this protective film is damaged, a new one is formed. However, galvanized steel cannot be used in environments requiring high corrosion resistance, such as prolonged exposure to high temperature and humidity or immersion in seawater.

[0004] To further improve the corrosion resistance of galvanized steel, existing technologies involve chromate passivation. However, chromate passivation generates a large amount of industrial waste that harms the environment, resulting in poor environmental performance. It has gradually been replaced by inorganic protective film technology that forms a three-dimensional -Si-OM cross-linked structure through the dehydration condensation reaction of organosilanes.

[0005] Existing technologies use KH-560 silane as the main film-forming substance to form an inorganic physical shielding layer on the surface of galvanized steel to improve its corrosion resistance. However, the density deviation of a single silane film affects its corrosion resistance and can no longer adequately meet the high corrosion resistance requirements of galvanized steel. Summary of the Invention

[0006] To address the issue that the density deviation of a single silane film results in the inorganic coating's inability to adequately meet the high corrosion resistance requirements of galvanized steel, this invention provides an inorganic resin coating, its preparation process, and its application in electro-galvanized steel sheets.

[0007] The inorganic resin coating provided by this invention is achieved through the following technical solution:

[0008] An inorganic resin coating, comprising component A and component B, wherein the mass ratio of component A to component B is 100:(10-40);

[0009] Component A is mainly composed of epoxy silane, crosslinking agent, C1-2 alcohol, deionized water, and pH adjuster; the crosslinking agent includes at least one of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltriethoxysilane, methylphenyldiethoxysilane, and phenyldiethoxysilane.

[0010] The C1-2 alcohol is either methanol or ethanol;

[0011] The pH adjuster is acetic acid or propionic acid;

[0012] The mass ratio of the C1-2 alcohol to the deionized water is (70-80):(20-30);

[0013] The combined mass of the C1-2 alcohol and the deionized water accounts for 80-96 wt% of component A.

[0014] The mass ratio of the epoxy silane, the methyltrimethoxysilane, and the phenyltriethoxysilane is (4-8:(0.5-2):(0.5-2);

[0015] Component B is a titanium-silicon compound sol, which is mainly a hydrolytic copolymer formed by titanate and silicate ester.

[0016] The inorganic coating formed by this invention has good density and strong film adhesion, which can play an excellent anti-corrosion and enhancement effect, so that the galvanized steel treated with inorganic resin coating has excellent corrosion resistance.

[0017] Preferably, the titanate is at least one of tetraethyl titanate, tetrabutyl titanate, and tetraisopropylbutyl titanate; and the silicate is at least one of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate.

[0018] Preferably, the epoxy silane is at least one selected from 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidylpropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0019] Preferably, component A further includes methacryloxysilane and mercaptosilane, wherein the molar ratio of the propylene double bond group in the methacryloxysilane to the mercapto group in the mercaptosilane is 1:(1-1.2); and the total mass of the methacryloxysilane and mercaptosilane accounts for 0.2-2 wt% of the total mass of component A.

[0020] Preferably, the methacryloyloxysilane is at least one of 3-(methacryloyloxy)propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-trimethoxysilane propylene acrylate, and 3-acryloyloxypropylmethyldimethoxysilane.

[0021] Preferably, the mercaptosilane is at least one of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

[0022] Preferably, component A further includes a water-soluble photoinitiator, wherein the water-soluble photoinitiator is at least one of photoinitiator 2959, photoinitiator 8700, and photoinitiator 6992.

[0023] Under the action of a water-soluble photoinitiator, the propylene double bond group in methacryloyloxysilane undergoes a free radical polymerization reaction with the mercapto group in mercaptosilane, further improving the density of the inorganic protective film, thereby improving the corrosion resistance and wear resistance of galvanized steel after inorganic resin coating treatment.

[0024] Preferably, it further includes component C, wherein the mass ratio of component C to components A and B is (1-10):100:(10-40); component C comprises a water-soluble metal salt, surface carboxylated modified nano-inorganic filler, and deionized water, wherein the surface carboxylated modified nano-inorganic filler is one or more combinations of carboxylated modified graphene, carboxylated modified carbon nanotubes, carboxylated modified halloysite nanotubes, carboxylated modified boron nitride nanosheets, and carboxylated modified molybdenum disulfide nanosheets.

[0025] Preferably, the cation in the water-soluble metal salt is the metal ion Me. n+ Me n+ Specifically Ag + Cu + Cu 2+ Fe 3 + Fe 2+ Zn + Co 2+ Any one of the following; the anion in the water-soluble metal salt is nitrate or sulfate.

[0026] Metal particles Me released from water-soluble metal salts n+ Esterification and crosslinking with hydroxyl-OH and carboxyl-COOH groups firmly embeds the surface-carboxylated modified nano-inorganic fillers into the formed inorganic protective film matrix, endowing the formed inorganic protective film with good barrier properties, wear resistance, corrosion resistance, weather resistance and hygiene safety.

[0027] The method for preparing inorganic resin coatings provided by this invention is achieved through the following technical solution:

[0028] The preparation method of inorganic resin coatings includes the following steps:

[0029] Preparation of component A: Mix epoxy silane, methacryloxy silane, mercaptosilane, crosslinking agent, C1-2 alcohol, and deionized water evenly, then add pH adjuster to adjust the pH of the system to 3-4, and hydrolyze at 30-50℃ for 4-24h to obtain component A;

[0030] Preparation of component B: After mixing ethanol, deionized water, titanate, and silicate evenly, hydrolyze for 0.5-2 hours to form a hydrolytic copolymer to obtain component B;

[0031] Preparation of component C: Water-soluble metal salt, surface carboxylated modified nano-inorganic filler, and deionized water are mixed evenly to form component C;

[0032] Mix components A, B, and C at a mass ratio of 100:(10-40):(1-10) to obtain an inorganic resin coating. When using, add a water-soluble photoinitiator to the inorganic resin coating and mix thoroughly. The curing conditions for the inorganic resin coating are: under ultraviolet light irradiation, cure at 80-120℃ for 30-60 minutes.

[0033] The inorganic resin coating is applied to the surface of electro-galvanized steel sheets for corrosion protection, which can improve the antibacterial safety performance, wear resistance and corrosion resistance of electro-galvanized steel sheets.

[0034] In summary, the present invention has the following advantages:

[0035] 1. The inorganic coating formed by the present invention has the advantages of good density and excellent film adhesion, which can play a good barrier role and improve the overall anti-corrosion effect. This makes the galvanized steel treated with inorganic resin coating have excellent corrosion resistance and wear resistance, and better meet the high corrosion resistance requirements of galvanized steel.

[0036] 2. The preparation method of the inorganic resin coating in this invention is relatively simple and easy to realize industrial production.

[0037] 3. In this invention, the inorganic resin coating is cured with ultraviolet light, which allows the propylene double bond groups contained in the methacryloyloxysilane and the mercapto groups contained in the mercaptosilane to undergo free radical polymerization under the action of a water-soluble photoinitiator, further improving the density of the inorganic protective film, thereby improving the corrosion resistance and wear resistance of the galvanized steel treated with the inorganic resin coating. Detailed Implementation

[0038] To further understand the inventiveness and technical advancements of this invention, the preferred embodiments of this invention will be discussed in detail below with reference to examples and comparative examples.

[0039] Example: An inorganic resin coating is composed of component A and component B in a mass ratio of 100:(10-40).

[0040] Component A is made of epoxy silane, crosslinking agent, C1-2 alcohol, deionized water, and pH adjuster.

[0041] The crosslinking agent includes at least one of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltriethoxysilane, methylphenyldiethoxysilane, and phenyldiethoxysilane.

[0042] The epoxy silane is at least one of 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidylpropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0043] The C1-2 alcohol is either methanol or ethanol. The pH adjuster is acetic acid or propionic acid.

[0044] The mass ratio of C1-2 alcohol to the deionized water is (70-80):(20-30).

[0045] The combined mass of C1-2 alcohol and the deionized water accounts for 80-96 wt% of component A.

[0046] The mass ratio of epoxy silane to crosslinking agent is (4-8):(1-2).

[0047] Component B is a titanium silicate compound sol. The titanium silicate compound sol is mainly a hydrolytic copolymer formed from titanate and silicate esters. The titanate ester is at least one of tetraethyl titanate, tetrabutyl titanate, and tetraisopropylbutyl titanate. The silicate ester is at least one of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate.

[0048] A method for preparing an inorganic resin coating includes the following steps:

[0049] Preparation of component A: Mix epoxy silane, methacryloxy silane, mercaptosilane, crosslinking agent, C1-2 alcohol, and deionized water evenly, then add pH adjuster to adjust the pH of the system to 3-4, and hydrolyze at 30-50℃ for 4-24h to obtain component A;

[0050] Preparation of component B: After mixing ethanol, deionized water, titanate, and silicate evenly, hydrolyze for 0.5-2 hours to form a hydrolytic copolymer to obtain component B;

[0051] Component A and component B are mixed evenly at a mass ratio of 100:(10-40) to obtain an inorganic resin coating.

[0052] Curing conditions for inorganic resin coatings: Curing at 80-120℃ for 60-120 minutes.

[0053] Preferably, component A is composed of epoxy silane, crosslinking agent, C1-2 alcohol, deionized water, pH adjuster, methacryloxysilane, mercapto-containing silane, and water-soluble photoinitiator. The molar ratio of the propylene double bond group in the methacryloxysilane to the mercapto group in the mercapto-containing silane is 1:(1-1.2). The total mass of the methacryloxysilane and the mercapto-containing silane accounts for 0.2-2 wt% of the total mass of component A.

[0054] Methacryloxysilane is at least one of 3-(methacryloyloxy)propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-trimethoxysilane propylene acrylate, and 3-acryloyloxypropylmethyldimethoxysilane.

[0055] The mercaptosilane is at least one of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

[0056] The water-soluble photoinitiator is at least one of photoinitiator 2959, photoinitiator 8700, and photoinitiator 6992.

[0057] Preferably, a method for preparing an inorganic resin coating includes the following steps:

[0058] Preparation of component A: Mix epoxy silane, methacryloxy silane, mercaptosilane, crosslinking agent, C1-2 alcohol, and deionized water evenly, then add pH adjuster to adjust the pH of the system to 3-4, and hydrolyze at 30-50℃ for 4-24h to obtain component A;

[0059] Preparation of component B: After mixing ethanol, deionized water, titanate, and silicate evenly, hydrolyze for 0.5-2 hours to form a hydrolytic copolymer to obtain component B;

[0060] Mix components A and B at a mass ratio of 100:(10-40) to obtain an inorganic resin coating. When using, add a water-soluble photoinitiator to the inorganic resin coating and mix thoroughly. The curing conditions for the inorganic resin coating are: under ultraviolet light irradiation, cure at 80-120℃ for 30-60 minutes.

[0061] An inorganic resin coating is composed of component A, component B, and component C in a mass ratio of 100:(10-40):(1-10). Component A is made of epoxy silane, crosslinking agent, C1-2 alcohol, deionized water, pH adjuster, methacryloyloxysilane, mercapto-containing silane, and water-soluble photoinitiator.

[0062] Component C consists of water-soluble metal salts, surface-carboxylated modified nano-inorganic fillers, and deionized water.

[0063] The surface carboxylation modified nano-inorganic filler is one or more combinations of carboxylation modified graphene, carboxylation modified carbon nanotubes, carboxylation modified halloysite nanotubes, carboxylation modified boron nitride nanosheets, and carboxylation modified molybdenum disulfide nanosheets.

[0064] The cation in water-soluble metal salts is the metal ion Me. n+ Me n+ For Ag + Cu + Cu 2+ Fe 3+ Fe 2+ Zn + Co 2+ Any one of them. The anion in water-soluble metal salts is nitrate or sulfate.

[0065] A method for preparing an inorganic resin coating includes the following steps:

[0066] Preparation of component A: Mix epoxy silane, methacryloxy silane, mercaptosilane, crosslinking agent, C1-2 alcohol, and deionized water evenly, then add pH adjuster to adjust the pH of the system to 3-4, and hydrolyze at 30-50℃ for 4-24h to obtain component A;

[0067] Preparation of component B: After mixing ethanol, deionized water, titanate, and silicate evenly, hydrolyze for 0.5-2 hours to form a hydrolytic copolymer to obtain component B;

[0068] Preparation of component C: Water-soluble metal salt, surface carboxylated modified nano-inorganic filler, and deionized water are mixed evenly to form component C;

[0069] Mix components A, B, and C at a mass ratio of 100:(10-40):(1-10) to obtain an inorganic resin coating. When using, add a water-soluble photoinitiator to the inorganic resin coating and mix thoroughly. The curing conditions for the inorganic resin coating are: under ultraviolet light irradiation, cure at 80-120℃ for 30-60 minutes.

[0070] Example 1: An inorganic resin coating is composed of component A and component B in a mass ratio of 100:10.

[0071] Component A consists of 3-glycidyl etheroxypropyltrimethoxysilane KH560 (CAS: 2530-83-8), methyltrimethoxysilane MTMS (CAS: 1185-55-3), phenyltriethoxysilane PTES (CAS: 2996-92-1), ethanol (CAS: 64-17-5), glacial acetic acid, and deionized water.

[0072] The volume ratio of deionized water to ethanol is 1:4.

[0073] The total mass ratio of deionized water and ethanol to the total mass ratio of 3-glycidyl etheroxypropyltrimethoxysilane KH560, phenyltriethoxysilane PTES, and methyltrimethoxysilane MTMS is 19:1.

[0074] Component B is a hydrolytic copolymer formed from tetrabutyl titanate (CAS: 5593-70-4), ethyl silicate (CAS: 11099-06-2), and an aqueous solution of ethanol (the volume ratio of deionized water to ethanol is 1:4).

[0075] A method for preparing an inorganic resin coating includes the following steps:

[0076] The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution, 4 parts by weight of 3-glycidyl ether oxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, and 0.5 parts by weight of methyltrimethoxysilane MTMS and pour them into a reaction vessel. Stir magnetically at 240 r / min for 5 min. Add glacial acetic acid to adjust the pH value to 3.5. Heat to 40℃ and maintain at 40℃ for 12 h to hydrolyze to obtain component A.

[0077] The preparation method of component B is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. 96 parts by weight of the ethanol aqueous solution, 2 parts by weight of tetrabutyl titanate and 2 parts by weight of ethyl silicate are poured into a reaction vessel and magnetically stirred at 240 r / min for 5 min. Glacial acetic acid is added to adjust the pH value to 3.0. Hydrolysis is carried out at room temperature for 2.0 h to obtain component B-titanium silicon compound sol.

[0078] Component A and component B are added to the reactor at a mass ratio of 100:10 and magnetically stirred at 240 r / min for 5 min. After mixing evenly, the inorganic resin coating can be obtained.

[0079] Instructions for using inorganic resin coatings: Immerse the galvanized steel sheet for 45 seconds, then cure at 120°C for 30 minutes.

[0080] Specifically, the galvanized steel sheet is sanded with sandpaper of 500#, 800#, 1000#, and 1500# specifications, ultrasonically cleaned in acetone solution for 5 minutes, then rinsed with deionized water to remove residual solution, and then alkaline washed with hyaluronic acid aqueous solution. After immersing in 2.0wt% hyaluronic acid aqueous solution for 300 seconds, the substrate is removed, rinsed, and dried. The pre-treated galvanized steel sheet is then immersed in inorganic resin coating for 45 seconds and placed in an oven at 120℃ for 30 minutes to cure, thus forming an inorganic protective film on the surface of the galvanized steel sheet.

[0081] The difference between Example 2 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:20.

[0082] The difference between Example 3 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:30.

[0083] The difference between Example 4 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:40.

[0084] The difference between Comparative Example 1 and Example 1 is that the inorganic resin coating is component A.

[0085] The difference between Comparative Example 2 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:5.

[0086] The difference between Comparative Example 3 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:45.

[0087] Performance Testing: 1. The bonding performance of the inorganic protective film layer was determined according to GB / T 9286-2021 "Cross-cut test of paint and varnish film". 2. The contact angle was measured using an FCA2000L6 contact angle meter. During the test, the droplet was pressed down to two graduations, allowing it to contact the sample surface and remain stationary for 5 seconds. Five different measurement points were selected for each sample, and the average value was taken as the contact angle of the sample. 3. The corrosion resistance performance was determined using a CHI660E electrochemical workstation to perform electrochemical tests on galvanized steel sheets and inorganic protective films. The electrochemical workstation was a three-electrode system, with the working electrode being the test sample, the auxiliary electrode being a platinum electrode, and the reference electrode being a saturated calomel electrode (SCE). The experiment was conducted at room temperature, using a 3.5% NaCl solution as the test solution. Only a 1 cm² area of ​​the substrate was left during the test. 2The test surface is insulated by encapsulating the remaining parts with 704 silicone. The working electrode is immersed in the solution for a period of time until the open-circuit potential stabilizes, then the polarization curve is obtained. The electrochemical test scan range is -0.8 V to -0.1 V, and the scan rate is 0.001 V / s. The corrosion potential / V and corrosion inhibition efficiency (%) are recorded. The higher the corrosion potential, the more difficult the metal is to corrode. The magnitude of the corrosion potential reflects the ease with which the metal corrodes. 4. Neutral Salt Spray Test: The neutral salt spray test is conducted according to GB / T 10125-2012 "Artificial Atmosphere Corrosion Test - Salt Spray Test". To eliminate subjective visual errors and better judge the corrosion degree of each sample in the 5% NaCl neutral salt spray test, the mass change of the sample before and after corrosion is calculated using the weight loss method. Corrosion products are removed according to the standard specified in ISO 8407. Corrosion rate V1 = (M0 - M1) / ST, where V1 is the corrosion rate, g / m³. 2 •h; M0 is the mass of the sample before salt spray corrosion (g); M1 is the mass of the sample after salt spray corrosion (g); S is the sample area exposed to salt spray environment (m²). 2 T represents the test time in hours. The sample size was φ2cm × 0.5cm, and the corrosion time was 24 hours.

[0088] Table 1: Test parameters of inorganic protective films in Examples 1-4 and Comparative Examples 1-3

[0089] Adhesion rating / level Contact angle ° Corrosion potential / V Corrosion inhibition efficiency / % <![CDATA[Corrosion rate g / m 2 ·h]]> Example 1 2 81.4 -0.459 95.15 1.285 Example 2 2 81.9 -0.452 96.89 1.223 Example 3 2 82.3 -0.448 97.61 1.197 Example 4 3 81.5 -0.454 96.27 1.232 Comparative Example 1 2 80.7 -0.465 92.43 1.368 Comparative Example 2 2 80.9 -0.462 93.89 1.341 Comparative Example 3 3 81.6 -0.456 95.73 1.375

[0090] Based on Examples 1-4 and Comparative Examples 1-3, and referring to Table 1, it can be seen that the inorganic composite protective film formed by silane + titanium silane exhibits relatively good corrosion resistance, with a corrosion inhibition efficiency ≥95%. It should be noted that the amounts of components A and B need to be adjusted. The mass ratio of components A to B should ideally be 100:(10-40). Insufficient addition of component B will not significantly improve corrosion resistance, while excessive addition will affect the bonding strength and density of the coating, leading to a decrease in adhesion and corrosion inhibition efficiency.

[0091] The difference between Example 5 and Example 1 is that the inorganic resin coating is composed of component A and component B in a mass ratio of 100:20.

[0092] Component A consists of 3-glycidyl etheroxypropyltrimethoxysilane KH560, methyltrimethoxysilane MTMS, phenyltriethoxysilane PTES, γ-mercaptopropyltriethoxysilane (CAS: 14814-09-6), 3-(methacryloyloxy)propyltrimethoxysilane (CAS: 2530-85-0), ethanol, glacial acetic acid, deionized water, and photoinitiator 2959.

[0093] A method for preparing an inorganic resin coating includes the following steps:

[0094] The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution and 3.4 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, 0.5 parts by weight of methyltrimethoxysilane MTMS, 0.29 parts by weight of γ-mercaptopropyltriethoxysilane KH590, and 0.31 parts by weight of 3-(methacryloyloxy)propyltrimethoxysilane KH570 into a reaction vessel, stir magnetically at 240 r / min for 5 min, add glacial acetic acid to adjust the pH value to 4.0, heat to 40℃, and maintain at 40℃ for 16 h to hydrolyze to obtain component A.

[0095] The preparation method of component B is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. 96 parts by weight of the ethanol aqueous solution, 2 parts by weight of tetrabutyl titanate and 2 parts by weight of ethyl silicate are poured into a reaction vessel and magnetically stirred at 240 r / min for 5 min. Glacial acetic acid is added to adjust the pH value to 3.0. Hydrolysis is carried out at room temperature for 2.0 h to obtain component B-titanium silicon compound sol.

[0096] Add components A and B to the reactor at a mass ratio of 100:20 and stir magnetically at 240 r / min for 5 min. When using, add 0.1 parts of photoinitiator 2959, stir magnetically at 240 r / min for 5 min under light-protected conditions, and the inorganic resin coating can be obtained after mixing evenly.

[0097] Instructions for using inorganic resin coatings: Immerse the galvanized steel sheet for 45 seconds, then cure at 120℃ for 20 minutes, followed by ultraviolet irradiation with an energy of 1000 mJ / cm². 2 Cured by irradiation for 30 seconds, and finally cured at 120°C for 10 minutes.

[0098] Specifically, the galvanized steel sheet is sanded with 500#, 800#, 1000#, and 1500# sandpaper, ultrasonically cleaned in acetone solution for 5 minutes, then rinsed with deionized water to remove residual solution, and then alkaline washed with hyaluronic acid aqueous solution. After immersion in 2.0wt% hyaluronic acid aqueous solution for 300 seconds, the substrate is removed, rinsed, and dried. The pre-treated galvanized steel sheet is then immersed in inorganic resin coating for 45 seconds, placed in an oven, cured at 120℃ for 20 minutes, and then cured with an ultraviolet curing lamp with an ultraviolet light energy of 1000mJ / cm². 2 After irradiation for 30 seconds and curing at 120°C for 10 minutes, an inorganic protective film can be formed on the surface of the galvanized steel sheet.

[0099] The difference between Example 6 and Example 5 is as follows: The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution and 3 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, 0.5 parts by weight of methyltrimethoxysilane MTMS, 0.49 parts by weight of γ-mercaptopropyltriethoxysilane KH590, and 0.51 parts by weight of 3-(methacryloyloxy)propyltrimethoxysilane KH570 into a reaction vessel, stir magnetically at 240 r / min for 5 min, add glacial acetic acid to adjust the pH value to 4.0, heat to 40°C, and maintain at 40°C for 16 h to hydrolyze to obtain component A;

[0100] The difference between Example 7 and Example 5 is as follows: The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution and 2.8 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, 0.5 parts by weight of methyltrimethoxysilane MTMS, 0.58 parts by weight of γ-mercaptopropyltriethoxysilane KH590, and 0.62 parts by weight of 3-(methacryloyloxy)propyltrimethoxysilane KH570 into a reaction vessel, stir magnetically at 240 r / min for 5 min, add glacial acetic acid to adjust the pH value to 4.0, heat to 40°C, and maintain at 40°C for 16 h to hydrolyze to obtain component A.

[0101] Table 2: Test parameters of the inorganic protective film in Examples 2 and 5-7

[0102] Adhesion rating / level Contact angle ° Corrosion potential / V Corrosion inhibition efficiency / % <![CDATA[Corrosion rate g / m 2 ·h]]> Example 2 2 81.9 -0.452 96.89 1.223 Example 5 2 77.8 -0.448 97.95 1.168 Example 6 1 72.4 -0.445 99.08 1.105 Example 7 1 68.2 -0.444 99.21 1.092

[0103] Combining Examples 1 and 5-7 with Table 2, it can be seen that the introduction of methacryloxysilane and mercaptosilane into component A leads to an increase in the adhesion and corrosion resistance of the formed inorganic protective film as the content of these two compounds increases. The adhesion level improves from Grade 2 to Grade 1, the corrosion inhibition efficiency increases from 96.89% to 99.21%, and the corrosion rate decreases from 1.223 g / m³. 2 • h increased to 1.092 g / m 2 The contact angle decreased from 81.9° to 65.2°.

[0104] The difference between Example 8 and Example 2 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:1.

[0105] Component C consists of deionized water, copper sulfate, and carboxylated modified graphene.

[0106] The carboxylated modified graphene is TimesGraph carboxylated graphene TNRGOC from Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences.

[0107] A method for preparing an inorganic resin coating includes the following steps:

[0108] The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution, 4 parts by weight of 3-glycidyl ether oxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, and 0.5 parts by weight of methyltrimethoxysilane MTMS and pour them into a reaction vessel. Stir magnetically at 240 r / min for 5 min. Add glacial acetic acid to adjust the pH value to 3.5. Heat to 40℃ and maintain at 40℃ for 12 h to hydrolyze to obtain component A.

[0109] The preparation method of component B is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. 96 parts by weight of the ethanol aqueous solution, 2 parts by weight of tetrabutyl titanate and 2 parts by weight of ethyl silicate are poured into a reaction vessel and magnetically stirred at 240 r / min for 5 min. Glacial acetic acid is added to adjust the pH value to 3.0. Hydrolysis is carried out at room temperature for 2.0 h to obtain component B-titanium silicon compound sol.

[0110] The preparation method of component C is as follows: 100 parts by weight of deionized water are poured into a reaction vessel, 5 parts by weight of anhydrous copper sulfate are added, and the mixture is magnetically stirred at 240 r / min for 5 min. After the anhydrous copper sulfate is fully dissolved, 1 part by weight of carboxylated modified graphene is added, and the mixture is magnetically stirred at 240 r / min for 5 min. Ultrasonic dispersion is then started with an ultrasonic frequency of 44 kHz and an ultrasonic power of 1200 W. The mixture is ultrasonically dispersed for 30 min to obtain component C.

[0111] Components A, B, and C are added to a reaction vessel in a mass ratio of 100:20:1 and magnetically stirred at 240 r / min for 5 min. After mixing evenly, the inorganic resin coating is obtained.

[0112] Instructions for using inorganic resin coatings: Immerse the galvanized steel sheet for 45 seconds, then cure at 120°C for 30 minutes.

[0113] Specifically, the galvanized steel sheet is sanded with sandpaper of 500#, 800#, 1000#, and 1500# specifications, ultrasonically cleaned in acetone solution for 5 minutes, then rinsed with deionized water to remove residual solution, and then alkaline washed with hyaluronic acid aqueous solution. After immersing in 2.0wt% hyaluronic acid aqueous solution for 300 seconds, the substrate is removed, rinsed, and dried. The pre-treated galvanized steel sheet is then immersed in inorganic resin coating for 45 seconds and placed in an oven at 120℃ for 30 minutes to cure, thus forming an inorganic protective film on the surface of the galvanized steel sheet.

[0114] The difference between Example 9 and Example 8 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:5.

[0115] The difference between Example 10 and Example 8 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:5.

[0116] The difference between Comparative Example 3 and Example 9 is that component C consists of deionized water, copper sulfate, and hydroxylated modified graphene. The hydroxylated modified graphene is TimesGraph hydroxylated graphene TNRGOH from Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences.

[0117] The preparation method of component C is as follows: 100 parts by weight of deionized water are poured into a reaction vessel, 5 parts by weight of anhydrous copper sulfate are added, and the mixture is magnetically stirred at 240 r / min for 5 min. After the anhydrous copper sulfate is fully dissolved, 1 part by weight of hydroxylated modified graphene is added, and the mixture is magnetically stirred at 240 r / min for 5 min. Ultrasonic dispersion is then started with an ultrasonic frequency of 44 kHz and an ultrasonic power of 1200 W. The mixture is ultrasonically dispersed for 30 min to obtain component C.

[0118] Table 3: Test parameters of the inorganic protective film in Examples 2, 8-10 and Comparative Example 3

[0119] Adhesion rating / level Contact angle ° Corrosion potential / V Corrosion inhibition efficiency / % <![CDATA[Corrosion rate g / m 2 ·h]]> Example 2 2 81.9 -0.452 96.89 1.223 Example 8 2 82.3 -0.449 97.82 1.172 Example 9 2 83.1 -0.446 98.89 1.117 Example 10 2 83.5 -0.445 99.11 1.101 Comparative Example 3 3 80.2 -0.450 98.04 1.159

[0120] Based on Examples 2, 8-10, and Comparative Example 3, and referring to Table 3, it can be seen that the addition of component C is beneficial to improving the corrosion resistance of the inorganic protective film. When the mass ratio of component C to component A is (5-10):100, the improvement in the corrosion resistance of the inorganic protective film is more significant. Replacing carboxylated modified graphite with hydroxylated modified graphene improves the corrosion resistance of the inorganic protective film, but the improvement is not as significant as that of carboxylated modified graphite, and it leads to a decrease in the adhesion of the inorganic protective film. Therefore, choosing carboxylated modified graphite can better improve the corrosion resistance and film bonding strength of the inorganic protective film.

[0121] The difference between Example 11 and Example 5 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:1.

[0122] Component A consists of 3-glycidyl etheroxypropyltrimethoxysilane KH560, methyltrimethoxysilane MTMS, phenyltriethoxysilane PTES, γ-mercaptopropyltriethoxysilane (CAS: 14814-09-6), 3-(methacryloyloxy)propyltrimethoxysilane (CAS: 2530-85-0), ethanol, glacial acetic acid, deionized water, and photoinitiator 2959.

[0123] Component C consists of deionized water, copper sulfate, and carboxylated modified graphene.

[0124] A method for preparing an inorganic resin coating includes the following steps:

[0125] The preparation method of component A is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. Take 95 parts by weight of the ethanol aqueous solution and 3 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane KH560, 0.5 parts by weight of phenyltriethoxysilane PTES, 0.5 parts by weight of methyltrimethoxysilane MTMS, 0.49 parts by weight of γ-mercaptopropyltriethoxysilane KH590, and 0.51 parts by weight of 3-(methacryloyloxy)propyltrimethoxysilane KH570 into a reaction vessel, stir magnetically at 240 r / min for 5 min, add glacial acetic acid to adjust the pH value to 4.0, heat to 40℃, and maintain at 40℃ for 16 h to hydrolyze to obtain component A.

[0126] The preparation method of component B is as follows: Deionized water and ethanol are mixed evenly at a volume ratio of 1:4 to obtain an ethanol aqueous solution. 96 parts by weight of the ethanol aqueous solution, 2 parts by weight of tetrabutyl titanate and 2 parts by weight of ethyl silicate are poured into a reaction vessel and magnetically stirred at 240 r / min for 5 min. Glacial acetic acid is added to adjust the pH value to 3.0. Hydrolysis is carried out at room temperature for 2.0 h to obtain component B-titanium silicon compound sol.

[0127] The preparation method of component C is as follows: 100 parts by weight of deionized water are poured into a reaction vessel, 5 parts by weight of anhydrous copper sulfate are added, and the mixture is magnetically stirred at 240 r / min for 5 min. After the anhydrous copper sulfate is fully dissolved, 1 part by weight of carboxylated modified graphene is added, and the mixture is magnetically stirred at 240 r / min for 5 min. Ultrasonic dispersion is then started with an ultrasonic frequency of 44 kHz and an ultrasonic power of 1200 W. The mixture is ultrasonically dispersed for 30 min to obtain component C.

[0128] Add components A, B, and C to a reaction vessel in a mass ratio of 100:20:1 and stir magnetically at 240 r / min for 5 min. When using, add 0.1 parts of photoinitiator 2959, stir magnetically at 240 r / min for 5 min under light-protected conditions, and the inorganic resin coating can be obtained after mixing evenly.

[0129] Instructions for using inorganic resin coatings: Immerse the galvanized steel sheet for 45 seconds, then cure at 120℃ for 20 minutes, followed by ultraviolet irradiation with an energy of 1000 mJ / cm². 2 Cured by irradiation for 30 seconds, and finally cured at 120°C for 10 minutes.

[0130] Specifically, the galvanized steel sheet is sanded with 500#, 800#, 1000#, and 1500# sandpaper, ultrasonically cleaned in acetone solution for 5 minutes, then rinsed with deionized water to remove residual solution, and then alkaline washed with hyaluronic acid aqueous solution. After immersion in 2.0wt% hyaluronic acid aqueous solution for 300 seconds, the substrate is removed, rinsed, and dried. The pre-treated galvanized steel sheet is then immersed in inorganic resin coating for 45 seconds, placed in an oven, cured at 120℃ for 20 minutes, and then cured with an ultraviolet curing lamp with an ultraviolet light energy of 1000mJ / cm². 2 After irradiation for 30 seconds and curing at 120°C for 10 minutes, an inorganic protective film will be formed on the surface of the galvanized steel sheet.

[0131] The difference between Example 12 and Example 11 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:5.

[0132] The difference between Example 13 and Example 11 is that the inorganic resin coating is composed of component A, component B and component C in a mass ratio of 100:20:10.

[0133] The difference between Example 14 and Example 12 is that component C is composed of deionized water, copper nitrate, cobalt nitrate, and carboxylated modified boron nitride nanosheets.

[0134] The preparation of carboxylated modified boron nitride nanosheets is as follows: 1.0 g of tris(hydroxymethyl)aminomethane (CAS: 77-86-1) was dissolved in 150 ml of deionized water, the pH was adjusted to 8.5 using dilute hydrochloric acid solution, then 50 ml of anhydrous ethanol was added, and after mixing thoroughly, 1.0 g of boron nitride nanosheets (sheet diameter: 1-3 μm, specific surface area: 30 m²) were added. 2 / g, Chihe New Materials Technology Nanjing Co., Ltd.) was ultrasonically vibrated for 10 min (ultrasonic frequency 44kHz, ultrasonic power 800W) to make it uniform, and then 0.40g dopamine hydrochloride (CAS:62-31-7) was added. The mixture was stirred at room temperature for 24h, and then washed and centrifuged with deionized water and ethanol. The product was placed in a vacuum drying oven for vacuum drying at 60 ℃ / 8h to obtain a gray-black powder.

[0135] The preparation method of component C is as follows: 100 parts by weight of deionized water are poured into a reaction vessel, 4 parts by weight of copper nitrate and 1 part by weight of cobalt nitrate are added, and the mixture is magnetically stirred at 240 r / min for 5 min. After the anhydrous copper sulfate is fully dissolved, 1 part by weight of carboxylated modified boron nitride nanosheets are added, and the mixture is magnetically stirred at 240 r / min for 5 min. Ultrasonic dispersion is then started with an ultrasonic frequency of 44 kHz and an ultrasonic power of 1200 W for 30 min to obtain component C.

[0136] The difference between Comparative Example 4 and Example 12 is that component C is composed of deionized water, copper sulfate, and hydroxylated modified graphene. The preparation method of component C is as follows: 100 parts by weight of deionized water are poured into a reaction vessel, 5 parts by weight of anhydrous copper sulfate are added, and the mixture is magnetically stirred at 240 r / min for 5 min. After the anhydrous copper sulfate is fully dissolved, 1 part by weight of hydroxylated modified graphene is added, and the mixture is magnetically stirred at 240 r / min for 5 min. Ultrasonic dispersion is then started at a frequency of 44 kHz and a power of 1200 W for 30 min to obtain component C.

[0137] Table 4: Test parameters of the inorganic protective film in Examples 5, 11-14 and Comparative Example 4

[0138] Adhesion rating / level Contact angle ° Corrosion potential / V Corrosion inhibition efficiency / % <![CDATA[Corrosion rate g / m 2 ·h]]> Example 5 2 77.8 -0.448 97.95 1.168 Example 11 1 78.4 -0.446 98.75 1.121 Example 12 1 79.2 -0.442 99.58 1.005 Example 13 1 79.5 -0.441 99.77 0.989 Example 14 1 83.4 -0.443 99.29 1.013 Comparative Example 4 2 76.1 -0.446 98.69 1.125

[0139] Based on Examples 5, 11-14 and Table 4, it can be seen that the addition of component C is beneficial to improving the corrosion resistance of the inorganic protective film. When the filler of component C is in the mass ratio of component C to component A of (5-10):100, the corrosion resistance of the inorganic protective film is significantly improved.

[0140] Based on Examples 12 and 4, and referring to Table 4, it can be seen that replacing carboxylated modified graphite with hydroxylated modified graphene improves the corrosion resistance of the inorganic protective film to some extent, but the improvement is not as significant as that of carboxylated modified graphite, and it also leads to a decrease in the adhesion of the inorganic protective film. Therefore, choosing carboxylated modified graphite can better improve the corrosion resistance and film bonding strength of the inorganic protective film.

[0141] Combining Examples 12 and 14 with Table 4, it can be seen that, under the same addition amount, the inorganic protective film prepared from the C component containing carboxylated modified boron nitride nanosheets exhibits significantly improved corrosion resistance and hydrophobic properties.

[0142] In summary, the inorganic resin coating consists of components A, B, and C in a mass ratio of 100:20:5. Component A comprises 3-glycidyl etheroxypropyltrimethoxysilane KH560, methyltrimethoxysilane MTMS, phenyltriethoxysilane PTES, γ-mercaptopropyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, ethanol, glacial acetic acid, deionized water, and photoinitiator 2959. Component B is prepared by hydrolyzing 96 parts by weight of an aqueous ethanol solution with 2 parts by weight of tetrabutyl titanate and 2 parts by weight of ethyl silicate. Component C is prepared from deionized water, copper sulfate, and carboxylated modified graphene. The prepared inorganic protective film exhibits excellent adhesion and corrosion resistance, better meeting the high corrosion resistance requirements of galvanized steel.

[0143] It should be noted that this specific embodiment is merely an explanation of the technical solution of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. An inorganic resin coating, characterized in that: It includes component A, component B and component C, wherein the mass ratio of component C to component A and component B is (1-10):100:(10-40); Component A is made of epoxy silane, crosslinking agent, methacryloxysilane, mercapto-containing silane, water-soluble photoinitiator, C1-2 alcohol, deionized water, and pH adjuster; the crosslinking agent includes at least one of methyltrimethoxysilane, dimethyldimethoxysilane, phenyltriethoxysilane, methylphenyldiethoxysilane, and phenyldiethoxysilane. The C1-2 alcohol is either methanol or ethanol; The pH adjuster is acetic acid or propionic acid; The mass ratio of the C1-2 alcohol to the deionized water is (70-80):(20-30); The combined mass of the C1-2 alcohol and the deionized water accounts for 80-96 wt% of component A; The mass ratio of the epoxy silane to the crosslinking agent is (4-8):(1-2); The molar ratio of the propylene double bond group in the methacryloxysilane to the mercapto group in the mercapto-containing silane is 1:(1-1.2); and the total mass of the methacryloxysilane and the mercapto-containing silane accounts for 0.2-2 wt% of the total mass of component A. Component B is a titanium-silicon compound sol, which is mainly a hydrolytic copolymer formed by titanate and silicate ester. The C component includes copper sulfate, surface carboxylated modified nano-inorganic filler, and deionized water; wherein the surface carboxylated modified nano-inorganic filler is one or more combinations of carboxylated modified graphene, carboxylated modified carbon nanotubes, carboxylated modified halloysite nanotubes, carboxylated modified boron nitride nanosheets, and carboxylated modified molybdenum disulfide nanosheets.

2. The inorganic resin coating according to claim 1, characterized in that: The titanate is at least one of tetraethyl titanate and tetrabutyl titanate; the silicate is at least one of methyl silicate, ethyl silicate, propyl silicate, and butyl silicate.

3. The inorganic resin coating according to claim 1, characterized in that: The epoxy silane is at least one of 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidylpropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

4. The inorganic resin coating according to claim 1, characterized in that: The methacryloyloxysilane is at least one of 3-(methacryloyloxy)propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-trimethoxysilane propylene acrylate, and 3-acryloyloxypropylmethyldimethoxysilane; the mercapto-containing silane is at least one of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

5. The inorganic resin coating according to claim 1, characterized in that: The water-soluble photoinitiator is at least one of photoinitiator 2959, photoinitiator 8700, and photoinitiator 6992.

6. A method for preparing an inorganic resin coating according to any one of claims 1-5, characterized in that: Includes the following steps: Preparation of component A: Mix epoxy silane, methacryloxy silane, mercaptosilane, crosslinking agent, C1-2 alcohol, and deionized water evenly, then add pH adjuster to adjust the pH of the system to 3-4, and hydrolyze at 30-50℃ for 4-24h to obtain component A; Preparation of component B: After mixing ethanol, deionized water, titanate, and silicate evenly, hydrolyze for 0.5-2 hours to form a hydrolytic copolymer to obtain component B; Preparation of component C: Water-soluble metal salt, surface carboxylated modified nano-inorganic filler, and deionized water are mixed evenly to form component C; Mix components A, B, and C at a mass ratio of 100:(10-40):(1-10) to obtain an inorganic resin coating. When using, add a water-soluble photoinitiator to the inorganic resin coating and mix thoroughly. The curing conditions for the inorganic resin coating are: under ultraviolet light irradiation, cure at 80-120℃ for 30-60 minutes.

7. The application of an inorganic resin coating according to any one of claims 1-5 in the corrosion protection of galvanized steel sheet surface.