Photothermal dual-cured multi-hybrid coatings, layers, methods of making and applications thereof

Abstract

The application provides a kind of light-heat dual-curing multi-hybrid coating, coating, its preparation method and application. The light-heat dual-curing multi-hybrid coating includes, by mass fraction: polybutadiene epoxy resin 5.0-15.0 parts, polyol polymer 10.0-20.0 parts, filler 3.0-9.0 parts, active diluent 40.0-60.0 parts, blocked isocyanate resin 2.0-8.0 parts, liquid latent epoxy accelerator 0.2-0.3 parts, vinyl siloxane 0.5-2.0 parts, and photoinitiator 3.0-6.0 parts. The coating formed by the coating provided by the application has good adhesion and exhibits excellent insulation and protection performance; the coating requires short curing time and can be quickly cured under light-heat dual-curing conditions.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a photothermal dual-curing multi-component hybrid coating, coating layer, its preparation method, and its application. Background Technology

[0002] The power battery is a core component of new energy vehicles, generating a significant amount of heat during operation. If this heat cannot be effectively dissipated, it can lead to high temperatures or even overheating, affecting battery life and potentially causing safety hazards. Therefore, effectively controlling battery temperature has become a crucial issue in the development of new energy vehicles. A water-cooled plate is a heat dissipation system that uses water circulation to control battery temperature. Its principle is to utilize the cooling water flowing inside the battery to absorb heat and then dissipate it through the cooling system, thereby achieving the goal of controlling battery temperature.

[0003] Currently, with the maturation of lithium iron phosphate batteries, industries such as energy storage are experiencing rapid growth, leading to a surge in demand for water-cooled plates. During use, water-cooled plates require an insulating and anti-corrosion coating to meet the electrical insulation requirements between the battery cells and the plate, while also providing corrosion protection. One commonly used type of insulating and anti-corrosion coating is powder coating. Powder coatings typically require curing temperatures of 180°C and above, resulting in high energy consumption. Furthermore, the baking lines used in the curing process occupy a large area, leading to high site, equipment, and energy costs. Additionally, pure UV free radical curing coatings suffer from drawbacks such as oxygen inhibition, difficulty in deep curing, large volume shrinkage during curing, and poor adhesion. When water-cooled plates are made of aluminum alloy, the low surface tension of aluminum makes it difficult for conventional coatings to achieve good adhesion, thus affecting performance. Therefore, providing an insulating and anti-corrosion coating that easily forms good adhesion to the substrate surface and can cure quickly is of great significance. Summary of the Invention

[0004] To solve all or part of the above-mentioned technical problems, the present invention provides the following technical solutions:

[0005] One objective of this invention is to provide a photothermal dual-curing multi-component hybrid coating, wherein the raw materials of the coating, by weight, include:

[0006] 5.0-15.0 parts of polybutadiene epoxy resin;

[0007] 10.0-20.0 parts of polyol polymer;

[0008] 3.0-9.0 parts of filler;

[0009] 40.0-60.0 parts of reactive diluent;

[0010] Blocked isocyanate resin, 2.0-8.0 parts;

[0011] 0.2-0.3 parts of liquid latent epoxy accelerator;

[0012] Vinylsiloxane 0.5-2.0 parts;

[0013] 3.0-6.0 parts of photoinitiator.

[0014] The coating provided by this invention can form a coating with good adhesion on a substrate (such as an aluminum substrate, an aluminum alloy substrate, etc.), and the formed coating has excellent insulation properties and protective functions. Specifically, the coating has a variety of polar groups such as vinyl, siloxane, isocyanate, epoxy, and hydroxyl groups. These polar groups cooperate with each other to form "grafts" on the substrate, thereby enhancing the adhesion of the coating to the substrate. Furthermore, the coating is a photothermal dual-curing coating, which can further improve the adhesion of the formed coating during photothermal dual curing. In addition, the coating can quickly set and completely cure under the action of photothermal curing, requiring a short curing time and high efficiency.

[0015] The photothermal dual-curing multi-component hybrid coating is, for example, a single-component coating.

[0016] In some embodiments, the polyol polymer comprises the reaction product of epoxy resin, dimer acid, and diethanolamine. Because the dimer acid molecule contains aliphatic long chains, it reduces surface tension and acts as an internal plasticizer, giving the coating excellent wettability. Furthermore, the polar groups such as double bonds in the dimer acid can further promote the adhesion of the coating to the substrate. Additionally, if a simple physical mixture of epoxy resin, dimer acid, and diethanolamine is added to the coating system of this invention, the diethanolamine will react with the epoxy resin and polybutadiene epoxy resin, leading to instability in the coating system and preventing the formation of good protective properties.

[0017] In some embodiments, the dimer acid includes C 18 -C 36 Dimeric fatty acids.

[0018] In some preferred embodiments, the dimer acid includes C 36 Dimeric fatty acids, wherein C 36 Dimeric fatty acids contain double bonds and are pale yellow, transparent, viscous liquids.

[0019] In some embodiments, the C 36 The dimer content in the dimer fatty acid is above 95wt%, and the relative molecular weight is 500-600.

[0020] In some embodiments, the epoxy resin includes one or a combination of more of neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, or 1,6-hexanediol diglycidyl ether.

[0021] In some embodiments, the method for preparing the polyol polymer includes:

[0022] Under inert atmosphere conditions, the first mixed reaction system containing the epoxy resin, dimer acid and basic catalyst is subjected to a first reaction at a temperature of 110-130°C to obtain an intermediate product.

[0023] The second mixed reaction system containing the intermediate product and diethanolamine is reacted at a temperature of 85-105°C to obtain the polyol polymer.

[0024] In some embodiments, the molar ratio of the epoxy resin to the dimer acid in the first mixed reaction system is 2.4-2.6:1.

[0025] In some embodiments, the first reaction is terminated when the acid value of the first mixed reaction system is below 1.5 mg KOH / g.

[0026] In some embodiments, the molar ratio of the intermediate product to diethanolamine in the second mixed reaction system is 1:1.1-1.3.

[0027] In some embodiments, the reaction time of the second reaction is 2-3 hours.

[0028] In some embodiments, the alkaline catalyst includes one or a combination of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, or tetraethylammonium bromide.

[0029] In some embodiments, the amount of alkaline catalyst used is 0.1-0.2 wt% of the total mass of the first mixed reaction system.

[0030] In a typical embodiment, the method for preparing the polyol polymer specifically includes:

[0031] A first mixed reaction system is provided, comprising epoxy resin, dimer acid, and basic catalyst, wherein the molar ratio of epoxy resin to dimer acid is 2.4-2.6:1, and the amount of basic catalyst added is 0.1-0.2 wt% of the total amount of the first mixed reaction system; an inert gas (e.g., nitrogen) is introduced into the first mixed reaction system and stirred for at least 30 minutes until the air in the first mixed reaction system is completely replaced; then the temperature of the first mixed reaction system is raised to 110-130°C and the reaction is maintained at this temperature, with the acid value measured every hour until the acid value is <1.5 mg KOH / g, at which point the reaction is terminated, and an intermediate product is obtained;

[0032] The intermediate product is cooled to 85-105°C and mixed with diethanolamine at a molar ratio of 1:1.1-1.3. The mixture is kept at this temperature for 2-3 hours. Excess diethanolamine is removed by vacuum distillation, and the product is cooled to obtain the polyol polymer.

[0033] In some embodiments, the polybutadiene epoxy resin contains epoxy groups, carbon-carbon double bonds, and hydroxyl groups.

[0034] In some embodiments, the polybutadiene epoxy resin has a relative molecular weight of 5000-10000. Resins with this molecular weight have moderate reactivity and low shrinkage after film formation.

[0035] In some embodiments, the vinylsiloxane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltri(methoxyethoxy)silane.

[0036] In some embodiments, the coating may further include 1.5-2.0 parts of additives. The additives may be those commonly used in existing coatings, and the present invention does not impose any particular limitation on them.

[0037] In some embodiments, the additives include one or more of defoamers, dispersants, leveling agents or rheology modifiers, but are not limited thereto.

[0038] The filler can be any filler commonly used in existing coatings. This invention does not impose any particular limitation on this. For example, the filler selected according to the actual situation may include one or more of the following: talc powder, silica powder, barium sulfate, or mica powder, but is not limited thereto.

[0039] In some embodiments, the reactive diluent includes tricyclodecanediethanol diacrylate (DCPDA), isobornyl methacrylate (IBOMA), acrylmorpholine (ACMO), cyclotrimethylolpropane methyl acetal acrylate (CTFA), or tetrahydrofuran acrylate (THFA).

[0040] In some preferred embodiments, the reactive diluent comprises DCPDA, IBOMA, ACMO, CTFA, and THFA in a mass ratio of 8-10:20-22.5:2-5:5-9:10-12.5. This compounded reactive diluent has sufficient solubility to dissolve photoinitiators (e.g., TPO), while maintaining flexibility, hardness, and wettability. This allows the coating to spread better on aluminum with low surface tension and balances the flexibility and hardness of the coating.

[0041] In some embodiments, the unblocking temperature of the blocked isocyanate resin is higher than that of the liquid latent epoxy accelerator. The latent epoxy accelerator has a lower unblocking temperature, thus it is unblocked first to promote the ring-opening self-polymerization of epoxy groups. The blocked isocyanate resin has a higher unblocking temperature, thus it is unblocked later. After unblocking, the blocked isocyanate resin reacts with the polyol polymer and polybutadiene epoxy resin, thereby forming a denser coating and achieving excellent anti-corrosion performance.

[0042] In some embodiments, the unblocking temperature of the blocked isocyanate resin is 140°C or higher.

[0043] In some embodiments, the blocked isocyanate resin includes at least one of Evonik's EP-B 1186A and Wuhan Shiquanxing's S-3175. The solid content of the blocked isocyanate resin is preferably 55 wt% or more.

[0044] In some embodiments, the unsealing temperature of the liquid latent epoxy accelerator is 80-100°C.

[0045] In some embodiments, the liquid latent epoxy accelerator includes at least one of 2-ethyl-4-methylimidazole and Shanghai Qianxing Materials QXA101. The liquid latent epoxy accelerator has, for example, the appearance of a brown viscous liquid with an average particle size of, for example, 2-10 μm.

[0046] In some embodiments, the photoinitiator includes one or a combination of more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO) or 1-hydroxycyclohexylphenyl methyl ketone (184).

[0047] In some embodiments, the coating further includes 0.5-1.5 parts of a colorant. The colorant may, for example, include a black colorant comprising a black dye and an organic solvent, and the solid content of the black colorant may be, for example, 5-35 wt%. In some preferred embodiments, the black colorant includes Y856 black colorant.

[0048] A second objective of this invention is to provide a method for preparing the photothermal dual-curing multi-component hybrid coating as described in any one of the above claims, comprising:

[0049] Under inert atmosphere conditions, the first mixed reaction system containing epoxy resin, dimer acid and basic catalyst is subjected to a first reaction at a temperature of 110-130℃ to obtain an intermediate product.

[0050] The second mixed reaction system containing the intermediate product and diethanolamine was reacted at a temperature of 85-105°C to obtain a polyol polymer.

[0051] The first mixture containing 5.0-15.0 parts of polybutadiene epoxy resin, 10.0-20.0 parts of polyol polymer, 2.0-4.0 parts of additives, 3.0-9.0 parts of filler and a first part of reactive diluent is uniformly mixed to obtain the first material;

[0052] The coating is obtained by uniformly mixing the first material, 2.0-8.0 parts of blocked isocyanate resin, 0.2-0.3 parts of liquid latent epoxy accelerator, 0.5-2.0 parts of vinylsiloxane, 3.0-6.0 parts of photoinitiator, and a second part of reactive diluent.

[0053] The total mass percentage of the first part of the reactive diluent and the second part of the reactive diluent is 40.0-60.0 parts.

[0054] In some embodiments, the preparation method specifically includes: first grinding the first material to a fineness of less than 20 μm, and then uniformly mixing the first material with the blocked isocyanate resin, liquid latent epoxy accelerator, vinyl siloxane, photoinitiator, and a second part of reactive diluent to form the coating.

[0055] In a typical embodiment, the method for preparing the coating specifically includes:

[0056] Under stirring, the polybutadiene epoxy resin, polyol polymer, additives, fillers, and part of the reactive diluent in the specified mass fractions are added sequentially, and dispersed at a linear speed of 20-30 m / s for 25-30 min to obtain a uniform mixture. Then, the uniform mixture is ground to a fineness of less than 20 μm to obtain the first material.

[0057] The first material is mixed with the specified mass fractions of black pigment, blocked isocyanate resin, liquid latent epoxy accelerator, vinyl siloxane, photoinitiator, and remaining reactive diluent. The mixture is dispersed at a linear velocity of 20-30 m / s for 25-30 min, then filtered through a filter with a mesh size of 200 mesh or less, and packaged to obtain a coating.

[0058] A third objective of this invention is to provide the application of the aforementioned photothermal dual-curing multi-component hybrid coating in the preparation of insulating and anti-corrosion coatings, including insulating and anti-corrosion coatings for water-cooled plates of automobiles (e.g., new energy vehicles).

[0059] The fourth objective of this invention is to provide a coating comprising the cured product of the photothermal dual-curing multi-component hybrid coating described in any of the above technical solutions.

[0060] The fifth objective of this invention is to provide a method for preparing the coating, comprising: first photocuring the photothermal dual-curing multi-component hybrid coating as described in any of the above technical solutions, and then performing thermal curing to obtain the coating.

[0061] In some embodiments, the light intensity for photocuring is 10-160 mW / cm². 2 The temperature for heat curing is 180-200℃.

[0062] In some embodiments, the photocuring time is 30-60 seconds, and the thermal curing time is 1-3 minutes. The photocuring time refers to a single photocuring cycle. For example, when multiple coatings are applied to the substrate to form a coating of the desired thickness, 30-60 seconds of photocuring is performed after each coating, and finally, thermal curing is performed after all coatings are completed. The coating of this invention can achieve complete curing within 5 minutes (the total time for photocuring and thermal curing).

[0063] In some embodiments, the method for preparing the coating specifically includes:

[0064] The coating is heated to 35-45°C, and then a multi-layer structure is sequentially formed on the substrate using the coating. The first layer of the multi-layer structure is applied at a concentration of 10-20 mW / cm². 2 The second layer is cured by irradiation with light intensity for 30-60 seconds, and then cured with light at 130-160 mW / cm². 2 Photocuring is performed by irradiating the light with an intensity of 50-60 seconds.

[0065] Then, the multilayer structure is thermally cured at a temperature of 180-2000℃ for 1-3 minutes to obtain the coating.

[0066] In a typical embodiment, the method for preparing the coating includes:

[0067] Provided the aforementioned photothermal dual-curing multi-component hybrid coating;

[0068] The substrate is degreased, sanded, and dusted; areas that do not require coating are masked.

[0069] The coating is heated to 35-45℃ and sprayed onto the substrate where the coating is desired. It is then cured using a mercury lamp at a light intensity of 10-20 mW / cm². 2 The irradiation time is 30-60 seconds, forming a first layer structure with a thickness of 60-70 μm;

[0070] The coating is heated to 35-45℃ and sprayed onto the substrate where the coating is desired. It is then cured using a mercury lamp at a light intensity of 130-160 mW / cm². 2 Irradiation time is 50-60s, forming a second layer structure with a thickness of 60-70μm, thus obtaining a double-layer structure with a total thickness of 120-140μm;

[0071] The double-layer structure is thermosetting at a temperature of 180-200℃ for 1-3 minutes, and then cooled to obtain the coating.

[0072] The sixth objective of this invention is to provide a water-cooled plate for new energy vehicles, comprising a water-cooled plate substrate and an insulating and anti-corrosion coating formed on the water-cooled plate substrate, wherein the insulating and anti-corrosion coating comprises the aforementioned coating.

[0073] Compared with the prior art, the present invention has at least the following beneficial effects:

[0074] (1) Existing pure UV free radical photocurable coatings have disadvantages such as oxygen inhibition, large curing volume shrinkage, and difficulty in deep curing. For example, when the substrate is aluminum alloy, due to the low surface tension of aluminum alloy, general coatings have difficulty having good adhesion, resulting in problems such as easy coating peeling. However, the coating provided by this invention contains a variety of polar groups such as vinyl groups, siloxanes, hydroxyl groups, isocyanate groups, and epoxy groups. These polar groups cooperate with each other to form "grip" on the substrate, increasing the adhesion to the substrate (e.g., aluminum, aluminum alloy substrate).

[0075] (2) Furthermore, the coating provided by the present invention contains a polyol polymer formed by the reaction of epoxy resin, dimer acid and diethanolamine. Since the dimer acid molecule structure contains aliphatic long chains, it can reduce the surface tension of the coating, so that the coating has good wettability, play an internal plasticizing role, and improve the flexibility of the coating. In addition, the polar groups (such as double bonds) contained in the dimer acid can further improve the adhesion of the coating formed by the coating to the substrate.

[0076] (3) Furthermore, in the coating provided by the present invention, a latent epoxy accelerator with a relatively low unblocking temperature and a blocked isocyanate resin with a relatively high unblocking temperature are used; the latent epoxy accelerator is unblocked first to promote the ring-opening self-polymerization of epoxy groups, and then the blocked isocyanate resin is unblocked. After unblocking, it can react with polyol polymers and polybutadiene epoxy resin. Multiple reactions make the formed coating more dense, thereby improving its anti-corrosion performance.

[0077] (4) The coating provided by the present invention is a photothermal dual-curing coating. Photocuring can quickly set the coating, and thermal curing can fully cure the coating in depth, releasing the shrinkage stress of UV free radical curing. Photothermal dual curing can improve the adhesion of the coating. In addition, the curing time required for the coating is short, which is conducive to improving production efficiency. Detailed Implementation

[0078] The present invention is further illustrated below by way of examples, but the invention is not limited to the scope of the examples described herein. All raw materials used in the following examples are commercially available, and test methods not specifically specified are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0079] The raw materials used in the embodiments and comparative examples of this invention and their sources are as follows:

[0080] Additives: BYK-2152 dispersant, BYK-1790 defoamer, BYK-333 leveling agent, and GARAMITE 7305 rheology modifier from BYK Additives (Shanghai) Co., Ltd.

[0081] Fillers: Talc powder HS-368, silica powder GS-1250, barium sulfate GY-1250 from Jiangxi Guangyuan Chemical Co., Ltd., and mica powder BT-4 from Chuzhou Baota.

[0082] Black pigment: Huihai Chemical Y856;

[0083] Liquid latent epoxy accelerator: QXA101 from Shanghai Qianxing Materials, with an unsealing temperature of 80-100℃;

[0084] Blocked isocyanate resins: Evonik Specialty Chemicals (Shanghai) Co., Ltd.'s EP-B 1186A, with an unblocking temperature of 150℃; Wuhan Shiquanxing New Material Technology Co., Ltd.'s S-3175, with an unblocking temperature of 140℃;

[0085] Dimer acid, epoxy resin, basic catalyst, diethanolamine, reactive diluent, photoinitiator, 2-ethyl-4-methylimidazolium, vinylsiloxane, and polybutadiene epoxy resin are commercially available standardized products.

[0086] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments. These embodiments are implemented on the premise of the technical solution of the invention, and provide detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0087] Example 1

[0088] This embodiment provides a photothermal dual-curing multi-component hybrid coating and its preparation method, as detailed below:

[0089] (1) Preparation of polyol polymers

[0090] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, and add C according to a molar ratio of neopentyl glycol diglycidyl ether to dimer acid of 2.4:1. 36 Dimeric fatty acids and 0.2 g of tetramethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 120°C and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mg KOH / g, at which point the reaction was terminated.

[0091] The product obtained from the above reaction was cooled to 95°C, and then diethanolamine was added at a molar ratio of 1:1.2. The mixture was kept at this temperature for 2.5 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain the polyol polymer.

[0092] (2) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight to obtain reactive diluent for later use.

[0093] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0094] Under stirring, 10 parts of polybutadiene epoxy resin, 20 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE7305, 3 parts of talc HS-368, 2 parts of silica powder GS-1250, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a uniform mixture. The uniform mixture was then ground to a fineness of 20 μm to obtain the first material.

[0095] Then, add 1 part of black pigment, 5 parts of blocked isocyanate resin EP-B 1186A, 0.2 parts of liquid latent epoxy accelerator QXA101, 0.5 parts of vinyltrimethoxysilane, 2.5 parts of photoinitiator 1173, 3 parts of photoinitiator TPO, and 30 parts of the above-prepared reactive diluent to the first material. Disperse at a linear velocity of 20 m / s for 30 min, and then filter and package through a 200-mesh filter to obtain a multi-component hybrid coating that is cured by both photothermal and chemical processes.

[0096] The coating is prepared using the photothermal dual-curing multi-component hybrid coating of this embodiment, as detailed below:

[0097] The workpiece (6061 aluminum plate) is degreased, polished, and dusted. Areas that do not need to be painted are masked.

[0098] Heat the above coating to 35°C and spray it onto the area to be coated using a spray gun, with a thickness of approximately 60 μm.

[0099] Curing is performed using a mercury lamp with a light intensity of approximately 10 mW / cm². 2 Irradiation time was 60 seconds, and the first layer structure was obtained;

[0100] Heat the coating to 35℃, then apply a second coat using a spray gun to the desired area, with a thickness of approximately 60μm, for a total thickness of about 120μm. Perform a second curing using a mercury lamp with a light intensity of approximately 130mW / cm². 2 An irradiation time of 60 seconds was used to obtain a double-layer structure.

[0101] The double-layer structure was thermosetting at 200°C for 1 minute, and then cooled to obtain the final coating.

[0102] Example 2

[0103] This embodiment provides a photothermal dual-curing multi-component hybrid coating and its preparation method, as detailed below:

[0104] (1) Preparation of polyol polymers

[0105] In a four-necked flask, add 100 g of 1,6-hexanediol diglycidyl ether, and add C at a molar ratio of 1,6-hexanediol diglycidyl ether to dimer acid of 2.5:1. 36 Dimeric fatty acids and 0.4 g of tetramethylammonium bromide were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 125°C and the reaction was maintained at this temperature, and the acid value was measured every hour until the acid value was <1.5 mg KOH / g, at which point the reaction was terminated.

[0106] The product obtained from the above reaction was cooled to 85°C, and then diethanolamine was added at a molar ratio of 1:1.3. The reaction was kept at this temperature for 3 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain a polyol polymer.

[0107] (2) Preparation of reactive diluent:

[0108] Mix DCPDA:IBOMA:ACMO:CTFA:THFA in a weight ratio of 10:20:5:5:12 to obtain an active diluent for later use.

[0109] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0110] Under stirring, 15 parts of polybutadiene epoxy resin, 15 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE7305, 3 parts of talc HS-368, 3 parts of barium sulfate GY-1250, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 25 m / s for 25 min to obtain a homogeneous mixture. The homogeneous mixture was then ground to a fineness of 20 μm to obtain the first material.

[0111] Then, add 1 part of black pigment, 4 parts of blocked isocyanate resin EP-B 1186A, 0.3 parts of liquid latent epoxy accelerator 2-ethyl-4-methylimidazolium, 0.5 parts of vinyltriethoxysilane, 1.5 parts of photoinitiator 1173, 1 part of photoinitiator 184, 3 parts of photoinitiator TPO, and 35 parts of the above-prepared reactive diluent to the first material. Disperse at a linear velocity of 20 m / s for 30 min, and then filter and package through a 200-mesh filter to obtain a photothermal dual-curing multi-component hybrid coating.

[0112] The coating is prepared using the photothermal dual-curing multi-component hybrid coating of this embodiment, as detailed below:

[0113] The workpiece (6061 aluminum plate) is degreased, polished, and dusted. Areas that do not need to be painted are masked.

[0114] Heat the above coating to 40°C and spray it onto the area to be coated using a spray gun, with a thickness of approximately 65μm.

[0115] Curing is performed using a mercury lamp with a light intensity of approximately 20 mW / cm². 2 Irradiation time was 30 seconds, and the first layer structure was obtained;

[0116] Heat the coating to 40°C and apply a second coat using a spray gun to the desired areas, achieving a thickness of approximately 65μm, for a total thickness of about 130μm. Then, perform a second curing process using a mercury lamp with a light intensity of approximately 160mW / cm². 2 An irradiation time of 50 seconds was used to obtain a double-layer structure.

[0117] The double-layer structure was thermosetting at 190℃ for 2 minutes, and then cooled to obtain the final coating.

[0118] Example 3

[0119] This embodiment provides a photothermal dual-curing multi-component hybrid coating and its preparation method, as detailed below:

[0120] (1) Preparation of polyol polymers

[0121] In a four-necked flask, add 100 g of 1,4-butanediol diglycidyl ether, and add C according to a molar ratio of 1,4-butanediol diglycidyl ether to dimer acid of 2.6:1. 36 Dimeric fatty acids and 0.3 g of tetraethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 115℃ and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mgKOH / g, at which point the reaction was terminated.

[0122] The product obtained from the above reaction was cooled to 90°C, and then diethanolamine was added at a molar ratio of 1:1.2. The mixture was kept at this temperature for 2.5 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain a polyol polymer.

[0123] (2) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22:3:9:10 by weight to obtain reactive diluent for later use.

[0124] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0125] Under stirring, 12 parts of polybutadiene epoxy resin, 18 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.2 parts of rheology modifier GARAMITE7305, 5 parts of mica powder BT-4 from Chuzhou Pagoda, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 25 m / s for 30 min to obtain a uniform mixture. The uniform mixture was then ground to a fineness of 20 μm to obtain the first material.

[0126] Then, 1.2 parts of black pigment, 6 parts of blocked isocyanate resin S-3175, 0.3 parts of liquid latent epoxy accelerator 2-ethyl-4-methylimidazolium, 1 part of vinyltris(methoxyethoxy)silane, 2 parts of photoinitiator 1173, 0.5 parts of photoinitiator 184, 2 parts of photoinitiator TPO, and 35 parts of the above-prepared reactive diluent were added to the first material. The mixture was dispersed at a linear velocity of 25 m / s for 25 min, and then filtered through a 200-mesh filter and packaged to obtain a photothermal dual-curing multi-component hybrid coating.

[0127] The coating is prepared using the photothermal dual-curing multi-component hybrid coating of this embodiment, as detailed below:

[0128] The workpiece (6061 aluminum plate) is degreased, polished, and dusted. Areas that do not need to be painted are masked.

[0129] Heat the above coating to 45°C and spray it onto the area to be coated using a spray gun, with a thickness of approximately 70μm.

[0130] Curing is performed using a mercury lamp with a light intensity of approximately 15 mW / cm². 2 Irradiation time was 45 seconds, and the first layer structure was obtained;

[0131] Heat the coating to 45°C and apply a second coat using a spray gun to the desired areas, achieving a thickness of approximately 70μm, for a total thickness of about 140μm. Then, use a mercury lamp for secondary curing at a light intensity of approximately 145mW / cm². 2 An irradiation time of 55 seconds was used to obtain a double-layer structure.

[0132] The structure was thermosetting at 180°C for 3 minutes, and then cooled to obtain the final coating.

[0133] Example 4

[0134] This embodiment provides a photothermal dual-curing multi-component hybrid coating and its preparation method, as detailed below:

[0135] (1) Preparation of polyol polymers

[0136] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, and add C according to a molar ratio of neopentyl glycol diglycidyl ether to dimer acid of 2.4:1. 36 Dimeric fatty acids and 0.2 g of tetramethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 110℃ and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mgKOH / g, at which point the reaction was terminated.

[0137] The product obtained from the above reaction was cooled to 105°C, and then diethanolamine was added at a molar ratio of 1:1.1. The reaction was kept at this temperature for 2 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain a polyol polymer.

[0138] (2) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight to obtain reactive diluent for later use.

[0139] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0140] Under stirring, 5 parts of polybutadiene epoxy resin, 20 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.2 parts of rheology modifier GARAMITE7305, 3 parts of mica powder BT-4 from Chuzhou Pagoda, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a uniform mixture. The uniform mixture was then ground to a fineness of 20 μm to obtain the first material.

[0141] Then, 0.5 parts of black pigment, 2 parts of blocked isocyanate resin EP-B 1186A, 0.2 parts of liquid latent epoxy accelerator QXA101, 2 parts of vinyltrimethoxysilane, 1.5 parts of photoinitiator 1173, 1.5 parts of photoinitiator TPO, and 20 parts of the above-prepared reactive diluent were added to the first material. The mixture was dispersed at a linear velocity of 20 m / s for 30 min, and then filtered through a 200-mesh filter and packaged to obtain a multi-component hybrid coating that is cured by both photothermal and chemical processes.

[0142] Then, using the coating material of this embodiment, a coating is formed in the same manner as in Example 1.

[0143] Example 5

[0144] This embodiment provides a photothermal dual-curing multi-component hybrid coating and its preparation method, as detailed below:

[0145] (1) Preparation of polyol polymers

[0146] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, and add C according to a molar ratio of neopentyl glycol diglycidyl ether to dimer acid of 2.4:1. 36Dimeric fatty acids and 0.2 g of tetramethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 130°C and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mg KOH / g, at which point the reaction was terminated.

[0147] The product obtained from the above reaction was cooled to 95°C, and then diethanolamine was added at a molar ratio of 1:1.3. The reaction was maintained at this temperature for 2.5 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain the polyol polymer.

[0148] (2) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight to obtain reactive diluent for later use.

[0149] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0150] Under stirring, 10 parts of polybutadiene epoxy resin, 10 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.2 parts of defoamer BYK-1790, 0.1 parts of leveling agent BYK-333, 0.9 parts of rheology modifier GARAMITE7305, 9 parts of mica powder BT-4 from Chuzhou Pagoda, and 30 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a uniform mixture. The uniform mixture was then ground to a fineness of 20 μm to obtain the first material.

[0151] Then, 1.5 parts of black pigment, 8 parts of blocked isocyanate resin EP-B 1186A, 0.2 parts of liquid latent epoxy accelerator 2-ethyl-4-methylimidazolium, 2 parts of vinyltrimethoxysilane, 3 parts of photoinitiator 1173, 3 parts of photoinitiator TPO, and 30 parts of the above-prepared reactive diluent were added to the first material. The mixture was dispersed at a linear velocity of 20 m / s for 30 min, and then filtered through a 200-mesh filter and packaged to obtain a multi-component hybrid coating that is cured by both photothermal and chemical processes.

[0152] Then, using the coating material of this embodiment, a coating is formed in the same manner as in Example 1.

[0153] Example 6

[0154] The only difference between Example 6 and Example 1 is that the active diluent was prepared in the weight ratio of DCPDA:IBOMA:ACMO:CTFA:THFA = 10:22:5:9:10, while the rest was carried out in the same manner as in Example 1, and the results obtained were comparable to those in Example 1.

[0155] Comparative Example 1

[0156] This comparative example provides a coating that does not contain the polyol polymer and blocked isocyanate resin of the present invention. This coating is a pure free radical photocurable coating, as detailed below:

[0157] (1) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight to obtain reactive diluent for later use.

[0158] (2) Preparation of pure free radical photocurable coatings

[0159] Under stirring, 30 parts of bisphenol A epoxy diacrylate resin 3016-20D from Aijianmeng, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE7305, 3 parts of talc HS-368, 2 parts of silica powder GS-1250, and 20 parts of the above-prepared reactive diluent were added sequentially. After dispersing at a linear speed of 20 m / s for 30 mm, a uniform mixture was obtained. The mixture was then ground to a fineness of 20 μm to obtain the first material.

[0160] Then, add 1 part black pigment, 0.5 part vinyltrimethoxysilane, 2.5 parts photoinitiator 1173, 3 parts photoinitiator TPO, and 30 parts of the above-prepared reactive diluent to the first material. Disperse at a linear velocity of 20 m / s for 30 min, then filter and package with a 200-mesh filter to obtain the coating.

[0161] The coating was prepared using the pure free radical photocurable coating of this comparative example, as detailed below:

[0162] The workpiece (6061 aluminum plate) is degreased, polished, and dusted. Areas that do not need to be painted are masked.

[0163] Heat the above-mentioned coating to 35°C and spray it onto the area to be coated using a spray gun, with a thickness of approximately 65μm.

[0164] Curing is performed using a mercury lamp with a light intensity of approximately 20 mW / cm². 2 Irradiation time was 30 seconds, and the first layer structure was obtained;

[0165] Heat the paint to 35°C, and use a spray gun to apply a second coat to the area to be coated, with a thickness of about 65μm and a total thickness of about 130μm.

[0166] A secondary curing process is performed using a mercury lamp, with a light intensity of approximately 130 mW / cm². 2 Irradiation time is 60 seconds, followed by cooling to obtain the final coating.

[0167] Comparative Example 2

[0168] This comparative example provides a coating and its preparation method, wherein C is not used in the preparation process of the polyol polymer used as a raw material in the coating. 36 Dimeric fatty acids, specifically as follows:

[0169] (1) Preparation of polyol polymers

[0170] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, purge the container with nitrogen gas and stir for more than 30 mm until the air in the container is completely replaced; raise the temperature to 95°C and maintain the temperature for reaction, add diethanolamine at a molar ratio of neopentyl glycol diglycidyl ether to diethanolamine of 2.2:1, maintain the temperature for 2.5 hours, remove excess diethanolamine by vacuum distillation to obtain the polyol polymer.

[0171] (2) Prepare the active diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight and set aside.

[0172] (3) Preparation of photothermal curing coatings

[0173] Under stirring, 10 parts of polybutadiene epoxy resin, 20 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE7305, 3 parts of talc HS-368, 2 parts of silica powder GS-1250, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a uniform mixture. The uniform mixture was then ground to a fineness of 20 μm to obtain the first material.

[0174] Then, add 1 part of black pigment, 5 parts of blocked isocyanate resin EP-B 1186A, 0.2 parts of liquid latent epoxy accelerator 2-ethyl-4-methylimidazolium, 0.5 parts of vinyltrimethoxysilane, 2.5 parts of photoinitiator 1173, 3 parts of photoinitiator TPO, and 30 parts of the above-prepared reactive diluent to the first material. Disperse at a linear velocity of 20 m / s for 30 min, then filter through a 200-mesh filter and package to obtain a photothermal curing coating.

[0175] The coating was prepared using the photothermal curing coating of this comparative example, as follows:

[0176] The workpiece (6061 aluminum plate) is degreased, polished, and dusted. Areas that do not need to be painted are masked.

[0177] Heat the above coating to 35°C and spray it onto the area to be coated using a spray gun to a thickness of approximately 60 μm.

[0178] Curing is performed using a mercury lamp with a light intensity of approximately 10 mW / cm². 2 Irradiation time was 60 seconds, and the first layer structure was obtained;

[0179] Heat the coating to 35°C, then apply a second coat using a spray gun to the desired areas, with a thickness of approximately 60μm, for a total thickness of about 120μm. Perform a second curing process using a mercury lamp with a light intensity of approximately 130mW / cm². 2 An irradiation time of 60 seconds was used to obtain a double-layer structure.

[0180] The double-layer structure was thermosetting at 200℃ for 1 minute, and then cooled to obtain the final coating.

[0181] Comparative Example 3

[0182] This comparative example provides a coating and its preparation method, wherein the coating uses an intermediate product of a polyol polymer and a resin without blocked isocyanates, as detailed below:

[0183] (1) Preparation of polyol polymer intermediates

[0184] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, and add C according to a molar ratio of neopentyl glycol diglycidyl ether to dimer acid of 2.4:1. 36 Dimeric fatty acids and 0.2 g of tetramethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 120°C and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mg KOH / g. The reaction was then stopped and cooled to room temperature to obtain the polyol polymer intermediate.

[0185] (2) Preparation of reactive diluent: Mix DCPDA:IBOMA:ACMO:CTFA:THFA = 8:22.5:2:7:12.5 by weight to obtain reactive diluent for later use.

[0186] (3) Preparation of multi-component hybrid coatings with photothermal dual curing

[0187] Under stirring, 10 parts of polybutadiene epoxy resin, 20 parts of the above-prepared polyol polymer intermediate, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE 7305, 3 parts of talc HS-368, 2 parts of silica powder GS-1250, and 20 parts of the above-prepared reactive diluent were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a homogeneous mixture. The homogeneous mixture was then ground to a fineness of 20 μm to obtain the first material.

[0188] Then, add 1 part of black pigment, 0.3 parts of liquid latent epoxy accelerator QXA101, 0.5 parts of vinyltrimethoxysilane, 2.5 parts of photoinitiator 1173, 3 parts of photoinitiator TPO, and 30 parts of the above-prepared reactive diluent to the first material. Disperse at a linear velocity of 20 m / s for 30 min, and then filter and package through a 200-mesh filter to obtain a photothermal dual-curing multi-component hybrid coating.

[0189] Then, using the paint from this comparative example, a coating was formed in the same manner as in Comparative Example 2.

[0190] Comparative Example 4

[0191] This comparative example provides a coating and its preparation method, wherein all reactive diluents in the coating are IBOMA, as detailed below:

[0192] (1) Preparation of polyol polymers

[0193] In a four-necked flask, add 100 g of neopentyl glycol diglycidyl ether, and add C according to a molar ratio of neopentyl glycol diglycidyl ether to dimer acid of 2.4:1. 36 Dimeric fatty acids and 0.2 g of tetramethylammonium chloride were added; nitrogen gas was introduced into the container and stirred for more than 30 minutes until the air in the container was completely replaced; the temperature was raised to 120℃ and the reaction was maintained at that temperature, and the acid value was measured every hour until the acid value was <1.5 mgKOH / g, at which point the reaction was terminated.

[0194] The product obtained from the above reaction was cooled to 95°C, and then diethanolamine was added at a molar ratio of 1:1.2. The mixture was kept at this temperature for 2.5 hours. After the reaction was completed, excess diethanolamine was removed by vacuum distillation to obtain the polyol polymer.

[0195] (2) Preparation of multi-component hybrid coatings with dual photothermal curing

[0196] Under stirring, 10 parts of polybutadiene epoxy resin, 20 parts of the polyol polymer prepared above, 0.3 parts of dispersant BYK-2152, 0.3 parts of defoamer BYK-1790, 0.2 parts of leveling agent BYK-333, 1.0 parts of rheology modifier GARAMITE7305, 3 parts of talc HS-368, 2 parts of silica powder GS-1250, and 20 parts of reactive diluent IBOMA were added sequentially. The mixture was dispersed at a linear speed of 20 m / s for 30 min to obtain a homogeneous mixture. The homogeneous mixture was then ground to a fineness of 20 μm to obtain the first material.

[0197] Then, 1 part of black pigment, 5 parts of blocked isocyanate resin EP-B 1186A, 0.2 parts of liquid latent epoxy accelerator QXA101, 0.5 parts of vinyltrimethoxysilane, 2.5 parts of photoinitiator 1173, 3 parts of photoinitiator TPO, and 30 parts of reactive diluent IBOMA were added to the first material. The mixture was dispersed at a linear velocity of 20 m / s for 30 min, and then filtered through a 200-mesh filter and packaged to obtain a multi-component hybrid coating that is cured by both photothermal and chemical processes.

[0198] Then, using the paint from this comparative example, a coating was formed in the same manner as in Comparative Example 2.

[0199] The coatings in the above embodiments and comparative examples were subjected to performance tests. The substrate in all embodiments and comparative examples was 6061 aluminum plate. The test results are shown in Table 1, and the specific test methods used are as follows:

[0200] 1. Adhesion: Refer to standard GB / T 9286, adhesion requirement is level 0.

[0201] 2. Flexibility: The coating does not peel off or crack when the crankshaft radius is 25mm and the angle is 180°.

[0202] 3. Leakage current: Use an insulation withstand voltage tester, test conditions DC3000V@60S, voltage rise time 5S, and the leakage current should be ≤0.1mA.

[0203] 4. High temperature and high humidity aging: Place the coating sample at 85℃ and 85% humidity for 1000 hours. Visually inspect the surface of the sample after the test. There should be no blistering, peeling or other obvious changes. Slight color changes are allowed. After drying, the adhesion should be grade 0 and still meet the insulation requirements.

[0204] 5. Temperature shock resistance: Place the coated sample in an alternating temperature environment of (-40±2)℃-(85±2)℃. The transition time between the two extreme temperatures is within 2 minutes. The test object is kept in each extreme temperature environment for 15 minutes. After 1000 cycles, visually inspect the surface condition of the sample after the test. After wiping dry, the adhesion is required to be level 0, and the insulation requirements must still be met.

[0205] Table 1. Performance test results of the coatings prepared in Examples 1-5 and Comparative Examples 1-4

[0206]

[0207] As shown in Table 1, the coatings formed by the photothermal dual-curing multi-component hybrid coatings in Examples 1-5 of this invention meet the technical specifications. Comparative Example 1 is a pure free radical photocuring coating. The test data shows that the coating has poor adhesion to aluminum. After high temperature, high humidity, and temperature shock tests, the adhesion weakens and even peels off directly. Comparing Comparative Example 2 and Example 1, it can be seen that when the polyol polymer is prepared without the addition of dimer acid, the film is relatively hard and brittle after film formation. After high temperature, high humidity, and temperature shock tests, the adhesion weakens. The intermediate product of the polyol polymer in Comparative Example 3 is a flexible epoxy resin, which can improve the flexibility and dry adhesion of the coating. However, because no blocked isocyanate is added, the wet adhesion is somewhat poor, and the adhesion weakens during high temperature and high humidity aging tests. In Comparative Example 4, all reactive diluents used are IBOMA. IBOMA has particularly large self-shrinkage and self-cracking occurs during the photocuring stage.

[0208] Comparative Example 5

[0209] This comparative example provides a coating formed by an insulating powder coating:

[0210] The insulating powder coating is INXH EPP200, an automotive insulating and anti-corrosion powder coating; manufacturer: Xinhe New Materials Co., Ltd.

[0211] The above-mentioned insulating powder coating is used to form a coating. Specifically, the substrate is degreased, sanded, and dusted. Areas that do not need to be sprayed are masked. The electrostatic spraying voltage is 60-100KV, the thickness is 120-140μm, and the coating is baked at 180℃ for 30 minutes to obtain the coating.

[0212] The performance test structures of the coatings in Example 1 and Comparative Example 5 are shown in Table 2:

[0213] Table 2. Performance test results of the coatings prepared in Example 1 and Comparative Example 5.

[0214] Example 1 Comparative Example 5 Production process Two light curing processes and one heat curing process. Heat curing once Curing time Within 5 minutes Approximately 30 minutes Production efficiency high Low Energy consumption Low high

[0215] Compared to Comparative Example 5, the coating of the present invention has high production efficiency and low energy consumption, and can replace existing automotive insulating powder coatings.

[0216] All aspects, embodiments, features, and examples of this invention are to be regarded as illustrative in all respects and are not intended to limit the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0217] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0218] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.

Claims

1. A multi-component hybrid coating with dual photothermal curing, characterized in that, The raw materials of the coating, by weight, include: 5.0-15.0 parts of polybutadiene epoxy resin; 10.0-20.0 parts of polyol polymer; 3.0-9.0 parts of filler; 40.0-60.0 parts of reactive diluent, wherein the reactive diluent comprises DCPDA, IBOMA, ACMO, CTFA and THFA in a mass ratio of 8-10:20-22.5:2-5:5-9:10-12.5; Blocked isocyanate resin, 2.0-8.0 parts; 0.2-0.3 parts of liquid latent epoxy accelerator; Vinylsiloxane 0.5-2.0 parts; Photoinitiator 3.0-6.0 parts; The preparation method of the polyol polymer includes: under an inert atmosphere, carrying out a first mixed reaction system containing epoxy resin, dimer acid and alkaline catalyst at a temperature of 110-130°C to obtain an intermediate product; and carrying out a second mixed reaction system containing the intermediate product and diethanolamine at a temperature of 85-105°C to obtain the polyol polymer.

2. The coating according to claim 1, characterized in that: The dimer acid includes C 18 -C 36 Dimeric fatty acids.

3. The coating according to claim 2, characterized in that: The dimer acid includes C 36 Dimer fatty acids.

4. The coating according to claim 1, characterized in that: The epoxy resin includes one or a combination of more of neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, or 1,6-hexanediol diglycidyl ether.

5. The coating according to claim 1, characterized in that: In the first mixed reaction system, the molar ratio of the epoxy resin to the dimer acid is 2.4-2.6:

1.

6. The coating according to claim 1, characterized in that: The first reaction is terminated when the acid value of the first mixed reaction system is below 1.5 mg KOH / g.

7. The coating according to claim 1, characterized in that: In the second mixed reaction system, the molar ratio of the intermediate product to diethanolamine is 1:1.1-1.

3.

8. The coating according to claim 1, characterized in that: The reaction time for the second mixed reaction system is 2-3 hours.

9. The coating according to claim 1, characterized in that: The alkaline catalyst includes one or a combination of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, or tetraethylammonium bromide.

10. The coating according to claim 1, characterized in that: The polybutadiene epoxy resin contains epoxy groups, carbon-carbon double bonds and hydroxyl groups; and / or, the relative molecular weight of the polybutadiene epoxy resin is 500-10000.

11. The coating according to claim 1, characterized in that: The filler includes one or a combination of talc, silica powder, barium sulfate, or mica powder.

12. The coating according to claim 1, characterized in that: The unblocking temperature of the blocked isocyanate resin is higher than that of the liquid latent epoxy accelerator.

13. The coating according to claim 12, characterized in that: The unblocking temperature of the blocked isocyanate resin is 140°C or higher, and the unblocking temperature of the liquid latent epoxy accelerator is 80-100°C.

14. The coating according to claim 1, characterized in that: The blocked isocyanate resin includes at least one of LEIC's EP-B 1186A and Wuhan Shiquanxing's S-3175.

15. The coating according to claim 1, characterized in that: The liquid latent epoxy accelerator includes at least one of 2-ethyl-4-methylimidazole and QXA101 from Shanghai Qianxing Materials.

16. The coating according to claim 1, characterized in that: The photoinitiator includes one or a combination of more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or 1-hydroxycyclohexylphenyl ketone.

17. The coating according to claim 1, characterized in that: The coating also includes 1.5-2.0 parts of additives, which include one or more of defoamers, dispersants, leveling agents or rheology modifiers.

18. The coating according to claim 1, characterized in that: The coating also includes 0.5-1.5 parts of colorant.

19. The coating according to claim 18, characterized in that: The colorant includes black colorant.

20. The coating according to claim 1, characterized in that: The vinylsiloxane includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltri(methoxyethoxy)silane.

21. A method for preparing the photothermal dual-curing multi-component hybrid coating according to any one of claims 1 to 20, characterized in that, include: Under inert atmosphere conditions, the first mixed reaction system containing epoxy resin, dimer acid and basic catalyst is subjected to a first reaction at a temperature of 110-130℃ to obtain an intermediate product. The second mixed reaction system containing the intermediate product and diethanolamine was reacted at a temperature of 85-105°C to obtain a polyol polymer. The first mixture containing 5.0-15.0 parts of polybutadiene epoxy resin, 10.0-20.0 parts of polyol polymer, 3.0-9.0 parts of filler and the first part of reactive diluent is uniformly mixed to obtain the first material; The coating is obtained by uniformly mixing the first material, 2.0-8.0 parts of blocked isocyanate resin, 0.2-0.3 parts of liquid latent epoxy accelerator, 0.5-2.0 parts of vinylsiloxane, 3.0-6.0 parts of photoinitiator, and a second part of reactive diluent. The total mass fraction of the first and second portions of reactive diluent is 40.0-60.0 parts.

22. The application of the photothermal dual-curing multi-component hybrid coating according to any one of claims 1 to 20 in the preparation of an insulating and anti-corrosion coating, wherein the insulating and anti-corrosion coating includes an insulating and anti-corrosion coating for automotive water-cooled panels.

23. A coating, characterized in that: The coating comprises the cured product of the photothermal dual-curing multi-component hybrid coating as described in any one of claims 1 to 20.

24. The method for preparing the coating according to claim 23, characterized in that: First, the photothermal dual-curing multi-component hybrid coating according to any one of claims 1 to 20 is photocured, and then thermally cured to obtain the coating.

25. The preparation method according to claim 24, characterized in that: The light intensity for photocuring is 10-160 mW / cm², and the temperature for thermocuring is 180-200℃.

26. The preparation method according to claim 24, characterized in that: The photocuring time is 30-60 seconds, and the thermal curing time is 1-3 minutes.

27. A water-cooled plate for new energy vehicles, comprising a water-cooled plate substrate and an insulating and anti-corrosion coating formed on the water-cooled plate substrate, characterized in that: The insulating and anti-corrosion coating includes the coating described in claim 23.

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