Coating applicable to various substrates and application

Abstract

The invention belongs to the technical field of coatings, and particularly relates to a coating suitable for various base materials and application. The coating comprises the following raw materials: acrylic resin, fluorocarbon resin, polyester resin, a flatting agent, a curing agent and a solvent for the coating, the acrylic resin comprises modified acrylic resin, and the acrylic resin comprises the following raw materials: a monomer, an initiator, a solvent for resin, an accelerant and a coupling agent; adding a monomer and a coupling agent into a head tank, uniformly mixing, adding an initiator, uniformly mixing to obtain a mixed liquid in the head tank, putting part of the solvent for resin into a reaction kettle, heating to a reflux state, starting to dropwise add the mixed liquid in the head tank, keeping the temperature after dropwise adding, cooling, adding an accelerant, uniformly mixing, adding the residual solvent for resin, and stirring to obtain a mixture; the modified acrylic resin is obtained. The coating can be applied to various substrates. The coating containing the acrylic resin and other resins is prepared, the acrylic resin can be well compatible with other resins, the alcohol resistance of the coating is good when the coating is applied, and the resistance of the coating to be separated from a base material is high.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to coatings suitable for a variety of substrates and their applications. Background Art

[0002] Most acrylic resins have poor compatibility with other resins in coatings, such as fluorocarbon resins, and the coatings are also prone to detachment and lack alcohol resistance when applied to substrates. The present invention aims to prepare a coating containing acrylic resin and other resins, wherein the acrylic resin has good compatibility with other resins, the coating has good alcohol resistance when applied, and the coating has strong resistance to detachment from the substrate. Summary of the invention

[0003] The present invention aims at the deficiencies of the prior art, provides a coating suitable for a variety of substrates, and provides related applications of the coating.

[0004] The technical solution of the present invention is as follows: In a first aspect, the present invention provides a coating suitable for a variety of substrates, wherein the coating comprises at least the following raw materials: acrylic resin, fluorocarbon resin, polyester resin, leveling agent, curing agent, and coating solvent.

[0005] In some implementations, the coating solvent includes butyl acetate, and the coating is prepared by mixing raw materials thereof.

[0006] In the second aspect, the present invention improves acrylic resin, the acrylic resin includes modified acrylic resin, the modified acrylic resin includes at least the following raw materials: monomer, initiator, resin solvent, promoter, coupling agent; the preparation method of the modified acrylic resin includes the following steps: Add monomer and coupling agent to the high-level tank, mix evenly, then add initiator, mix evenly again to obtain a mixed liquid in the high-level tank, put part of the resin solvent into the reactor, heat it to reflux state, start to drop the mixed liquid in the high-level tank, keep warm after the dropwise addition, then cool down and add accelerator, mix evenly, then add the remaining resin solvent to obtain modified acrylic resin.

[0007] In some implementations, the method for preparing the modified acrylic resin further comprises the following steps: The equipment used for the preparation includes a high-level tank and a reaction kettle, the high-level tank is connected to the reaction kettle, and the installation height of the high-level tank is higher than the reaction kettle; Add monomer and coupling agent to the high-level tank, mix evenly, then add initiator, mix evenly again to obtain a mixed liquid in the high-level tank, put part of the resin solvent into the reactor, heat to reflux state, temperature 100-150°C, start to drop the mixed liquid in the high-level tank, the drop time is 3-5 hours, after the drop addition is completed, keep warm for 1-4 hours, then cool to 60-70°C, add accelerator, mix evenly, then add the remaining resin solvent to dilute, to obtain modified acrylic resin.

[0008] In some implementations, the resin solvent includes butyl acetate, the monomer includes at least one of methyl methacrylate, isooctyl acrylate, acrylic acid, isobornyl methacrylate, and hydroxyethyl methacrylate, the initiator includes a peroxide initiator, and the peroxide initiator includes tert-butyl peroxy-3,5,5-trimethylhexanoate; and the coupling agent includes a vinyl silane coupling agent.

[0009] It should be noted that when preparing the modified acrylic resin, the inventors first introduced a vinyl-containing silane coupling agent and a variety of special acrylic monomers to copolymerize to modify the compatibility and alcohol resistance of the acrylic resin, and then added a promoter to enhance the material's adhesion to the substrate and alcohol resistance, and finally obtained an acrylic copolymer mixture material containing a silane coupling agent, namely, a modified acrylic resin.

[0010] In some implementations, by weight, methyl methacrylate is 10-20 parts, isooctyl acrylate is 20-40 parts, acrylic acid is 1-3 parts, isobornyl methacrylate is 20-30 parts, hydroxyethyl methacrylate is 10-20 parts, initiator is 2-4 parts, resin solvent is 30-40 parts, accelerator is 0.1-2 parts, and coupling agent is 0.1-3 parts.

[0011] In a third aspect, the present invention improves the accelerator, the accelerator includes a homemade accelerator, and the preparation method of the homemade accelerator includes the following steps: Weigh sodium tungstate and dissolve it in deionized water to obtain a metal salt solution; Weigh terephthalic acid and dissolve it in a mixed solvent to obtain a ligand solution; The metal salt solution and the ligand solution are mixed, transferred to a high-pressure reactor, sealed, heated, and kept reacting. After the reaction is completed, a suspension containing metal organic clusters is obtained; The suspension was cooled and filtered to obtain a solid product; washing the solid product, and drying after washing to obtain a dried solid product; The dried solid product is ultrasonically dispersed in anhydrous toluene, and after dispersion, methyltriethoxysilane and triethylamine are added or not to react to obtain a self-made promoter.

[0012] In some implementations, the mixed solvent includes DMF and toluene.

[0013] In some implementations, in the method for preparing a homemade promoter, a metal salt solution and a ligand solution are mixed, transferred to a high-pressure reactor, sealed and heated at 150-200° C., and the reaction is maintained for 12-36 hours. After the reaction is completed, a suspension containing metal organic clusters is obtained.

[0014] In some implementations, when methyltriethoxysilane and triethylamine are added to react, the relevant steps are: The dried solid product was ultrasonically dispersed in anhydrous toluene. After dispersion, methyltriethoxysilane and triethylamine were added. Under nitrogen protection, the mixture was heated to 60-90°C and stirred for reaction for 3-8 hours. After the reaction, the mixture was cooled to room temperature and filtered to obtain a homemade promoter, wherein the solid-liquid ratio of the dried solid product to methyltriethoxysilane was 2 g:0.5-1 mL.

[0015] In a fourth aspect, the present invention provides an application of the coating suitable for a variety of substrates on a variety of substrates, wherein the coating can be sprayed and / or cured on a variety of substrates after the viscosity is adjusted, wherein the substrates include bare steel plates, PET, EVA, stainless steel, and galvanized plates; the viscosity is adjusted as follows: the viscosity of the coating is adjusted, and the viscosity of the coating is measured to be 22-28 seconds at 25°C using the coating-4 cup method.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention prepares a coating containing acrylic resin and provides related applications of the coating. When preparing the coating, the acrylic resin is first modified and then the promoter is improved. Specifically: (1) The present application provides method 1 to improve the preparation method of acrylic resin and provides examples 1 to 3. In method 1, different monomer combinations (methyl methacrylate, isooctyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate) are used to adjust the amount and conditions of initiator, solvent, promoter and coupling agent to obtain an acrylic resin with high compatibility and alcohol resistance. The preparation adopts a dropwise addition method. After adding the mixed liquid to the high-level tank, it is added dropwise to the reactor and the reaction temperature and time are controlled. (2) The present application provides method 2 to improve the promoter for acrylic resin and provides examples 4 to 7. In method 2, sodium tungstate and terephthalic acid are used to prepare metal organic clusters, and the surface is modified by methyltriethoxysilane and triethylamine to enhance its bonding strength with the substrate. In addition, by adjusting the heating temperature and the ratio of reactants, the performance of the accelerator is optimized, and the performance of the acrylic resin can be further improved when applied. (3) The present application provides method 3 for preparing coatings for different substrates, and methods for using the coatings. Examples 8 to 42 and comparative examples 1 to 5 are provided, and examples 1 to 7 are applied to examples 8 to 42, and the finished products of examples 8 to 42 and comparative examples 1 to 5 are tested.

[0017] 2. Other explanations: 1. Technical problems: 1) The difference in the reaction rate of each monomer will lead to uneven polymer chain structure, which will lead to a lack of consistency in the microstructure of the generated polymer, thereby affecting its mechanical properties and chemical stability. 2) The present invention requires that acrylic resins can show better performance on different substrates when applied to a variety of substrates. However, since the raw materials contain hydrophobic monomers and hydrophilic monomers, this combination may lead to poor compatibility, thereby reducing the adhesion of the coating. Poor compatibility between different monomers will lead to phase separation inside the polymer, affecting the performance of the coating. Especially when applied to different substrates, the compatibility problem will be more obvious. 2. Technical means adopted by the present invention: 1) The monomers and coupling agents are gradually mixed in the high-level tank, and then the initiator is mixed, and the mixed solution is added dropwise to the reactor, the dropping time is controlled, the reaction temperature is optimized, the uniformity of the reaction is ensured, and the problem of excessive growth of local polymer chains is avoided, thereby forming a polymer with a consistent microstructure. 2) It should be noted that butyl acetate evaporates quickly, butyl acetate is usually added first, and the reaction temperature is low. However, in this application, butyl acetate is not added at the beginning, but is added in batches at different reaction stages to increase the reaction temperature. It is found that the technical solution of this application can more effectively mix various monomers, prevent phase separation, and ensure good compatibility between all monomers during the reaction, thereby making the generated polymer have higher structural uniformity and excellent adhesion properties. 3) Synergistic effect of coupling agent and promoter: When using coupling agent and promoter, the promoter provides an active center, so that the resin can react better during the curing process, and the coupling agent forms a strong chemical bond between the substrate and the coating. After improving the promoter, its synergistic effect is further enhanced. The coupling agent and monomer are first mixed and prepared, which can pre-modify multiple monomers. The promoter is added after cooling, and the acrylic copolymer mixture is further modified to obtain a modified acrylic resin.

[0018] In summary, the present invention prepares a coating containing acrylic resin and other resins. The acrylic resin has good compatibility with other resins. The prepared coating can be applied to a variety of substrates, and the coating formed by the coating has good alcohol resistance and strong resistance to detachment from the substrate. The homemade accelerator can further improve the bonding strength between the coating and the substrate. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. The experimental methods used below are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, can all be obtained from commercial sources.

[0020] 1. Improved acrylic resin Method 1: The raw materials include monomers, initiators, solvents, accelerators, and coupling agents, which are as follows by weight: 1. Monomers include: 10-20 parts of methyl methacrylate; 20-40 parts of isooctyl acrylate; 1-3 parts of acrylic acid; Isobornyl methacrylate 20-30 parts; 10-20 parts of hydroxyethyl methacrylate; 2. Initiators include: Peroxide initiator: tert-butyl peroxy-3,5,5-trimethylhexanoate, 2-4 parts; 3. Solvents include: 30-40 parts of butyl acetate; 4. Accelerators include: Adhesion promoter 0.1-2 parts; 5. Coupling agent Vinyl silane coupling agent 0.1-3 parts.

[0021] The preparation method of modified acrylic resin comprises the following specific steps: 1. The equipment used for preparation includes a high-level tank and a reactor. The high-level tank is connected to the reactor, and the installation height of the high-level tank is higher than the reactor.

[0022] 2. Add monomer and coupling agent to the high-level tank, mix evenly, then add initiator, mix evenly again, and obtain the mixed liquid in the high-level tank. Add part of butyl acetate to the reactor, heat to reflux state, temperature 100-150℃, start dripping the mixed liquid in the high-level tank, and the dripping time is 3-5 hours. After the dripping is completed, keep warm for 1-4 hours, then cool to 60-70℃, add accelerator, mix evenly, then add the remaining butyl acetate to dilute, detect and adjust the solid content, obtain modified acrylic resin, and package.

[0023] Method 1 is further implemented by way of example below: By weight, refer to Table 1: Example 1: Add 5 kinds of monomers and coupling agents to the header tank, mix them evenly, then add the initiator, mix them evenly again, and obtain the mixed liquid in the header tank. Add 15 parts of butyl acetate into the reactor, heat it to reflux state, the temperature is 125°C, and start dripping the mixed liquid in the header tank for 4 hours. After the dripping is completed, keep warm for 2 hours, then cool it to 65°C, add the accelerator, mix evenly, then add 20 parts of butyl acetate to dilute, detect and adjust the solid content, obtain the modified acrylic resin, and package it. The rest is the same as method 1.

[0024] Example 2: Add 5 kinds of monomers and coupling agents to the header tank, mix them evenly, then add the initiator, mix them evenly again, and obtain the mixed liquid in the header tank. Add 15 parts of butyl acetate into the reactor, heat it to reflux state, the temperature is 125°C, and start dripping the mixed liquid in the header tank for 3.5 hours. After the dripping is completed, keep warm for 2 hours, then cool it to 60°C, add the promoter, mix evenly, add 15 parts of butyl acetate to dilute, detect and adjust the solid content, obtain the modified acrylic resin, and package it. The rest is the same as method 1.

[0025] Example 3: Add 5 kinds of monomers and coupling agents to the header tank, mix them evenly, then add the initiator, mix them evenly again, and obtain the mixed liquid in the header tank. Add 20 parts of butyl acetate into the reactor, heat it to reflux state, the temperature is 125°C, and start dripping the mixed liquid in the header tank for 5 hours. After the dripping is completed, keep warm for 2 hours, then cool it to 70°C, add the promoter, mix evenly, then add 20 parts of butyl acetate to dilute, detect and adjust the solid content, obtain the modified acrylic resin, and package it. The rest is the same as method 1.

[0026] Table 1

[0027] The purity of the raw materials in the examples and comparative examples and the manufacturers from which they can be purchased are provided below: 1. Monomer: Methyl methacrylate, 99% purity, manufacturer: Sigma-Aldrich, product number: M55909; Isooctyl acrylate, 99.5% purity, Jinan Century Tongda Chemical Co., Ltd.; Acrylic acid, 99% purity, Jiangsu Pulex Biotechnology Co., Ltd.; Isobornyl methacrylate, 99% purity, Quzhou Fangda Chemical Co., Ltd.; Hydroxyethyl methacrylate, 98% purity, Qingdao Reinars Polymer Materials Co., Ltd.; 2. Initiator: Tert-butyl peroxy-3,5,5-trimethylhexanoate, 97% purity, Shanghai Myril Biochemical Technology Co., Ltd.; 3. Solvent: Butyl acetate, 99.5% purity, Shanghai Boer Chemical Reagent Co., Ltd.; 4. Accelerator: Adhesion promoter, manufacturer: BYK, product number: BYK-4510, effective content: 100%; 5. Coupling agent Vinyl silane coupling agent, 99% purity, Hubei Zhonglong Kangsheng Fine Chemical Co., Ltd.

[0028] (II) Further improvement of accelerator Method 2: The steps of preparing the homemade accelerator are as follows: Weigh sodium tungstate and dissolve it in deionized water to obtain a metal salt solution.

[0029] Terephthalic acid is weighed and dissolved in a mixed solvent to obtain a ligand solution, wherein the mixed solvent comprises DMF and toluene.

[0030] The metal salt solution and the ligand solution are mixed and transferred to a high-pressure reactor, which is sealed and heated to maintain the reaction. After the reaction is completed, a suspension containing metal organic clusters is obtained.

[0031] The suspension was cooled to room temperature and filtered to obtain a solid product.

[0032] The solid product was washed alternately with anhydrous ethanol and deionized water until the filtrate became colorless.

[0033] Then, the solid product is vacuum dried to obtain a dried solid product.

[0034] The dried solid product is ultrasonically dispersed in anhydrous toluene. After dispersion, methyltriethoxysilane and triethylamine are added. Under nitrogen protection, the mixture is heated and stirred for reaction. After the reaction, the mixture is cooled to room temperature and filtered to obtain a promoter.

[0035] Method 2 is further implemented by way of example below: Example 4 Weigh 2 g of sodium tungstate and dissolve it in 20 mL of deionized water to obtain a metal salt solution.

[0036] Weigh 1.5 g of terephthalic acid and dissolve it in 30 mL of a mixed solvent to obtain a ligand solution, wherein the mixed solvent has a ratio of DMF to toluene of 1:1 by mass.

[0037] The metal salt solution and the ligand solution were mixed and transferred to a high-pressure reactor, which was sealed and heated at 180°C for 24 hours. After the reaction was completed, a suspension containing metal organic clusters was obtained.

[0038] The suspension was cooled to room temperature and filtered to obtain a solid product.

[0039] The solid product was washed alternately with anhydrous ethanol and deionized water until the filtrate became colorless.

[0040] Then, the solid product was vacuum dried at 60° C. to obtain a dried solid product.

[0041] Take 2 g of the dried solid product and ultrasonically disperse it in 50 mL of anhydrous toluene. After dispersion, add 1 mL of methyltriethoxysilane and 3-5 drops of triethylamine (about 0.2 mL). Under nitrogen protection, heat to 80°C and stir to react for 6 hours. After the reaction, cool to room temperature and filter to obtain the promoter.

[0042] Example 5 Different from Example 4, the heating temperature is changed, specifically: The metal salt solution and the ligand solution were mixed and transferred to a high-pressure reactor, which was sealed and heated at 200°C for 24 hours. After the reaction was completed, a suspension containing metal organic clusters was obtained.

[0043] The remaining steps are the same as those in Example 4.

[0044] Example 6 Different from Example 4, the amount of silane used is reduced, specifically: Take 2 g of the dried solid product and ultrasonically disperse it in 50 mL of anhydrous toluene. After dispersion, add 0.5 mL of methyltriethoxysilane and 3-5 drops of triethylamine (about 0.2 mL). Under nitrogen protection, heat to 80°C and stir to react for 6 hours. After the reaction, cool to room temperature and filter to obtain the promoter.

[0045] The remaining steps are the same as those in Example 4.

[0046] Example 7 Different from Example 4, no surface modification is performed, specifically: 2 g of the dried solid product was taken and ultrasonically dispersed in 50 mL of anhydrous toluene to obtain a promoter.

[0047] The remaining steps are the same as those in Example 4.

[0048] (III) Application Method 3: The present application provides a method for preparing a coating, and the specific steps are as follows: Prepare the raw materials required for each component, including acrylic resin, fluorocarbon resin, polyester resin, leveling agent, curing agent, and solvent. Stir and mix the raw materials according to weight to obtain a coating.

[0049] The specific steps for using the paint are as follows: Adjust the construction viscosity: adjust the prepared coating to the required construction viscosity, use the Tu-4 cup to measure the construction viscosity, measure at 25°C, and control the viscosity between 22-28 seconds to obtain the treated coating.

[0050] Substrate treatment: Before coating, the surface of the substrate is cleaned to remove dust, oil, etc. to ensure a good combination of the coating and the substrate to obtain a treated substrate.

[0051] Coating: Spray the treated coating onto the treated substrate. During spraying, use an air spray gun with a spraying pressure of 0.3-0.5 MPa and a spraying thickness of 25-70 μm to obtain a sprayed substrate.

[0052] Baking: After coating, the sprayed substrate is placed in an oven for baking and curing. The curing temperature is set to 90° C. and the baking time is 30 minutes to obtain a composite material.

[0053] Method 3 is further implemented below through examples and comparative examples: 1. When the substrate is bare steel plate: Example 8 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 1. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a bare steel plate.

[0054] Example 9 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 2. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a bare steel plate.

[0055] Example 10 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 3. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the method for using the coating in Method 3. Wherein, the substrate is a bare steel plate.

[0056] Embodiment 11 Different from Example 10, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 4. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a bare steel plate.

[0057] The rest is the same as Example 10.

[0058] Example 12 Different from Example 10, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 5. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a bare steel plate.

[0059] The rest is the same as Example 10.

[0060] Example 13 Different from Example 10, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 6. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a bare steel plate.

[0061] The rest is the same as Example 10.

[0062] Embodiment 14 Different from Example 10, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 7. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a bare steel plate.

[0063] The rest is the same as Example 10.

[0064] Comparative Example 1 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is an existing product, and its manufacturer model is: 100% content, Paraloid B-44, Rohm and Haas Company. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a bare steel plate.

[0065] 2. When the substrate is PET: Embodiment 15 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 1. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is PET.

[0066] Example 16 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 2. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is PET.

[0067] Embodiment 17 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 3. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is PET.

[0068] Embodiment 18 Different from Example 17, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 4. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is PET.

[0069] The rest is the same as Example 17.

[0070] Embodiment 19 Different from Example 17, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 5. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is PET.

[0071] The rest is the same as Example 17.

[0072] Embodiment 20 Different from Example 17, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 6. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is PET.

[0073] The rest is the same as Example 17.

[0074] Embodiment 21 Different from Example 17, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 7. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is PET.

[0075] The rest is the same as Example 17.

[0076] Comparative Example 2 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is an existing product, and its manufacturer model is: 100% content, Paraloid B-44, Rohm and Haas Company. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is PET.

[0077] 3. When the substrate is EVA: Embodiment 22 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 1. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is EVA.

[0078] Embodiment 23 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 2. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is EVA.

[0079] Embodiment 24 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 3. The raw materials are stirred and mixed according to weight to obtain a coating. Then, a composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is EVA.

[0080] Embodiment 25 Different from Example 24, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 4. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is EVA.

[0081] The rest is the same as Example 24.

[0082] Embodiment 26 Different from Example 24, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 5. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is EVA.

[0083] The rest is the same as Example 24.

[0084] Embodiment 27 Different from Example 24, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 6. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is EVA.

[0085] The rest is the same as Example 24.

[0086] Embodiment 28 Different from Example 24, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 7. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is EVA.

[0087] The rest is the same as Example 24.

[0088] Comparative Example 3 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is an existing product, and its manufacturer model is: 100% content, Paraloid B-44, Rohm and Haas Company. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is EVA.

[0089] 4. When the substrate is stainless steel: Embodiment 29 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 1. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is stainless steel.

[0090] Embodiment 30 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 2. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is stainless steel.

[0091] Embodiment 31 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 3. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is stainless steel.

[0092] Embodiment 32 Different from Example 31, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 4. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is stainless steel.

[0093] The rest is the same as Example 31.

[0094] Embodiment 33 Different from Example 31, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 5. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is stainless steel.

[0095] The rest is the same as Example 31.

[0096] Embodiment 34 Different from Example 31, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 6. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is stainless steel.

[0097] The rest is the same as Example 31.

[0098] Embodiment 35 Different from Example 31, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 7. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is stainless steel.

[0099] The rest is the same as Example 31.

[0100] Comparative Example 4 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is an existing product, and its manufacturer model is: 100% content, Paraloid B-44, Rohm and Haas Company. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Among them, the substrate is stainless steel.

[0101] 5. When the substrate is galvanized sheet: Embodiment 36 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 1. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a galvanized sheet.

[0102] Embodiment 37 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 2. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a galvanized sheet.

[0103] Embodiment 38 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is the modified acrylic resin prepared in Example 3. The raw materials are stirred and mixed according to weight to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a galvanized sheet.

[0104] Embodiment 39 Different from Example 38, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 4. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a galvanized sheet.

[0105] The rest is the same as Example 38.

[0106] Embodiment 40 Different from Example 38, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 5. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a galvanized sheet.

[0107] The rest is the same as Example 38.

[0108] Embodiment 41 Different from Example 38, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 6. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a galvanized sheet.

[0109] The rest is the same as Example 38.

[0110] Embodiment 42 Different from Example 38, referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is prepared according to the method of Example 3, but the accelerator is changed, and the accelerator is the accelerator of Example 7. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the method of using the coating of Method 3. Wherein, the substrate is a galvanized sheet.

[0111] The rest is the same as Example 38.

[0112] Comparative Example 5 Referring to Table 2, the raw materials required for each component are prepared, wherein the acrylic resin is an existing product, and its manufacturer model is: 100% content, Paraloid B-44, Rohm and Haas Company. The raw materials are stirred and mixed according to weight parts to obtain a coating. Then, the composite material is obtained by referring to the coating use method of method 3. Wherein, the substrate is a galvanized sheet.

[0113] Table 2

[0114] (IV) Testing The composite materials of Examples 8 to 35 and Comparative Examples 1 to 4 were tested: 1.Performance under normal conditions: The test is carried out in accordance with GB / T9286-2021 / ISO2409:2020 Scratch test for paints and varnishes. The test results are rated in accordance with the above standards and divided into 0-5 levels, 0-good and 5-poor.

[0115] 2. Water resistance Place the sample in a 40℃ constant temperature water tank and soak for 10 days. After 10 days, take out the sample, dry it, and test it according to GB / T9286-2021 / ISO2409:2020 Paint and varnish cross-cut test. The test results are rated according to the above standards and divided into 0-5 levels, 0-good, 5-poor.

[0116] 3. Alcohol resistance Use an alcohol abrasion tester, set a pressure of 1kg, use alcohol as the test medium, and record the number of times the coating is wiped until it becomes transparent or wrinkled.

[0117] It should be noted that "GB / T9286-2021 / ISO2409:2020 Scratch test for paints and varnishes" can evaluate the resistance of the coating to detachment from the substrate.

[0118] The results of the above tests are shown in Table 3.

[0119] Table 3

[0120] analyze: First, the present application provides a method 1 to improve the preparation method of acrylic resin, and provides examples 1 to 3. In method 1, different monomer combinations (methyl methacrylate, isooctyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate) are used, and the amount and conditions of the initiator, solvent, promoter and coupling agent are adjusted to obtain an acrylic resin with high compatibility and alcohol resistance. The preparation adopts a dropwise addition method, after adding the mixed liquid to the high-level tank, it is added dropwise to the reactor and the reaction temperature and time are controlled.

[0121] Then the present application provides method 2 to improve the promoter for acrylic resin, and provides examples 4-7. In method 2, sodium tungstate and terephthalic acid are used to prepare metal organic clusters, and methyltriethoxysilane and triethylamine are used for surface modification to enhance their binding force with the substrate. In addition, the performance of the promoter is optimized by adjusting the heating temperature and the ratio of reactants, and thus the performance of the acrylic resin can be improved when applied. It should be noted that, through Example 5, it was found that: when reacted at 200°C, the metal organic cluster formed a more stable coordination structure, the chemical activity of the promoter was higher, and the adhesion was stronger. Through Example 6, it was found that: when methyltriethoxysilane was used as a silane modifier, its dosage was reduced to 0.5 mL, which would lead to a decrease in the binding force between the final product (promoter) and the substrate, but when the dosage was reduced, the cost could be saved to a certain extent, so it is suitable for some occasions with lower adhesion requirements. Through Example 7, it is found that when no modification is performed, although the preparation process can be simplified and the amount of raw materials can be reduced, the subsequent bonding between the resin and the substrate will decrease, which is inferior to that of Examples 4 to 6, indicating that modification has a significant effect on improving the performance of the accelerator. However, Example 7 is still better than Examples 1 to 3 in subsequent applications, which shows that multiple factors such as performance and cost can be balanced according to actual needs.

[0122] Next, the present application provides method 3 for preparing coatings for different substrates, and methods for using the coatings. Examples 8 to 42 and comparative examples 1 to 5 are provided, and examples 1 to 7 are applied to examples 8 to 42, and the finished products of examples 8 to 42 and comparative examples 1 to 5 are tested.

[0123] Referring to Table 3, we can see from the data: When the improved acrylic resin prepared by method 1 of the present application is applied to different substrates, its bonding effect with the substrate is better than that of the existing acrylic resin.

[0124] Furthermore, the accelerator prepared by method 2 of the present application can further improve the bonding effect between the acrylic resin and the substrate.

[0125] When comparing different substrates, the improved acrylic resin of the present application performs better when applied to a PET substrate, but this is relative, and the changing factors need to be controlled when making comparisons, such as comparing Example 8, Example 15, Example 22, Example 29, and Example 36 at the same time.

[0126] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A coating suitable for a variety of substrates, characterized in that: The coating comprises at least the following raw materials: acrylic resin, fluorocarbon resin, polyester resin, leveling agent, curing agent, and coating solvent. The acrylic resin includes a modified acrylic resin, and the modified acrylic resin includes at least the following raw materials: a monomer, an initiator, a resin solvent, a promoter, and a coupling agent; and the preparation method of the modified acrylic resin includes the following steps: Add monomer and coupling agent to the high-level tank, mix evenly, then add initiator, mix evenly again to obtain a mixed liquid in the high-level tank, put part of the resin solvent into the reactor, heat it to reflux state, start to drop the mixed liquid in the high-level tank, keep warm after the dropwise addition, then cool down and add accelerator, mix evenly, then add the remaining resin solvent to obtain modified acrylic resin.

2. The coating material applicable to various substrates according to claim 1, characterized in that: The preparation method of the modified acrylic resin also includes the following steps: The equipment used for the preparation includes a high-level tank and a reaction kettle, the high-level tank is connected to the reaction kettle, and the installation height of the high-level tank is higher than the reaction kettle; Add monomer and coupling agent to the high-level tank, mix evenly, then add initiator, mix evenly again to obtain a mixed liquid in the high-level tank, put part of the resin solvent into the reactor, heat to reflux state, temperature 100-150°C, start to drop the mixed liquid in the high-level tank, the drop time is 3-5 hours, after the drop addition is completed, keep warm for 1-4 hours, then cool to 60-70°C, add accelerator, mix evenly, then add the remaining resin solvent to dilute, to obtain modified acrylic resin.

3. The coating material applicable to various substrates according to claim 1, characterized in that: The coating solvent includes butyl acetate, and the coating is prepared by mixing the raw materials thereof.

4. The coating material applicable to various substrates according to claim 1, characterized in that: The resin solvent includes butyl acetate, the monomer includes at least one of methyl methacrylate, isooctyl acrylate, acrylic acid, isobornyl methacrylate, and hydroxyethyl methacrylate, the initiator includes a peroxide initiator, and the peroxide initiator includes tert-butyl peroxy-3,5,5-trimethylhexanoate; and the coupling agent includes a vinyl silane coupling agent.

5. The coating material applicable to various substrates according to claim 4, characterized in that: By weight, 10-20 parts of methyl methacrylate, 20-40 parts of isooctyl acrylate, 1-3 parts of acrylic acid, 20-30 parts of isobornyl methacrylate, 10-20 parts of hydroxyethyl methacrylate, 2-4 parts of initiator, 30-40 parts of resin solvent, 0.1-2 parts of accelerator, and 0.1-3 parts of coupling agent.

6. The coating material applicable to various substrates according to claim 1, characterized in that: The accelerator includes a self-made accelerator, and the preparation method of the self-made accelerator includes the following steps: Weigh sodium tungstate and dissolve it in deionized water to obtain a metal salt solution; Weigh terephthalic acid, and dissolve it in a mixed solvent to obtain a ligand solution; The metal salt solution and the ligand solution are mixed, transferred to a high-pressure reactor, sealed, heated, and kept reacting. After the reaction is completed, a suspension containing metal organic clusters is obtained; The suspension was cooled and filtered to obtain a solid product; washing the solid product, and drying after washing to obtain a dried solid product; The dried solid product is ultrasonically dispersed in anhydrous toluene, and after dispersion, methyltriethoxysilane and triethylamine are added or not to react to obtain a self-made promoter.

7. The coating material applicable to various substrates according to claim 6, characterized in that: The mixed solvent includes DMF and toluene.

8. The coating material applicable to various substrates according to claim 6, characterized in that: In the preparation method of the homemade promoter, the metal salt solution and the ligand solution are mixed, transferred to a high-pressure reactor, sealed and heated at 150-200°C, and the reaction is maintained for 12-36 hours. After the reaction is completed, a suspension containing metal organic clusters is obtained.

9. The coating material applicable to various substrates according to claim 6, characterized in that: When methyltriethoxysilane and triethylamine are added to react, the mixture is heated to 60-90°C under nitrogen protection and stirred for reaction for 3-8 hours. After the reaction, the mixture is cooled to room temperature and filtered to obtain a homemade promoter, wherein the solid-liquid ratio of the dried solid product to methyltriethoxysilane is 2 g:0.5-1 mL.

10. Use of the coating suitable for various substrates according to any one of claims 1 to 9 on various substrates, characterized in that: After the viscosity of the coating is adjusted, it can be sprayed and / or cured on a variety of substrates, wherein the substrates include bare steel plates, PET, EVA, stainless steel, and galvanized plates; the viscosity is adjusted as follows: the viscosity of the coating is adjusted, and the viscosity of the coating is measured to be 22-28 seconds at 25° C. using the coating-4 cup method.

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