High-adhesive-force primer for vehicles and preparation method of high-adhesive-force primer

Abstract

The invention relates to the technical field of primer, in particular to high-adhesion primer for a vehicle and a preparation method of the high-adhesion primer. The high-adhesion primer for the vehicle comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 20-30 parts of amino resin, 4-6 parts of granules, 2-4 parts of pigment, 2-4 parts of polyethylene glycol, 0.6-0.8 part of a defoaming agent, 0.6-0.8 part of a flatting agent and 0.06-0.08 part of modified cardanol. In the second base material, hydroxyethyl methylacrylate is polymerized to form an organic shell, dibenzoyl peroxide initiates free radical crosslinking, diallyl phthalate serves as a cross-linking agent to form a wear-resistant polymer network, microspheres can form a core-shell structure through physical mixing and chemical modification, the hardness is enhanced through an inner core of the microspheres, and the wear resistance of the microspheres is improved. The interface bonding between the shell and the resin matrix is improved, so that the automotive primer is stably bonded with a coating surface, and the adhesive force of the automotive primer is improved.

Description

Technical Field

[0001] The invention relates to the technical field of primers, in particular to a high-adhesion automotive primer and a preparation method thereof. Background Art

[0002] Automotive primer is the first layer of coating in the automotive painting process. Its main function is to enhance the adhesion between the substrate and the topcoat, laying the foundation for subsequent topcoat spraying. It is a key link in ensuring the quality and service life of the automotive paint.

[0003] In the prior art, existing automotive primers lack polar groups in their resin base, resulting in weak bonding ability with metal interfaces. This reduces the density of the primer coating and affects the primer's adhesion. Based on this, the present invention provides a high-adhesion automotive primer and a method for preparing the same. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-adhesion automotive primer and a preparation method thereof. The high-adhesion automotive primer prepared by the present invention not only has good adhesion performance, but also has excellent wear resistance, thereby effectively improving the performance of the automotive primer.

[0005] To achieve the above object, the present invention provides the following technical solutions: In a first aspect, the present invention provides a high-adhesion automotive primer comprising the following raw materials in parts by weight: 40 to 60 parts of epoxy resin, 20 to 30 parts of amino resin, 4 to 6 parts of granular material, 2 to 4 parts of pigment, 2 to 4 parts of polyethylene glycol, 0.6 to 0.8 parts of defoaming agent, 0.6 to 0.8 parts of leveling agent, and 0.06 to 0.08 parts of modified cardanol; The preparation of the granular material comprises the following steps: S1: Preparation of the first base material. The raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water. The mass ratio of the raw materials is 1: (0.2-0.4): (0.1-0.3): (0.1-0.3): (4-6); S2: Preparation of the second base material, wherein the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of the raw materials is 1: (1.5-2.5): (0.04-0.06): (0.8-1.2); S3: preparing microspheres, mixing the first base material and the second base material to prepare microspheres; S4: Microsphere modification, modifying the microspheres prepared in S3 to obtain granular materials.

[0006] Furthermore, the method for preparing the first base material is: magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water are weighed as needed and added into a mixer, and the mixer is set at 200-300 r / min and stirred for 20-30 minutes to obtain the first base material.

[0007] Furthermore, the method for preparing the second base material is: weighing isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate as needed and adding them into a water bath, setting the water bath temperature to 40-42°C, connecting the water bath to a magnetic stirrer, setting the speed of the magnetic stirrer to 120-160 r / min, and stirring at a constant temperature for 10-20 minutes to obtain the second base material.

[0008] Furthermore, the method for preparing the microspheres is as follows: the first base material is added to the mixer, the mixer is set to 800-1000 r / min for stirring, and the stirring time is 10-20 min. During the stirring process, the second base material is added to the mixer at a uniform speed, and then the modified cardanol is added to the mixer, the mixer is set to 400-600 r / min, and the stirring is carried out for 20-30 min to obtain a mixed solution.

[0009] Furthermore, the mixed liquid is added to a reactor, nitrogen is introduced into the reactor, the pressure is set to 0.4-0.6 MPa, the temperature is set to 60-80°C, the speed is set to 300-500 r / min, and the mixture is stirred at a constant temperature for 6-8 hours. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 4-6. The obtained product is filtered and washed with water to obtain a filter cake. The filter cake is sent to an oven, the oven is set at 40-50°C, and dried for 4-6 hours. The obtained product is ground to a particle size of 4-10 μm to obtain microspheres.

[0010] Furthermore, the microsphere modification method is as follows: the microspheres are added to a mixer, 1-butyl-3-methylimidazole chloride is added to the mixer, the mixer is set to 60-80 r / min and stirred for 1-3 hours, the obtained product is rinsed with deionized water, and then sent to an oven, the oven is set to 50-60 ° C, and dried for 2-3 hours, the dried product and polydiallyldimethylammonium chloride are added to the mixer, the mixer is set to 200-300 r / min and stirred for 10-20 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water to obtain a mixture, and mixed The material and the treatment liquid are added to a mixer, the mass of the treatment liquid is 16% to 22% of the mass of the mixed material, the mixer is set at 400 to 600 r / min and stirred for 20 to 30 minutes, and then ultrasonic dispersion treatment is carried out for 10 to 20 minutes. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent to an oven, the oven is set at 50 to 60° C., and dried for 4 to 6 hours to obtain a granular material, wherein the mass of 1-butyl-3-methylimidazole chloride is 2% to 3% of the mass of the microspheres, and the mass of polydiallyldimethylammonium chloride is 1% to 2% of the mass of the microspheres.

[0011] Furthermore, the treatment liquid is prepared by the following method: silicon dioxide, antimony tin oxide and deionized water are mixed, sodium hydroxide solution is added, the pH value is adjusted to 10-11, and then ultrasonic dispersion treatment is performed for 20-30 minutes to prepare the treatment liquid, wherein the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1: (0.4-0.6): (2-4), and the particle size of silicon dioxide and antimony tin oxide is 10-40 nm.

[0012] Furthermore, the modified cardanol is prepared by the following method: cardanol and epichlorohydrin are added to a flask, followed by adding potassium hydroxide, heating to 60-70°C, and reflux reaction for 2-4 hours. The obtained product is washed with deionized water and then subjected to reduced pressure distillation to prepare modified cardanol, wherein the mass ratio of cardanol to epichlorohydrin is 1:(1.4-1.6), and the mass of potassium hydroxide is 4%-6% of the mass of cardanol.

[0013] Furthermore, the defoaming agent is an organosilicon defoaming agent, and the leveling agent is polydimethylsiloxane.

[0014] In a second aspect, the present invention also provides a method for preparing a high-adhesion automotive primer, comprising the following steps: weighing epoxy resin, amino resin, granular material, pigment, polyethylene glycol, defoaming agent and leveling agent as needed and adding them into a mixer, setting the mixer to 1000-1400 r / min and stirring for 30-40 minutes to obtain a high-adhesion automotive primer.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, particulate materials are added during the preparation of the automotive primer, wherein the first base material uses magnesium hydroxide as an inorganic core to provide rigid support, polyvinyl pyrrolidone is used as a dispersant to ensure the uniformity of mixing of the materials, the second base material uses hydroxyethyl methacrylate to polymerize to form an organic shell, dibenzoyl peroxide triggers free radical crosslinking, and diallyl phthalate is used as a crosslinking agent to form a wear-resistant polymer network. The microspheres can form a core-shell structure through physical mixing and chemical modification, and the core is used to enhance the hardness, and the shell improves the interface bonding with the resin matrix, thereby ensuring that the automotive primer is firmly bonded to the coating surface and improving the adhesion of the automotive primer.

[0016] 2. In the present invention, the epoxy groups of the modified cardanol are covalently cross-linked with the epoxy groups in the epoxy resin or the hydroxyl groups in the amino resin to form a dense network structure, thereby enhancing the chemical bonding between the primer and the metal substrate. At the same time, the epoxy groups of the modified cardanol and the surface of the microspheres, such as 1-butyl-3-methylimidazole chloride, produce electrostatic adsorption, thereby promoting the uniform dispersion of the particles in the resin matrix, reducing interface defects, and reducing the risk of particles falling off the primer coating surface during friction, thereby effectively improving the wear resistance of the automotive primer. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 A flow chart of a high-adhesion automotive primer and its preparation method is proposed for the invention; Figure 2 The present invention provides a flow chart for preparing granular materials for a high-adhesion automotive primer and a preparation method thereof. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0019] It should be noted that the raw materials used in the following examples are all commercially available raw materials.

[0020] Example 1:

[0021] S1: Preparation of the first base material. The raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water. The mass ratio of the raw materials is 1:0.2:0.1:0.1:4; The first base material is prepared by weighing magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water as needed and adding them into a mixer, setting the mixer at 200 r / min and stirring for 20 minutes to prepare the first base material; S2: Preparation of the second base material, wherein the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of the raw materials is 1:1.5:0.04:0.8; The second base material is prepared by weighing isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide, and diallyl phthalate as needed and adding them to a water bath, setting the water bath temperature to 40° C., connecting the water bath to a magnetic stirrer, setting the magnetic stirrer speed to 120 rpm, and stirring at constant temperature for 10 minutes to prepare the second base material. S3: preparing microspheres, mixing the first base material and the second base material to prepare microspheres; The method for preparing microspheres is as follows: the first base material is added to the mixer, the mixer is set to 800r / min for stirring, and the stirring time is 10min. During the stirring process, the second base material is added to the mixer at a uniform speed, and then the modified cardanol is added to the mixer, the mixer is set to 400r / min, and the stirring is carried out for 20min to obtain a mixed solution, which is added to the reactor. Nitrogen is introduced into the reactor, the pressure is set to 0.4Mpa, the temperature is set to 60°C, the speed is set to 300r / min, and the constant temperature stirring is carried out for 6h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 4. The obtained product is filtered and washed with water to obtain a filter cake. The filter cake is sent to an oven, the oven is set to 40°C, and dried for 4h. The obtained product is ground to a particle size of 4μm to obtain microspheres. S4: microsphere modification, modifying the microspheres prepared in S3 to obtain granular materials; The method for modifying the microspheres is as follows: the microspheres are added to a mixer, 1-butyl-3-methylimidazole chloride is added to the mixer, the mixer is set to 60 r / min and stirred for 1 hour, the obtained product is rinsed with deionized water, and then sent to an oven, the oven is set to 50°C, and dried for 2 hours, the dried product and polydiallyldimethylammonium chloride are added to the mixer, the mixer is set to 200 r / min and stirred for 10 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water to prepare a mixture, the mixture and the treatment liquid are added to the mixer, the mass of the treatment liquid is 16% of the mass of the mixture, the mixer is set to 400 r / min and stirred for 20 minutes, and then ultrasonic dispersion is performed. The treatment time is 10 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water and then sent to an oven, the oven is set at 50°C, and the drying treatment is performed for 4 hours to obtain a granular material, wherein the mass of 1-butyl-3-methylimidazole chloride is 2% of the mass of the microspheres, and the mass of polydiallyldimethylammonium chloride is 1% of the mass of the microspheres. The treatment liquid is prepared by the following method: silicon dioxide, antimony tin oxide and deionized water are mixed, sodium hydroxide solution is added, the pH value is adjusted to 10, and then ultrasonic dispersion treatment is performed for 20 minutes to obtain a treatment liquid, wherein the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.4:2, and the particle size of silicon dioxide and antimony tin oxide is 10 nm; Modified cardanol is prepared by the following method: cardanol and epichlorohydrin are added to a flask, followed by addition of potassium hydroxide, the temperature is raised to 60°C, and the reaction is refluxed for 2 hours. The resulting product is washed with deionized water and then subjected to reduced pressure distillation to obtain modified cardanol, wherein the mass ratio of cardanol to epichlorohydrin is 1:1.4, and the mass of potassium hydroxide is 4% of the mass of cardanol; 40 parts of epoxy resin, 20 parts of amino resin, 4 parts of granular material, 2 parts of pigment, 2 parts of polyethylene glycol, 0.6 parts of silicone defoamer and 0.6 parts of polydimethylsiloxane were weighed and added into a mixer. The mixer was set at 1000 r / min and stirred for 30 minutes to prepare a high-adhesion automotive primer.

[0022] Example 2:

[0023] S1: Preparation of the first base material. The raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water. The mass ratio of the raw materials is 1:0.3:0.2:0.2:5; The first base material is prepared by weighing magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water as needed and adding them into a mixer, setting the mixer at 250 r / min and stirring for 25 minutes to prepare the first base material; S2: Preparation of the second base material, the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of the raw materials is 1:2:0.05:1; The second base material is prepared by weighing isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide, and diallyl phthalate as needed and adding them to a water bath, setting the water bath temperature to 41° C., connecting the water bath to a magnetic stirrer, setting the magnetic stirrer speed to 140 rpm, and stirring at constant temperature for 15 minutes to prepare the second base material. S3: preparing microspheres, mixing the first base material and the second base material to prepare microspheres; The method for preparing microspheres is as follows: the first base material is added to the mixer, the mixer is set to 900r / min for stirring, and the stirring time is 15min. During the stirring process, the second base material is added to the mixer at a uniform speed, and then the modified cardanol is added to the mixer, the mixer is set to 500r / min, and the stirring is carried out for 25min to obtain a mixed solution, which is added to the reactor. Nitrogen is introduced into the reactor, the pressure is set to 0.5Mpa, the temperature is set to 70°C, the speed is set to 400r / min, and the constant temperature stirring is carried out for 7h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 5. The obtained product is filtered and washed with water to obtain a filter cake. The filter cake is sent to an oven, the oven is set to 45°C, and dried for 5h. The obtained product is ground to a particle size of 7μm to obtain microspheres. S4: microsphere modification, modifying the microspheres prepared in S3 to obtain granular materials; The method for modifying the microspheres is as follows: the microspheres are added to a mixer, 1-butyl-3-methylimidazole chloride is added to the mixer, the mixer is set at 70 r / min and stirred for 2 hours, the obtained product is rinsed with deionized water, and then sent to an oven, the oven is set at 55°C, and dried for 2.5 hours, the dried product and polydiallyldimethylammonium chloride are added to the mixer, the mixer is set at 250 r / min and stirred for 15 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water to prepare a mixture, the mixture and the treatment liquid are added to the mixer, the mass of the treatment liquid is 19% of the mass of the mixture, the mixer is set at 500 r / min and stirred for 25 minutes, and then ultrasonic dispersion treatment is performed. , the treatment time is 15min, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water and sent to an oven, the oven is set at 55°C, and dried for 5h to obtain a granular material, wherein the mass of 1-butyl-3-methylimidazole chloride is 2.5% of the mass of the microspheres, and the mass of polydiallyldimethylammonium chloride is 1.5% of the mass of the microspheres. The treatment liquid is prepared by the following method: silicon dioxide, antimony tin oxide and deionized water are mixed, sodium hydroxide solution is added, the pH value is adjusted to 10.5, and then ultrasonic dispersion treatment is performed for 25min to obtain a treatment liquid, wherein the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.5:3, and the particle size of silicon dioxide and antimony tin oxide is 30nm; Modified cardanol is prepared by the following method: cardanol and epichlorohydrin are added to a flask, followed by addition of potassium hydroxide, the temperature is raised to 65°C, and the reaction is refluxed for 3 hours. The resulting product is washed with deionized water and then subjected to reduced pressure distillation to obtain modified cardanol, wherein the mass ratio of cardanol to epichlorohydrin is 1:1.5, and the mass of potassium hydroxide is 5% of the mass of cardanol; 50 parts of epoxy resin, 25 parts of amino resin, 5 parts of granular material, 3 parts of pigment, 3 parts of polyethylene glycol, 0.7 parts of silicone defoamer and 0.7 parts of polydimethylsiloxane were weighed and added into a mixer. The mixer was set at 1200 r / min and stirred for 35 minutes to prepare a high-adhesion automotive primer.

[0024] Example 3:

[0025] S1: Preparation of the first base material. The raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water. The mass ratio of the raw materials is 1:0.4:0.3:0.3:6; The first base material is prepared by weighing magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water as needed and adding them into a mixer, setting the mixer at 300 r / min and stirring for 30 minutes to prepare the first base material; S2: Preparation of the second base material, the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of the raw materials is 1:2.5:0.06:1.2; The second base material is prepared by weighing isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide, and diallyl phthalate as needed and adding them to a water bath, setting the water bath temperature to 42° C., connecting the water bath to a magnetic stirrer, setting the magnetic stirrer speed to 160 rpm, and stirring at constant temperature for 20 minutes to prepare the second base material; S3: preparing microspheres, mixing the first base material and the second base material to prepare microspheres; The method for preparing microspheres is as follows: the first base material is added to the mixer, the mixer is set to 1000r / min for stirring, and the stirring time is 20min. During the stirring process, the second base material is added to the mixer at a uniform speed, and then the modified cardanol is added to the mixer, the mixer is set to 600r / min, and the stirring is carried out for 30min to obtain a mixed solution, and the mixed solution is added to the reactor, nitrogen is introduced into the reactor, the pressure is set to 0.6Mpa, the temperature is set to 80°C, the speed is set to 500r / min, and the constant temperature stirring is carried out for 8h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 6, the obtained product is filtered and washed with water to obtain a filter cake, the filter cake is sent to an oven, the oven is set to 50°C, and dried for 6h. The obtained product is ground to a particle size of 10μm to obtain microspheres; S4: microsphere modification, modifying the microspheres prepared in S3 to obtain granular materials; The method for modifying the microspheres is as follows: the microspheres are added to a mixer, 1-butyl-3-methylimidazole chloride is added to the mixer, the mixer is set at 80 r / min and stirred for 3 hours, the obtained product is rinsed with deionized water, and then sent to an oven, the oven is set at 60°C, and dried for 3 hours, the dried product and polydiallyldimethylammonium chloride are added to the mixer, the mixer is set at 300 r / min and stirred for 20 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water to prepare a mixture, the mixture and the treatment liquid are added to the mixer, the mass of the treatment liquid is 22% of the mass of the mixture, the mixer is set at 600 r / min and stirred for 30 minutes, and then ultrasonic dispersion is performed. The treatment time is 20 minutes, the obtained product is centrifuged and the precipitate is taken, the precipitate is washed with deionized water and then sent to an oven, the oven is set at 60°C, and the drying treatment is performed for 6 hours to obtain a granular material, wherein the mass of 1-butyl-3-methylimidazole chloride is 3% of the mass of the microspheres, and the mass of polydiallyldimethylammonium chloride is 2% of the mass of the microspheres. The treatment liquid is prepared by the following method: silicon dioxide, antimony tin oxide and deionized water are mixed, sodium hydroxide solution is added, the pH value is adjusted to 11, and then ultrasonic dispersion treatment is performed for 30 minutes to obtain a treatment liquid, wherein the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.6:4, and the particle size of silicon dioxide and antimony tin oxide is 40 nm; Modified cardanol is prepared by the following method: cardanol and epichlorohydrin are added to a flask, followed by addition of potassium hydroxide, the temperature is raised to 70°C, and the reaction is refluxed for 4 hours. The resulting product is washed with deionized water and then subjected to reduced pressure distillation to obtain modified cardanol, wherein the mass ratio of cardanol to epichlorohydrin is 1:1.6, and the mass of potassium hydroxide is 6% of the mass of cardanol; 60 parts of epoxy resin, 30 parts of amino resin, 6 parts of granular material, 4 parts of pigment, 4 parts of polyethylene glycol, 0.8 parts of silicone defoamer and 0.8 parts of polydimethylsiloxane were weighed and added into a mixer. The mixer was set at 1400 r / min and stirred for 40 minutes to prepare a high-adhesion automotive primer.

[0026] Comparative Example 1: The difference between this comparative example and Example 1 is that: in this comparative example, no microsphere modification treatment is performed, that is, microspheres are used as granular materials.

[0027] Comparative Example 2: The difference between this comparative example and Example 1 is that this comparative example does not contain modified cardanol.

[0028] Comparative Example 3: The difference between this comparative example and Example 1 is that in this comparative example, an equal amount of nano-silicon dioxide is used to replace the granular material.

[0029] Comparative Example 4: This comparative example differs from Example 1 in that this comparative example does not contain granular material.

[0030] Performance test: The high adhesion automotive primers prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were subjected to performance tests, and the test data obtained are recorded in the following table:

[0031] In the performance test, the test method in GB / T 5210-2006 was used to test the adhesion performance of the high-adhesion automotive primers prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. The test method in GB / T 23988 was used to test the abrasion resistance performance of the high-adhesion automotive primers prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4.

[0032] It can be seen that the adhesion performance and wear resistance of the high-adhesion automotive primers prepared in Comparative Examples 1, 2, 3, and 4 are all lower than those in Examples 1, 2, and 3. This shows that: by adding particulate materials during the preparation of the automotive primer, wherein the first base material uses magnesium hydroxide as an inorganic core to provide rigid support, polyvinyl pyrrolidone is used as a dispersant to ensure the uniformity of mixing of the materials, the second base material uses hydroxyethyl methacrylate to polymerize to form an organic shell, dibenzoyl peroxide initiates free radical crosslinking, and diallyl phthalate is used as a crosslinking agent to form a wear-resistant polymer network, the microspheres can form a core-shell structure through physical mixing and chemical modification, the core is used to enhance hardness, and the shell improves the interfacial bonding with the resin matrix, thereby making the automotive primer firmly bonded to the coating surface, thereby improving the adhesion of the automotive primer; The epoxy groups of the modified cardanol undergo covalent cross-linking with the epoxy groups in the epoxy resin or the hydroxyl groups in the amino resin to form a dense network structure, thereby enhancing the chemical bonding between the primer and the metal substrate. At the same time, the epoxy groups of the modified cardanol produce electrostatic adsorption with the surface of the microspheres, such as 1-butyl-3-methylimidazole chloride, to promote the uniform dispersion of the particles in the resin matrix, reduce interface defects, and reduce the risk of particles falling off the primer coating surface during friction, thereby effectively improving the wear resistance of the automotive primer.

[0033] Comparing and analyzing the relevant data in the table shows that the high-adhesion automotive primer prepared by the present invention not only has good adhesion performance, but also has excellent wear resistance. This shows that the high-adhesion automotive primer provided by the present invention has a broader market prospect and is more suitable for promotion.

[0034] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0035] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-adhesion automotive primer, characterized by: The invention comprises the following raw materials in parts by weight: 40 to 60 parts of epoxy resin, 20 to 30 parts of amino resin, 4 to 6 parts of granular material, 2 to 4 parts of pigment, 2 to 4 parts of polyethylene glycol, 0.6 to 0.8 parts of defoaming agent, 0.6 to 0.8 parts of leveling agent and 0.06 to 0.08 parts of modified cardanol; The preparation of the granular material comprises the following steps: S1: Preparation of the first base material. The raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water. The mass ratio of the raw materials is 1: (0.2-0.4): (0.1-0.3): (0.1-0.3): (4-6); S2: Preparation of the second base material, wherein the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of the raw materials is 1: (1.5-2.5): (0.04-0.06): (0.8-1.2); S3: preparing microspheres, mixing the first base material and the second base material to prepare microspheres; S4: Microsphere modification, modifying the microspheres prepared in S3 to obtain granular materials.

2. The high adhesion vehicle primer according to claim 1, characterized in that: The method for preparing the first base material is: magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water are weighed as needed and added into a mixer, and the mixer is set at 200-300 r / min and stirred for 20-30 minutes to obtain the first base material.

3. The high adhesion vehicle primer according to claim 1, characterized in that: The method for preparing the second base material is as follows: isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate are weighed as needed and added into a water bath, the water bath is set to heat up to 40-42° C., a magnetic stirrer is connected to the water bath, the speed of the magnetic stirrer is set to 120-160 r / min, and constant temperature stirring is performed for 10-20 minutes to obtain the second base material.

4. The high adhesion vehicle primer according to claim 1, characterized in that: The method for preparing the microspheres is as follows: the first base material is added to a mixer, the mixer is set to 800-1000 r / min for stirring, and the stirring time is 10-20 minutes. During the stirring process, the second base material is added to the mixer at a uniform speed, and then the modified cardanol is added to the mixer, the mixer is set to 400-600 r / min, and the stirring is carried out for 20-30 minutes to obtain a mixed solution.

5. The high adhesion vehicle primer according to claim 4, characterized in that: The mixed liquid is added to a reactor, nitrogen is introduced into the reactor, the pressure is set to 0.4-0.6 MPa, the temperature is set to 60-80°C, the speed is set to 300-500 r / min, and the mixture is stirred at a constant temperature for 6-8 hours. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 4-6. The obtained product is filtered and washed with water to obtain a filter cake. The filter cake is sent to an oven, the oven is set at 40-50°C, and dried for 4-6 hours. The obtained product is ground to a particle size of 4-10 μm to obtain microspheres.

6. The high adhesion vehicle primer according to claim 1, characterized in that: The microsphere modification method comprises the following steps: adding microspheres to a mixer, adding 1-butyl-3-methylimidazole chloride to the mixer, setting the mixer at 60-80 r / min and stirring for 1-3 hours, rinsing the obtained product with deionized water, and then placing the product in an oven at 50-60° C. for drying for 2-3 hours, adding the dried product and polydiallyldimethylammonium chloride to the mixer, setting the mixer at 200-300 r / min and stirring for 10-20 minutes, centrifuging the obtained product and taking a precipitate, washing the precipitate with deionized water to obtain a mixture, and The treatment liquid is added into a mixer, the mass of the treatment liquid is 16% to 22% of the mass of the mixture, the mixer is set at 400 to 600 r / min and stirred for 20 to 30 minutes, and then ultrasonic dispersion treatment is carried out for 10 to 20 minutes. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent to an oven, the oven is set at 50 to 60° C., and dried for 4 to 6 hours to obtain a granular material, wherein the mass of 1-butyl-3-methylimidazole chloride is 2% to 3% of the mass of the microspheres, and the mass of polydiallyldimethylammonium chloride is 1% to 2% of the mass of the microspheres.

7. The high adhesion vehicle primer according to claim 6, characterized in that: The treatment liquid is prepared by the following method: silicon dioxide, antimony tin oxide and deionized water are mixed, sodium hydroxide solution is added, the pH value is adjusted to 10-11, and then ultrasonic dispersion treatment is performed for 20-30 minutes to prepare the treatment liquid, wherein the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1: (0.4-0.6): (2-4), and the particle sizes of silicon dioxide and antimony tin oxide are 10-40 nm.

8. The high adhesion vehicle primer according to claim 1, characterized in that: The modified cardanol is prepared by the following method: cardanol and epichlorohydrin are added to a flask, followed by the addition of potassium hydroxide, the temperature is raised to 60-70°C, and the reaction is refluxed for 2-4 hours. The obtained product is washed with deionized water and then subjected to reduced pressure distillation to obtain the modified cardanol, wherein the mass ratio of cardanol to epichlorohydrin is 1:(1.4-1.6), and the mass of potassium hydroxide is 4%-6% of the mass of the cardanol.

9. The high-adhesion vehicle primer according to claim 1, characterized in that: The defoaming agent is an organosilicon defoaming agent, and the leveling agent is polydimethylsiloxane.

10. A method for preparing a high-adhesion automotive primer according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: epoxy resin, amino resin, granular material, pigment, polyethylene glycol, defoamer and leveling agent are weighed as needed and added into a mixer; the mixer is set at 1000-1400 r / min and stirred for 30-40 minutes to prepare a high-adhesion automotive primer.

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