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 present invention relates to the technical field of primers, and specifically to a high-adhesion automotive primer and a preparation method thereof. Background Art

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

[0003] In the prior art, the polar groups in the resin matrix of existing automotive primers are insufficient, and the bonding ability with the metal interface is weak, resulting in a decrease in the density of the primer coating and affecting the adhesion performance of the primer. Based on this, the present invention provides a high-adhesion automotive primer and a preparation method thereof. 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, effectively improving the service performance of the automotive primer.

[0005] To achieve the above purpose, the present invention provides the following technical solutions: In the first aspect, the present invention provides a high-adhesion automotive primer, which 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 particulate material, 2 - 4 parts of pigment, 2 - 4 parts of polyethylene glycol, 0.6 - 0.8 parts of defoamer, 0.6 - 0.8 parts of leveling agent, and 0.06 - 0.08 parts of modified cashew phenol; The preparation of the particulate material comprises the following steps: S1: Preparation of the first base material. The raw materials of the first base material consist of magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride, and deionized water, and the mass ratio of each raw material is 1:(0.2 - 0.4):(0.1 - 0.3):(0.1 - 0.3):(4 - 6); S2: Preparation of the second base material. The raw materials of the second base material consist of isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate, and the mass ratio of each raw material is 1:(1.5 - 2.5):(0.04 - 0.06):(0.8 - 1.2); S3: Preparation of microspheres. The first base material and the second base material are mixed to prepare microspheres; S4: Modification of microspheres. The microspheres prepared in S3 are subjected to modification treatment to obtain the particulate material.

[0006] Further, the method for preparing the first base material is as follows: Weigh magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water as required and add them into a mixer. The mixer is set to stir at 200 - 300 r / min for 20 - 30 min to obtain the first base material.

[0007] Further, the method for preparing the second base material is as follows: Weigh isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide and diallyl phthalate as required and add them into a water bath. The water bath is set to heat up to 40 - 42 °C. The water bath is connected to a magnetic stirrer, and the magnetic stirrer is set to rotate at a speed of 120 - 160 r / min for constant-temperature stirring for 10 - 20 min to obtain the second base material.

[0008] Further, the method for preparing the microspheres is as follows: The first base material is added into a mixer, and the mixer is set to stir at 800 - 1000 r / min for 10 - 20 min. During the stirring process, the second base material is evenly added into the mixer. Then, modified cashew phenol is added into the mixer. The mixer is set to 400 - 600 r / min and stirred for 20 - 30 min to obtain a mixed solution.

[0009] Further, the mixed solution is added into a reaction kettle. Nitrogen is introduced into the reaction kettle, the pressure is set to 0.4 - 0.6 Mpa, the temperature is set to 60 - 80 °C, and the rotation speed is set to 300 - 500 r / min for constant-temperature stirring for 6 - 8 h. 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 subjected to suction filtration and water washing to obtain a filter cake. The filter cake is sent into an oven, and the oven is set to 40 - 50 °C for drying for 4 - 6 h. The obtained product is ground, and the grinding particle size is 4 - 10 μm to obtain the microspheres.

[0010] Further, the method for modifying the microspheres is as follows: The microspheres are added into a mixer, and 1-butyl-3-methylimidazolium chloride is added into the mixer. The mixer is set to stir at 60 - 80 r / min for 1 - 3 h. The obtained product is rinsed with deionized water and then sent into an oven. The oven is set at 50 - 60 °C for drying treatment for 2 - 3 h. The product obtained from the drying treatment and poly(diallyldimethylammonium chloride) are added into the mixer. The mixer is set to stir at 200 - 300 r / min for 10 - 20 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water to obtain a mixed material. The mixed material and the treatment liquid are added into the mixer. The mass of the treatment liquid is 16% - 22% of the mass of the mixed material. The mixer is set to stir at 400 - 600 r / min for 20 - 30 min, and then ultrasonic dispersion treatment is carried out for 10 - 20 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent into an oven. The oven is set at 50 - 60 °C for drying treatment for 4 - 6 h to obtain granular material. Among them, the mass of 1-butyl-3-methylimidazolium chloride is 2% - 3% of the mass of the microspheres, and the mass of poly(diallyldimethylammonium chloride) is 1% - 2% of the mass of the microspheres.

[0011] Further, the treatment liquid is prepared by the following method: Silicon dioxide, antimony tin oxide and deionized water are mixed and then sodium hydroxide solution is added, and the pH value is adjusted to 10 - 11. Then ultrasonic dispersion treatment is carried out for 20 - 30 min to obtain the treatment liquid. Among them, 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.

[0012] Further, the modified cardanol is prepared by the following method: Cardanol and epichlorohydrin are added into a flask, and then potassium hydroxide is added. The temperature is raised to 60 - 70 °C and reflux reaction is carried out for 2 - 4 h. The obtained product is washed with deionized water and then subjected to vacuum distillation treatment to obtain the modified cardanol. Among them, 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] Further, the defoaming agent is selected as an organosilicon defoaming agent, and the leveling agent is selected as polydimethylsiloxane.

[0014] In the second aspect, the present invention also provides a preparation method of a high-adhesion vehicle primer, including the following steps: Weigh epoxy resin, amino resin, granular material, pigment, polyethylene glycol, defoaming agent and leveling agent as required and add them into a mixer. The mixer is set to stir at 1000 - 1400 r / min for 30 - 40 min to obtain the high-adhesion vehicle primer.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. In the present invention, during the preparation of the automotive primer, particulate materials are added. Among them, the first base material uses magnesium hydroxide as the inorganic core to provide rigid support, and polyvinylpyrrolidone is used as a dispersant to ensure the uniformity of the mixing of various materials. The second base material polymerizes with hydroxyethyl methacrylate to form an organic shell, benzoyl peroxide initiates free radical crosslinking, and diallyl phthalate is used as a crosslinking agent to form a wear-resistant polymer network. Through physical mixing and chemical modification, the microspheres can form a core-shell structure, using its inner core to enhance hardness and the outer shell to improve the interfacial bonding with the resin matrix, thereby enabling the automotive primer to firmly bond with the coated surface and improving the adhesion of the automotive primer.

[0016] 2. In the present invention, the epoxy groups of the modified cardanol undergo covalent crosslinking with the epoxy groups in the epoxy resin or the hydroxyl groups in the amino resin to form a dense network structure, enhancing the chemical bonding between the primer and the metal substrate. At the same time, the epoxy groups of the modified cardanol have electrostatic adsorption with, for example, 1-butyl-3-methylimidazolium chloride on the surface of the microspheres, promoting the uniform dispersion of the particulate materials in the resin matrix, reducing interfacial defects, and reducing the risk of particle detachment on the coated surface of the primer during the friction process, effectively improving the wear resistance of the automotive primer. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 FIG. is a flowchart of a high-adhesion automotive primer and its preparation method proposed by the invention; Figure 2 FIG. is a flowchart of the preparation of particulate materials for a high-adhesion automotive primer and its preparation method proposed by the invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0018] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0019] It should be noted that the raw materials used in the following embodiments 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, polyvinylpyrrolidone, sodium nitrite, sodium chloride, and deionized water, and the mass ratio of each raw material is 1:0.2:0.1:0.1:4; The method for preparing the first base material is as follows: Weigh magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water as required and add them to a mixer. The mixer is set to stir at 200 r / min for 20 min to obtain the first base material; S2: Preparation of the second base material. The raw materials of the second base material are composed of isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide and diallyl phthalate, and the mass ratio of each raw material is 1:1.5:0.04:0.8; The method for preparing the second base material is as follows: Weigh isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide and diallyl phthalate as required and add them to a water bath. The water bath is set to heat up to 40 °C. The water bath is connected to a magnetic stirrer, and the magnetic stirrer is set to a rotation speed of 120 r / min and stirred at a constant temperature for 10 min to obtain the second base material; S3: Preparation of microspheres. The first base material and the second base material are mixed and prepared to obtain microspheres; The method for preparing microspheres is as follows: The first base material is added to a mixer, and the mixer is set to stir at 800 r / min for 10 min. During the stirring process, the second base material is uniformly added to the mixer. Then, modified cashew phenol is added to the mixer. The mixer is set to 400 r / min and stirred for 20 min to obtain a mixed solution. The mixed solution is added to a reaction kettle. Nitrogen is introduced into the reaction kettle, the pressure is set to 0.4 Mpa, the temperature is set to 60 °C, and the rotation speed is set to 300 r / min. Stir at a constant temperature for 6 h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 4. The obtained product is subjected to suction filtration and water washing to obtain a filter cake. The filter cake is sent to an oven, and the oven is set to 40 °C and dried for 4 h. The obtained product is ground, and the grinding particle size is 4 μm to obtain microspheres; S4: Modification of microspheres. The microspheres prepared in S3 are subjected to modification treatment to obtain granular materials; The method for modifying the microspheres is as follows: The microspheres are added to a mixer, and 1-butyl-3-methylimidazolium chloride is added to the mixer. The mixer is set to stir at 60 r / min for 1 h. The obtained product is rinsed with deionized water and then sent into an oven. The oven is set at 50 °C for drying treatment for 2 h. The product obtained from the drying treatment and poly(diallyldimethylammonium chloride) are added to the mixer. The mixer is set to stir at 200 r / min for 10 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water to obtain a mixed material. The mixed material and the treatment liquid are added to the mixer. The mass of the treatment liquid is 16% of the mass of the mixed material. The mixer is set to stir at 400 r / min for 20 min, and then ultrasonic dispersion treatment is carried out for 10 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent into an oven. The oven is set at 50 °C for drying treatment for 4 h to obtain granular materials. Among them, the mass of 1-butyl-3-methylimidazolium chloride is 2% of the mass of the microspheres, and the mass of poly(diallyldimethylammonium 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 and then sodium hydroxide solution is added, and the pH value is adjusted to 10. Then ultrasonic dispersion treatment is carried out for 20 min to obtain the treatment liquid. Among them, the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.4:2, and the particle sizes of silicon dioxide and antimony tin oxide are 10 nm; The modified cashew phenol is prepared by the following method: Cashew phenol and epichlorohydrin are added to a flask, and then potassium hydroxide is added. The temperature is raised to 60 °C and reflux reaction is carried out for 2 h. The obtained product is washed with deionized water and then subjected to vacuum distillation to obtain the modified cashew phenol. Among them, the mass ratio of cashew phenol to epichlorohydrin is 1:1.4, and the mass of potassium hydroxide is 4% of the mass of cashew phenol; Weigh 40 parts of epoxy resin, 20 parts of amino resin, 4 parts of granular materials, 2 parts of pigment, 2 parts of polyethylene glycol, 0.6 part of organosilicon defoamer and 0.6 part of polydimethylsiloxane and add them to a mixer. The mixer is set to stir at 1000 r / min for 30 min to obtain a high-adhesion automotive primer.

[0022] Example 2:

[0023] S1: Preparation of the first base material. The raw materials of the first base material consist of magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water, and the mass ratio of each raw material is 1:0.3:0.2:0.2:5; The method for preparing the first base material is: Weigh magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water as required and add them to a mixer. The mixer is set to stir at 250 r / min for 25 min to obtain the first base material; S2: Preparation of the second base material. The raw materials of the second base material consist of isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate, and the mass ratio of each raw material is 1:2:0.05:1; The method for preparing the second base material is as follows: Weigh isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate as needed and add them to a water bath. The water bath is set to heat up to 41°C. The water bath is connected to a magnetic stirrer, and the magnetic stirrer is set at a rotation speed of 140 r / min for constant-temperature stirring for 15 min to obtain the second base material; S3: Preparation of microspheres. The first base material and the second base material are mixed to prepare microspheres; The method for preparing microspheres is as follows: Add the first base material to a mixer, and the mixer is set to stir at 900 r / min for 15 min. During the stirring process, the second base material is evenly added to the mixer. Then, modified cashew phenol is added to the mixer, and the mixer is set at 500 r / min and stirred for 25 min to obtain a mixed solution. The mixed solution is added to a reaction kettle. Nitrogen is introduced into the reaction kettle, the pressure is set at 0.5 Mpa, the temperature is set at 70°C, and the rotation speed is set at 400 r / min for constant-temperature stirring for 7 h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 5. The obtained product is subjected to suction filtration and water washing to obtain a filter cake. The filter cake is sent to an oven, and the oven is set at 45°C for drying for 5 h. The obtained product is ground to a particle size of 7 μm to obtain microspheres; S4: Modification of microspheres. The microspheres prepared in S3 are modified to obtain granular materials; The method for modifying the microspheres is as follows: The microspheres are added into a mixer, and 1-butyl-3-methylimidazolium chloride is added into the mixer. The mixer is set to stir at 70 r / min for 2 h. The obtained product is rinsed with deionized water and then sent into an oven. The oven is set at 55 °C for drying treatment for 2.5 h. The product obtained from the drying treatment and poly(diallyldimethylammonium chloride) are added into the mixer. The mixer is set to stir at 250 r / min for 15 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water to obtain a mixed material. The mixed material and the treatment liquid are added into the mixer. The mass of the treatment liquid is 19% of the mass of the mixed material. The mixer is set to stir at 500 r / min for 25 min, and then ultrasonic dispersion treatment is carried out for 15 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent into an oven. The oven is set at 55 °C for drying treatment for 5 h to obtain granular material. Among them, the mass of 1-butyl-3-methylimidazolium chloride is 2.5% of the mass of the microspheres, and the mass of poly(diallyldimethylammonium 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 and then sodium hydroxide solution is added, and the pH value is adjusted to 10.5. Then ultrasonic dispersion treatment is carried out for 25 min to obtain the treatment liquid. Among them, the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.5:3, and the particle sizes of silicon dioxide and antimony tin oxide are 30 nm; The modified cardanol is prepared by the following method: Cardanol and epichlorohydrin are added into a flask, and then potassium hydroxide is added. The temperature is raised to 65 °C and reflux reaction is carried out for 3 h. The obtained product is washed with deionized water and then subjected to vacuum distillation to obtain the modified cardanol. Among them, the mass ratio of cardanol to epichlorohydrin is 1:1.5, and the mass of potassium hydroxide is 5% of the mass of cardanol; Weigh 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 part of silicone defoamer and 0.7 part of polydimethylsiloxane and add them into a mixer. The mixer is set to stir at 1200 r / min for 35 min to obtain a high-adhesion automotive primer.

[0024] Example 3:

[0025] S1: Preparation of the first base material. The raw materials of the first base material consist of magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water, and the mass ratio of each raw material is 1:0.4:0.3:0.3:6; The method for preparing the first base material is as follows: Weigh magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite, sodium chloride and deionized water as required and add them into a mixer. The mixer is set to stir at 300 r / min for 30 min to obtain the first base material; S2: Preparation of the second base material. The raw materials of the second base material consist of isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate, and the mass ratio of each raw material is 1:2.5:0.06:1.2; The method for preparing the second base material is as follows: Weigh isopentane, 2-hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate as required and add them to a water bath kettle. The water bath kettle is set to heat up to 42°C. The water bath kettle is connected to a magnetic stirrer, and the magnetic stirrer is set at a rotation speed of 160 r / min for constant-temperature stirring for 20 min to obtain the second base material; S3: Preparation of microspheres. The first base material and the second base material are mixed to prepare microspheres; The method for preparing microspheres is as follows: Add the first base material to a mixer, and the mixer is set to stir at 1000 r / min for 20 min. During the stirring process, add the second base material to the mixer at a uniform speed. Then add modified cashew phenol to the mixer. The mixer is set at 600 r / min and stirred for 30 min to obtain a mixed solution. The mixed solution is added to a reaction kettle. Nitrogen is introduced into the reaction kettle, the pressure is set to 0.6 Mpa, the temperature is set to 80°C, and the rotation speed is set to 500 r / min for constant-temperature stirring for 8 h. After cooling to room temperature, hydrochloric acid is added to the obtained product to adjust the pH value to 6. The obtained product is subjected to suction filtration and water washing to obtain a filter cake. The filter cake is sent to an oven, and the oven is set at 50°C for drying for 6 h. The obtained product is ground to a particle size of 10 μm to obtain microspheres; S4: Modification of microspheres. The microspheres prepared in S3 are modified to obtain particulate materials; The method for modifying the microspheres is as follows: The microspheres are added into a mixer, and 1-butyl-3-methylimidazolium chloride is added into the mixer. The mixer is set to stir at 80 r / min for 3 h. The obtained product is rinsed with deionized water and then sent into an oven. The oven is set at 60 °C for drying treatment for 3 h. The product obtained from the drying treatment and poly(diallyldimethylammonium chloride) are added into the mixer. The mixer is set to stir at 300 r / min for 20 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water to obtain a mixed material. The mixed material and the treatment liquid are added into the mixer. The mass of the treatment liquid is 22% of the mass of the mixed material. The mixer is set to stir at 600 r / min for 30 min, and then ultrasonic dispersion treatment is carried out for 20 min. The obtained product is centrifuged and the precipitate is taken. The precipitate is washed with deionized water and then sent into an oven. The oven is set at 60 °C for drying treatment for 6 h to obtain granular materials. Among them, the mass of 1-butyl-3-methylimidazolium chloride is 3% of the mass of the microspheres, and the mass of poly(diallyldimethylammonium 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 and then sodium hydroxide solution is added, and the pH value is adjusted to 11. Then ultrasonic dispersion treatment is carried out for 30 min to obtain the treatment liquid. Among them, the mass ratio of silicon dioxide, antimony tin oxide and deionized water is 1:0.6:4, and the particle sizes of silicon dioxide and antimony tin oxide are 40 nm; The modified cardanol is prepared by the following method: Cardanol and epichlorohydrin are added into a flask, and then potassium hydroxide is added. The temperature is raised to 70 °C and reflux reaction is carried out for 4 h. The obtained product is washed with deionized water and then subjected to vacuum distillation to obtain the modified cardanol. Among them, the mass ratio of cardanol to epichlorohydrin is 1:1.6, and the mass of potassium hydroxide is 6% of the mass of cardanol; Weigh 60 parts of epoxy resin, 30 parts of amino resin, 6 parts of granular materials, 4 parts of pigment, 4 parts of polyethylene glycol, 0.8 part of silicone defoamer and 0.8 part of polydimethylsiloxane and add them into a mixer. The mixer is set to stir at 1400 r / min for 40 min to obtain a high-adhesion automotive primer.

[0026] Comparative Example 1. The difference between this comparative example and Example 1 is that: In this comparative example, the microspheres are not modified, that is, the microspheres are used as the granular materials.

[0027] Comparative Example 2. The difference between this comparative example and Example 1 is that: This comparative example does not contain the 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 selected to replace the granular materials.

[0029] Comparative Example 4. The difference between this comparative example and Example 1 is that this comparative example does not contain particulate matter.

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

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

[0032] It can be seen that the adhesion performance and abrasion resistance performance of the high-adhesion automotive primer prepared in Comparative Examples 1, 2, 3 and 4 are lower than those in Examples 1, 2 and 3; this shows that: by adding particulate matter in the preparation process of the automotive primer, among which, the first base material uses magnesium hydroxide as the inorganic core to provide rigid support, polyvinylpyrrolidone is used as a dispersant to ensure the mixing uniformity of each material, the second base material polymerizes with 2-hydroxyethyl methacrylate to form an organic shell, benzoyl peroxide initiates free radical crosslinking, diallyl phthalate is used as a crosslinking agent to form an abrasion-resistant polymer network, and the microspheres can form a core-shell structure through physical mixing and chemical modification, using its inner core to enhance hardness and the outer shell to improve the interfacial bonding with the resin matrix, so that the automotive primer is firmly bonded to the coating surface, improving the adhesion of the automotive primer; The epoxy group of the modified cashew phenol undergoes covalent crosslinking with the epoxy group in the epoxy resin or the hydroxyl group in the amino resin to form a dense network structure, enhancing the chemical bonding between the primer and the metal substrate. At the same time, the epoxy group of the modified cashew phenol has electrostatic adsorption with 1-butyl-3-methylimidazolium chloride on the surface of the microspheres, promoting the uniform dispersion of the particulate matter in the resin matrix, reducing interfacial defects, and reducing the risk of particle shedding on the primer coating surface during the friction process, effectively improving the abrasion resistance performance of the automotive primer.

[0033] By comparing and analyzing the relevant data in the table, it can be known that the high-adhesion automotive primer prepared by the present invention not only has good adhesion performance, but also has excellent abrasion resistance performance. This shows that the high-adhesion automotive primer provided by the present invention has a broader market prospect and is more suitable for popularization.

[0034] In the description of this specification, the descriptions referring to the terms "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0035] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A high adhesion vehicle primer, characterized in that: 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 pellets comprises the following steps: S1: preparation of the first base material, wherein the raw materials of the first base material are composed of magnesium hydroxide, polyvinyl pyrrolidone, sodium nitrite, sodium chloride and deionized water, and 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, the raw materials of the second base material are composed of isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate, and the mass ratio of each raw material 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 for stirring 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: weigh isopentane, hydroxyethyl methacrylate, dibenzoyl peroxide and diallyl phthalate as needed and add them into a water bath, set the water bath to heat up to 40-42° C., connect the water bath to a magnetic stirrer, set the speed of the magnetic stirrer to 120-160 r / min, and stir at a constant temperature 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 into a mixer, the mixer is set at 800-1000 r / min for stirring, the stirring time is 10-20 min, during the stirring process, the second base material is added into the mixer at a uniform speed, and then the modified cardanol is added into the mixer, the mixer is set at 400-600 r / min, and the stirring is performed for 20-30 min to obtain a mixed solution.

5. The high adhesion vehicle primer according to claim 4, characterized in that: The mixed liquid is added into 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 rotation 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, and the pH value is adjusted to 4-6. The obtained product is filtered and washed with water to obtain a filter cake, which is sent to an oven 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 is as follows: the microspheres are added into a mixer, 1-butyl-3-methylimidazole chloride is added into the mixer, the mixer is set at 60-80 r / min for stirring for 1-3 hours, the obtained product is rinsed with deionized water, and then sent into an oven, the oven is set at 50-60° C., and dried for 2-3 hours, the dried product and polydiallyldimethylammonium chloride are added into the mixer, the mixer is set at 200-300 r / min for stirring for 10-20 minutes, the obtained product is centrifuged and a precipitate is taken, the precipitate is washed with deionized water to obtain a mixture, and the mixture and The treatment liquid is added into the 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 for stirring for 20 to 30 minutes, and then ultrasonic dispersion treatment is carried out for 10 to 20 minutes. The obtained product is centrifuged to obtain a precipitate, the precipitate is washed with deionized water and 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 into a flask, and then potassium hydroxide is added, the temperature is raised to 60-70° C., and the reflux reaction is carried out for 2-4 hours. The obtained product is washed with deionized water, and then subjected to reduced pressure distillation to prepare 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 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 vehicle 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 required and added into a mixer, and the mixer is set at 1000-1400 r / min for stirring for 30-40 minutes to prepare a high-adhesion vehicle primer.

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