CN115093741A - Carbon nanotube automobile coating self-repairing coating, coating and self-repairing method - Google Patents
Carbon nanotube automobile coating self-repairing coating, coating and self-repairing method Download PDFInfo
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Abstract
The invention belongs to the technical field of coatings, and relates to a carbon nanotube automobile coating self-repairing coating, a coating and a self-repairing method. The invention utilizes the carbon nano tube to aim at different performances of an electric pulse layer, a middle coating layer, a colored paint layer and a clear paint layer of an automobile coating, adjusts the response of the viscosity of core liquid of different coatings to the temperature to control the natural flowing performance of the core liquid, changes the interfacial tension between the carbon nano tube and the core liquid of different coatings, controls the release speed of the core liquid from the nano tube in different layers and realizes the targeted repair layer by layer.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a carbon nanotube automobile coating self-repairing coating, a coating and a self-repairing method.
Background
When the automobile is used, various damages can be caused to the coating of the automobile body, the appearance of the automobile body is affected, the automobile body is rusted, and even the service life of the automobile is prolonged. In recent years, some paint patents with self-repairing function are successively introduced, such as patents CN01659719A, US8330, US08915, CN102390147A, CN104177983A, CN108410361A and CN 102963060A. Most of these patents are based on self-healing microcapsule paints. The microcapsule technology is that certain specific materials are coated in an inert shell to prepare microcapsules, and the microcapsules are added in a coating to prepare the self-repairing coating. After the coating generates micro-cracks, the microcapsules embedded in the matrix are broken under the action of external force to release the core material. The released core material is contacted with a catalyst to carry out polymerization reaction and solidification. Due to the contact randomness of the core material and the catalyst, the core material can not be subjected to polymerization reaction completely, and the self-repairing rate of the material is reduced. The mechanical properties of the microcapsules are reduced by the influence of the solvent in the coating and are difficult to maintain for a long period of time. Another disadvantage of microcapsule technology is the small size and wall thickness of the capsules, which allows storage of only limited amounts of healing fluid. The long-acting barrier property of the microcapsule self-repairing coating can be effectively exerted only when the scratch width is smaller than the coating thickness. The walls of the microcapsules are typically made of silicon and an organic composite material. After the microcapsules are damaged, the volume of the capsules collapses, and the flatness of a repair area is seriously influenced.
Automotive coatings typically consist of an electrical pulse layer, a middle coat layer, a color coat layer, and a clear coat layer. The function of each coating is different. The current self-repairing coating does not consider different functions of each layer, and does not treat the different functions separately for layered repairing. The repair layer has poor durability.
Disclosure of Invention
The electrophoresis layer is a primer directly attached to a steel plate of a vehicle body, mainly has the functions of rust prevention and the improvement of the binding force of a paint layer. The antirust capacity of the electrophoretic layer is the most important and the most critical of the four paint layers of the vehicle paint. The middle coating mainly enhances the ultraviolet resistance, protects the electrophoresis layer, improves the antirust capacity, gives consideration to the smoothness and the impact resistance of the paint surface, and finally provides some adhesive force for the colored paint layer. The color paint layer provides various colors, and provides the most direct color perception for us. The clear paint layer is the outermost transparent paint layer of the automobile paint, so that the gloss of the paint surface is improved, and slight scraping is prevented. The invention provides a self-repairing coating, a coating and a self-repairing method of a carbon nano tube automobile coating aiming at different functions of each layer, which can repair layers and improve the durability of multiple layers.
In order to realize the technical scheme of the invention, the technical scheme is as follows:
the material of the carbon nanotube core repair liquid depends on the position in the repair coating. Preferably, the diameter of the carbon nano tube is 100-200 nm, and the length-diameter ratio and the diameter ratio are more than 1000: 1.
the vehicle paint coating is divided into an electrophoresis layer, a middle coating, a colored paint layer and a clear paint layer. According to different functions of the electrophoresis layer, the middle coating layer, the colored paint layer and the clear paint layer, different carbon nano tube self-repairing coatings are respectively adopted to self-repair the electrophoresis layer, the middle coating layer, the colored paint layer and the clear paint layer in a layered mode. The specific details are described below. The electrophoresis layer self-repairing carbon nano tube contains a corrosion inhibitor and a resin primer. The main components by mass are: 5-10% of mercaptobenzothiazole, 35-45% of resin primer, 30-40% of benzotriazole, 5-8% of zinc powder, 5-10% of carbon tetrachloride, 10-15% of polyaluminum chloride, 0.5% of emulsifier, 0.5-1% of defoamer, 0.5-2% of surfactant and 1.0-2.5% of adhesion promoter. When the electrophoresis layer is damaged, the primer is firstly released from the carbon nano tube quickly, and the electrophoresis layer is firstly repaired. The corrosion inhibitor in the electrophoretic layer self-repairing carbon nano tube capsule core reacts with the aluminum alloy matrix at the bottom of the scratch to form passivation oxidation, so that the metal car body is protected at the first time, and meanwhile, the binding force between the repairing coating and the metal is enhanced.
The middle coating carbon nano tube stores the middle coating paint. The main components by mass are: 30-40% of modified epoxy resin, 10-15% of polyvinyl butyral, 15-20% of polydimethylsiloxane, 5-10% of amino resin, 3-7% of color additive, 10-15% of carbon tetrachloride, 5-10% of superfine titanium iron powder, 0.5-1.5% of emulsifier, 0.5-2% of assistant and 0.5-1% of defoaming agent. The paint mainly strengthens ultraviolet resistance, protects an electrophoresis layer, improves antirust capacity, gives consideration to the smoothness and impact resistance of a paint surface, and provides some adhesive force for a colored paint layer. And when the paint layer is damaged, the middle coating releases the middle coating paint after the carbon nano tubes of the electrophoresis layer are damaged, and covers the electrophoresis layer.
The self-repairing carbon nano tube of the color paint layer is filled with a coloring material which takes amino acrylic resin and amino polyester resin as main materials. The main components by mass are: 35-45% of amino acrylic resin, 35-45% of amino polyester resin, 10-15% of alcohol solvent, 15-20% of color additive, 0.5-1.5% of emulsifier, 3-5% of curing agent, 0.5-2% of auxiliary agent and 0.5-1% of defoaming agent. The pigments of amino acrylic resin and amino polyester resin are liquid before the nanotube is broken. The carbon nano tube of the color paint layer releases core liquid after the carbon nano tube of the middle coating layer.
The varnish layer is filled with varnish in the self-repairing carbon nano tube. The varnish is liquid before the nanotubes are broken. And (4) after the nanotubes are damaged, enabling the varnish to be in contact with air and solidifying. The varnish layer self-repairs the carbon nano tube and finally releases core liquid. The varnish core liquid comprises the following components in parts by mass: 70-80% of methacrylate and methacrylic acid copolymer resin, 20-30% of alcohol solvent, 0.5-2% of surfactant, 2-5% of auxiliary agent and 2-5% of defoaming agent.
And (3) release speed control: the control of the release speed of the core liquid is realized by simultaneously controlling the flowability of the core liquid and the interfacial tension and the capillary force between the core liquid and the carbon nano tube
(1) The flowing property of the tube core liquid is controlled by controlling the response of the viscosity of the tube core liquid to the temperature. The concrete implementation conditions are that the electrophoretic layer repairing liquid starts to naturally flow out from the damaged nano tubes at about zero degree, and the core liquids of the middle coating layer, the colored paint layer and the clear paint layer respectively naturally flow out at different elevated temperatures. The flowing time of the core liquid from the nanotube is less than 2 minutes.
(2) The viscosity of the core liquid of the electrophoresis layer reaches the natural flowing performance at 0-30 ℃. The core liquid of the middle coating, the color paint layer and the clear paint layer respectively reach natural flowing performance at 40-55 ℃, 60-80 ℃ and more than 80 ℃. Thereby ensuring that the core liquid of the electrophoretic layer firstly releases and repairs the electrophoretic layer. Along with the heating temperature rising to 40 ℃, 60 ℃ and 80 ℃, the repair liquid of the middle coating, the colored paint layer and the clear paint layer is respectively released in sequence at different temperatures, and the damaged coating is repaired layer by layer from the lowest layer to the outside.
(3) The release speed of the repair liquid in different layers is controlled by controlling the wettability of the nanotube wall and the wettability of the repair coating of different coatings. The outflow of the core liquid from the damaged nanotubes is controlled by the viscosity and capillary force of the core liquid, respectively. By controlling the interfacial tension, when the viscosities of the core liquids of the electrophoretic layer, the intermediate coating layer, the colored paint layer and the clear paint layer reach zero, 40 ℃, 60 ℃ and 80 ℃ respectively to reach natural flowing performance, the capillary force is close to the minimum value.
The release speed of the core liquid of the carbon nano tube in the electrophoretic layer is greater than that of the core liquid of the carbon nano tube in the middle coating layer, that of the core liquid of the nano tube in the colored paint layer is greater than that of the core liquid of the nano tube in the varnish layer.
By controlling the release speed of the self-repairing core liquid in different layers and controlling the coating components, the aim of simulating the repairing during primary processing is achieved.
The proportion of the carbon nano tube in the repairing liquid of the electrophoresis layer, the middle coating layer, the color paint layer and the clear paint layer is as follows:
the carbon nano tube is 10 to 15 percent in electrophoretic layer repair liquid (5 to 10 percent of mercaptobenzothiazole, 35 to 45 percent of resin primer, 30 to 40 percent of benzotriazole, 5 to 8 percent of zinc powder, 5 to 10 percent of carbon tetrachloride, 10 to 15 percent of polyaluminium chloride, 0.5 percent of emulsifier, 0.5 to 1 percent of defoamer, 0.5 to 2 percent of surfactant and 1.0 to 2.5 percent of adhesion promoter), the repair liquid of middle coating (30 to 40 percent of modified epoxy resin, 10 to 15 percent of polyvinyl butyral, 15 to 20 percent of polydimethylsiloxane, 5 to 10 percent of amino resin, 3 to 7 percent of color additive, 10 to 15 percent of carbon tetrachloride, 5 to 10 percent of superfine titanium iron powder, 0.5 to 1.5 percent of emulsifier, 0.5 to 2 percent of assistant (such as acrylate leveling agent) and 0.5 to 2 percent of surfactant, 0.5-1 percent of defoaming agent, 20-30 percent of the repair liquid for the colored paint layer (35-45 percent of amino acrylic resin, 35-45 percent of amino polyester resin, 10-15 percent of alcohol solvent, 15-20 percent of color additive, 0.5-1.5 percent of emulsifier, 3-5 percent of curing agent, 0.5-2 percent of auxiliary agent (such as hydrogenated castor oil pigment dispersant), 0.5-1 percent of surfactant and 0.5-1 percent of defoaming agent. ) The proportion of 10-15 percent, and the proportion of 3-5 percent in the varnish layer repair liquid (the main components are methacrylate and methacrylic acid copolymer resin (70-80 percent), alcohol solvent 20-30 percent, surfactant 0.5-2 percent, accessory ingredient polydimethylsiloxane 2-5 percent (such as polydimethylsiloxane) and defoaming agent 2-5 percent).
Mutual compatibility of the nanotube and the repair liquid: in order to improve the mutual compatibility between the surface of the nanotube and the repair liquid and increase the affinity between the nanotube and the repair liquid, the surface of the carbon nanotube is treated by metal ions Fe 3+ And (5) activating treatment.
Activating and modifying the surface of the carbon nano tube: soaking carbon nanotube in 0.1-0.3M FeCl 3 The solution was left for about two hours. FeCl 3 Rinsing the carbon nano tube soaked by the solution with deionized water for multiple times, and drying at 80 ℃.
Has the advantages that:
(1) the repair area and depth are increased by using carbon nanotubes.
(2) The carbon nano tube is used for repairing different performances of an electric pulse layer, a middle coating layer, a colored paint layer and a clear paint layer of an automobile coating step by step.
(3) The proportion of the carbon nano tube in the repair liquid is prepared according to the performances of the electric pulse layer, the middle coating layer, the colored paint layer and the clear paint layer, so that the service life of a self-repair area is prolonged, and the self-repair function is realized.
(4) The surface of the carbon nano tube is activated and modified, the mutual compatibility of the carbon nano tube and the repair liquid is improved, the proportion of the carbon nano tube in the repair liquid is improved, and the performance of the coating main body is kept.
(5) The response of the viscosity of the core liquid of different coatings to the temperature is adjusted to control the natural flowing performance of the core liquid, the interfacial tension between the carbon nano tube and the core liquid of different coatings is changed, and the release speed of the core liquid from the nano tube in different layers is controlled.
Detailed Description
Example 1: preparation of electrophoretic layer repairing liquid
Under the protection of nitrogen, 5-10% of mercaptobenzothiazole (Hefeijianjia chemical Co., Ltd.), 35-45% of resin primer (alkyd resin, Fenyang Tang (Shanghai) practical Co., Ltd.), 30-40% of benzotriazole (Guangzhou macro engineering Biotechnology Co., Ltd.), 5-8% of zinc powder, 5-10% of carbon tetrachloride, 10-15% of polyaluminium chloride, 0.5% of emulsifier and 1.0-2.5% of adhesion promoter are ultrasonically stirred and mixed for 2 hours or more according to the mass ratio until all phases are uniformly mixed. Adding superfine zinc powder 5-10%, ultrasonic stirring and mixing for 5 hr, adding defoaming agent 0.5-1% and surfactant 0.5-2%, ultrasonic stirring and mixing.
Under the protection of nitrogen, heating the prepared liquid to 160 ℃, adding 5-10% of modified carbon nano tubes, stirring for 5 hours until the carbon nano tubes are uniformly mixed in the coating, and then canning, sealing and storing under the protection of nitrogen.
Example 2: preparation of intermediate coating repairing liquid
Under the protection of nitrogen, 30-40% of modified epoxy resin (MODEPICS, wasteland chemical ), 10-15% of polyvinyl butyral (Tianjin Huachangyuan industrial and trade company, Ltd.), 15-20% of polydimethylsiloxane (201 methyl silicone oil, Heshensi industry, Ltd.), 5-10% of amino resin (alkyd resin, Fenyang Tang (Shanghai) practical company, Ltd.), 10-15% of carbon tetrachloride and 0.5-1.5% of emulsifier are ultrasonically stirred and mixed for 2 hours or more to uniformly mix the phases, 5-10% of superfine ferrotitanium powder, 3-7% of color additive, 5 hours or more to ultrasonically stir and mix the phases for 5 hours or more, 0.5-2% of auxiliary acrylate and 0.5-1% of defoamer are simultaneously added, and the phases are ultrasonically stirred and uniformly mixed.
Under the protection of nitrogen, the prepared liquid is heated to 160 ℃, 5 to 10 percent of modified carbon nano tubes are added and stirred for 5 hours until the carbon nano tubes are evenly mixed in the coating.
Under the protection of nitrogen, the self-repairing coating prepared by the method is canned, sealed and stored.
Example 3: preparation of colored paint layer repairing liquid
Under the protection of nitrogen, 35-45% of amino acrylic resin (Guangdong Boxing new material science and technology Co., Ltd.), 35-45% of amino polyester resin (Fenyang Tang (Shanghai) practice Co., Ltd.), 10-15% of alcohol solvent, 15-20% of color additive, 0.5-1.5% of emulsifier, 3-5% of curing agent, 0.5-2% of auxiliary hydrogenated castor oil and 0.5-1% of defoaming agent are ultrasonically stirred and mixed for 2 hours or more according to the mass ratio to uniformly mix the phases. Under the protection of nitrogen, heating the prepared liquid to 160 ℃, adding 5-10% of modified carbon nano tubes, stirring for 5 hours until the modified carbon nano tubes are uniformly mixed in the coating, and under the protection of nitrogen, canning, sealing and storing.
Example 4: preparation of varnish layer repairing liquid
Under the protection of nitrogen, according to the mass ratio, 70-80% of methacrylate (Qingdao Ruimasi high polymer material Co., Ltd.) and methacrylic acid copolymer resin (Shanghai Borley chemical Co., Ltd., model BM99), 20-30% of alcohol solvent, 0.5-2% of surfactant, 2-5% of auxiliary agent polydimethylsiloxane and 2-5% of defoaming agent are ultrasonically stirred and mixed for 2 hours or more, so that all phases are uniformly mixed. Under the protection of nitrogen, heating the prepared liquid to 160 ℃, adding 3-5% of modified carbon nano tubes, stirring for 5 hours until the modified carbon nano tubes are uniformly mixed in the coating, and under the protection of nitrogen, canning, sealing and storing.
Application method
1. The carbon nano tubes filled with the electrophoretic layer repairing liquid, the intermediate coating repairing liquid, the colored paint layer repairing liquid and the clear paint layer repairing liquid are respectively mixed into the primer, the intermediate coating paint, the colored paint layer paint and the clear paint layer paint in a proportion of about 15%.
2. Spraying car paint according to a common spraying mode
3. Painted surface repair
When the paint surface is damaged, the electrophoretic layer repair liquid flows out of the carbon nano tube immediately above zero degree to form a first layer of repair, and the metal shell is immediately prevented from contacting with air and water. If the temperature is lower than zero degree, the electrophoretic repairing layer is repaired by slightly heating (the temperature is not higher than 30 ℃) by using an electric blower, and the metal shell is prevented from contacting with air and water.
Heating the damaged part to 40-55 ℃ by using an electric blower after two minutes, and releasing the middle coating repairing liquid;
heating the damaged part to 60-80 ℃ by using an electric blower after two minutes, and releasing the colored paint layer repairing liquid;
and after two minutes, heating the damaged part to be more than 80 ℃ by using an electric blower, releasing the varnish, completing the layer-by-layer repair of the paint surface, and strengthening the repair function.
Characterization of coating performance and self-repair performance after coating damage
1. The carbon nano tube self-repairing coating can keep stable at 250 ℃,
2. the scratch of the carbon nano tube self-repairing coating sample is basically completely healed, and the healed part is almost completely consistent with the coating matrix,
3. the impact strength of the coating is 50-55 impact strength/cm 2 ,
4. After the self-repairing coating is soaked in a 3.5% sodium chloride solution for 96 hours, the corrosion condition of the metal substrate at the scratch position is observed by a microscope, and the self-repairing coating has no obvious corrosion phenomenon and is basically consistent with the original coating.
Claims (7)
1. A carbon nanotube automobile self-repairing coating is characterized in that: the automobile coating repairing method comprises an electrophoresis layer, a middle coating and a varnish layer, wherein carbon nano tubes filled with electrophoresis layer repairing liquid are distributed in the electrophoresis layer, the middle coating is distributed with carbon nano tubes filled with middle coating repairing liquid, the varnish layer is distributed with carbon nano tubes filled with colored varnish layer repairing liquid, and the varnish layer is filled with liquid varnish, wherein the release speed of the electrophoresis layer repairing liquid is greater than the release speed of the middle coating repairing liquid is greater than the release speed of the colored varnish layer repairing liquid is greater than the release speed of the liquid varnish, and the speed control is used for completing layered repairing of the automobile coating.
2. A carbon nanotube automobile coating self-repairing coating is characterized in that: electrophoretic layer paints, mid-coat paints, color paint layer paints and clear paint layer paints comprising an electrophoretic layer, a mid-coat layer, a color paint layer and a clear paint layer, respectively, for forming the automotive coating of claim 1:
the electrophoretic layer coating comprises the carbon nano tube filled with electrophoretic layer repairing liquid, and the electrophoretic layer repairing liquid comprises the following components in parts by mass: 5-10% of mercaptobenzothiazole, 35-45% of resin primer, 30-40% of benzotriazole, 5-8% of zinc powder, 5-10% of carbon tetrachloride, 10-15% of polyaluminum chloride, 0.5% of emulsifier, 0.5-1% of defoamer, 0.5-2% of surfactant and 1.0-2.5% of adhesion promoter;
the intermediate coating comprises the carbon nano tube filled with the intermediate coating repairing liquid, wherein the intermediate coating repairing liquid comprises the following components in parts by mass: 30-40% of modified epoxy resin, 10-15% of polyvinyl butyral, 15-20% of polydimethylsiloxane, 5-10% of amino resin, 3-7% of color additive, 10-15% of carbon tetrachloride, 5-10% of superfine titanium iron powder, 0.5-1.5% of emulsifier, 0.5-2% of assistant and 0.5-1% of defoaming agent;
the color paint layer coating comprises the carbon nano tubes filled with the color paint layer repairing liquid, wherein the color paint layer repairing liquid comprises the following components in parts by mass: 35-45% of amino acrylic resin, 35-45% of amino polyester resin, 10-15% of alcohol solvent, 15-20% of color additive, 0.5-1.5% of emulsifier, 3-5% of curing agent, 0.5-2% of auxiliary agent and 0.5-1% of defoaming agent;
the varnish layer coating comprises the carbon nano tube filled with varnish layer repairing liquid, wherein the varnish layer repairing liquid consists of the following components in parts by mass: 70-80% of methacrylate (Nantong Runfeng petrochemical company, Ltd.) and methacrylic acid copolymer resin, 20-30% of alcohol solvent, 0.5-2% of surfactant, 2-5% of auxiliary agent and 2-5% of defoaming agent.
3. The carbon nanotube automotive coating self-healing coating of claim 2, wherein: the preparation method of the electrophoretic layer coating, the intermediate coating or the colored paint layer coating comprises the following steps: under the protection of inert gas, uniformly mixing the electrophoretic layer repairing liquid, the intermediate coating layer repairing liquid or the colored paint layer repairing liquid, adding the carbon nano tubes under the heating condition, fully stirring until the carbon nano tubes are filled with the electrophoretic layer repairing liquid, the intermediate coating layer repairing liquid or the colored paint layer repairing liquid, and then sealing and storing.
4. The carbon nanotube automotive coating self-healing coating of claim 3, wherein: the mass content of the carbon nano tube in the electrophoretic layer coating, the middle coating and the colored paint layer coating is 5-10 percent respectively.
5. The carbon nanotube automotive coating self-healing coating of claim 3, wherein: the diameter of the carbon nano tube is 100-200 nm, and the length-diameter ratio is more than 1000: 1.
6. the carbon nanotube automotive coating self-healing coating of claim 3, wherein: the carbon nano tube is made of Fe 3+ After the activation treatment, the activation method comprises soaking the carbon nano-tube in 0.1-0.3M FeCl 3 In the solution, the carbon nanotubes are sufficiently activated, and then washed and dried.
7. The self-repairing method of the carbon nanotube automobile self-repairing coating of claim 1, comprising the steps of: after the automobile coating is damaged, firstly controlling the temperature to be 0-30 ℃ so that the electrophoretic layer repairing liquid flows out and the electrophoretic layer is repaired; then, controlling the middle coating repairing liquid to flow out at the temperature of 40-55 ℃ and finishing the middle coating repairing; then controlling the temperature to be 60-80 ℃, releasing the colored paint layer repairing liquid and finishing the colored paint layer repairing; and finally, raising the temperature to release the varnish layer and finish the varnish layer repair.
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