Reinforced high-wear-resistant stain-resistant film-coated plate and preparation method thereof

Abstract

The invention relates to the technical field of film-coated plates, and provides a preparation method of a reinforced high-wear-resistant and stain-resistant film-coated plate, which comprises the following steps: step 1, carrying out surface activation treatment on a metal substrate, and sequentially carrying out alkali washing, acid washing and micro-etching on the metal substrate by adopting ultrasonic assistance, so that a nano-scale microporous structure is constructed on the surface of the metal substrate, and the pore diameter is controlled to be 50-200nm; the roughness Ra reaches 1.5 to 3.0 [mu] m; step 2, preparing a stain-resistant surface layer, and mixing a fluorine-containing acrylate monomer, a silane coupling agent KH-570 and an initiator potassium persulfate; by constructing a multi-layer functional gradient system, leap-type improvement of the comprehensive performance of the laminated plate is achieved, the bonding layer and the substrate form the dual effects of mechanical interlocking and chemical bonding in combination with an electromagnetic induction auxiliary hot pressing technology, the firmness of a laminated film is improved, and the service life of the laminated plate is prolonged. And graphene oxide treated by plasma and modified nano silicon dioxide of the wear-resistant enhancement layer have a synergistic effect, so that the wear loss is remarkably reduced, and the service life is prolonged.

Description

Technical Field

[0001] This invention relates to the field of coated board technology, specifically to an enhanced, highly wear-resistant and stain-resistant coated board and its preparation method. Background Technology

[0002] Laminated panels are made by laminating a layer of film onto a metal substrate, using a high-gloss or iridescent film, and then coating the surface with a professional adhesive. Laminated panels have a bright luster, a wide variety of colors and patterns to choose from, are waterproof and fireproof, have excellent durability and stain resistance, and superior UV protection. Different brands of laminated panels have different substrate materials and thicknesses, as well as different lamination materials and thicknesses. There are also architectural laminated panels made from materials such as poplar wood.

[0003] With the rapid development of modern architectural decoration, home appliance manufacturing, and transportation, higher requirements are being placed on the surface performance of metal-coated panels. Traditional coated panels generally suffer from insufficient wear resistance, leading to easy scratches; poor stain resistance, making it difficult to remove contaminants; and weak interlayer adhesion, causing film peeling. These problems are mostly caused by insufficient performance of the surface coating and immature hot-pressing processes during manufacturing. Therefore, there is a need for a reinforced, highly wear-resistant and stain-resistant coated panel and its preparation method. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an enhanced high wear-resistant and stain-resistant coated board and its preparation method, which solves the problems of insufficient wear resistance leading to easy surface scratches, poor stain resistance making it difficult to remove pollutants, and weak interlayer bonding causing film peeling, which are common problems in traditional coated boards.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a reinforced, highly wear-resistant and stain-resistant coated board includes the following steps: Step 1: Perform surface activation treatment on the metal substrate. Use ultrasonic assistance to sequentially perform alkaline washing, acid washing and micro-etching on the metal substrate to build a nanoscale microporous structure on the surface of the metal substrate. The pore size is controlled between 50 and 200 nm and the roughness Ra reaches 1.5 to 3.0 μm. Step 2: Prepare the stain-resistant surface layer by mixing fluorinated acrylate monomers, silane coupling agent KH-570, and potassium persulfate initiator in a mass ratio of 100:(5-8):(0.3-0.5). The mixture is then cured under ultraviolet light to form a gradient cross-linked structure on the surface of the wear-resistant reinforcement layer. The curing energy is 300-500 mJ / cm². 2 This results in a stain-resistant surface layer; Step 3: Prepare the wear-resistant reinforcement layer by melt-blending TPO resin, nano-silica, graphene oxide, and antioxidant 1010 in a mass ratio of 100:(8-15):(0.5-2):(0.5-1). The wear-resistant reinforcement layer is prepared by casting, with the casting temperature controlled at 180-220℃ and the traction speed maintained at 15-25m / min. Step 4: Prepare the adhesive layer by mixing silane-modified polyester, maleic anhydride-grafted POE, triphenylmethane triisocyanate, and trimethylolpropane triacrylate in a mass ratio of (15-25):(30-40):(5-10):(3-5). The mixing temperature is maintained at 65-75℃ and the mixing time is maintained at 40-60 minutes. The adhesive layer is then obtained by extrusion molding. Step 5: Prepare the anti-corrosion backing film layer by mixing maleic anhydride-grafted polyethylene, linear low-density polyethylene, silicon micro powder, graphene oxide and antioxidant, and then compounding them through a three-layer co-extrusion equipment. The mass ratio of the four raw materials is (50-70):(30-50):(10-20):(0.5-1.5):(0.3-0.8). The co-extrusion die temperature is 175-185℃, and an anti-corrosion backing film layer with a total thickness of 50-80μm is obtained. Step 6: Perform gradient hot pressing composite. The stain-resistant surface layer, wear-resistant reinforcement layer, adhesive layer, metal substrate and anti-corrosion back film layer are stacked in sequence and subjected to a three-stage hot pressing process to obtain a reinforced, high wear-resistant and stain-resistant coated board.

[0006] Preferably, the micro-etching treatment in step one uses an acidic etching solution with the following components: 10-20 g / L copper sulfate, 5-15 g / L ammonium persulfate, and 3-8 g / L citric acid. The treatment temperature is 45-55°C, and the treatment time is 2-5 minutes, so that a honeycomb micro-nano composite structure is formed on the metal surface.

[0007] Preferably, in step three, the surface of the nano-silica is pre-treated with vinyltrimethoxysilane with a grafting rate of 15-25%, and the graphene oxide in step three needs to be subjected to plasma treatment to increase the content of oxygen-containing functional groups on its surface to 30-40 wt%.

[0008] Preferably, the preparation process of the silane-modified polyester in step four is as follows: ethylene tert-carbonate, vinyl benzoate, and 3-methacryloyloxypropyltrimethoxysilane are subjected to solution polymerization at a mass ratio of (0.8-1.2):(0.3-0.5):1, the reaction temperature is 75-85℃, and the reaction time is 4-6h, to obtain a silane-modified polyester with a number average molecular weight Mn of 8000-15000.

[0009] Preferably, in step six, the hot pressing adopts electromagnetic induction-assisted hot pressing technology, which generates eddy current heating inside the metal substrate, making the temperature of the metal substrate 10-20°C higher than that of the surface film material, realizing heat conduction from the inside out, and promoting interfacial diffusion and chemical bonding between the adhesive layer and the metal substrate.

[0010] Preferably, the induction frequency of the electromagnetic induction-assisted hot pressing is 50–80 kHz, and the power density is 0.5–1.5 kW / cm². 2 The distance between the induction coil and the metal substrate is controlled at 3-5 mm.

[0011] Preferably, the specific steps of the three-stage hot pressing process in step six are as follows: S1. First stage preheating pressure: maintain the temperature environment at 120-140℃ and the pressure environment at 0.3-0.5MPa for 10-15 seconds. S2, the second stage of main hot pressing, the temperature environment is maintained at 160-180℃, the pressure environment is maintained at 0.6-0.8MPa, and the time lasts for 20-30s; S3, the third stage of shaping pressure, the temperature environment is maintained at 100~120℃, the pressure environment is maintained at 0.2~0.3MPa, and the time lasts for 15~20s.

[0012] Preferably, after hot-pressing composite in step six, a plasma surface post-treatment process is required. This process involves forming a dense cross-linked structure with a depth of 0.5–1.0 μm on the dirt-resistant surface using atmospheric pressure glow discharge technology. The treatment power is maintained at 200–300 W, and the treatment time lasts for 10–20 seconds.

[0013] Preferably, steps two through five employ an online synchronous coating-curing-composite process. Between each step, a tension control system is used to maintain the membrane tension at a constant 50–80 N / m to prevent interlayer slippage and wrinkles during multilayer composite.

[0014] A reinforced, highly wear-resistant and stain-resistant coated panel, comprising, from top to bottom: A stain-resistant surface layer, wherein the stain-resistant surface layer is a fluorinated silicone-modified polyacrylate coating with a thickness of 3-8 μm; The wear-resistant reinforcing layer is a nano-silica / graphene oxide composite modified TPO film with a thickness of 0.2-0.5 mm. The adhesive layer is a double-network structure adhesive formed by blending silane-modified polyester and maleic anhydride-grafted POE, with a thickness of 80-120 μm. A metal substrate, which serves as the skeletal support structure for the coated plate and bears all mechanical loads; The anti-corrosion backing layer is a multilayer co-extruded PE film co-modified with graphene oxide and silicon micropowder.

[0015] This invention provides a reinforced, highly wear-resistant and stain-resistant coated board and its preparation method. It has the following beneficial effects: 1. This invention achieves a leapfrog improvement in the overall performance of the coated board by constructing a multi-layer functional gradient system. Combined with electromagnetic induction-assisted hot pressing technology, the adhesive layer and the substrate form a dual effect of mechanical interlocking and chemical bonding, which improves the firmness of the coating. Furthermore, the wear-resistant reinforcement layer, with the synergistic effect of plasma-treated graphene oxide and modified nano-silica, significantly reduces wear and extends service life.

[0016] 2. This invention adopts an online synchronous coating-curing-composite integrated process, combined with three-stage gradient hot pressing and electromagnetic induction assisted heating technology, which greatly optimizes the production process and energy efficiency. By introducing a full-process tension control system and plasma post-treatment process, interlayer slippage and wrinkle defects are effectively avoided. At the same time, this process does not require solvent evaporation, highlighting weather resistance and long-term corrosion resistance. Attached Figure Description

[0017] Figure 1 This is a flowchart of a method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to the present invention; Figure 2 This is a three-dimensional cross-sectional view of an enhanced wear-resistant and stain-resistant coated board according to the present invention.

[0018] The components include: 1. Stain-resistant surface layer; 2. Wear-resistant reinforcing layer; 3. Adhesive layer; 4. Metal substrate; 5. Anti-corrosion back film layer. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example: As part of this application, please refer to the appendix. Figure 1 This invention provides a method for preparing a reinforced, highly wear-resistant and stain-resistant coated board, comprising the following steps: Step 1: Perform surface activation treatment on the metal substrate 4. Use ultrasonic assistance to perform alkali washing, acid washing and micro-etching on the metal substrate 4 in sequence to build a nanoscale microporous structure on the surface of the metal substrate 4. The pore size is controlled between 50 and 200 nm and the roughness Ra reaches 1.5 to 3.0 μm. The micro-etching process uses an acidic etching solution with the following components: 10-20 g / L copper sulfate, 5-15 g / L ammonium persulfate, and 3-8 g / L citric acid. The treatment temperature is 45-55°C, and the treatment time is 2-5 minutes, which causes a honeycomb micro-nano composite structure to form on the metal surface.

[0021] Step 2: Prepare the stain-resistant surface layer 1 by mixing fluorinated acrylate monomer, silane coupling agent KH-570, and potassium persulfate initiator in a mass ratio of 100:(5-8):(0.3-0.5). The mixture is then cured under ultraviolet light to form a gradient cross-linked structure on the surface of the wear-resistant reinforcing layer 2, with a curing energy of 300-500 mJ / cm². 2 A stain-resistant surface layer 1 is obtained; Step 3: Prepare the wear-resistant reinforcing layer 2 by melt-blending TPO resin, nano-silica, graphene oxide, and antioxidant 1010 in a mass ratio of 100:(8~15):(0.5~2):(0.5~1). Prepare the wear-resistant reinforcing layer 2 by casting, with the casting temperature controlled at 180~220℃ and the traction speed maintained at 15~25m / min. In this process, the surface of nano-silica is pre-modified with vinyltrimethoxysilane, with a grafting rate of 15-25%. In step three, the graphene oxide needs to be plasma-treated to increase the content of oxygen-containing functional groups on its surface to 30-40 wt%.

[0022] Step 4: Prepare adhesive layer 3 by mixing silane-modified polyester, maleic anhydride-grafted POE, triphenylmethane triisocyanate, and trimethylolpropane triacrylate in a mass ratio of (15-25):(30-40):(5-10):(3-5). The mixing temperature is maintained at 65-75℃ and the mixing time is maintained at 40-60 minutes. The adhesive layer 3 is obtained by extrusion molding. The preparation process of silane-modified polyester is as follows: vinyl tert-carbonate, vinyl benzoate, and 3-methacryloyloxypropyltrimethoxysilane are subjected to solution polymerization at a mass ratio of (0.8-1.2):(0.3-0.5):1, the reaction temperature is 75-85℃, and the reaction time is 4-6h, to obtain silane-modified polyester with a number average molecular weight Mn of 8000-15000.

[0023] Step 5: Prepare the anti-corrosion backing film layer 5 by mixing maleic anhydride grafted polyethylene, linear low-density polyethylene, silicon micro powder, graphene oxide and antioxidant, and then compounding them through a three-layer co-extrusion equipment. The mass ratio of the four raw materials is (50-70):(30-50):(10-20):(0.5-1.5):(0.3-0.8). The co-extrusion die temperature is 175-185℃, and an anti-corrosion backing film layer 5 with a total thickness of 50-80μm is obtained. Step 6: Perform gradient hot pressing composite. Stack the stain-resistant surface layer 1, wear-resistant reinforcement layer 2, adhesive layer 3, metal substrate 4 and anti-corrosion back film layer 5 in sequence and perform a three-stage hot pressing process to obtain a reinforced high wear-resistant and stain-resistant coated board. The hot pressing process employs electromagnetic induction-assisted hot pressing technology, generating eddy current heating within the metal substrate 4. This raises the temperature of the metal substrate 4 by 10–20°C compared to the surface film material, achieving heat conduction from the inside out. This promotes interfacial diffusion and chemical bonding between the adhesive layer 3 and the metal substrate 4. The induction frequency of the electromagnetic induction-assisted hot pressing is 50–80 kHz, and the power density is 0.5–1.5 kW / cm². 2 The distance between the induction coil and the metal substrate 4 is controlled at 3-5 mm; The specific steps of the three-stage hot pressing process are as follows: S1. First stage preheating pressure: maintain the temperature environment at 120-140℃ and the pressure environment at 0.3-0.5MPa for 10-15 seconds. S2, the second stage of main hot pressing, the temperature environment is maintained at 160-180℃, the pressure environment is maintained at 0.6-0.8MPa, and the time lasts for 20-30s; S3, the third stage of shaping pressure, the temperature environment is maintained at 100~120℃, the pressure environment is maintained at 0.2~0.3MPa, and the time lasts for 15~20s.

[0024] After hot pressing and bonding, a plasma surface post-treatment process is required. A dense cross-linked structure with a depth of 0.5 to 1.0 μm is formed on the dirt-resistant surface layer 1 by using atmospheric pressure glow discharge technology. The treatment power is maintained at 200 to 300 W and the treatment time lasts for 10 to 20 seconds.

[0025] Steps two through five all employ an online synchronous coating-curing-composite process. Between each step, a tension control system is used to maintain the membrane tension at a constant 50–80 N / m to prevent interlayer slippage and wrinkles during multilayer composite.

[0026] Based on the above-described reinforced, highly wear-resistant and stain-resistant coated board and its preparation method, as another aspect of this application, please refer to the appendix. Figure 2 A reinforced, highly wear-resistant and stain-resistant coated panel, comprising, from top to bottom: Stain-resistant surface layer 1, which is a fluorinated silicone modified polyacrylate coating with a thickness of 3-8 μm; Wear-resistant reinforcing layer 2 is a nano-silica / graphene oxide composite modified TPO film with a thickness of 0.2-0.5 mm; Adhesive layer 3 is a double-network structure adhesive formed by blending silane-modified polyester and maleic anhydride-grafted POE, with a thickness of 80-120 μm. Metal substrate 4 serves as the skeleton support structure for the coated plate, bearing all mechanical loads. The anti-corrosion backing layer 5 is a multilayer co-extruded PE film co-modified with graphene oxide and silicon micropowder.

[0027] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a reinforced, highly wear-resistant and stain-resistant coated board, characterized in that, Includes the following steps: Step 1: Surface activation treatment of metal substrate (4) is carried out. Ultrasonic aid is used to perform alkaline washing, acid washing and micro-etching on metal substrate (4) in sequence to build a nanoscale microporous structure on the surface of metal substrate (4). The pore size is controlled at 50-200nm and the roughness Ra reaches 1.5-3.0μm. Step 2: Preparation of the stain-resistant surface layer (1): Fluorinated acrylate monomer, silane coupling agent KH-570, and initiator potassium persulfate are mixed in a mass ratio of 100:(5~8):(0.3~0.5). The mixture is then cured with ultraviolet light to form a gradient cross-linked structure on the surface of the wear-resistant reinforcing layer (2). The curing energy is 300~500mJ / cm. 2 , thus obtaining a stain-resistant surface layer (1); Step 3: Prepare the wear-resistant reinforcing layer (2). Melt-blend TPO resin, nano silica, graphene oxide, and antioxidant 1010. The mass ratio of the four raw materials is 100:(8~15):(0.5~2):(0.5~1). Prepare the wear-resistant reinforcing layer (2) by casting. The casting temperature is controlled at 180~220℃ and the traction speed is maintained at 15~25m / min to obtain the wear-resistant reinforcing layer (2). Step 4: Prepare the adhesive layer (3). Mix silane-modified polyester, maleic anhydride-grafted POE, triphenylmethane triisocyanate, and trimethylolpropane triacrylate in a mass ratio of (15-25):(30-40):(5-10):(3-5). Maintain the mixing temperature at 65-75°C and continue mixing for 40-60 minutes. Extrude the mixture to obtain the adhesive layer (3). Step 5: Prepare the anti-corrosion backing film layer (5). Mix maleic anhydride-grafted polyethylene, linear low-density polyethylene, silicon micro powder, graphene oxide and antioxidant, and then composite them through a three-layer co-extrusion equipment. The mass ratio of the four raw materials is (50-70):(30-50):(10-20):(0.5-1.5):(0.3-0.8). The co-extrusion die temperature is 175-185℃, and an anti-corrosion backing film layer (5) with a total thickness of 50-80μm is obtained. Step 6: Perform gradient hot pressing composite. Stack the stain-resistant surface layer (1), wear-resistant reinforcement layer (2), adhesive layer (3), metal substrate (4) and anti-corrosion back film layer (5) in sequence and perform a three-stage hot pressing process to obtain a reinforced high wear-resistant and stain-resistant coated board.

2. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, In step one, the micro-etching treatment uses an acidic etching solution with the following components: 10-20 g / L copper sulfate, 5-15 g / L ammonium persulfate, and 3-8 g / L citric acid. The treatment temperature is 45-55°C, and the treatment time is 2-5 minutes, which causes a honeycomb micro-nano composite structure to form on the metal surface.

3. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, In step three, the surface of nano-silica is pre-modified with vinyltrimethoxysilane with a grafting rate of 15-25%. In step three, the graphene oxide needs to be treated with plasma to increase the content of oxygen-containing functional groups on its surface to 30-40 wt%.

4. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, The preparation process of the silane-modified polyester in step four is as follows: ethylene tert-carbonate, vinyl benzoate, and 3-methacryloyloxypropyltrimethoxysilane are subjected to solution polymerization at a mass ratio of (0.8-1.2):(0.3-0.5):1, the reaction temperature is 75-85℃, and the reaction time is 4-6h, to obtain a silane-modified polyester with a number average molecular weight Mn of 8000-15000.

5. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, In step six, the hot pressing adopts electromagnetic induction-assisted hot pressing technology to generate eddy current heating inside the metal substrate (4), so that the temperature of the metal substrate (4) is 10-20°C higher than that of the surface film material, realizing heat conduction from the inside out, and promoting the interfacial diffusion and chemical bonding between the adhesive layer (3) and the metal substrate (4).

6. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 5, characterized in that, The electromagnetic induction-assisted hot pressing has an induction frequency of 50–80 kHz and a power density of 0.5–1.5 kW / cm². 2 The distance between the induction coil and the metal substrate (4) is controlled at 3-5 mm.

7. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, The specific steps of the three-stage hot pressing process in step six are as follows: S1. First stage preheating pressure: maintain the temperature environment at 120-140℃ and the pressure environment at 0.3-0.5MPa for 10-15 seconds. S2, the second stage of main hot pressing, the temperature environment is maintained at 160-180℃, the pressure environment is maintained at 0.6-0.8MPa, and the time lasts for 20-30s; S3, the third stage of shaping pressure, the temperature environment is maintained at 100~120℃, the pressure environment is maintained at 0.2~0.3MPa, and the time lasts for 15~20s.

8. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, In step six, after hot-pressing composite, a plasma surface post-treatment process is required. A dense cross-linked structure with a depth of 0.5 to 1.0 μm is formed on the dirt-resistant surface layer (1) by using atmospheric pressure glow discharge technology. The treatment power is maintained at 200 to 300 W and the treatment time lasts for 10 to 20 seconds.

9. The method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to claim 1, characterized in that, Steps two through five all employ an online synchronous coating-curing-composite process. Between each step, a tension control system is used to maintain the membrane tension at a constant 50–80 N / m to prevent interlayer slippage and wrinkles during multilayer composite.

10. A reinforced, highly wear-resistant and stain-resistant coated board, prepared by the method for preparing a reinforced, highly wear-resistant and stain-resistant coated board according to any one of claims 1 to 9, characterized in that, From top to bottom, they include: The stain-resistant surface layer (1) is a fluorinated silicone modified polyacrylate coating with a thickness of 3 to 8 μm. Wear-resistant reinforcing layer (2), wherein the wear-resistant reinforcing layer (2) is a nano-silica / graphene oxide composite modified TPO film with a thickness of 0.2-0.5 mm; The adhesive layer (3) is a double-network structure adhesive formed by blending silane-modified polyester and maleic anhydride-grafted POE, with a thickness of 80-120 μm. Metal substrate (4), which serves as the skeleton support structure of the coated plate and bears all mechanical loads; The anti-corrosion backing layer (5) is a multilayer co-extruded PE film modified with graphene oxide / silicon micropowder.

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