Metallic interior wall decorative plate and preparation method thereof

Abstract

The invention relates to the technical field of building decoration materials, and particularly discloses a metal texture interior wall decoration plate and a preparation method thereof. The interior wall decorative plate with the metal texture sequentially comprises a base plate, a permeation enhancing layer, an adhesive layer and a metal facing layer from bottom to top. The permeation enhancing layer is prepared from the following raw materials in parts by mass: 80 to 120 parts of modified polyurethane resin, 40 to 60 parts of self-crosslinking silicone acrylic emulsion, 4 to 8 parts of nano silicon dioxide, 40 to 60 parts of reactive diluent, 3 to 6 parts of silane coupling agent, 2 to 4 parts of organic fluoride, 3 to 5 parts of curing agent A, 2 to 4 parts of photoinitiator, 2 to 4 parts of dispersing agent and 1 to 2 parts of defoaming agent. The metal texture interior wall decorative plate prepared by the invention has excellent interlayer bonding strength and water resistance.

Description

A metallic-textured interior wall panel and its preparation method Technical Field

[0001] This application relates to the technical field of building decoration materials, and more specifically, it relates to a metallic-textured interior wall decoration panel and its preparation method. Background Technology

[0002] With the acceleration of urbanization and the increasing demand for high-quality, aesthetically pleasing, and environmentally friendly materials in the building decoration industry, the market demand for metal decorative panels, as an important material in modern building decoration, continues to expand. Currently, most mainstream products are composites made by bonding inorganic substrates such as calcium silicate boards and cement fiber boards with metal finishes such as aluminum plates using adhesives. Due to the low porosity, low surface energy, and strong chemical inertness of substrates such as calcium silicate boards, ordinary adhesives are difficult to use for strong wetting and anchoring. Existing technologies typically employ physical grinding, adding physical leveling layers, or using highly polar adhesives to attempt to improve adhesion. However, in the long run, under the cyclical changes in indoor temperature and humidity, the internal stress caused by the difference in thermal expansion coefficients between the substrate and the finish layer, as well as the aging of the adhesive layer itself, can still easily lead to interface failure, resulting in problems such as blistering and peeling of the finish layer, affecting both decorative effect and safety.

[0003] Patent application CN121019055A discloses a hot-pressed aluminum composite decorative panel, comprising, from top to bottom, an aluminum decorative panel, an adhesive layer, a pull-out strength enhancement layer, and a calcium silicate board. The pull-out strength enhancement layer includes a reinforcing layer and a leveling layer. The thickness of the reinforcing layer is less than or equal to the thickness of the calcium silicate board. The reinforcing layer is located within the base layer, and the leveling layer is located between the adhesive layer and the calcium silicate board. The bottom surface of the aluminum decorative panel is bonded to the upper surface of the adhesive layer, the lower surface of the adhesive layer is bonded to the leveling layer, and the lower surface of the leveling layer is simultaneously bonded to the reinforcing layer and the calcium silicate board. While this design incorporates a pull-out strength enhancement layer (reinforcing layer + leveling layer) to improve adhesion, this structure only provides physical leveling and simple reinforcement. Long-term use still easily leads to problems such as interlayer delamination and aluminum plate bulging. Furthermore, the pull-out strength enhancement layer has a complex structure and a cumbersome manufacturing process.

[0004] Patent application CN111761889A discloses a three-dimensional metallic-finished integrated insulation and decorative panel. Its features include a substrate, an insulation board, a clear primer layer, a molding paint layer, a colored primer layer, and a metallic topcoat layer. The clear primer layer, molding paint layer, colored primer layer, and metallic topcoat layer sequentially cover one side of the substrate, and the other side of the substrate is connected to the insulation board. The clear primer layer is a two-component water-based epoxy coating; the molding paint layer is made of molding paint, which includes a masterbatch and sand; the colored primer layer is a two-component water-based polyurethane coating; and the metallic topcoat layer is a two-component water-based polyurethane coating. This design uses a multi-layered paint application to achieve the metallic finish. However, the paint layers adhere to the substrate surface and are susceptible to peeling, blistering, and bulging due to long-term temperature and humidity changes. Summary of the Invention

[0005] In view of the problems of easy peeling and bulging caused by poor interfacial bonding between metal veneer and inorganic substrate in the prior art, this application provides a metallic textured interior wall decoration panel and its preparation method.

[0006] In a first aspect, this application provides a metallic-textured interior wall decorative panel, employing the following technical solution: A metallic-textured interior wall decorative panel, comprising, from bottom to top, a substrate, a permeation layer, an adhesive layer, and a metallic finish layer, wherein the permeation layer is prepared by comprising the following raw materials in parts by weight: 80-120 parts modified polyurethane resin, 40-60 parts self-crosslinking silicone-acrylic emulsion, 4-8 parts nano-silica, 40-60 parts reactive diluent, 3-6 parts silane coupling agent, 2-4 parts organic fluoride, and curing agent A. The modified polyurethane resin comprises the following raw materials in parts by weight: 70-80 parts oligomeric polyol, 17-31 parts diisocyanate, 15-20 parts bisphenol A epoxy resin, 1.7-11 parts polyhydroxy acrylate monomer, 0.05-0.1 parts organotin catalyst, and 0.02-0.06 parts polymerization inhibitor; the adhesive layer comprises the following raw materials in parts by weight: Component A: 70-85 parts polyether polyurethane prepolymer, 5-10 parts tackifier, 2-4 parts antioxidant, 3-6 parts toughening agent, and 0.07-0.1 parts organotin catalyst; Component B: 8.5-13 parts polyetheramine, 4-5.5 parts adipate dihydrazide, and 0.1-0.15 parts 2-ethyl-4-methylimidazole.

[0007] In this technical solution, a composite interface system consisting of a permeation layer and an adhesive layer is constructed between the inorganic substrate and the aluminum veneer layer to synergistically achieve a stable interlayer bond. The permeation layer, utilizing a low-viscosity modified resin system, penetrates into the substrate micropores and forms a dense cross-linked network through photo-thermal dual curing. Simultaneously, a silane coupling agent enables chemical bonding with the substrate, thus completing the initial strengthening from physical anchoring to chemical bonding. The adhesive layer leverages the rapid curing characteristic of polyurethane under hot pressure to achieve high-strength adhesion to the upper and lower interfaces. Furthermore, the flexible segments of the polyether-type polyurethane effectively absorb and dissipate internal stresses caused by differences in the thermal expansion coefficients of the materials. Together, these two components ensure the interlayer bond strength and overall structural stability of the decorative panel.

[0008] Preferably, the method for preparing the modified polyurethane resin includes the following steps: under an inert atmosphere, oligomeric polyol, diisocyanate and organotin catalyst are mixed evenly, heated to 70-75°C, reacted for 4-5 hours, cooled to 60-65°C, bisphenol A type epoxy resin is added, reacted for 2-2.5 hours, cooled, polyhydroxy acrylate monomer and polymerization inhibitor are added, heated to 65-70°C, reacted for another 5-6 hours, cooled, and the modified polyurethane resin is obtained.

[0009] Preferably, the oligomeric polyol is at least one of polyether polyol and polyester polyol, and its number average molecular weight is not higher than 1000.

[0010] Preferably, the polyhydroxy acrylate monomer is pentaerythritol triacrylate.

[0011] Preferably, the organotin catalyst is dibutyltin dilaurate.

[0012] In this technical solution, firstly, the mechanical strength of the resin is improved by chemically grafting rigid epoxy segments; secondly, by introducing photocurable multifunctional acrylate groups, the resin can form a three-dimensional network with high cross-linking density during UV curing, thereby obtaining higher mechanical strength.

[0013] Preferably, the raw materials of the modified polyurethane resin further include 2 to 4 parts by weight of phosphate ester-containing acrylate monomers.

[0014] Preferably, in the method for preparing the modified polyurethane resin, after adding the polyhydroxy acrylate monomer, the method further includes the step of adding an acrylate monomer containing a phosphate ester.

[0015] Preferably, the phosphate-containing acrylate monomer is methacryloyloxyethyl phosphate.

[0016] In this technical solution, the phosphate-containing acrylate monomer introduced can introduce its phosphate groups into the polymer chain after participating in resin copolymerization. These groups can form a strong polar interaction with hydroxyl groups and other groups on the surface of the inorganic substrate, thereby introducing additional bonding force at the resin-substrate interface.

[0017] Preferably, the solid content of the self-crosslinking silicone-acrylic emulsion is 40%~50%, and the glass transition temperature is not higher than 10°C.

[0018] In this technical solution, during the water evaporation and film formation process of the emulsion, the active silanol groups on its molecular chain can undergo a condensation reaction to form a stable siloxane crosslinking network. This crosslinking structure can significantly improve the hardness and mechanical strength of the coating, and also enhance the water resistance and heat resistance of the coating itself. These improved properties help to enhance the coating's tolerance to changes in temperature and humidity.

[0019] Preferably, the bisphenol A type epoxy resin is epoxy resin E-51.

[0020] In this technical solution, bisphenol A type epoxy resin E-51 with low molecular weight and moderate viscosity is selected. It can undergo a grafting reaction with polyurethane prepolymer, thereby introducing rigid epoxy segments into the polyurethane network through chemical bonds. This structural design effectively increases the crosslinking density of the resin matrix, resulting in a significant enhancement in the mechanical strength of the modified resin.

[0021] Preferably, the reactive diluent is either isobornyl acrylate or tripropylene glycol diacrylate.

[0022] In this technical solution, the viscosity of the system is effectively reduced during the construction phase, thereby enhancing the wetting and penetration ability of the components in the permeation layer onto the calcium silicate board substrate. In the subsequent UV curing stage, the acrylate double bonds in their molecules can participate in the free radical polymerization reaction initiated by the photoinitiator, copolymerizing with components such as modified polyurethane resin to become part of the final cured network.

[0023] Preferably, the silane coupling agent is selected from at least one of silane coupling agent KH550 and silane coupling agent KH560.

[0024] Preferably, the organofluorine compound is perfluorooctyltriethoxysilane.

[0025] In this technical solution, the perfluoroalkyl chain can endow the coating with durable hydrophobic and oleophobic properties; while the silaneoxy group at its end can be hydrolyzed after application, and then undergo a condensation reaction with the active groups on the coating network and substrate surface to form chemical bonds, thereby stably anchoring the hydrophobic function at the interface.

[0026] Preferably, the curing agent A is an epoxy curing agent.

[0027] In this technical solution, during the thermosetting stage, the epoxy curing agent promotes the cross-linking reaction of the epoxy groups introduced in the modified polyurethane resin, and together with the acrylate network formed by UV curing, they construct an interpenetrating network structure, thereby enhancing the mechanical strength and adhesion durability of the permeation layer.

[0028] Preferably, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0029] Preferably, the dispersant is sodium polycarboxylate.

[0030] Preferably, the defoamer is an organosilicone defoamer.

[0031] Preferably, the polyether-type polyurethane prepolymer is a polyether-type MDI-terminated polyurethane prepolymer with an NCO content of 10% to 15%.

[0032] In this technical solution, on the one hand, the appropriate NCO content ensures that the prepolymer has sufficient chemical reactivity, enabling it to efficiently crosslink with the curing agent in component B and the active hydrogen groups on the interface to form a strong and tough polyurethane film; on the other hand, this content range allows the adhesive to maintain suitable initial viscosity and open time while possessing high final bond strength, thereby achieving good coating operability and sufficient interface wetting in the hot-pressing composite process.

[0033] Preferably, the tackifier is a petroleum resin.

[0034] In this technical solution, during the construction phase, petroleum resin can effectively reduce the viscosity of the adhesive, improve its wetting and spreading ability on the surfaces of the penetration layer and the metal finish layer, thereby enhancing initial adhesion. After curing, petroleum resin, as a non-reactive component, is dispersed in the polyurethane film, which can adjust the modulus and toughness of the adhesive layer, helping to improve the flexibility and stress distribution of the adhesive layer while maintaining sufficient bond strength.

[0035] Preferably, the antioxidant is antioxidant 1010.

[0036] Preferably, the toughening agent is polyamide wax micro powder.

[0037] In this technical solution, polyamide wax micropowder acts as a toughening agent, which can be uniformly dispersed in the adhesive film after the adhesive has cured. Its addition can effectively improve the toughness, peel resistance, and impact resistance of the cured adhesive layer without significantly sacrificing the modulus and bond strength of the adhesive layer.

[0038] Preferably, the metal finish layer comprises, from bottom to top, a metal base layer, a white adhesive layer, a transfer film layer, and an elastic topcoat layer.

[0039] Preferably, the thickness of the metal base layer is 0.5~1.0 mm.

[0040] Preferably, the white adhesive layer is made from environmentally friendly white latex and has a thickness of 10-15 μm; preferably, the elastic topcoat layer is a water-based polyurethane topcoat and has a thickness of 10-15 μm.

[0041] Preferably, the substrate is an asbestos-free fiber calcium silicate board with a thickness of 5-12 mm.

[0042] More preferably, the substrate is an asbestos-free fiber calcium silicate board with a thickness of 5-8 mm.

[0043] Secondly, this application provides a method for preparing a metallic interior wall decorative panel, comprising the following steps: S1: mixing nano-silica, dispersant and part of reactive diluent, then adding modified polyurethane resin, self-crosslinking silicone-acrylic emulsion, the remaining reactive diluent, silane coupling agent, organofluorine compound and defoamer, adding curing agent A and photoinitiator, mixing evenly to obtain a penetration-enhancing coating; S2: mixing polyether-type polyurethane prepolymer, tackifier, antioxidant, toughening agent and organotin catalyst evenly at 90~100℃ to obtain component A; mixing polyetheramine, adipate dihydrazide and 2-ethyl-4-methylimidazole evenly to obtain component B; before use, mixing component A and component B evenly to obtain an adhesive; S3: after pretreating the substrate, uniformly coating the penetration-enhancing coating on the substrate surface, curing to obtain a penetration-enhancing layer; S4: coating the adhesive on the surface of the penetration-enhancing layer, bonding the metal decorative layer, hot-pressing composite, post-treatment, to obtain the final product.

[0044] Preferably, the coating amount of the penetration-enhancing layer is 100~150g / m². 2 .

[0045] Preferably, the curing process includes sequential UV curing and thermal curing.

[0046] Preferably, the thermosetting temperature is 80~85℃ and the time is 30~40min.

[0047] Preferably, the coating amount of the adhesive is 150~200g / m². 2 .

[0048] Preferably, the hot pressing parameters are: pressure of 0.8~1.0MPa, temperature of 90~120℃, and time of 10~12min.

[0049] In this technical solution, the substrate surface is first pretreated and coated with a permeation-enhancing layer. By first curing with UV light and then with heat, the components of the permeation-enhancing layer are rapidly shaped and fully cross-linked, forming a strong and tough transition layer that is chemically anchored to the substrate. Subsequently, a highly reactive polyurethane adhesive is applied and laminated with an aluminum finish layer. Under hot pressing conditions, the adhesive layer itself is fully cured and forms a strong bond with the underlying permeation-enhancing layer and the upper aluminum finish layer.

[0050] In summary, this application has the following beneficial effects: This application constructs a composite interface system of a permeation layer and an adhesive layer between the substrate and the aluminum veneer layer. The permeation layer achieves a high-strength bond with the inorganic substrate through the permeability of the low molecular weight resin and the chemical bonding of the silane coupling agent. The adhesive layer effectively dissipates the internal stress caused by the difference in the thermal expansion coefficients of the materials by utilizing the stress-buffering capacity of highly flexible polyurethane. The two layers complement each other and work synergistically to ensure the interlayer bonding strength and overall structural stability of the decorative panel. Detailed Implementation

[0051] The present application will be further described in detail below with reference to the embodiments.

[0052] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application are all commercially available.

[0053] The solid content of the self-crosslinking silicone-acrylic emulsion is 40%~50%, and the glass transition temperature is not higher than 10℃.

[0054] Preparation Examples 1-5 Preparation Example 1 The preparation method of the modified polyurethane resin in this preparation example includes the following steps: Under a nitrogen atmosphere, 700g of polyethylene adipate (number average molecular weight 1000), 168g of isophorone diisocyanate, and 0.5g of dibutyltin dilaurate are added sequentially to a dry reaction vessel. The temperature is raised to 70°C, and the mixture is stirred for 4 hours. The temperature is lowered to 60°C, and 150g of epoxy resin E-51 (hydroxyl content 0.5%) is added. The mixture is kept warm and stirred for 2 hours. The temperature is lowered to 50°C, and 17.3g of pentaerythritol triacrylate and 0.2g of p-hydroxyanisole are added. The temperature is raised to 70°C, and the mixture is stirred for another 5 hours until the NCO content is below 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0055] In this preparation example, the initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.00.

[0056] Preparation Example 2: The preparation method of the modified polyurethane resin in this preparation example includes the following steps: Under a nitrogen atmosphere, 800g of polypropylene glycol (number average molecular weight 600), 310g of isophorone diisocyanate, and 1.0g of dibutyltin dilaurate are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the mixture is stirred for 5 hours. The temperature is lowered to 65°C, and 200g of epoxy resin E-51 (hydroxyl content 0.5%) is added. The mixture is kept warm and stirred for 2.5 hours. The temperature is lowered to 50°C, and 19g of pentaerythritol triacrylate and 0.2g of p-hydroxyanisole are added. The temperature is raised to 65°C, and the mixture is stirred for another 6 hours until the NCO content is lower than 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0057] In this preparation example, the initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.00.

[0058] Preparation Example 3: The preparation method of the modified polyurethane resin in this preparation example includes the following steps: Under a nitrogen atmosphere, 400g of polybutylene adipate (number average molecular weight 1000), 400g of polypropylene glycol (number average molecular weight 600), 260g of isophorone diisocyanate, and 0.9g of dibutyltin dilaurate are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the reaction is stirred for 4.5h. The temperature is lowered to 65°C, and 180g of epoxy resin E-51 (hydroxyl content 0.5%) is added. The reaction is kept at this temperature and stirred for 2.5h. The temperature is lowered to 50°C, and 74.6g of pentaerythritol triacrylate and 0.5g of p-hydroxyanisole are added. The temperature is raised to 65°C, and the reaction is stirred for another 5.5h until the NCO content is below 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0059] In this preparation example, the initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 0.96.

[0060] Preparation Example 4: The preparation method of the modified polyurethane resin in this preparation example includes the following steps: Under a nitrogen atmosphere, 400g of polybutylene adipate (number average molecular weight 1000), 400g of polypropylene glycol (number average molecular weight 600), 310g of isophorone diisocyanate, and 0.9g of dibutyltin dilaurate are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the reaction is stirred for 4.5h. The temperature is lowered to 65°C, and 180g of epoxy resin E-51 (hydroxyl content 0.5%) is added. The reaction is kept at this temperature and stirred for 2.5h. The temperature is lowered to 50°C, and 113g of pentaerythritol triacrylate, 20g of 2-hydroxyethyl methacrylate phosphate, and 0.6g of p-hydroxyanisole are added. The temperature is slowly raised to 65°C, and the reaction is stirred for another 6h until the NCO content is lower than 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0061] In this preparation example, the initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.02.

[0062] Preparation Example 5: The preparation method of the modified polyurethane resin in this preparation example includes the following steps: Under a nitrogen atmosphere, 400g of polybutylene adipate (number average molecular weight 1000), 400g of polypropylene glycol (number average molecular weight 600), 310g of isophorone diisocyanate, and 0.9g of dibutyltin dilaurate are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the reaction is stirred for 4.5h. The temperature is lowered to 65°C, and 180g of epoxy resin E-51 (hydroxyl content 0.5%) is added. The reaction is kept at this temperature and stirred for 2.5h. The temperature is lowered to 50°C, and 55g of pentaerythritol triacrylate, 40g of 2-hydroxyethyl methacrylate phosphate, and 0.4g of p-hydroxyanisole are added. The temperature is slowly raised to 65°C, and the reaction is stirred for another 6h until the NCO content is lower than 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0063] In this preparation example, the initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.03.

[0064] Example 1: The metallic interior wall panel of this example comprises, from bottom to top, a substrate, a permeation-enhancing layer, an adhesive layer, and an aluminum veneer layer. The permeation-enhancing layer is prepared using the following raw materials in parts by weight: 800g modified polyurethane resin, 400g self-crosslinking silicone-acrylic emulsion, 40g nano-silica, 400g reactive diluent, 30g silane coupling agent, 20g organic fluoride, 30g curing agent A, 20g photoinitiator, 20g dispersant, and 10g defoamer; wherein, the substrate is an asbestos-free fiber calcium silicate board with a thickness of 5... mm; the modified polyurethane resin is from Preparation Example 1, the solid content of the self-crosslinking silicone-acrylic emulsion is 40%, the particle size distribution of the nano silica is 1~50nm; the reactive diluent is isobornyl acrylate, the silane coupling agent is silane coupling agent KH550, the organofluorine is perfluorooctyltriethoxysilane, the curing agent A is epoxy curing agent T31, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the dispersant is sodium polyacrylate with a solid content of 40%, and the defoamer is an organosilicon defoamer with a solid content of 30%.

[0065] The adhesive layer is prepared by the following raw materials in parts by weight: Component A: 700g of polyether polyurethane prepolymer, 50g of tackifier, 20g of antioxidant, 30g of toughening agent and 0.7g of dibutyltin dilaurate; Component B: 85g of polyetheramine 230, 40g of adipate dihydrazide and 1.2g of 2-ethyl-4-methylimidazole.

[0066] Among them, the polyether-type polyurethane prepolymer is a polyether-type MDI-terminated polyurethane prepolymer with an NCO content of 10% by mass; the tackifier is hydrogenated C9 petroleum resin with a softening point of 85℃; the antioxidant is antioxidant 1010; and the toughening agent is polyamide wax micro powder with a particle size of 1~5μm.

[0067] This embodiment also provides a method for preparing a metallic-textured interior wall decorative panel, comprising the following steps: S1: Nano-silica, dispersant, and 50% by weight of reactive diluent are added to a high-speed disperser, the speed is adjusted to 2000 r / min, and the dispersion is carried out for 30 min. Then, modified polyurethane resin, self-crosslinking silicone-acrylic emulsion, the remaining reactive diluent, silane coupling agent, organic fluoride, and defoamer are added, the speed is adjusted to 1200 r / min, and the stirring is carried out for 60 min. Curing agent A and photoinitiator are added, the speed is adjusted to 800 r / min, and the stirring is carried out for 20 min to obtain a penetration-enhancing coating layer; S2: Polyether-type polyurethane prepolymer is added to a reaction vessel, the temperature is raised to 90°C, and pulverized... Tackifier: Stir for 30 min, add antioxidant, toughening agent and dibutyltin dilaurate, adjust the speed to 1000 r / min, stir for 40 min, mix evenly to obtain component A; Mix polyetheramine 230, adipate dihydrazide and 2-ethyl-4-methylimidazole evenly to obtain component B; Before use, mix component A and component B evenly to obtain adhesive; S3: Mechanically roughen one side of the substrate to a roughening depth of approximately 0.15±0.05 mm, wipe the surface with anhydrous ethanol to remove dust and oil, dry in a 60℃ oven for 2 h, cool to room temperature, and evenly coat the penetration layer coating onto the roughened surface of the substrate using a scraper, with a coating amount of 100 g / m². 2 Let stand for 15 minutes; then perform UV curing using a 365nm UV lamp with an irradiation intensity of 800mJ / cm². 2 Irradiation time: 30s; then heat curing in an 80℃ oven for 30min. After heat curing, cool to room temperature and wipe the surface of the thickening layer with acetone. If the surface is not sticky and the coating does not dissolve, the curing is considered successful; a uniform and dense thickening layer is obtained; S4: Apply adhesive evenly to the surface of the thickening layer, with a coating amount of 150g / m². 2 The pre-treated aluminum veneer layer (the side away from the veneer layer) is aligned and bonded to the substrate coated with adhesive. It is then placed in a hot press for hot pressing and bonding. The hot pressing temperature is initially set to 90℃, the hot pressing pressure to 0.8MPa, and the hot pressing time to 5 minutes. Then, the temperature is increased to 120℃, the hot pressing pressure to 0.8MPa, and the hot pressing time to 5 minutes. After that, it is placed in an environment of 25℃ and 50% relative humidity for 72 hours for curing. Then, it is cut, the edges are polished, the surface is cleaned, and burrs and excess adhesive are removed to obtain a metallic interior wall decoration panel.

[0068] The preparation method of the aluminum decorative layer includes the following steps: Take an aluminum alloy plate with a thickness of 0.5 mm, degrease and alkaline wash it on both sides, wash it with pure water, and dry it. Then, apply environmentally friendly white latex (solid content of about 45%) evenly to one side of the aluminum alloy plate by roller coating, control the wet film thickness, and dry it at 80℃ for 5 min to form a white glue layer with a thickness of about 10 μm. Then, attach the decorative side of the PET heat transfer film (thickness of 20 μm) with a predetermined metal pattern to the white glue layer, put it into a hot press, and hot press it at 120℃ and 0.6MPa for 60 s. After cooling, peel off the PET base film, roll coat it with water-based polyurethane topcoat, and bake it at 85℃ for 15 min to form an elastic topcoat layer with a thickness of 10 μm, thus obtaining the aluminum decorative layer.

[0069] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 28.5 MPa; the average water-saturated flexural strength was 26.6 MPa; the average tensile strength was 0.95 MPa; and the maximum single tensile strength was 1.10 MPa.

[0070] Example 2: The metallic interior wall panel of this example comprises, from bottom to top, a substrate, a permeation layer, an adhesive layer, and an aluminum veneer layer. The permeation layer is prepared using the following raw materials in parts by weight: 1200g modified polyurethane resin, 600g self-crosslinking silicone-acrylic emulsion, 80g nano-silica, 600g reactive diluent, 60g silane coupling agent, 40g organic fluoride, 50g curing agent A, 40g photoinitiator, 40g dispersant, and 20g defoamer. The substrate is an asbestos-free fiber calcium silicate board with a thickness of 8mm. The modified polyurethane resin is from Preparation Example 2, the self-crosslinking silicone-acrylic emulsion has a solid content of 50%, and the nano-silica has a particle size distribution of 1-50nm. The reactive diluent is tripropylene glycol diacrylate, and the silane coupling agent includes 30g of silane coupling agent KH550 and 30g of silane coupling agent KH560. 30g, the organofluorine compound is perfluorooctyltriethoxysilane, the curing agent A is epoxy curing agent T31, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the dispersant is sodium polyacrylate, the solid content is 40%, and the defoamer is organosilicon defoamer, the solid content is 30%.

[0071] The adhesive layer is prepared by the following raw materials in parts by weight: Component A: 850g of polyether-type MDI-terminated polyurethane prepolymer, 100g of tackifier, 40g of antioxidant, 60g of toughening agent and 1g of dibutyltin dilaurate; Component B: 103g of polyetheramine 230, 48.5g of adipate dihydrazide and 1.5g of 2-ethyl-4-methylimidazole.

[0072] Among them, the polyether-type polyurethane prepolymer is a polyether-type MDI-terminated polyurethane prepolymer with an NCO content of 10% by mass; the tackifier is hydrogenated C9 petroleum resin with a softening point of 85℃; the antioxidant is antioxidant 1010; and the toughening agent is polyamide wax micro powder with a particle size of 1~5μm.

[0073] This embodiment also provides a method for preparing a metallic-textured interior wall decorative panel, including the following steps: S1: Nano-silica, dispersant, and 50% by weight of reactive diluent are added to a high-speed disperser, the speed is adjusted to 2000 r / min, and the dispersion is carried out for 30 min. Then, modified polyurethane resin, self-crosslinking silicone-acrylic emulsion, the remaining reactive diluent, silane coupling agent, organofluorine compound, and defoamer are added, the speed is adjusted to 1200 r / min, and the stirring is carried out for 60 min. Curing agent A and photoinitiator are added, the speed is adjusted to 800 r / min, and the stirring is carried out for 20 min to obtain a penetration-enhancing coating; S2: Polyether-type polyurethane prepolymer is added to a reaction vessel, the temperature is raised to 100°C, and pulverized thickener is added. Stir for 30 minutes, cool to 45℃, add antioxidant, toughening agent and dibutyltin dilaurate, adjust the speed to 1000 r / min, stir for 40 minutes, mix evenly to obtain component A; mix polyetheramine 230, adipate dihydrazide and 2-ethyl-4-methylimidazole evenly to obtain component B; before use, mix component A and component B evenly to obtain adhesive; S3: Mechanically roughen one side of the substrate to a roughening depth of about 0.15±0.05mm, wipe the surface with anhydrous ethanol to remove dust and oil, dry in a 60℃ oven for 2 hours, cool to room temperature, and use a scraper to evenly coat the penetration layer coating on the roughened surface of the substrate with a coating amount of 150g / m 2 Let stand for 25 minutes; then perform UV curing using a 365nm UV lamp with an irradiation intensity of 800mJ / cm². 2 Irradiation time: 40s; then heat-curing in an 85℃ oven for 40min. After heat curing, cool to room temperature and wipe the surface of the thickening layer with acetone. If the surface is not sticky and the coating does not dissolve, the curing is considered successful; a uniform and dense thickening layer is obtained; S4: Apply adhesive evenly to the surface of the thickening layer, with a coating amount of 200g / m². 2 The pre-treated aluminum veneer layer (the side away from the veneer layer) is aligned and bonded to the substrate coated with adhesive. It is then placed in a hot press for hot pressing and bonding. The hot pressing temperature is initially set to 90℃, the hot pressing pressure to 1.0MPa, and the hot pressing time to 7 minutes. Then, the temperature is increased to 120℃, the hot pressing pressure to 1.0MPa, and the hot pressing time to 5 minutes. After curing in an environment of 25℃ and 50% relative humidity for 72 hours, the surface is cut, ground, and cleaned to remove burrs and excess adhesive, resulting in a metallic interior wall decorative panel.

[0074] The preparation method of the aluminum decorative layer includes the following steps: Take an aluminum alloy plate with a thickness of 1.0 mm, degrease and alkali wash it on both sides, wash it with pure water, and dry it. Then, apply environmentally friendly white latex (solid content of about 45%) evenly to one side of the aluminum alloy plate by roller coating, control the wet film thickness, and dry it at 80℃ for 7 minutes to form a white glue layer with a thickness of about 15 μm. Then, attach the decorative side of the PET heat transfer film (thickness of 30 μm) with a predetermined metal pattern to the white glue layer, put it into a hot press, and hot press it at 120℃ and 0.6MPa for 60 seconds. After cooling, peel off the PET base film, roll coat it with water-based polyurethane topcoat, and bake it at 85℃ for 15 minutes to form an elastic topcoat layer with a thickness of 15 μm, thus obtaining the aluminum decorative layer.

[0075] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 30.3 MPa; the average saturated flexural strength was 28.1 MPa; the average tensile strength was 1.05 MPa; and the maximum single tensile strength was 1.18 MPa.

[0076] Example 3 differs from Example 2 in that: the metallic interior wall panel of this example comprises, from bottom to top, a substrate, a permeation layer, an adhesive layer, and an aluminum veneer layer. The preparation of the permeation layer includes the following raw materials in parts by weight: 1000g modified polyurethane resin, 500g self-crosslinking silicone-acrylic emulsion, 65g nano-silica, 510g reactive diluent, 46g silane coupling agent, 30g organic fluoride, 40g curing agent A, 30g photoinitiator, 30g dispersant, and 15g defoamer; wherein, the substrate is an asbestos-free fiber calcium silicate board with a thickness of 8mm; the modified polyurethane resin is from Preparation Example 3, the solid content of the self-crosslinking silicone-acrylic emulsion is 50%, and the nano-silica particle size distribution is 1~50nm; the reactive diluent is tripropylene glycol diacrylate, and the silane coupling agent includes 30g of silane coupling agent KH550 and 30g of silane coupling agent KH560. 16g, the organofluorine compound is perfluorooctyltriethoxysilane, the curing agent A is epoxy curing agent T31, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the dispersant is sodium polyacrylate, the solid content is 40%, and the defoamer is organosilicon defoamer, the solid content is 30%.

[0077] The adhesive layer is prepared using the following raw materials in parts by weight: Component A: 750g of polyether-type MDI-terminated polyurethane prepolymer, 80g of tackifier, 30g of antioxidant, 45g of toughening agent, and 0.8g of dibutyltin dilaurate; Component B: 131.5g of polyetheramine 230, 55.5g of adipate dihydrazide, and 1.0g of 2-ethyl-4-methylimidazolium. The polyether-type polyurethane prepolymer is a polyether-type MDI-terminated polyurethane prepolymer with an NCO content of 15% by weight; the tackifier is hydrogenated C9 petroleum resin with a softening point of 85℃; the antioxidant is antioxidant 1010; and the toughening agent is polyamide wax micropowder with a particle size of 1~5μm.

[0078] Everything else is the same as in Example 2.

[0079] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 31.0 MPa; the average saturated flexural strength was 29.0 MPa; the average tensile strength was 1.08 MPa; and the maximum single tensile strength was 1.21 MPa.

[0080] Example 4 The difference between this example and Example 3 is that the modified polyurethane resin is derived from Example 4.

[0081] Everything else is the same as in Example 3.

[0082] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 31.8 MPa; the average saturated flexural strength was 29.8 MPa; the average tensile strength was 1.10 MPa; and the maximum single tensile strength was 1.23 MPa.

[0083] Example 5 The difference between this example and Example 3 is that the modified polyurethane resin is derived from Example 5.

[0084] Everything else is the same as in Example 3.

[0085] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 32.5 MPa; the average water-saturated flexural strength was 30.5 MPa; the average tensile strength was 1.15 MPa; and the maximum single tensile strength was 1.26 MPa.

[0086] The difference between Comparative Example 1 and Example 2 is that the preparation method of the modified polyurethane resin in this comparative example includes the following steps: Under a nitrogen atmosphere, 800g of polypropylene glycol (number average molecular weight 4000), 56g of isophorone diisocyanate, and 0.9g of organotin catalyst are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the reaction is stirred for 4.5h. The temperature is lowered to 65°C, 200g of epoxy resin E-51 is added, and the reaction is maintained at this temperature and stirred for 2.5h. The temperature is lowered to 50°C, 13.4g of pentaerythritol triacrylate and 0.6g of p-hydroxyanisole are added, and the temperature is raised to 65°C. The reaction is continued to be stirred for 6h until the NCO content is lower than 0.5%. Heating is stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0087] The initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.00.

[0088] Everything else is the same as in Example 2.

[0089] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 26.0 MPa; the average saturated flexural strength was 23.5 MPa; the average tensile strength was 0.82 MPa; and the maximum single tensile strength was 0.90 MPa.

[0090] The difference between Comparative Example 2 and Example 2 is that no tackifier was added to the adhesive.

[0091] Everything else is the same as in Example 2.

[0092] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 27.7 MPa; the average water-saturated flexural strength was 23.4 MPa; the average tensile strength was 0.85 MPa; and the maximum single tensile strength was 0.96 MPa.

[0093] The difference between Comparative Example 3 and Example 2 is that the preparation method of the modified polyurethane resin in this comparative example includes the following steps: Under a nitrogen atmosphere, 800g of polypropylene glycol (number average molecular weight 600), 310g of isophorone diisocyanate, and 1.0g of organotin catalyst are added sequentially to a dry reaction vessel. The temperature is raised to 75°C, and the reaction is stirred for 5 hours. The temperature is lowered to 55°C, and 36.5g of pentaerythritol triacrylate and 0.6g of p-hydroxyanisole are added. The temperature is raised to 65°C, and the reaction is stirred for another 6 hours until the NCO content is lower than 0.5%. Heating is then stopped, and the mixture is cooled to room temperature to obtain the modified polyurethane resin.

[0094] The initial molar ratio (R value) of isocyanate groups to total hydroxyl groups is approximately 1.00.

[0095] Everything else is the same as in Example 2.

[0096] Test results: The obtained metallic interior wall decorative panels were subjected to flexural strength and tensile strength tests. According to GB / T 7019-2024, the test results showed that: the average dry flexural strength was 26.3 MPa; the average saturated flexural strength was 22.5 MPa; the average tensile strength was 0.81 MPa; and the maximum single tensile strength was 0.90 MPa.

[0097] The test results above show that in Examples 1-5 and Comparative Examples 1-3, the modified polyurethane resin structure effectively improved the crosslinking density and rigidity of the resin, thereby directly and significantly enhancing the flexural strength of the decorative panel. The further introduction of methacryloyloxyethyl phosphate strengthened the interfacial bonding between the infiltration layer and the substrate, simultaneously improving the tensile strength and water resistance of the decorative panel. In contrast, Comparative Example 1, which used high-molecular-weight pure polyether to prepare the modified polyurethane resin, not only resulted in a significant decrease in the flexural strength of the decorative panel but also a marked reduction in the flexural strength under saturated water conditions. In Comparative Example 2, the lack of a tackifier led to insufficient interfacial bonding, resulting in a significant decrease in both tensile strength and water resistance. Comparative Example 3, which did not add epoxy resin E-51 to the modified polyurethane resin, lacked the support of rigid epoxy groups, resulting in a decrease in crosslinking density, reduced resin rigidity and interfacial compatibility, and a significant decrease in both dry flexural strength and tensile strength.

[0098] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A metallic-textured interior wall panel, characterized in that, From bottom to top, the layers consist of a substrate, a permeation layer, an adhesive layer, and a metal finish layer. The permeation layer is prepared using the following raw materials in parts by weight: 80-120 parts modified polyurethane resin, 40-60 parts self-crosslinking silicone-acrylic emulsion, 4-8 parts nano-silica, 40-60 parts reactive diluent, 3-6 parts silane coupling agent, 2-4 parts organic fluoride, and curing agent A. The modified polyurethane resin comprises the following raw materials in parts by weight: 70-80 parts oligomeric polyol, 17-31 parts diisocyanate, 15-20 parts bisphenol A epoxy resin, 1.7-11 parts polyhydroxy acrylate monomer, 0.05-0.1 parts organotin catalyst, and 0.02-0.06 parts polymerization inhibitor; the adhesive layer comprises the following raw materials in parts by weight: Component A: 70-85 parts polyether polyurethane prepolymer, 5-10 parts tackifier, 2-4 parts antioxidant, 3-6 parts toughening agent, and 0.07-0.1 parts organotin catalyst; Component B: 8.5-13 parts polyetheramine, 4-5.5 parts adipate dihydrazide, and 0.1-0.15 parts 2-ethyl-4-methylimidazole.

2. The metallic-textured interior wall panel according to claim 1, characterized in that, The method for preparing the modified polyurethane resin includes the following steps: under an inert atmosphere, oligomeric polyol, diisocyanate and organotin catalyst are mixed evenly, heated to 70~75℃, reacted for 4~5h, cooled to 60~65℃, bisphenol A type epoxy resin is added, reacted for 2~2.5h, cooled, polyhydroxy acrylate monomer and polymerization inhibitor are added, heated to 65~70℃, reacted for 5~6h, cooled, and the modified polyurethane resin is obtained.

3. The metallic interior wall panel according to claim 2, characterized in that, The oligomeric polyol is at least one of polyether polyol and polyester polyol, and its number average molecular weight is not higher than 1000.

4. The metallic interior wall panel according to claim 2, characterized in that, The polyhydroxy acrylate monomer is pentaerythritol triacrylate.

5. The metallic-textured interior wall panel according to claim 1, characterized in that, The raw materials of the modified polyurethane resin also include 2 to 4 parts by weight of phosphate ester-containing acrylate monomers.

6. The metallic-textured interior wall panel according to claim 2, characterized in that, In the preparation method of the modified polyurethane resin, after adding the polyhydroxy acrylate monomer, the method further includes the step of adding an acrylate monomer containing a phosphate ester.

7. The metallic-textured interior wall panel according to claim 1, characterized in that, The reactive diluent is either isobornyl acrylate or tripropylene glycol diacrylate.

8. The metallic-textured interior wall panel according to claim 1, characterized in that, The polyether-type polyurethane prepolymer is a polyether-type MDI-terminated polyurethane prepolymer with an NCO content of 10%~15%.

9. The metallic-textured interior wall panel according to claim 1, characterized in that, The thickener is petroleum resin.

10. A method for preparing a metallic-textured interior wall panel as described in any one of claims 1 to 9, characterized in that, The process includes the following steps: S1: After mixing nano-silica, dispersant, and part of the reactive diluent, add modified polyurethane resin, self-crosslinking silicone-acrylic emulsion, the remaining reactive diluent, silane coupling agent, organofluorine compound, and defoamer. Add curing agent A and photoinitiator, and mix evenly to obtain a penetration-enhancing coating; S2: At 90~100℃, mix polyether-type polyurethane prepolymer, tackifier, antioxidant, toughening agent, and organotin catalyst evenly to obtain component A; mix polyetheramine, adipate dihydrazide, and 2-ethyl-4-methylimidazole evenly to obtain component B; before use, mix component A and component B evenly to obtain an adhesive; S3: After pretreating the substrate, the infiltration layer coating is evenly applied to the substrate surface and cured to obtain the infiltration layer; S4: Apply adhesive to the surface of the permeation layer, attach the metal finishing layer, hot-press to bond, and then perform post-treatment to obtain the final product.