High-weather-resistance decorative plate and preparation method thereof

Abstract

The invention discloses a high-weather-resistance decorative plate and a preparation method thereof, and belongs to the technical field of plates. The high-weather-resistance decorative plate comprises a base plate and melamine impregnated bond paper attached to the surface of the base plate through a hot pressing technology. The melamine-impregnated bond paper is obtained by sequentially impregnating raw paper in urea-formaldehyde resin and antibacterial melamine-formaldehyde resin. The preparation method comprises the following steps: firstly, impregnating the raw paper in the urea-formaldehyde resin and the antibacterial melamine-formaldehyde resin; the antibacterial melamine formaldehyde resin is obtained by carrying out a composite reaction on melamine, formaldehyde, (2S)-2-amino-3-hydroxyglutaric acid and antibacterial polyethylene glycol; the antibacterial polyethylene glycol is obtained through a composite reaction of a composite antibacterial filler, sodium methyl silicate, polyethylene glycol and cysteine; the composite antibacterial filler is prepared by the following steps: firstly, by adopting a method of combining molten urea and thermal polycondensation, taking silver nitrate as a silver source and taking citric acid as a pore-forming agent, preparing silver-loaded graphite phase carbon nitride rich in mesopores in situ, and then reacting the silver-loaded graphite phase carbon nitride with phosphorus oxychloride, pentaerythritol and phosphorus oxychloride in sequence.

Description

Technical Field

[0001] The present invention relates to a highly weather-resistant decorative board and a preparation method thereof. Background Art

[0002] With the problems faced by the solid wood furniture industry such as lack of wood resources, low utilization rate, and high cost, artificial boards have gradually become the mainstream alternatives. Among various artificial board materials, melamine-formaldehyde (MF) resin impregnated paper decorative panels have developed rapidly due to their characteristics such as colorless transparency and high bonding strength. However, despite many advantages of this material, it still has some significant limitations, especially problems in terms of hydrophobicity, weather resistance, and abrasion resistance.

[0003] Specifically, the surfaces of traditional MF resin decorative panels lack effective hydrophobic structures, which makes them prone to absorbing moisture, thus resulting in swelling and deformation. Especially in humid environments, these boards are more likely to mildew and delaminate, greatly limiting their application scope.

[0004] When applied to outdoor environments, factors such as ultraviolet radiation and temperature changes will cause the aging, fading, and brittle fracture of the material. Currently, the decorative layers on the market generally lack effective ultraviolet absorbers or weather-resistant film protection measures, and the weather resistance of ordinary coatings can only be maintained for 3 to 5 years, which means frequent maintenance is required to maintain their aesthetics and functionality.

[0005] Due to the relatively low surface hardness, these boards are easily scratched and worn after long-term use, which not only affects the aesthetics but also shortens the service life. Existing technologies mostly rely on the design of a single resin matrix and lack the design of nano-enhanced materials or elastic layers to improve their abrasion resistance.

[0006] Therefore, it is particularly important to develop a highly weather-resistant decorative board with excellent hydrophobicity and abrasion resistance. Summary of the Invention

[0007] The purpose of the present invention is to provide a highly weather-resistant decorative board and a preparation method thereof to solve the technical problems mentioned in the above background art.

[0008] The technical solution for achieving the purpose of the present invention is as follows: In a first aspect, the present invention provides a highly weather-resistant decorative board, including a substrate and a melamine impregnated film paper attached to the surface of the substrate through a hot pressing process. The melamine impregnated film paper is obtained by successively impregnating the base paper in urea-formaldehyde resin and antibacterial melamine-formaldehyde resin, and the antibacterial melamine-formaldehyde resin is obtained by the composite reaction of melamine, formaldehyde, (2S)-2-amino-3-hydroxyglutaric acid, and antibacterial polyethylene glycol.

[0009] Further, the antibacterial polyethylene glycol is obtained by the composite reaction of polyethylene glycol with a composite antibacterial filler, cysteine, and a hydrophobic organosilicon.

[0010] Further, the composite antibacterial filler is prepared by first using a method combining molten urea and thermal polycondensation, using silver nitrate as the silver source and citric acid as the pore-forming agent to in-situ prepare silver-loaded graphitic carbon nitride with rich mesopores, and then reacting the silver-loaded graphitic carbon nitride with phosphorus oxychloride, pentaerythritol, and phosphorus oxychloride in sequence.

[0011] Further, the hydrophobic organosilicon includes sodium methyl silicate, perfluorodecyltrimethoxysilane, and perfluorohexylethyltrimethoxysilane.

[0012] In a second aspect, a preparation method of a highly weather-resistant decorative board as described in the first aspect includes the following preparation steps: A1. Preparation of melamine impregnated film paper; A1.1 Preparation of urea-formaldehyde resin adhesive solution: Stir and mix 100 parts by mass of urea-formaldehyde resin, 0.06 - 0.1 part by mass of curing agent, 0.02 - 0.04 part by mass of release agent, and 0.02 - 0.04 part by mass of penetrant evenly; A1.2 Preparation of antibacterial melamine-formaldehyde resin adhesive solution: Stir and mix 100 parts by mass of antibacterial melamine-formaldehyde resin, 0.06 - 0.1 part by mass of curing agent, 0.02 - 0.04 part by mass of release agent, and 0.02 - 0.04 part by mass of penetrant evenly; A1.3 Secondary impregnation: First, put the base paper into the urea-formaldehyde resin adhesive solution to be completely soaked, take it out, scrape off the excess adhesive solution on the surface, and dry it to obtain the base paper impregnated once; put the base paper impregnated once into the urea-formaldehyde resin adhesive solution for impregnation, take it out, scrape off the excess adhesive solution on the surface, dry and cool it to obtain the melamine impregnated film paper; A2. Preparation of weather-resistant decorative board: Place the prepared melamine impregnated film paper and the substrate together on a hot press, hot press them, and then take them out and cool to room temperature to obtain the weather-resistant decorative board.

[0013] Further, the preparation steps of the antibacterial melamine-formaldehyde resin are as follows: First, mix 160 - 162 parts by mass of 37% formaldehyde solution and 130 - 134 parts by mass of water and stir for 5 - 10 min, then adjust the pH to 8 - 9 with 30% sodium hydroxide solution, then raise the temperature to 50 - 60 °C, add 100 parts by mass of melamine and 0.03 - 0.3 part by mass of (2S)-2-amino-3-hydroxypentanedioic acid, raise the temperature to 85 - 90 °C within 30 min, after clarification, add 1 - 5 parts by mass of antibacterial polyethylene glycol and continue to react for 100 - 120 min. After the reaction ends, immediately cool it to room temperature in an ice-water bath and discharge to obtain the antibacterial melamine-formaldehyde resin.

[0014] Furthermore, the preparation method of the antibacterial polyethylene glycol is as follows: At 90 °C, polyethylene glycol is mixed with toluene that is 10 - 15 times its mass, and then heated to 90 °C. After stirring at 800 - 1000 rpm for 1.8 - 2.2 h, triethylamine and a composite antibacterial filler are added in sequence. The temperature is maintained at 90 °C for reaction for 14 - 16 h, cooled to room temperature, and toluene is removed by suction filtration. During the suction filtration process, toluene is removed by washing multiple times with ethyl acetate, and then triethylamine hydrochloride generated during the reaction is removed by washing multiple times with water. Finally, it is placed in a vacuum drying oven and dried at 100 °C overnight until constant weight, then naturally cooled to 60 °C, cysteine and p-toluenesulfonic acid are added and stirred evenly. Subsequently, the temperature is raised to 105 - 115 °C, and after reacting for 5 - 7 h, the temperature is raised to 140 °C until no more water is generated, and the reaction ends. Finally, the temperature is lowered to 90 °C for reduced-pressure distillation, and the catalyst p-toluenesulfonic acid precipitates and separates out as colorless crystals, and then is added to hot water at 90 °C. After stirring and reacting for 1.5 - 2.5 h, hydrophobic organosilicon is slowly added dropwise, and stirred and reacted at 80 - 90 °C for 1.5 - 2.5 h to obtain antibacterial polyethylene glycol; wherein, the mass ratio of polyethylene glycol, triethylamine, composite antibacterial filler, cysteine, p-toluenesulfonic acid, hot water, and hydrophobic organosilicon is 15 - 25: 4 - 6: 5 - 7: 4 - 6: 0.0012 - 0.0024: 100: 4 - 6.

[0015] Furthermore, the preparation method of the composite antibacterial filler is as follows: 3.5 - 4.5 parts by mass of phosphorus-modified silver-loaded graphitic carbon nitride, 0.112 - 0.168 parts by mass of pentaerythritol, and 0.4 - 0.6 parts by mass of phosphorus oxychloride are heated to 75 - 85 °C and kept warm for 1.5 - 2.5 h, then heated to 100 °C and stirred at 800 - 1200 rpm, and reacted overnight until basically no hydrogen chloride gas is generated, and then cooled to room temperature and filtered by suction. During the suction filtration process, it is washed 3 times with dichloromethane and diethyl ether respectively. Finally, the solid is placed in a vacuum drying oven at 80 °C and dried to constant weight to obtain the composite antibacterial filler.

[0016] Further, the preparation method of the phosphorus-modified silver-loaded graphitic carbon nitride is as follows: Heat 20 parts by mass of urea to 150 °C until it is completely melted, then add 5 - 5.2 parts by mass of a 0.022% silver nitrate solution, stir for 8 - 12 min, then add 5 - 5.2 parts by mass of a 0.05% citric acid solution, continue to stir for 12 - 18 min, and then transfer it to a preheated crucible, quickly transfer it to a nitrogen-purged muffle furnace, calcine at 550 ± 5 °C for 2.5 - 3.5 h, with a heating rate of 5 °C / min, cool and grind to obtain silver-loaded graphitic carbon nitride with rich mesopores; Mix 3 parts by mass of the silver-loaded graphitic carbon nitride with rich mesopores with 25% dilute sulfuric acid and stir for 46 - 50 h, then centrifuge at a speed of 8000 r / min for 5 min, discard the supernatant, add 100 parts by mass of deionized water and centrifuge again to remove the supernatant, repeat the above steps until the supernatant is neutral; Then dry in a vacuum drying oven at 80 °C for 24 h, then mix with 86 - 87 parts by mass of toluene, ultrasonically disperse for 10 - 20 min, add 0.4 - 0.6 parts by mass of phosphorus oxychloride and 2.7 - 3.3 parts by mass of triethylamine, react at 55 - 65 °C for 2.5 - 3.5 h, filter to remove toluene, during the filtration process, wash with ethyl acetate multiple times to remove toluene, and then wash with water multiple times to remove the triethylamine hydrochloride generated during the reaction, place in a vacuum drying oven and dry at 100 °C overnight until constant weight to obtain the phosphorus-modified silver-loaded graphitic carbon nitride.

[0017] Further, after the hot pressing in step A2, heat-treat at 120 - 140 °C for 11 - 13 h.

[0018] Adopting the above technical solution, the present invention has the following beneficial effects: The highly weather-resistant decorative board disclosed by the present invention comprises a substrate and a melamine impregnated film paper attached to the surface of the substrate through a hot pressing process; wherein, the melamine impregnated film paper is obtained by successively impregnating base paper in urea formaldehyde resin and antibacterial melamine formaldehyde resin; the antibacterial melamine formaldehyde resin is obtained by the composite reaction of melamine, formaldehyde, (2S)-2-amino-3-hydroxyglutaric acid, and antibacterial polyethylene glycol, and (2S)-2-amino-3-hydroxyglutaric acid reacts with formaldehyde through an amino group and then undergoes dehydration condensation with melamine formaldehyde; the antibacterial polyethylene glycol is obtained by the composite reaction of a composite antibacterial filler, hydrophobic organosilicon, polyethylene glycol, and cysteine; the composite antibacterial filler is prepared by in-situ preparing mesoporous silver-loaded graphitic carbon nitride using a method combining molten urea and thermal polycondensation, with silver nitrate as the silver source and citric acid as the pore-forming agent, and then the silver-loaded graphitic carbon nitride is grafted onto the surface of the silver-loaded graphitic carbon nitride through reaction with phosphorus oxychloride after activation with dilute sulfuric acid. After the reaction of the hydroxyl group of phosphorus chloride and pentaerythritol for grafting, the remaining hydroxyl groups of pentaerythritol continue to react with phosphorus oxychloride to graft the spirophosphate chloride onto the surface of the composite antibacterial filler; the highly weather-resistant decorative board prepared by the present invention has good hydrophobicity, weather resistance, flame retardancy, flexibility, and antibacterial property, and can effectively eliminate formaldehyde and volatile organic compounds in the room.

[0019] The present invention prepares antibacterial polyethylene glycol by successively reacting polyethylene glycol with a composite antibacterial filler, cysteine, and hydrophobic organosilicon. First, the composite antibacterial filler is grafted through the reaction of a phosphorus-chlorine bond, the carboxyl group of cysteine, and the hydroxyl group of polyethylene glycol with the silicon hydroxyl group of hydrophobic organosilicon. By introducing the composite antibacterial filler into the antibacterial polyethylene glycol and adding the antibacterial polyethylene glycol into the antibacterial melamine formaldehyde resin, good antibacterial property is imparted to the melamine impregnated film paper, and the flame retardancy of the melamine impregnated film paper is effectively enhanced. Among them, the introduction of cysteine can impart good antioxidant and weather resistance to the melamine impregnated film paper, and the introduction of hydrophobic organosilicon can impart good hydrophobicity to the melamine impregnated film paper.

[0020] The present invention uses a method combining molten urea and thermal polycondensation, with silver nitrate as the silver source and citric acid as the pore-forming agent, to in-situ prepare mesoporous silver-loaded graphitic carbon nitride. On the one hand, introducing silver onto the graphitic carbon nitride can impart good antibacterial property to the highly weather-resistant decorative board. Secondly, the addition of citric acid leads to the formation of carbon vacancy defects in the graphitic carbon nitride skeleton. At the same time, silver coordinates with nitrogen atoms near the carbon vacancy in the form of ultra-small particles or clusters and is evenly dispersed on the surface of the defective carbon nitride. Under the synergistic effect of the carbon vacancy and silver, the energy band structure of the nitrogen atoms near the carbon vacancy is effectively regulated, the band gap energy is reduced, and an intermediate energy level is introduced, enabling the mesoporous silver-loaded graphitic carbon nitride to make full use of visible light. Under the action of light, •O2 is generated in the photocatalytic oxidation system of the mesoporous silver-loaded graphitic carbon nitride. -Anion radical, •OH radical and singlet oxygen 1 Abundant reactive oxygen species including O2, under the combined action with h VB + adsorb formaldehyde and volatile organic compounds in the air through the mesopores of silver-loaded graphitic carbon nitride with rich mesopores, and degrade them.

[0021] Finally, after the hot pressing in step A2 is completed, it is heat-treated at 120-140 °C for 11-13 h. The (2S)-2-amino-3-hydroxyglutaric acid in the antibacterial melamine formaldehyde resin reacts with the cysteine of the antibacterial polyethylene glycol and is gradually dehydrated and condensed at high temperature to form a pyridone acid ultraviolet absorber in the high weather resistance decorative board, further enhancing the weather resistance of the high weather resistance decorative board. Specific embodiments

[0022] In order to better understand the above technical solutions, the following will describe the above technical solutions in detail in combination with specific embodiments.

[0023] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0024] The following embodiments are only used to more clearly illustrate the technical solutions of the present invention, and cannot be used to limit the protection scope of the present invention.

[0025] The partial raw materials of the above-mentioned examples and comparative examples are as follows: Polyvinyl alcohol uses polyvinyl alcohol BP-05; Urea-formaldehyde resin has a solid content of 37.8%, a viscosity of 28 mPa·s, and a curing time of 55 s; The curing agent uses ammonium chloride; The mold release agent uses methyl silicone oil; The penetrant uses penetrant JFC; The substrate uses particleboard; The base paper uses wood grain paper with a grammage of 60 g / m 2 ; The hydrophobic silicone uses sodium methyl silicate; (Example 1) A preparation method of a high weather resistance decorative board includes the following preparation steps: A1. Preparation of melamine impregnated film paper; A1.1 Preparation of urea-formaldehyde resin glue solution: Stir and mix 100 parts by mass of urea-formaldehyde resin, 0.06 parts by mass of curing agent, 0.02 parts by mass of mold release agent, and 0.02 parts by mass of penetrant evenly; Preparation of A1.2 antibacterial melamine formaldehyde resin adhesive solution: Stir and mix evenly 100 parts by mass of antibacterial melamine formaldehyde resin, 0.06 part by mass of curing agent, 0.02 part by mass of mold release agent, and 0.02 part by mass of penetrant; A1.3 Secondary impregnation: First, put the base paper into the urea formaldehyde resin adhesive solution to be completely impregnated, take it out and scrape off the excess adhesive solution on the surface, and dry it at 150 °C for 90 s to obtain the base paper after the first impregnation; Impregnate and coat the base paper after the first impregnation with the urea formaldehyde resin adhesive solution, scrape off the excess adhesive solution on the surface, dry it at 180 °C for 90 s and then cool it to obtain the melamine impregnated film paper; The sizing amount for both the first impregnation and the second impregnation is 60 g / m 2 .

[0026] A2. Preparation of weather-resistant decorative board: Place the prepared melamine impregnated film paper and the substrate together on a hot press, heat press and then take it out, and perform heat treatment at 140 °C for 12 h, and cool to room temperature to obtain the weather-resistant decorative board; Among them, the hot pressing temperature is 190 °C, the hot pressing unit pressure is 2.5 MPa, and the hot pressing closing time is 30 s.

[0027] The preparation steps of the antibacterial melamine formaldehyde resin are as follows: First, mix 160 parts by mass of 37% formaldehyde solution and 130 parts by mass of water and stir for 5 min, then adjust the pH to 8 with 30% sodium hydroxide solution, then raise the temperature to 50 °C, add 100 parts by mass of melamine and 0.03 part by mass of (2S)-2-amino-3-hydroxyglutaric acid, raise the temperature to 85 °C within 30 min, add 1 part by mass of antibacterial polyethylene glycol after clarification and continue to react for 100 min. After the reaction ends, immediately cool it to room temperature in an ice-water bath and discharge it to obtain the antibacterial melamine formaldehyde resin.

[0028] The preparation method of the antibacterial polyethylene glycol is as follows: At 90 °C, mix polyethylene glycol with 10 times its mass of toluene, then heat it to 90 °C, stir at 800 rpm for 1.8 h, and then add triethylamine and composite antibacterial filler in sequence, maintain the temperature at 90 °C and react for 14 h, cool to room temperature, filter off toluene by suction filtration. During the suction filtration process, wash it with ethyl acetate multiple times to remove toluene, and then wash it with water multiple times to remove the triethylamine hydrochloride generated during the reaction. Finally, place it in a vacuum drying oven and dry it at 100 °C overnight until constant weight, then naturally cool it to 60 °C, add cysteine and p-toluenesulfonic acid and stir evenly, then raise the temperature to 105 °C, react for 5 h, then raise the temperature to 140 °C until no more water is generated, and the reaction ends. Finally, cool it to 90 °C and perform reduced pressure distillation. The catalyst p-toluenesulfonic acid precipitates and separates as colorless crystals, and then add it to hot water at 90 °C, stir and react for 1.5 h, and then slowly dropwise add hydrophobic organosilicon, and stir and react at 80 °C for 1.5 h to obtain the antibacterial polyethylene glycol; Among them, the mass ratio of polyethylene glycol, triethylamine, composite antibacterial filler, cysteine, p-toluenesulfonic acid, hot water, and hydrophobic organosilicon is 15:4:5:4:0.0012:100:4.

[0029] The preparation method of the composite antibacterial filler is as follows: Weigh 3.5 parts by mass of phosphorus-modified silver-loaded graphitic carbon nitride, 0.112 parts by mass of pentaerythritol, and 0.4 parts by mass of phosphorus oxychloride. Heat them up to 75 °C and keep the temperature for 1.5 h, then heat up to 100 °C and stir at 800 rpm. React overnight until no hydrogen chloride gas is generated basically. Then cool to room temperature and carry out suction filtration. During the suction filtration process, wash three times with dichloromethane and diethyl ether respectively. Finally, place the solid in a vacuum drying oven at 80 °C and dry to constant weight to obtain the composite antibacterial filler.

[0030] The preparation method of the phosphorus-modified silver-loaded graphitic carbon nitride is as follows: Heat 20 parts by mass of urea to 150 °C until the urea is completely melted. Then add 5 parts by mass of a 0.022% silver nitrate solution and stir for 8 min. Then add 5 parts by mass of a 0.05% citric acid solution and continue to stir for 12 min. Then transfer it to a preheated crucible and quickly transfer it to a nitrogen-purged muffle furnace. Calcinate at 545 °C for 2.5 h with a heating rate of 5 °C / min. After cooling, grind it to obtain silver-loaded graphitic carbon nitride rich in mesopores with a specific surface area of 101.4 m 2 *g -1 and a pore volume of 0.570 m 3 *g -1 Take 3 parts by mass of silver-loaded graphitic carbon nitride rich in mesopores and mix and stir it with 100 parts by mass of 25% dilute sulfuric acid for 46 h. Then centrifuge at a speed of 8000 r / min for 5 min, discard the supernatant, add 100 parts by mass of deionized water and centrifuge again to remove the supernatant. Repeat the above steps until the supernatant is neutral. Then dry in a vacuum drying oven at 80 °C for 24 h. Then mix it with 86 parts by mass of toluene and disperse it by ultrasonic wave for 10 min. Then add 0.4 parts by mass of phosphorus oxychloride and 2.7 parts by mass of triethylamine and react at 55 °C for 2.5 h. Filter to remove toluene. During the suction filtration process, wash with ethyl acetate multiple times to remove toluene, and then wash with water multiple times to remove the triethylamine hydrochloride generated during the reaction. Place it in a vacuum drying oven and dry at 100 °C overnight to constant weight to obtain the phosphorus-modified silver-loaded graphitic carbon nitride.

[0031] (Example 2) A preparation method of a high weather resistance decorative board includes the following preparation steps: A1. Preparation of melamine impregnated film paper; A1.1 Preparation of urea-formaldehyde resin adhesive solution: Stir and mix evenly 100 parts by mass of urea-formaldehyde resin, 0.08 parts by mass of curing agent, 0.03 parts by mass of demolding agent, and 0.03 parts by mass of penetrant; Preparation of A1.2 antibacterial melamine formaldehyde resin glue solution: Stir and mix evenly 100 parts by mass of antibacterial melamine formaldehyde resin, 0.08 part by mass of curing agent, 0.03 part by mass of release agent, and 0.03 part by mass of penetrant; A1.3 Secondary impregnation: First, put the base paper into the urea formaldehyde resin glue solution to be completely impregnated, take it out and scrape off the excess glue on the surface, dry at 150 °C for 90 s to obtain the base paper after the first impregnation; impregnate and coat the base paper after the first impregnation with the urea formaldehyde resin glue solution, scrape off the excess glue on the surface, dry at 180 °C for 90 s and cool to obtain the melamine impregnated film paper; the sizing amount for both the first impregnation and the second impregnation is 60 g / m 2 .

[0032] A2. Preparation of weather-resistant decorative board: Place the prepared melamine impregnated film paper and the substrate together on a hot press, heat press and then take out, heat-treat at 140 °C for 12 h, and cool to room temperature to obtain the weather-resistant decorative board; among them, the hot press temperature is 190 °C, the hot press unit pressure is 2.5 MPa, and the hot press closing time is 30 s.

[0033] The preparation steps of the antibacterial melamine formaldehyde resin are as follows: First, mix 161 parts by mass of 37% formaldehyde solution and 132 parts by mass of water and stir for 8 min, then adjust the pH to 8.5 with 30% sodium hydroxide solution, then raise the temperature to 55 °C, add 100 parts by mass of melamine and 0.17 part by mass of (2S)-2-amino-3-hydroxypentanedioic acid, raise the temperature to 88 °C within 30 min, add 6 parts by mass of antibacterial polyethylene glycol after clarification and continue to react for 110 min. After the reaction is completed, immediately cool to room temperature in an ice-water bath and discharge to obtain the antibacterial melamine formaldehyde resin.

[0034] The preparation method of the antibacterial polyethylene glycol is as follows: At 90 °C, mix polyethylene glycol with 13 times its mass of toluene, then heat to 90 °C, stir at 900 rpm for 2 h, then add triethylamine and composite antibacterial filler in sequence, maintain the temperature at 90 °C and react for 15 h, cool to room temperature, filter to remove toluene. During the filtration process, wash with ethyl acetate multiple times to remove toluene, and then wash with water multiple times to remove the triethylamine hydrochloride generated during the reaction. Finally, place it in a vacuum drying oven and dry at 100 °C overnight until constant weight, then naturally cool to 60 °C, add cysteine and p-toluenesulfonic acid and stir evenly, then raise the temperature to 110 °C, react for 6 h, then raise the temperature to 140 °C until no more water is generated, after the reaction is completed, finally cool to 90 °C and carry out vacuum distillation, the catalyst p-toluenesulfonic acid precipitates and separates as colorless crystals, then add it to hot water at 90 °C, stir and react for 2 h, and slowly dropwise add hydrophobic organosilicon, stir and react at 85 °C for 2 h to obtain the antibacterial polyethylene glycol; among them, the mass ratio of polyethylene glycol, triethylamine, composite antibacterial filler, cysteine, p-toluenesulfonic acid, hot water, and hydrophobic organosilicon is 20:5:6:5:0.0018:100:5.

[0035] The preparation method of the composite antibacterial filler is as follows: Weigh 4 parts by mass of phosphorus-modified silver-loaded graphitic carbon nitride, 0.140 parts by mass of pentaerythritol, and 0.5 parts by mass of phosphorus oxychloride. Heat the mixture to 80 °C and keep it warm for 2 h, then heat it to 100 °C and stir at 1000 rpm. React overnight until no hydrogen chloride gas is produced basically, and then cool it to room temperature. Carry out suction filtration. During the suction filtration process, wash it 3 times with dichloromethane and diethyl ether respectively. Finally, place the solid in a vacuum drying oven at 80 °C and dry it to a constant weight to obtain the composite antibacterial filler.

[0036] The preparation method of the phosphorus-modified silver-loaded graphitic carbon nitride is as follows: Heat 20 parts by mass of urea to 150 °C until the urea is completely melted, then add 5.1 parts by mass of a 0.022% silver nitrate solution. After stirring for 10 min, add 5.1 parts by mass of a 0.05% citric acid solution, continue to stir for 15 min, and then transfer it to a preheated crucible. Quickly transfer it to a nitrogen-purged muffle furnace and calcine it at 550 °C for 3 h with a heating rate of 5 °C / min. After cooling, grind it to obtain silver-loaded graphitic carbon nitride rich in mesopores with a specific surface area of 130.4 m 2 *g -1 and a pore volume of 0.588 m 3 *g -1 Take 3 parts by mass of silver-loaded graphitic carbon nitride rich in mesopores and mix it with 100 parts by mass of 25% dilute sulfuric acid and stir for 48 h. Then centrifuge at a speed of 8000 r / min for 5 min, discard the supernatant, add 100 parts by mass of deionized water and centrifuge again to remove the supernatant. Repeat the above steps until the supernatant is neutral. Then dry it in a vacuum drying oven at 80 °C for 24 h, then mix it with 86.5 parts by mass of toluene and ultrasonically disperse it for 15 min, add 0.5 parts by mass of phosphorus oxychloride and 3 parts by mass of triethylamine, react at 60 °C for 3 h, filter to remove toluene. During the suction filtration process, wash it with ethyl acetate multiple times to remove toluene, and then wash it with water multiple times to remove the triethylamine hydrochloride produced during the reaction. Place it in a vacuum drying oven and dry it at 100 °C overnight to a constant weight to obtain the phosphorus-modified silver-loaded graphitic carbon nitride.

[0037] (Example 3) A preparation method of a highly weather-resistant decorative board includes the following preparation steps: A1. Preparation of melamine impregnated film paper; A1.1 Preparation of urea-formaldehyde resin glue solution: Stir and mix evenly 100 parts by mass of urea-formaldehyde resin, 0.1 part by mass of curing agent, 0.04 part by mass of demolding agent, and 0.04 part by mass of penetrant; Preparation of A1.2 antibacterial melamine formaldehyde resin adhesive solution: Stir and mix evenly 100 parts by mass of antibacterial melamine formaldehyde resin, 0.1 part by mass of curing agent, 0.04 part by mass of release agent, and 0.04 part by mass of penetrant; A1.3 Secondary impregnation: First, put the base paper into the urea formaldehyde resin adhesive solution to be completely impregnated, take it out and scrape off the excess adhesive solution on the surface, and dry it at 150 °C for 90 s to obtain the base paper after the first impregnation; impregnate and coat the base paper after the first impregnation with the urea formaldehyde resin adhesive solution, scrape off the excess adhesive solution on the surface, dry it at 180 °C for 90 s and cool it to obtain the melamine impregnated film paper; the sizing amount for both the first impregnation and the second impregnation is 60 g / m 2 .

[0038] A2. Preparation of weather-resistant decorative board: Place the prepared melamine impregnated film paper and the substrate together on a hot press, heat press and then take it out, and heat-treat it at 140 °C for 12 h, and cool it to room temperature to obtain the weather-resistant decorative board; among them, the hot press temperature is 190 °C, the hot press unit pressure is 2.5 MPa, and the hot press closing time is 30 s.

[0039] The preparation steps of the antibacterial melamine formaldehyde resin are as follows: First, mix 162 parts by mass of 37% formaldehyde solution and 134 parts by mass of water and stir for 10 min, then adjust the pH to 9 with 30% sodium hydroxide solution, then raise the temperature to 60 °C, add 100 parts by mass of melamine and 0.3 part by mass of (2S)-2-amino-3-hydroxyglutaric acid, raise the temperature to 90 °C within 30 min, add 5 parts by mass of antibacterial polyethylene glycol after clarification and continue to react for 120 min. After the reaction is completed, immediately cool it to room temperature in an ice-water bath and discharge it to obtain the antibacterial melamine formaldehyde resin.

[0040] The preparation method of the antibacterial polyethylene glycol is as follows: At 90 °C, mix polyethylene glycol with 15 times its mass of toluene, then heat it to 90 °C, stir at 1000 rpm for 2.2 h, and then add triethylamine and composite antibacterial filler in sequence, maintain the temperature at 90 °C and react for 16 h, cool it to room temperature, filter off toluene by suction filtration. During the suction filtration process, wash it with ethyl acetate multiple times to remove toluene, and then wash it with water multiple times to remove the triethylamine hydrochloride generated during the reaction. Finally, place it in a vacuum drying oven and dry it at 100 °C overnight until constant weight, then naturally cool it to 60 °C, add cysteine and p-toluenesulfonic acid and stir evenly, then raise the temperature to 115 °C, react for 7 h, then raise the temperature to 140 °C until no more water is generated, and the reaction ends. Finally, cool it to 90 °C and distill it under reduced pressure. The catalyst p-toluenesulfonic acid precipitates and separates as colorless crystals, and then add it to hot water at 90 °C, stir and react for 2.5 h, and then slowly dropwise add hydrophobic silicone, and stir and react at 90 °C for 2.5 h to obtain the antibacterial polyethylene glycol; among them, the mass ratio of polyethylene glycol, triethylamine, composite antibacterial filler, cysteine, p-toluenesulfonic acid, hot water, and hydrophobic silicone is 25:6:7:6:0.0024:100:6.

[0041] The preparation method of the composite antibacterial filler is as follows: Weigh 4.5 parts by mass of phosphorus-modified silver-loaded graphitic carbon nitride, 0.168 parts by mass of pentaerythritol, and 0.6 parts by mass of phosphorus oxychloride. Heat the mixture to 85 °C and keep it warm for 2.5 h, then heat it to 100 °C and stir at 1200 rpm. React overnight until no hydrogen chloride gas is produced basically. Then cool it to room temperature and perform suction filtration. During the suction filtration process, wash it three times with dichloromethane and diethyl ether respectively. Finally, place the solid in a vacuum drying oven at 80 °C and dry it to a constant weight to obtain the composite antibacterial filler.

[0042] The preparation method of the phosphorus-modified silver-loaded graphitic carbon nitride is as follows: Heat 20 parts by mass of urea to 150 °C until it completely melts. Then add 5.2 parts by mass of a 0.022% silver nitrate solution and stir for 12 min. Then add 5.2 parts by mass of a 0.05% citric acid solution and continue to stir for 18 min. Then transfer it to a preheated crucible and quickly transfer it to a nitrogen-purged muffle furnace. Calcinate it at 555 °C for 3.5 h with a heating rate of 5 °C / min. After cooling, grind it to obtain silver-loaded graphitic carbon nitride rich in mesopores with a specific surface area of 104.6 m 2 *g -1 and a pore volume of 0.572 m 3 *g -1 Take 3 parts by mass of silver-loaded graphitic carbon nitride rich in mesopores and mix it with 100 parts by mass of 25% dilute sulfuric acid and stir for 50 h. Then centrifuge at a speed of 8000 r / min for 5 min, discard the supernatant, add 100 parts by mass of deionized water and centrifuge again to remove the supernatant. Repeat the above steps until the supernatant is neutral. Then dry it in a vacuum drying oven at 80 °C for 24 h. Then mix it with 87 parts by mass of toluene, ultrasonically disperse it for 20 min, add 0.6 parts by mass of phosphorus oxychloride and 3.3 parts by mass of triethylamine, and react at 65 °C for 3.5 h. Filter off the toluene. During the suction filtration process, wash it with ethyl acetate multiple times to remove the toluene, and then wash it with water multiple times to remove the triethylamine hydrochloride produced during the reaction. Place it in a vacuum drying oven and dry it at 100 °C overnight to a constant weight to obtain the phosphorus-modified silver-loaded graphitic carbon nitride.

[0043] (Comparative Example 1) The difference between Comparative Example 1 and Example 2 is that the antibacterial melamine formaldehyde resin is obtained by the composite reaction of melamine, formaldehyde, and antibacterial polyethylene glycol, and the remaining steps and components are the same as those in Example 2.

[0044] (Comparative Example 2) The difference between Comparative Example 2 and Example 2 is that the antibacterial melamine formaldehyde resin is obtained by the composite reaction of melamine, formaldehyde, and (2S)-2-amino-3-hydroxypentanedioic acid, and the remaining steps and components are the same as those in Example 2.

[0045] (Comparative Example 3) The difference between Comparative Example 3 and Example 2 is that the antibacterial melamine formaldehyde resin is obtained by the compound reaction of melamine, formaldehyde, (2S)-2-amino-3-hydroxyglutaric acid, and polyethylene glycol, and the remaining steps and components are the same as those in Example 2.

[0046] (Comparative Example 4) The difference between Comparative Example 4 and Example 2 is that the antibacterial polyethylene glycol is obtained by the compound reaction of a composite antibacterial filler, hydrophobic organosilicon, and polyethylene glycol, and the remaining steps and components are the same as those in Example 2.

[0047] (Comparative Example 5) The difference between Comparative Example 5 and Example 2 is that the antibacterial polyethylene glycol is obtained by the compound reaction of a composite antibacterial filler, polyethylene glycol, and cysteine, and the remaining steps and components are the same as those in Example 2.

[0048] (Comparative Example 6) The difference between Comparative Example 6 and Example 2 is that the antibacterial polyethylene glycol is obtained by the compound reaction of hydrophobic organosilicon, polyethylene glycol, and cysteine, and the remaining steps and components are the same as those in Example 2.

[0049] (Comparative Example 7) The difference between Comparative Example 7 and Example 2 is that the composite antibacterial filler is prepared in-situ by the method combining molten urea and thermal polycondensation, using silver nitrate as the silver source and citric acid as the pore-forming agent, and the remaining steps and components are the same as those in Example 2.

[0050] (Comparative Example 8) The difference between Comparative Example 8 and Example 2 is that the composite antibacterial filler is prepared in-situ by the method combining molten urea and thermal polycondensation. First, graphitic carbon nitride is prepared in-situ, and then the silver-loaded graphitic carbon nitride is reacted with phosphorus oxychloride, pentaerythritol, and phosphorus oxychloride in sequence, and the remaining steps and components are the same as those in Example 2.

[0051] (Comparative Example 9) The difference between Comparative Example 9 and Example 2 is that after the hot pressing in Step A2 of the preparation of the high weather resistance decorative board is completed, it is directly taken out and cooled, and the remaining steps and components are the same as those in Example 2.

[0052] (Effect Example) Abrasion resistance test: The abrasion resistance of the high weather resistance decorative boards prepared in the examples and comparative examples was tested in accordance with GB / T 17657—2022; Antibacterial property: Escherichia coli was used as the bacterial strain, and the antibacterial rate of the high weather resistance decorative boards prepared in the examples and comparative examples was tested according to GB / T 31402—2015; Flexibility measurement: Measure the curl radius of the melamine-impregnated decorative papers prepared in the test examples and comparative examples; Hydrophobicity test: Use Shengding Precision Instrument SDC-100S and select the ellipse method (20° < contact angle to be measured < 120°) for testing; Inject a small amount of water into a 1 ml syringe and drop it onto the surface of the highly weather-resistant decorative boards prepared in the examples and comparative examples drop by drop, and record the entire dynamic process of the water droplet contacting the specimen surface; Select the static CA after the water droplet stabilizes on the specimen surface, randomly and dispersedly take 3 different points on the specimen to record and take the average value, and observe whether the water penetrates and spreads on the specimen surface.

[0053] Weather resistance: Perform radiation and humidification in a Heraeus X450 irradiator according to ISO4892-2, Method A; To measure the weather resistance, take out the melamine-impregnated decorative papers prepared in the examples and comparative examples at 1000h, 2000h, and 3000h; Then measure the curl radius; When comparing with the sample before radiation, when the curl radius after radiation increases by less than 2% compared to before radiation, the weather resistance is determined to be good, between 2% and 5% is slightly poor, and greater than or equal to 5% is poor.

[0054] Formaldehyde elimination performance: The volume of the experimental reaction chamber is about 6 liters (20 cm × 20 cm × 15 cm), and the distance between the surface of the moisture-proof and antibacterial board for the cabinet and the quartz window at the top of the reaction chamber is about 10 cm. The reaction gas can only pass through between the surface of the moisture-proof and antibacterial board for the cabinet and the air inlet and outlet of the reaction chamber; During the photocatalytic reaction process, simulate sunlight will be provided vertically outside the reaction chamber; Put the moisture-proof and antibacterial boards for the cabinet in the examples and comparative examples into the reaction chamber and introduce gaseous formaldehyde with a concentration of about 100 ppm, turn on a 500 W xenon lamp, and measure the change in formaldehyde concentration within 60 minutes with a formaldehyde detector, measuring once every 10 seconds on average. The formaldehyde concentration is estimated according to the following formula:

[0055] Among them, ρ represents the density of formaldehyde, v1 is the volume (milliliters) of the initially added liquid formaldehyde solution, c(wt)% is the concentration of formaldehyde, k = 1.25 is the conversion coefficient, and v2 is the volume of the container (cubic meters).

[0056] The following Table 1 shows the performance test results of the highly weather-resistant decorative boards or their melamine-impregnated decorative papers prepared in the examples and comparative examples: Table 1

[0057] It can be seen from Table 1 that the highly weather-resistant decorative boards or their melamine-impregnated decorative papers prepared in Examples 1 to 3 have good abrasion resistance, antibacterial performance, flexibility measurement, hydrophobicity, and weather resistance, and can effectively eliminate formaldehyde and volatile organic compounds in the room.

[0058] The difference between Comparative Example 1 and Example 2 is that (2S)-2-amino-3-hydroxyglutaric acid was not added to the antibacterial melamine formaldehyde resin in Comparative Example 1 for the composite reaction; the weather resistance of the prepared highly weather-resistant decorative board is slightly worse than that of Example 2. This is because the presence of cysteine makes the highly weather-resistant decorative board have better antioxidant properties, and the coiling radius only increases by 3.53% after radiation compared to before radiation. Compared with Comparative Examples 2-4 where the coiling radius increases by >5% after radiation, it has better weather resistance; the contact angle is smaller, the hydrophobicity is poorer, and the wear resistance is slightly worse than that of Example 2. It may be that cysteine on the surface of the highly weather-resistant decorative board cannot react and crosslink with (2S)-2-amino-3-hydroxyglutaric acid, resulting in a decrease in the crosslinking density.

[0059] The difference between Comparative Example 2 and Example 2 is that antibacterial polyethylene glycol was not added to the antibacterial melamine formaldehyde resin in Comparative Example 2. The prepared highly weather-resistant decorative board has poor wear resistance, antibacterial performance, flexibility, hydrophobicity, and weather resistance, and cannot eliminate formaldehyde and volatile organic compounds in the room.

[0060] The difference between Comparative Example 3 and Example 2 is that polyethylene glycol was used instead of antibacterial polyethylene glycol in the antibacterial melamine formaldehyde resin in Comparative Example 3. The prepared highly weather-resistant decorative board has poor wear resistance, antibacterial performance, flexibility, hydrophobicity, and weather resistance, and cannot eliminate formaldehyde and volatile organic compounds in the room.

[0061] The difference between Comparative Example 4 and Example 2 is that antibacterial polyethylene glycol in Comparative Example 4 was not subjected to a composite reaction with cysteine. The prepared highly weather-resistant decorative board has poor weather resistance, a smaller contact angle, poorer hydrophobicity, and slightly worse wear resistance than that of Example 2.

[0062] The difference between Comparative Example 5 and Example 2 is that antibacterial polyethylene glycol in Comparative Example 5 was not subjected to a composite reaction with hydrophobic silicone. The prepared highly weather-resistant decorative board has poor flexibility, a smaller contact angle, poorer hydrophobicity, and slightly worse wear resistance than that of Example 2.

[0063] The difference between Comparative Example 6 and Example 2 is that composite antibacterial fillers were not added to the antibacterial polyethylene glycol in Comparative Example 6. The prepared highly weather-resistant decorative board has poor wear resistance, antibacterial performance, flexibility, and hydrophobicity, and cannot eliminate formaldehyde and volatile organic compounds in the room.

[0064] The difference between Comparative Example 7 and Example 2 is that the composite antibacterial filler in Comparative Example 7 did not react with phosphorus oxychloride, pentaerythritol, and phosphorus oxychloride in sequence; the dispersibility of the composite antibacterial filler in the highly weather-resistant decorative board is poor, and the wear resistance and flexibility of the highly weather-resistant decorative board are poor.

[0065] The difference between Comparative Example 8 and Example 2 is that the composite antibacterial filler in Comparative Example 8 was not silver-loaded; the antibacterial performance of the highly weather-resistant decorative board is poor, and the formaldehyde elimination ability is poor.

[0066] The difference between Comparative Example 9 and Example 2 is that after the hot pressing in Preparation Step A2 of the highly weather-resistant decorative board in Comparative Example 9, heat treatment was not carried out; the weather resistance, wear resistance, and hydrophobicity of the obtained highly weather-resistant decorative board are slightly worse.

[0067] In the specific embodiments described above, the purpose, technical solution, and beneficial effects of the present invention have been further described in detail. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A highly weather-resistant decorative board, comprising a substrate and a melamine impregnated film paper attached to the surface of the substrate by a hot pressing process, wherein the melamine impregnated film paper is obtained by impregnating base paper in urea-formaldehyde resin and antibacterial melamine formaldehyde resin in sequence, and is characterized in that, The antibacterial melamine formaldehyde resin is obtained by the composite reaction of melamine, formaldehyde, (2S)-2-amino-3-hydroxyglutaric acid, and antibacterial polyethylene glycol.

2. The high weather-resistant decorative board according to claim 1, characterized in that, The antibacterial polyethylene glycol is obtained by the composite reaction of polyethylene glycol with a composite antibacterial filler, cysteine, and hydrophobic organosilicon.

3. The highly weather-resistant decorative board according to claim 2, characterized in that, The composite antibacterial filler is prepared by first using a method combining molten urea and thermal polycondensation, using silver nitrate as the silver source and citric acid as the pore-forming agent to in-situ prepare silver-loaded graphitic carbon nitride with rich mesopores, and then reacting the silver-loaded graphitic carbon nitride with phosphorus oxychloride, pentaerythritol, and phosphorus oxychloride in sequence.

4. The high weather-resistant decorative board according to claim 2, wherein, The hydrophobic organosilicon includes sodium methyl silicate, perfluorodecyltrimethoxysilane, and perfluorohexylethyltrimethoxysilane.

5. A preparation method of the highly weather-resistant decorative board according to any one of claims 1 to 4, characterized in that, It includes the following preparation steps: A1. Preparation of melamine-impregnated decorative paper; A1.1 Preparation of urea-formaldehyde resin adhesive solution: Stir and mix evenly 100 parts by mass of urea-formaldehyde resin, 0.06 - 0.1 part by mass of curing agent, 0.02 - 0.04 part by mass of demolding agent, and 0.02 - 0.04 part by mass of penetrant. A1.2 Preparation of antibacterial melamine formaldehyde resin adhesive solution: Stir and mix evenly 100 parts by mass of antibacterial melamine formaldehyde resin, 0.06 - 0.1 part by mass of curing agent, 0.02 - 0.04 part by mass of demolding agent, and 0.02 - 0.04 part by mass of penetrant. A1.3 Secondary impregnation: First, put the base paper into the urea-formaldehyde resin adhesive solution to be completely soaked, take it out, scrape off the excess adhesive solution on the surface, and dry it to obtain the base paper after the first impregnation; put the base paper after the first impregnation into the urea-formaldehyde resin adhesive solution for impregnation, take it out, scrape off the excess adhesive solution on the surface, and dry and cool it to obtain the melamine-impregnated decorative paper. A2. Preparation of weather-resistant decorative board: Place the prepared melamine-impregnated decorative paper and the substrate together on a hot press, hot press them, and then take them out and cool to room temperature to obtain the weather-resistant decorative board.

6. The preparation method of the highly weather-resistant decorative board according to claim 5, characterized in that, The preparation steps of the antibacterial melamine formaldehyde resin are as follows: First, mix 160 - 162 parts by mass of 37% formaldehyde solution and 130 - 134 parts by mass of water and stir for 5 - 10 min, then adjust the pH to 8 - 9 with 30% sodium hydroxide solution, then raise the temperature to 50 - 60 °C, add 100 parts by mass of melamine and 0.03 - 0.3 part by mass of (2S)-2-amino-3-hydroxyglutaric acid, raise the temperature to 85 - 90 °C within 30 min, after clarification, add 1 - 5 parts by mass of antibacterial polyethylene glycol and continue to react for 100 - 120 min. After the reaction is completed, immediately cool it to room temperature in an ice-water bath and discharge it to obtain the antibacterial melamine formaldehyde resin.

7. The preparation method of the highly weather-resistant decorative board according to claim 6, characterized in that, The preparation method of the antibacterial polyethylene glycol is as follows: at 90 °C, polyethylene glycol is mixed with toluene which is 10 - 15 times its mass, and then heated to 90 °C. After stirring at 800 - 1000 rpm for 1.8 - 2.2 h, triethylamine and a composite antibacterial filler are added in sequence. The reaction is maintained at 90 °C for 14 - 16 h, cooled to room temperature, and toluene is removed by suction filtration. During the suction filtration process, toluene is removed by washing with ethyl acetate multiple times, and then triethylamine hydrochloride generated during the reaction is removed by washing with water multiple times. Finally, it is placed in a vacuum drying oven and dried at 100 °C overnight until constant weight, then naturally cooled to 60 °C, cysteine and p-toluenesulfonic acid are added and stirred evenly, then the temperature is raised to 105 - 115 °C, and after reacting for 5 - 7 h, the temperature is raised to 140 °C until no more water is generated, and the reaction ends. Finally, the temperature is lowered to 90 °C for reduced pressure distillation, and the catalyst p-toluenesulfonic acid is separated out as colorless crystals and then added to hot water at 90 °C. After stirring and reacting for 1.5 - 2.5 h, hydrophobic organosilicon is slowly added dropwise, and stirred and reacted at 80 - 90 °C for 1.5 - 2.5 h to obtain antibacterial polyethylene glycol; wherein, the mass ratio of polyethylene glycol, triethylamine, composite antibacterial filler, cysteine, p-toluenesulfonic acid, hot water, and hydrophobic organosilicon is 15 - 25: 4 - 6: 5 - 7: 4 - 6: 0.0012 - 0.0024: 100: 4 - 6.

8. The preparation method of the highly weather-resistant decorative board according to claim 6, characterized in that, The preparation method of the composite antibacterial filler is as follows: 3.5 - 4.5 parts by mass of phosphorus-modified silver-loaded graphitic carbon nitride, 0.112 - 0.168 parts by mass of pentaerythritol, and 0.4 - 0.6 parts by mass of phosphorus oxychloride are heated to 75 - 85 °C and kept warm for 1.5 - 2.5 h, then heated to 100 °C and stirred at 800 - 1200 rpm, and reacted overnight until basically no hydrogen chloride gas is generated, and then cooled to room temperature and suction filtered. During the suction filtration process, it is washed 3 times with dichloromethane and diethyl ether respectively. Finally, the solid is placed in a vacuum drying oven at 80 °C and dried until constant weight to obtain the composite antibacterial filler.

9. The preparation method of the highly weather-resistant decorative board according to claim 8, characterized in that, The preparation method of the phosphorus-modified silver-loaded graphitic carbon nitride is as follows: Heat 20 parts by mass of urea to 150 °C until the urea is completely melted, then add 5 - 5.2 parts by mass of a 0.022% silver nitrate solution, stir for 8 - 12 min, then add 5 - 5.2 parts by mass of a 0.05% citric acid solution, continue to stir for 12 - 18 min, then transfer it to a preheated crucible, quickly transfer it to a nitrogen-purged muffle furnace, calcine at 550 ± 5 °C for 2.5 - 3.5 h, with a heating rate of 5 °C / min, cool and grind to obtain silver-loaded graphitic carbon nitride with rich mesopores; Mix 3 parts by mass of the silver-loaded graphitic carbon nitride with rich mesopores with 25% dilute sulfuric acid and stir for 46 - 50 h, then centrifuge at a speed of 8000 r / min for 5 min, discard the supernatant, add 100 parts by mass of deionized water and centrifuge again to remove the supernatant, repeat the above steps until the supernatant is neutral; Then dry in a vacuum drying oven at 80 °C for 24 h, then mix with 86 - 87 parts by mass of toluene, ultrasonically disperse for 10 - 20 min, then add 0.4 - 0.6 parts by mass of phosphorus oxychloride and 2.7 - 3.3 parts by mass of triethylamine, react at 55 - 65 °C for 2.5 - 3.5 h, filter to remove toluene, during the filtration process, wash with ethyl acetate multiple times to remove toluene, then wash with water multiple times to remove the triethylamine hydrochloride generated during the reaction, place in a vacuum drying oven and dry at 100 °C overnight until constant weight to obtain phosphorus-modified silver-loaded graphitic carbon nitride.

10. The preparation method of the highly weather-resistant decorative board according to claim 5, wherein, After the hot pressing in step A2 is completed, heat-treat at 120 - 140 °C for 11 - 13 h.

Images