Veneer modified by bioactive components based on molecular nest technology and production process of veneer

Abstract

The invention provides a biologically active component modified veneer based on a molecular nest technology and a production process thereof, and the production process comprises the following steps: mixing eucalyptus wood shavings and an active modified adhesive, paving, pre-pressing, and hot-pressing and curing to obtain an active plain board; the preparation method comprises the following steps: pretreating decorative base paper by using a folium artemisiae argyi extract, impregnating by using an impregnating solution containing modified molecular nests, and drying to obtain active impregnated paper; and spraying an interface treating agent on the surface of the active plain board, drying with hot air, covering the active impregnated paper on the active plain board, and carrying out hot pressing, cooling and edge cutting to obtain the product. The invention provides a veneer modified by bioactive components based on a molecular nest technology. The mechanical property, antibacterial durability and fragrance retention time of the veneer are improved; the interface bonding force between the adhesive and the plant fibers is improved, the problem that active ingredients break out and release too early is solved, and the interface bonding strength between the plain board and the impregnated paper is enhanced.

Description

A decorative panel modified with bioactive ingredients based on molecular nesting technology and its manufacturing process Technical Field

[0001] This invention relates to the field of decorative panel manufacturing technology, specifically to a decorative panel modified with bioactive ingredients based on molecular nesting technology and its production process. Background Technology

[0002] With the improvement of people's living standards and increasing attention to health and environmental protection, interior decoration materials not only need to possess good mechanical properties to meet daily use needs, but also need to have functional properties such as antibacterial properties and pleasant fragrance to create a healthy and comfortable indoor environment. As a widely used interior decoration material, decorative panels have attracted much attention for performance optimization and innovative development. Modifying decorative panels using bioactive ingredients based on molecular nest technology provides a new approach and idea for improving their overall performance. Molecular nest technology is a technique based on constructing unique pore structures from specific materials to achieve effective loading and controlled release of active ingredients. In the field of decorative panel modification, the use of molecular nest technology combined with bioactive ingredients aims to endow decorative panels with a variety of superior properties.

[0003] While existing decorative panels and their manufacturing processes have improved their performance to some extent, several problems remain. Although some existing technologies attempt to apply molecular nests to decorative panel preparation to enhance mechanical properties, the synergistic mechanism between molecular nests and other components is not sufficiently understood, and the structure and performance of the molecular nests have not been fully optimized, resulting in insufficient improvement in the mechanical properties of the decorative panels. Existing antibacterial systems are often relatively simple, relying on a single antibacterial component or a simple antibacterial method. Such single antibacterial systems are prone to decreased antibacterial efficacy when facing complex and variable microbial environments. Furthermore, the release control of active antibacterial components is not precise enough, leading to premature burst release and rapid consumption of active components, resulting in a significant reduction in the antibacterial performance of the decorative panel in the later stages of use, failing to achieve long-term effective antibacterial protection. In addition, existing technologies for encapsulating and slow-release active aroma components to achieve fragrance functionality in decorative panels are not mature enough. Therefore, this invention provides a decorative panel modified with bioactive components based on molecular nest technology and its manufacturing process. Summary of the Invention

[0004] The purpose of this invention is to provide a decorative panel modified with bioactive ingredients based on molecular nesting technology and its production process, which improves the mechanical properties (MOR and MOE), antibacterial durability and aroma retention time of the decorative panel; improves the interfacial bonding force between adhesive and plant fiber and the problem of premature release of active ingredients, enhances the interfacial bonding strength between the raw board and the impregnated paper, and constructs a multi-level antibacterial system, solving the problem of insufficient effect and durability of single antibacterial methods.

[0005] On one hand, the present invention provides a production process for decorative panels modified with bioactive ingredients based on molecular nest technology, the steps of which include: S1, mixing eucalyptus wood shavings with an active modified adhesive, and then laying, pre-pressing and hot-pressing to obtain an active board; S2, pre-treating the decorative base paper with Artemisia argyi extract, then impregnating and drying it with an impregnation solution containing modified molecular nests to obtain an active impregnated paper; S3, spraying an interface treatment agent onto the surface of the active board and drying it with hot air, then covering it with the active impregnated paper, and then hot-pressing, cooling and trimming to obtain the final product.

[0006] Further, the preparation steps of the active ingredient board include: spraying an ethanol solution of pine needle extract into eucalyptus shavings and then sealing and stacking them; mixing PMDI adhesive with modified molecular nests and kaolin and ultrasonically dispersing the mixture to obtain a modified adhesive; mixing the stacked eucalyptus shavings with the modified adhesive and laying them out, and pre-pressing them at 1.5-2.5 MPa for 30-40 seconds; and hot-pressing the pre-pressed board at 185±5℃ and 3.5±0.5 MPa pressure for 25±5 seconds / mm board thickness to obtain the active ingredient board.

[0007] Furthermore, the concentration of the ethanol solution of the pine needle extract is 4.5-5.5 wt%, and its dosage is 1-2% of the oven-dry weight of eucalyptus shavings; the sealed stacking time is 20-24 hours.

[0008] Furthermore, the weight ratio of the PMDI adhesive, modified molecular nest, and kaolin is 100:4-6:2-4; the blending is carried out at 900-1000 rpm for 10-15 minutes, and the ultrasonic dispersion is carried out for 10-15 minutes.

[0009] Furthermore, the preparation method of the modified molecular nest includes: preparing hydroxyapatite nanorods by a hydrothermal method; mixing the hydroxyapatite nanorods with hexadecyltrimethylammonium bromide, adding tetraethyl orthosilicate, hydrolyzing and condensing under alkaline conditions, and calcining to form a porous material with radially gradient pore sizes; loading a mixture of Artemisia argyi essential oil and menthol into the porous material; and performing surface grafting treatment on the loaded porous material with silane coupling agent KH-560 to obtain the modified molecular nest.

[0010] Further, the hydrothermal reaction step includes: mixing equal volumes of 0.4-0.6 mol / L calcium nitrate aqueous solution and 0.2-0.4 mol / L diammonium hydrogen phosphate aqueous solution, adjusting the pH to 10 with ammonia water, hydrothermally reacting at 180-190℃ for 20-24 h, centrifuging, washing, and drying to obtain the final product.

[0011] Furthermore, the preparation steps of the active impregnated paper include: 80-90 g / m2 The base paper is impregnated in an aqueous solution of Artemisia argyi extract at a concentration of 3-5 wt% for 5-7 seconds, and then dried at 100-110℃. Modified molecular nests at a total weight of 5-7% are added to melamine resin and stirred evenly to obtain an impregnation solution. The pretreated base paper is passed through the impregnation solution at a speed of 8-10 m / min for 3-5 seconds, and then dried at 120-130℃ to obtain active impregnated paper with a degree of curing of 65-70%.

[0012] Further, in step S3, the preparation step of the interface treatment agent includes: dispersing 3-5% of the modified molecular nests, accounting for 35-45% of the total weight of the waterborne polyurethane emulsion, in the waterborne polyurethane emulsion with a solid content of 35-45%, then adding 0.1-0.3 wt% of wetting agent, and stirring at 300-400 rpm for 30-40 minutes; the coating amount of the interface treatment agent is 10-12 g / m². 2 .

[0013] Further, in step S3, the hot air drying temperature is 70-75℃, and the time is 3-5 minutes; the hot pressing process conditions include: temperature 180-190℃, pressure 2.4-2.8 MPa, and time 40-45 seconds; wherein the pressure control adopts a stepped approach: the pressure rises to 2.4-2.8 MPa within 0-10 seconds, is maintained for 20-25 seconds, and the pressure drops to 1.0 MPa within the last 10 seconds.

[0014] On the other hand, the present invention also provides a decorative panel modified with bioactive ingredients based on molecular nest technology, which is produced using the aforementioned production process.

[0015] The beneficial effects of this invention are as follows: In the production process of this invention, modified molecular nests and kaolin play a synergistic reinforcing role in PMDI adhesives, significantly improving the mechanical properties of the decorative panels. The modified molecular nests possess a unique radial gradient pore size porous structure, which, after grafting treatment with the silane coupling agent KH-560, can effectively load and slowly release active ingredients. Simultaneously, this porous structure allows it to act as a nano-reinforcing phase in the adhesive, increasing the interfacial bonding force between the adhesive and plant fibers. Kaolin, as a common inorganic filler, has good physicochemical stability and a certain reinforcing effect. When modified molecular nests and kaolin coexist in PMDI adhesives, they work together; the nanoscale porous structure of the modified molecular nests complements the sheet-like structure of the kaolin, further optimizing the internal structure of the adhesive and improving its strength and toughness. During the hot-press curing process, this optimized adhesive can better fill the gaps between fibers, forming a denser structure, thereby significantly improving the MOR (static bending strength) and MOE (modulus of elasticity) of the prepared active board and the final decorative panel.

[0016] This invention's production process constructs a multi-layered, multi-component antibacterial system, achieving highly efficient and long-lasting antibacterial effects. First, in the fiber pretreatment stage, a solution of ethanol extract from Masson pine needles is sprayed into eucalyptus fibers and then subjected to a sealed stacking process. The Masson pine needle extract imparts certain antibacterial properties to the fiber itself, forming the first layer of protection in the antibacterial system. Second, modified molecular nests successfully encapsulate and slowly release a complex of active ingredients including Artemisia argyi essential oil and menthol. These active ingredients possess broad-spectrum antibacterial properties and can achieve effective encapsulation and controlled slow release through the gradient pore structure of the modified molecular nests and the grafting effect of silane coupling agents, forming the core layer of the antibacterial system. Furthermore, the use of Artemisia argyi extract in the pretreatment of the decorative base paper further increases the antibacterial components; the addition of modified molecular nests to the impregnation solution also contributes to antibacterial activity. These antibacterial components at different levels and with different components work synergistically, exerting their effects from different angles, exhibiting an antibacterial rate of nearly 99% against the three tested bacteria. Moreover, this multi-layered antibacterial system makes the antibacterial function more durable, maintaining high antibacterial performance even after aging and wear processes.

[0017] In this invention, the radial gradient pore structure of the modified molecular nest and the silane coupling agent grafting treatment synergistically achieve effective encapsulation and controlled sustained release of active ingredients. Hydroxyapatite nanorods prepared by hydrothermal method are mixed with hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate is added. The mixture undergoes hydrolysis and condensation under alkaline conditions to form a porous material with a radial gradient pore size, providing ample loading space for the active ingredients. Different pore sizes can selectively load active ingredients with different properties, and the gradient structure facilitates the slow release of active ingredients. Furthermore, the surface grafting treatment of the loaded porous material with the silane coupling agent KH-560 further reduces or modifies the pore openings of the porous structure, creating a valve effect. This synergistic effect ensures that the active ingredients are not released prematurely during processing and use, but rather released slowly at a certain rate, thus guaranteeing that the decorative panel retains a noticeable fragrance and long-lasting antibacterial properties over a long period. For example, a noticeable fragrance is still present after 90 days, and the antibacterial and fragrance retention rates remain high after simulated aging.

[0018] This invention utilizes an interface treatment agent containing modified molecular nests, which plays a crucial synergistic role in connecting the active substrate and the active impregnated paper, thereby enhancing the overall performance of the decorative panel. The interface treatment agent is sprayed onto the surface of the active substrate and dried with hot air before the active impregnated paper is placed on top and subjected to hot pressing and other operations. The modified molecular nests in the interface treatment agent interact with the components in both the active substrate and the active impregnated paper. On one hand, the porous structure of the modified molecular nests can interlock with the components in the adhesive, enhancing the mechanical interlocking force at the interface. On the other hand, the silane coupling agent grafted onto the surface of the modified molecular nests can chemically react with the groups on the fiber surface and in the impregnated paper, forming chemical bonds. This synergistic effect of mechanical interlocking and chemical bonding significantly enhances the interfacial bonding strength between the substrate and the impregnated paper. Omitting the interface treatment agent leads to a significant decrease in mechanical properties, especially MOR (Mean Oxidation Ratio), and may also affect the migration channels of active ingredients from the core layer to the surface, resulting in reduced aroma persistence. This fully demonstrates the important synergistic role of the interface treatment agent in connecting the core layer and the decorative layer. Detailed Implementation

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

[0020] It should also be noted that the hydroxyapatite nanorods were purchased from Suzhou Beike Nanotechnology Co., Ltd., item number BkZNZ2020102066-01; Artemisia argyi essential oil was purchased from Shanghai Xinya New Material Technology Co., Ltd.; menthol was purchased from Shanghai Xier Biotechnology Co., Ltd.; Pinus massoniana needle extract was purchased from Baoji Liupanyun Biotechnology Co., Ltd.; PMDI adhesive was purchased from Wuhan Jushun Chemical Co., Ltd., CAS number 9016-87-9; kaolin was purchased from Shanghai Aladdin Reagent Co., Ltd., grade MFCD00062311; Artemisia argyi extract was purchased from Lanzhou Waterles Biotechnology Co., Ltd., 80-120 mesh; melamine resin was purchased from Xinxiang Xinli Industrial Co., Ltd.; waterborne polyurethane emulsion was purchased from Anhui Anda Huatai New Material Co., Ltd.; polyether-modified organosiloxane was purchased from Jiande Juhe New Material Co., Ltd., model JH-B248; other raw materials not specified are commercially available.

[0021] Example 1 This example provides a production process for decorative panels modified with bioactive ingredients based on molecular nest technology. The steps include: S1, mixing 0.5 mol / L calcium nitrate aqueous solution with 0.3 mol / L calcium nitrate aqueous solution... Equal volumes of diammonium hydrogen phosphate aqueous solution (mol / L) were mixed, and the pH of the mixture was adjusted to 10 with ammonia. The mixture was transferred to a high-pressure reactor and hydrothermally reacted at 185°C for 22 hours. After the reaction, the product was separated by centrifugation, washed repeatedly with deionized water and ethanol, and dried at 80°C to obtain hydroxyapatite nanorods. 10g of the hydroxyapatite nanorods and 2g of hexadecyltrimethylammonium bromide were added to a 500mL mixture of ethanol and water (volume ratio 3:1) and ultrasonically dispersed for 30 minutes. 20mL of tetraethyl orthosilicate was added at 500rpm, and the pH of the system was maintained at 9 with ammonia. The reaction was continued at 40°C for 12 hours, followed by hydrolysis and condensation. After centrifugation, washing, and drying, the mixture was calcined at 550°C for 4 hours to remove the hexadecyltrimethylammonium bromide template, resulting in a porous material with radially gradient pore sizes. Artemisia argyi essential oil and menthol were mixed in a weight ratio of 2:1 to obtain an active oil phase, totaling 45mL. 10g of the active oil phase was then reacted at 60°C. The porous carrier material was immersed in the active oil phase, continuously stirred, and vacuum degassed for 4 hours to allow the active ingredients to be fully adsorbed into the pores. After loading, the mixture was allowed to stand and cool, and the excess oil phase was discarded to obtain the loaded porous material. The loaded porous material was dispersed in 200 mL of anhydrous ethanol, and 5% (by weight of the porous material) of silane coupling agent KH-560 was added. The mixture was refluxed at 70 °C for 6 hours. After the reaction, the product was collected by centrifugation, washed with ethanol, and dried to obtain the modified molecular nest. 100 kg of eucalyptus wood shavings (dry weight) were weighed, and 1.5 kg (1.5% of the dry weight of the decorative panel) of a 5 wt% ethanol solution of pine needle extract was evenly sprayed onto the eucalyptus wood shavings using an atomizing device. After spraying, the decorative panel was transferred to a sealed environment and stacked for 22 hours to allow the extract to fully penetrate and adhere. PMDI adhesive with a weight ratio of 100:5:3 was mixed with the modified molecular nest and kaolin at 9500 °C. The modified adhesive was obtained by ultrasonic dispersion at rpm for 12 minutes and ultrasonic dispersion for 12 minutes; the pretreated eucalyptus shavings and the modified adhesive were mixed evenly in a mixer (the amount of adhesive was 8% of the dry weight of the decorative panel), and then laid into a uniform board using an air-jet paving machine; the board was fed into a pre-press and pre-pressed at 2.0 MPa for 35 seconds to remove air and preliminarily shape it; the pre-pressed board was fed into a hot press and hot-pressed at 185℃ and 3.5 MPa for curing, with the hot-pressing time set to 375 seconds (25 seconds / mm) according to the board thickness (15mm); after hot pressing, it was cooled and trimmed to obtain the active ingredient board; S2, 85 g / m 2The base paper was impregnated in a 4 wt% aqueous solution of Artemisia argyi extract for 6 seconds, and then dried at 105°C to a moisture content of 8%. 6 parts by weight of modified molecular nests were added to 100 parts by weight of melamine resin, and the mixture was stirred at 500 rpm for 20 minutes to ensure thorough mixing and obtain an active impregnation solution. The pretreated base paper was passed through the active impregnation solution at a speed of 9 m / min for 4 seconds to ensure uniform penetration. The paper was then fed into a drying channel and dried at 125°C until the resin curing degree reached 68%, resulting in active impregnated paper. S3: 100 parts by weight of a 40% solids content aqueous polyurethane emulsion were taken, and 4 parts by weight of modified molecular nests and 0.2 parts by weight of a wetting agent, polyether-modified organosiloxane, were added. The mixture was stirred at 350 rpm for 35 minutes to obtain an interface treatment agent. The interface treatment agent was sprayed onto the surface of the active material board and dried at 72°C for 4 minutes. The coating amount of the interface treatment agent was 11... g / m 2 Then, the active impregnated paper is placed on top and hot-pressed at a temperature of 185°C and a pressure of 2.6 MPa for 42 seconds. The pressure is controlled in a stepped manner: the pressure is increased to 2.6 MPa within 5 seconds, maintained for 22 seconds, and then reduced to 1.0 MPa within the last 10 seconds. After cooling and trimming, the decorative panel modified with bioactive ingredients based on molecular nest technology is obtained.

[0022] Example 2 This example provides a production process for decorative panels modified with bioactive ingredients based on molecular nest technology. The steps include: S1, mixing 0.6 mol / L calcium nitrate aqueous solution with 0.4 mol / L calcium nitrate aqueous solution... Equal volumes of diammonium hydrogen phosphate aqueous solution (mol / L) were mixed, and the pH of the mixture was adjusted to 10 with ammonia. The mixture was transferred to a high-pressure reactor and hydrothermally reacted at 190°C for 20 hours. After the reaction, the product was separated by centrifugation, washed repeatedly with deionized water and ethanol, and dried at 80°C to obtain hydroxyapatite nanorods. 10g of the hydroxyapatite nanorods and 2g of hexadecyltrimethylammonium bromide were added to a 500mL mixture of ethanol and water (volume ratio 3:1) and ultrasonically dispersed for 30 minutes. 20mL of tetraethyl orthosilicate was added at 500rpm, and the pH of the system was maintained at 9 with ammonia. The reaction was continued at 40°C for 12 hours, followed by hydrolysis and condensation. After centrifugation, washing, and drying, the mixture was calcined at 550°C for 4 hours to remove the hexadecyltrimethylammonium bromide template, resulting in a porous material with radially gradient pore sizes. Artemisia argyi essential oil and menthol were mixed in a weight ratio of 2:1 to obtain an active oil phase, totaling 40mL. The mixture was then calcined at 60°C. 0g of porous carrier material was immersed in the active oil phase, continuously stirred, and vacuum degassed for 4 hours to allow the active ingredients to be fully adsorbed into the pores. After loading, the mixture was allowed to stand and cool, and the excess oil phase was discarded to obtain the loaded porous material. The aforementioned loaded porous material was completely dispersed in 200mL of anhydrous ethanol, and 5% of silane coupling agent KH-560 relative to the weight of the porous material was added. The mixture was refluxed at 70℃ for 6 hours. After the reaction, the product was collected by centrifugation, washed with ethanol, and dried to obtain the modified molecular nest. 100kg of eucalyptus wood shavings were weighed, and 2kg (accounting for 2% of the dry weight of the decorative panel) of a 5.5wt% ethanol solution of pine needle extract was evenly sprayed onto the eucalyptus wood shavings using an atomizing device. After spraying, the decorative panel was transferred to a sealed environment and stacked for 20 hours to allow the extract to fully penetrate and adhere. PMDI adhesive with a weight ratio of 100:6:4 was mixed with the modified molecular nest and kaolin in a 1000 mL solution. The modified adhesive was obtained by ultrasonic dispersion at rpm for 10 minutes and ultrasonic dispersion for 10 minutes; the pretreated eucalyptus shavings and the modified adhesive were mixed evenly in a mixer (the amount of adhesive was 8% of the dry weight of the decorative panel), and then laid into a uniform board using an air-jet paving machine; the board was fed into a pre-press and pre-pressed at 1.5 MPa for 40 seconds to remove air and preliminarily shape it; the pre-pressed board was fed into a hot press and hot-pressed at 180℃ and 3.0 MPa for curing, with the hot-pressing time set to 300 seconds (20 seconds / mm) according to the board thickness (15mm); after hot pressing, the board was cooled and trimmed to obtain the active ingredient board; S2, 90 g / m 2The base paper was impregnated in a 5 wt% aqueous solution of Artemisia argyi extract for 5 seconds, and then dried at 100°C to a moisture content of 8%. 7 parts by weight of modified molecular nests were added to 100 parts by weight of melamine resin, and the mixture was stirred at 500 rpm for 20 minutes to ensure thorough mixing and obtain an active impregnation solution. The pretreated base paper was passed through the active impregnation solution at a speed of 8 m / min for 5 seconds to ensure uniform penetration. The paper was then fed into a drying channel and dried at 120°C until the resin curing degree reached 65%, resulting in active impregnated paper. S3: 100 parts by weight of a 45% solids content aqueous polyurethane emulsion were taken, and 5 parts by weight of modified molecular nests and 0.1 parts by weight of a wetting agent, polyether-modified organosiloxane, were added. The mixture was stirred at 300 rpm for 40 minutes to obtain an interface treatment agent. The interface treatment agent was sprayed onto the surface of the active material board and dried at 70°C for 5 minutes. The coating amount of the interface treatment agent was 12%. g / m 2 Then, the active impregnated paper is placed on top and hot-pressed at 180°C and 2.4 MPa for 45 seconds. The pressure is controlled in a stepped manner: the pressure is increased to 2.4 MPa within 10 seconds, maintained for 25 seconds, and then reduced to 1.0 MPa within the last 10 seconds. After cooling and trimming, the decorative panel modified with bioactive ingredients based on molecular nest technology is obtained.

[0023] Example 3 This example provides a production process for decorative panels modified with bioactive ingredients based on molecular nest technology. The steps include: S1, mixing 0.4 mol / L calcium nitrate aqueous solution with 0.2 mol / L calcium nitrate aqueous solution... Equal volumes of diammonium hydrogen phosphate aqueous solution (mol / L) were mixed, and the pH of the mixture was adjusted to 10 with ammonia. The mixture was transferred to a high-pressure reactor and hydrothermally reacted at 180°C for 24 hours. After the reaction, the product was separated by centrifugation, washed repeatedly with deionized water and ethanol, and dried at 80°C to obtain hydroxyapatite nanorods. 10g of the hydroxyapatite nanorods and 2g of hexadecyltrimethylammonium bromide were added to a 500mL mixture of ethanol and water (volume ratio 3:1) and ultrasonically dispersed for 30 minutes. 20mL of tetraethyl orthosilicate was added at 500rpm, and the pH of the system was maintained at 9 with ammonia. The reaction was continued at 40°C for 12 hours, followed by hydrolysis and condensation. After centrifugation, washing, and drying, the mixture was calcined at 550°C for 4 hours to remove the hexadecyltrimethylammonium bromide template, resulting in a porous material with radially gradient pore sizes. Artemisia argyi essential oil and menthol were mixed in a weight ratio of 2:1 to obtain an active oil phase, totaling 50mL. The mixture was then calcined at 60°C. 10g of porous carrier material was immersed in the active oil phase, continuously stirred, and vacuum degassed for 4 hours to allow the active ingredients to be fully adsorbed into the pores. After loading, the mixture was allowed to stand and cool, and the excess oil phase was discarded to obtain the loaded porous material. The aforementioned loaded porous material was completely dispersed in 200mL of anhydrous ethanol, and 5% of the weight of the porous material of silane coupling agent KH-560 was added. The mixture was refluxed at 70℃ for 6 hours. After the reaction, the product was collected by centrifugation, washed with ethanol, and dried to obtain the modified molecular nest. 100kg of eucalyptus wood shavings (dry weight) were weighed, and 1kg (1% of the dry weight of the decorative panel) of a 4.5wt% ethanol solution of pine needle extract was evenly sprayed onto the eucalyptus wood shavings using an atomizing device. After spraying, the decorative panel was transferred to a sealed environment and stacked for 24 hours to allow the extract to fully penetrate and adhere. PMDI adhesive with a weight ratio of 100:4:2 was mixed with the modified molecular nest and kaolin at 900°C. The modified adhesive was obtained by ultrasonic dispersion at rpm for 15 minutes and ultrasonic dispersion for 15 minutes; the pretreated eucalyptus shavings and the modified adhesive were mixed evenly in a mixer (the amount of adhesive was 8% of the oven-dry weight of the decorative panel), and then laid into a uniform board using an air-jet paving machine; the board was fed into a pre-press and pre-pressed at 2.5 MPa for 30 seconds to remove air and preliminarily shape it; the pre-pressed board was fed into a hot press and hot-pressed at 190℃ and 4.0 MPa for curing, with the hot-pressing time set to 450 seconds (30 seconds / mm) according to the board thickness (15mm); after hot pressing, it was cooled and trimmed to obtain the active ingredient board; S2, 80 g / m 2The base paper was impregnated in a 3wt% aqueous solution of Artemisia argyi extract for 7 seconds, and then dried at 110°C to a moisture content of 8%. 5 parts by weight of modified molecular nests were added to 100 parts by weight of melamine resin, and the mixture was stirred at 500 rpm for 20 minutes to ensure thorough mixing and obtain an active impregnation solution. The pretreated base paper was passed through the active impregnation solution at a speed of 10 m / min for 3 seconds to ensure uniform penetration. The paper was then fed into a drying channel and dried at 130°C until the resin curing degree reached 70%, resulting in active impregnated paper. S3: 100 parts by weight of a 35% solids content aqueous polyurethane emulsion were taken, and 3 parts by weight of modified molecular nests and 0.3 parts by weight of a wetting agent, polyether-modified organosiloxane, were added. The mixture was stirred at 400 rpm for 30 minutes to obtain an interface treatment agent. The interface treatment agent was sprayed onto the surface of the active material board and dried at 75°C for 3 minutes. The coating amount of the interface treatment agent was 10... g / m 2 Then, the active impregnated paper is placed on top and hot-pressed at 190°C and 2.8MPa for 40 seconds. The pressure is controlled in a stepped manner: the pressure is increased to 2.8MPa within 0 seconds, maintained for 20 seconds, and then reduced to 1.0MPa within the last 10 seconds. After cooling and trimming, the decorative panel modified with bioactive ingredients based on molecular nest technology is obtained.

[0024] Comparative Example 1 was adjusted based on Example 1. The difference from Example 1 is that the step of constructing a porous silica structure was omitted in the modified molecular nest preparation step, and hexadecyltrimethylammonium bromide and tetraethyl orthosilicate were not added. 10g of hydroxyapatite nanorods were directly used to load the active oil phase, and then KH-560 surface grafting was performed. This "non-porous structure carrier" was used in the subsequent raw board, impregnated paper and interface treatment agent.

[0025] Comparative Example 2 is an adjustment based on Example 1. The difference from Example 1 is that the loading step of the active oil phase is omitted in the modified molecular nest preparation step. Only a silica / hydroxyapatite porous material with gradient pore size is prepared and surface grafted with KH-560 to obtain an "empty molecular nest". All subsequent steps use this "empty molecular nest".

[0026] Comparative Example 3 is an adjustment based on Example 1. The difference from Example 1 is that in the modified molecular nest preparation step, the surface grafting treatment step of silane coupling agent KH-560 is omitted, and the porous material loaded with active ingredients is directly dried for subsequent steps.

[0027] Comparative Example 4 was adjusted based on Example 1. The difference from Example 1 is that in the preparation of the active ingredient board, the steps of spraying and stacking the eucalyptus wood shavings with the ethanol solution of pine needle extract were omitted. Instead, untreated eucalyptus wood shavings were directly mixed with the modified adhesive and laid out.

[0028] Comparative Example 5 is an adjustment based on Example 1. The difference from Example 1 is that in the preparation of the active ingredient board, the adhesive is not modified with modified molecular nests and kaolin, but is directly mixed with the pretreated decorative panel using pure PMDI adhesive.

[0029] Comparative Example 6 is an adjustment based on Example 1. The difference from Example 1 is that no modified molecular nests are added in the preparation of the active impregnation solution, and only melamine resin is used as the impregnation solution.

[0030] Comparative Example 7 is an adjustment based on Example 1. The difference from Example 1 is that in the preparation of the active impregnated paper, the step of pretreating the base paper with an aqueous solution of Artemisia argyi extract is omitted, and the base paper is directly immersed in the impregnation solution containing modified molecular nests.

[0031] Comparative Example 8 is an adjustment based on Example 1. The difference from Example 1 is that in the decorative panel forming step S3, the step of spraying the interface treatment agent is omitted, and the active impregnated paper is directly covered on the active ingredient board and hot-pressed.

[0032] Comparative Example 9 is an adjustment based on Example 1. The difference from Example 1 is that the composition of the active oil phase loaded in the modified molecular nest is changed. The active oil phase uses only a single component, Artemisia argyi essential oil, and the loading ratio remains unchanged in the total oil phase volume.

[0033] Comparative Example 10 is an adjustment based on Example 1. The difference from Example 1 is that in the adhesive modification, an equal amount of kaolin is used to completely replace the modified molecular nest, and the weight ratio of PMDI adhesive to kaolin is 100:8.

[0034] Experimental Example: The performance of the decorative panels prepared in Examples 1-3 and Comparative Examples 1-10 was investigated, and the following tests were conducted: Mechanical property test: Static bending strength (MOR) and modulus of elasticity (MOE) were tested according to GB / T 17657-2013 "Test Methods for Physical and Chemical Properties of Wood-based Panels and Decorative Wood-based Panels"; Anti-mold performance test: According to GB / T 18261-2013 "Test Methods for the Efficacy of Anti-mold Agents against Wood Molds and Discoloration Fungi", the specimens were inoculated with a mixed mold spore suspension and placed in a constant temperature and humidity chamber at 28±1℃ and relative humidity above 85% for 28 days. The surface mold growth was observed and the anti-mold level was evaluated (Level 0: no mold growth; Level 1: mold growth area <25%; Level 2: mold growth area 25%-50%; Level 3: mold growth area 50%-75%; Level 4: mold growth area >75%); Antibacterial test: According to GB / T The test conforms to ISO 21866-2008, "Determination of Antibacterial Properties and Antibacterial Effects of Antibacterial Coatings (Films)". The tested bacteria are Staphylococcus aureus (ATCC 6538, Gram-positive), Escherichia coli (ATCC 8739, Gram-negative), Klebsiella pneumoniae (ATCC 4352, Gram-negative), and Aspergillus niger (ATCC 16404, mold). For antiviral performance testing, ISO 21702:2019, "Determination of antiviral activity of plastics and other non-porous surfaces", was used, selecting influenza A virus H3N2 subtype and enterovirus EV71. The antiviral rate was calculated by measuring the logarithmic decrease in virus titer after 2 hours of contact with the decorative panel surface. The antiviral rate (%) was calculated as: [(control sample virus titer - sample virus titer) / control sample virus titer] × 100%. For the antioxidant performance test: the decorative panel to be tested was cut into standard samples of 50 mm × 50 mm. The sample surface was gently wiped with a lint-free cloth soaked in anhydrous ethanol to remove dust. The cleaned samples were then placed in a standard laboratory environment (temperature 23±2℃, humidity 50±5%) for 24 hours to equilibrate. DPPH was accurately weighed and dissolved in anhydrous ethanol to prepare a 0.1 mmol / L solution, which was stored in the dark and used immediately after preparation. The equilibrated sample was placed in a clean glass petri dish, and 10.0 mL was transferred... Prepare DPPH working solution to completely cover the sample surface; cover the petri dish with the lid and place it in the dark. Shake at 100 rpm for 60 minutes in a constant temperature shaker at 25°C; after the reaction, immediately use a pipette to aspirate the supernatant and measure its absorbance at 517 nm using a UV-Vis spectrophotometer, denoted as A1; take 10.0 mL of DPPH working solution, without contact with the sample, was placed in the dark under the same conditions for 60 minutes, and the absorbance was measured as a blank control A0. 10.0 mL of anhydrous ethanol was used to cover the sample of the same specification, and the absorbance was measured after the reaction. This was used to correct for potential interference from the sample's own color and served as a background control, denoted as A2. The DPPH free radical scavenging rate on the board surface = (A0 - A1 - A2) / A0 × 100%; where A0: absorbance of the blank control; A1: absorbance of the sample reaction solution; A2: absorbance of the sample background control. Each group of samples was tested in parallel three times, and the average value was taken as the final result. Aroma persistence and sustained-release performance test: A trained aroma evaluation team of 10 people smelled the board surface at 23℃ and 50% humidity on days 1, 7, 30, and 90 after production, recording the aroma intensity using a 5-point scale: 0 odorless, 1 faint, 2 discernible, 3 distinct, 4 strong, and characteristic aroma.

[0035] Environmental testing: The test was conducted according to GB / T 39600-2021 "Classification of Formaldehyde Emission from Wood-based Panels and Their Products". Samples were placed at 23℃, 50%RH, and 1.0m... 3 In a climate chamber with a ventilation rate of / h, after stabilization, air was extracted, and the formaldehyde concentration was determined using the acetylacetone spectrophotometric method. For ENF grade, the formaldehyde concentration was ≤0.025 mg / m³. 3 Durability Test: The decorative panels prepared in the examples and comparative examples were cut into flat specimens of 150mm × 150mm, and the edges were sealed with aluminum foil tape. One aging cycle was 24 hours, and the following sequence was followed: High temperature and high humidity stage: 8 hours at 40℃ and 90% relative humidity; Low temperature stage: 8 hours at -20℃, with no humidity control; High temperature drying stage: The specimens were transferred to a preheated drying oven and treated at 70℃ for 6 hours; Equilibrium stage: The specimens were removed and placed under standard atmospheric conditions at 23℃ and 50% relative humidity for 2 hours. The above cycle was repeated until the cumulative treatment time reached 168 hours. After aging, all specimens were placed under standard atmospheric conditions for at least 48 hours to reach equilibrium. The antibacterial performance and aroma sustained-release performance tests were repeated on the aged samples. The test results are shown in Tables 1 and 2 below: Table 1 Table 2 As can be seen from the foregoing, Examples 1-3 all demonstrated excellent comprehensive performance, verifying the reliability and effectiveness of this production process. Both MOR and MOE significantly exceeded national standards, thanks to the synergistic enhancement effect of the modified molecular nest and kaolin in the PMDI adhesive, as well as the optimized hot-pressing process. Antibacterial rates approaching 99% were observed against all tested bacteria, and antiviral rates against H3N2 influenza A virus and EV71 enterovirus were also above 99%. This is attributed to the successful encapsulation and sustained release of the Artemisia argyi essential oil and menthol complex active ingredients by the modified molecular nest, as well as the addition of Pine needle extract to the pretreatment of the decorative panel, forming a multi-layered, multi-component, three-dimensional antibacterial system. Furthermore, a noticeable aroma remained after 90 days, demonstrating the effective encapsulation and controlled sustained release of the active ingredients by the radial gradient pore structure and silane coupling agent grafting. Formaldehyde release was far below ENF levels (≤0.025 mg / m³). 3 The limits are met, satisfying the highest environmental standards. After simulated aging, the antibacterial and aroma functions are still highly retained, indicating that the entire system has strong structural stability and long-lasting function. Moreover, the DPPH free radical scavenging rate exceeds 86.8%, demonstrating high antioxidant performance.

[0036] Comparative Example 1 lacks a porous carrier, resulting in the absence of the core structure of the modified molecular nest, leading to a comprehensive decline in performance. Hydroxyapatite nanorods directly load the active ingredient, but their specific surface area and pore volume are much smaller than those of the porous silica-coated structure, resulting in low loading capacity, lack of gradient release function, and easy leakage. Therefore, antibacterial and aroma properties, especially durability, are significantly deteriorated, and mechanical properties also decrease due to the weakened reinforcement effect of the carrier.

[0037] Comparative Example 2: Empty molecular nests lack active ingredients, resulting in functional loss, but structural functions are partially retained. The molecular nests only have a carrier structure and do not load any active oil phase. Therefore, they are completely odorless and have extremely low antibacterial properties. However, because their porous structure still exists in the adhesive and impregnation layer, they still have a partial enhancing effect on mechanical properties, and their environmental friendliness is unaffected.

[0038] In Comparative Example 3, the ungrafted molecular nests exhibited a failed controlled-release mechanism for the active ingredient, resulting in rapid decay after the initial burst of release. The lack of KH-560 grafting meant the pore openings of the porous structure were not effectively reduced or modified, leading to rapid loss of the loaded active ingredient during processing and initial use. Therefore, while initial antibacterial properties and aroma were acceptable, durability was extremely poor, and performance deteriorated drastically after aging. Premature loss of the active ingredient may also slightly affect the uniformity of the gel layer, resulting in a slight decrease in mechanical properties.

[0039] Comparative Example 4, with its untreated decorative panel, lacks the inherent antibacterial layer, reducing the redundancy and long-term effectiveness of the antibacterial system. The absence of bulk modification of the decorative panel by pine needle extract means the antibacterial properties rely entirely on the modified molecular nests in the surface impregnated paper and adhesives. While the initial antibacterial performance is minimally affected, its durability and comprehensiveness are weaker than in the examples, particularly within the panel itself or at its edges, and after aging and wear.

[0040] Compared to pure PMDI adhesive in Comparative Example 5, the adhesive system has a single function, affecting both mechanical and functional properties. The adhesive lacks modified molecular nests and kaolin, thus losing two key functions: nano-reinforcement and slow-release antibacterial properties in the core layer. This leads to a decrease in mechanical properties (MOR, MOE), formaldehyde release approaching the upper limit of ENF, and the overall antibacterial function of the board relying entirely on the surface layer, resulting in weakened system functionality.

[0041] In Comparative Example 6, the impregnation solution lacked modified molecular nesting, resulting in the finishing layer losing its core sustained-release function and relying solely on melamine resin. This led to a short-lived fragrance and poor antibacterial properties, especially against mold. However, other properties, such as mechanical properties and environmental impact, were not significantly affected.

[0042] Comparative Example 7's untreated base paper affected the bonding and uniformity of the functional layers. Pretreatment of the base paper with Artemisia argyi extract improved the paper's affinity for subsequent active impregnation solutions and added an antibacterial layer. Omitting this step may slightly affect the distribution of the impregnation solution and interfacial bonding, resulting in a slight decrease in aroma persistence, but the impact on other properties is not significant.

[0043] Comparative Example 8, lacking an interface treatment agent, exhibited insufficient interfacial adhesion between the raw board and the impregnated paper, becoming a performance bottleneck. An interface treatment agent containing modified molecular nests is a crucial bridge connecting the core layer and the finishing layer, enhancing interfacial bonding strength. Omitting this agent leads to a significant decrease in mechanical properties, particularly MOR (Mean Oxidation Rate), and may also affect the migration pathways of active ingredients from the core layer to the surface, resulting in reduced aroma persistence.

[0044] In Comparative Example 9, the single essential oil loading resulted in the loss of the synergistic effect, and a decrease in the breadth and persistence of its functions. Using only Artemisia argyi essential oil, its antibacterial spectrum, particularly against mold and mosquito repellent, was weaker than the Artemisia argyi / menthol compound formulation. Experimental data showed that its antibacterial rate, especially against Aspergillus niger, and its aroma persistence were both lower than the examples, demonstrating the advantages of multi-component compound formulations.

[0045] In Comparative Example 10, kaolin was used to replace the modified molecular nest, and ordinary fillers were used to replace the functional carrier, resulting in the loss of the core sustained-release function. Kaolin was only used as an inert filler and lacked the ability to load and sustain-release active ingredients. Therefore, its antibacterial and aroma properties were almost completely lost, similar to Comparative Example 2. Furthermore, due to the different physicochemical properties of kaolin and the modified molecular nest, their modification effects on the adhesive differed, leading to slightly lower mechanical properties and a slightly higher formaldehyde release compared to the examples.

[0046] Finally, it should be noted that the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention; those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention; and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A manufacturing process for decorative panels modified with bioactive ingredients based on molecular nest technology, characterized in that, The steps include: S1. Eucalyptus wood shavings are mixed with an active modified adhesive, and then laid, pre-pressed and hot-pressed to cure, resulting in an active board. S2. After pretreating the decorative base paper with Artemisia argyi extract, impregnate it with an impregnation solution containing modified molecular nests and dry it to obtain active impregnated paper; S3. Spray an interface treatment agent on the surface of the active ingredient board and dry it with hot air, then cover it with the active impregnated paper, and obtain the final product after hot pressing, cooling and trimming.

2. The production process of a decorative panel modified with bioactive ingredients based on molecular nesting technology according to claim 1, characterized in that, The preparation steps of the active ingredient board include: spraying eucalyptus wood shavings with an ethanol solution of pine needle extract and then sealing and stacking them; mixing PMDI adhesive with modified molecular nests and kaolin and ultrasonically dispersing them to obtain a modified adhesive; mixing the stacked eucalyptus wood shavings with the modified adhesive and laying them out, and pre-pressing them at 1.5-2.5 MPa for 30-40 seconds; and hot-pressing the pre-pressed board blank at 185±5℃ and 3.5±0.5 MPa pressure for 25±5 seconds / mm board thickness to obtain the active ingredient board.

3. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 2, characterized in that, The concentration of the ethanol solution of the pine needle extract is 4.5-5.5 wt%, and its dosage is 1-2% of the oven-dry weight of eucalyptus shavings; the sealed stacking time is 20-24 hours.

4. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 2, characterized in that, The weight ratio of PMDI adhesive, modified molecular nests and kaolin is 100:4-6:2-4; the blending is carried out at 900-1000 rpm for 10-15 minutes, and the ultrasonic dispersion is carried out for 10-15 minutes.

5. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 1, characterized in that, The method for preparing the modified molecular nest includes: preparing hydroxyapatite nanorods by a hydrothermal method; mixing the hydroxyapatite nanorods with hexadecyltrimethylammonium bromide, adding tetraethyl orthosilicate, hydrolyzing and condensing under alkaline conditions, and calcining to form a porous material with radially gradient pore sizes; loading a mixture of Artemisia argyi essential oil and menthol into the porous material; and performing surface grafting treatment on the loaded porous material with silane coupling agent KH-560 to obtain the modified molecular nest.

6. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 5, characterized in that, The hydrothermal reaction step includes: mixing equal volumes of 0.4-0.6 mol / L calcium nitrate aqueous solution and 0.2-0.4 mol / L diammonium hydrogen phosphate aqueous solution, adjusting the pH to 10 with ammonia water, hydrothermally reacting at 180-190℃ for 20-24 h, centrifuging, washing, and drying to obtain the final product.

7. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 1, characterized in that, The preparation steps of the active impregnated paper include: 80-90 g / m 2 The base paper is impregnated in an aqueous solution of Artemisia argyi extract at a concentration of 3-5 wt% for 5-7 seconds, and then dried at 100-110℃. Modified molecular nests at a total weight of 5-7% are added to melamine resin and stirred evenly to obtain an impregnation solution. The pretreated base paper is passed through the impregnation solution at a speed of 8-10 m / min for 3-5 seconds, and then dried at 120-130℃ to obtain active impregnated paper with a degree of curing of 65-70%.

8. The production process of a decorative panel modified with bioactive ingredients based on molecular nesting technology according to claim 1, characterized in that, In step S3, the preparation step of the interface treatment agent includes: dispersing 3-5% of the modified molecular nests (by weight of the total waterborne polyurethane emulsion) in an waterborne polyurethane emulsion with a solid content of 35-45%, then adding 0.1-0.3 wt% of a wetting agent, and stirring at 300-400 rpm for 30-40 minutes; the coating amount of the interface treatment agent is 10-12 g / m². 2 .

9. The production process of a decorative panel modified with bioactive ingredients based on molecular nest technology according to claim 1, characterized in that, In step S3, the hot air drying temperature is 70-75℃ and the time is 3-5 minutes; the hot pressing process conditions include: temperature 180-190℃, pressure 2.4-2.8 MPa, and time 40-45 seconds; wherein the pressure control adopts a stepped approach: the pressure rises to 2.4-2.8 MPa within 0-10 seconds, is maintained for 20-25 seconds, and the pressure drops to 1.0 MPa within the last 10 seconds.

10. A decorative panel modified with bioactive ingredients based on molecular nesting technology, characterized in that, It is produced using the production process described in any one of claims 1-9.

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