High-wear-resistance veneer and preparation process thereof

Abstract

The invention belongs to the technical field of veneer preparation, and particularly relates to a high-wear-resistance veneer and a preparation process thereof. The high-wear-resistance veneer comprises a base material layer, a decorative layer and a wear-resistant surface layer, the wear-resistant surface layer contains modified wear-resistant particles, the modified wear-resistant particles are prepared by reaction of wear-resistant particles and a bridging agent, and the bridging agent is synthesized by reaction of 2-phenylbenzimidazole and bromophenylboronic acid; the wear-resistant particles are chemically modified through the bridging agent, so that the wear-resistant particles are connected with the bridging agent through boric acid ester bonds and then react with a resin matrix to form chemical bonds, and the modified wear-resistant particles are firmly anchored in the resin matrix; the dynamic reversible characteristic of boric acid ester bonds at the hot pressing temperature is utilized, so that the wear-resistant particles are directionally migrated to a surface stress concentration area in the hot pressing process, a surface-enriched distribution structure is formed, and the wear resistance of the veneer is remarkably improved; a flexible buffer layer is formed in the bottom layer area, internal stress is effectively released, and surface cracking is avoided.

Description

Technical Field

[0001] This invention belongs to the field of decorative panel preparation technology, specifically relating to a high wear-resistant decorative panel and its preparation process. Background Technology

[0002] With the improvement of people's living standards and the rapid development of the decoration and renovation industry, the demand for decorative panels, as an important material in furniture manufacturing, interior decoration, flooring installation and other fields, is increasing year by year. Decorative panels are usually composed of a substrate layer, a decorative layer and a surface protective layer. Among them, the wear resistance of the surface protective layer directly determines the service life and decorative effect of the decorative panel.

[0003] Currently, the main technical means to improve the wear resistance of decorative panels is to add wear-resistant particles, such as alumina, silicon dioxide, and silicon carbide, to the surface resin. The main methods of adding wear-resistant particles include physical blending and surface modification. Physical blending involves directly mixing the wear-resistant particles with the resin and then coating or impregnating them onto the surface base paper. The process is simple, but it has problems such as uneven dispersion of wear-resistant particles, easy sedimentation, and weak interfacial bonding with the resin matrix, which makes the wear-resistant particles easy to fall off during friction. Surface modification uses coupling agents to treat the surface of wear-resistant particles, such as silane coupling agents, which enhance the interfacial bonding between particles and resin by forming covalent bonds. However, it still has problems such as uneven particle distribution, inability to accumulate on the surface, and low utilization rate of wear-resistant particles.

[0004] Furthermore, during the hot-pressing curing process, the resin curing shrinkage is mismatched with the thermal expansion coefficient of the substrate, which easily generates internal stress, leading to micro-cracks on the surface and affecting the appearance quality and service life of the product. Under hot and cold cycling conditions, the internal stress is further aggravated, the micro-cracks expand, and eventually the decorative panel cracks and fails. How to effectively alleviate internal stress and avoid surface cracking while improving wear resistance is a technical problem that urgently needs to be solved in this field.

[0005] Therefore, developing a decorative panel with high wear resistance, excellent interfacial bonding strength, and good crack resistance, as well as its preparation process, has significant practical implications and broad application prospects. Summary of the Invention

[0006] The purpose of this invention is to provide a high wear-resistant decorative panel and its preparation process to solve the above-mentioned technical problems.

[0007] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows: A high wear-resistant decorative panel comprises, from bottom to top, a substrate layer, a decorative layer, and a wear-resistant surface layer. The wear-resistant surface layer contains modified wear-resistant particles, which are obtained by reacting the hydroxyl groups on the surface of the wear-resistant particles with a bridging agent via borate ester bonds. The bridging agent is obtained by reacting 2-phenylbenzimidazole and bromophenylboronic acid.

[0008] A process for preparing a highly wear-resistant decorative panel includes the following steps: S1. Mix the resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, and disperse them at 1200~1500 rpm for 20~40 min using a high-speed disperser to obtain a wear-resistant resin liquid. S2. Take the surface paper, immerse it in the wear-resistant resin liquid for 30~60s, apply 115~125% glue, and dry it in three stages to obtain the wear-resistant surface layer. S3. The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top, hot-pressed and cured for 24~48 hours to obtain a high wear-resistant decorative panel.

[0009] As a further improvement, the preparation method of the modified wear-resistant particles is as follows: take wear-resistant particles, disperse them in anhydrous ethanol, and sonicate them; add a bridging agent, stir evenly, and heat to 60~65℃ to react for 1~1.5h; after the reaction is completed, centrifuge, collect the precipitate, wash with anhydrous ethanol, and vacuum dry to obtain modified wear-resistant particles.

[0010] As a further improvement, the preparation method of the bridging agent is as follows: under a nitrogen atmosphere, 2-phenylbenzimidazole, bromophenylboronic acid, cuprous iodide, cesium carbonate and N,N-dimethylformamide are mixed and stirred until homogeneous, and then reacted at 110~130℃ for 8~12h; after the reaction is completed, the mixture is cooled to room temperature, the insoluble matter is removed by filtration, the filtrate is purified by column chromatography, the components are collected, concentrated under reduced pressure, and dried under vacuum to obtain the bridging agent.

[0011] As a further improvement, the mass ratio of the wear-resistant particles to the bridging agent is 100:1~5.

[0012] As a further improvement, the wear-resistant particles are selected from any one of alumina, silicon dioxide, silicon carbide, or zirconium oxide.

[0013] As a further improvement, the molar ratio of 2-phenylbenzimidazole, bromophenylboronic acid, cuprous iodide and cesium carbonate is 1:1.1~1.2:0.03~0.08:1.5~2.5; and the bromophenylboronic acid is any one of 2-bromophenylboronic acid, 3-bromophenylboronic acid or 4-bromophenylboronic acid.

[0014] As a further improvement, the resin is selected from any one of epoxy resin, melamine-formaldehyde resin, or phenolic resin; wherein the epoxy resin is a liquid bisphenol A type epoxy resin; the melamine-formaldehyde resin is a water-soluble or alcohol-soluble liquid resin; and the phenolic resin is a thermosetting methyl phenolic liquid resin.

[0015] As a further improvement, in step S1, the mass ratio of the resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole is 100:10~30:30~50:70~90:0.8~2.0.

[0016] As a further improvement, in step S2, the three-stage drying process is: 80~90℃ for 60s, 100~110℃ for 120s, and 120~130℃ for 60s; in step S3, the hot pressing conditions are: temperature 160~170℃, pressure 3.0~3.5MPa, time 240~300s, and the cooling method is: pressure holding and cooling to below 60℃ and then depressurizing.

[0017] Due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows: 1. The high wear-resistant decorative panel and its preparation process provided by this invention chemically modify wear-resistant particles using a bridging agent. The wear-resistant particles are connected to the bridging agent through borate ester bonds, and then react with the resin matrix to form stable chemical bonds, firmly anchoring the modified wear-resistant particles in the resin matrix. The borate ester bonds are dynamically reversible at the hot-pressing temperature, causing the wear-resistant particles to migrate directionally to the stress concentration area on the surface during the hot-pressing process, forming a surface-enriched distribution structure. This concentrates the wear-resistant particles on the surface where wear is most likely to occur, significantly improving the wear resistance of the decorative panel. The wear-resistant particles are sparse in the bottom layer, and the resin crosslinking density is relatively low, forming a flexible buffer layer that effectively releases the internal stress generated during hot-pressing curing and thermal cycling, preventing surface cracking of the decorative panel. The decorative panel exhibits excellent crack resistance stability. 2. The wear-resistant particles of this invention can be selected from a variety of materials such as alumina, silicon dioxide, silicon carbide, and zirconium oxide. The surface of these particles all has hydroxyl groups that can react with the boric acid groups in the bridging agent to form borate ester bonds. The resin matrix can be selected from a variety of resins such as epoxy resin, melamine-formaldehyde resin, and phenolic resin, all of which can chemically react with the bridging agent. Therefore, the technical solution of this invention has good universality and a wide range of applications, and appropriate materials and process parameters can be selected according to different application scenarios. Attached Figure Description

[0018] Figure 1 These are ATR-FTIR images of the bridging agent prepared in Example 1; Figure 2 This is an ATR-FTIR image of the modified wear-resistant particles prepared in Example 1. Detailed Implementation

[0019] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. 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. Where specific conditions are not specified in the embodiments, conventional conditions or manufacturer's conditions shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0020] In the embodiments and comparative examples of the present invention, the surface base paper is a highly permeable base paper used for resin impregnation, with a basis weight of 30-50 g / m², and its main component is cellulose fiber; the decorative layer is a printed decorative base paper with a decorative effect, with a basis weight of 60-120 g / m², and the surface is printed with wood grain, stone grain or other decorative patterns, which can be pre-impregnated with melamine-formaldehyde resin, and the pre-curing degree is controlled at 50-70%; the substrate layer is a wood-based panel or solid wood panel, selected from medium-density fiberboard, high-density fiberboard, particleboard, plywood, and oriented strand board; the specific specifications and parameters of the above materials are only for illustrative purposes and are not intended to limit the present invention. Those skilled in the art can select other materials that meet the requirements according to actual needs, without affecting the implementation of the technical solution of the present invention and the determination of the scope of protection.

[0021] Example 1: A process for preparing a high wear-resistant decorative panel, comprising the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.11 mol of 3-bromophenylboronic acid, 0.005 mol of cuprous iodide, 0.2 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 120 °C and reacted for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. The chemical formula for the reaction of 3-bromophenylboronic acid and 2-phenylbenzimidazole is as follows: ; The ATR-FTIR image of the bridging agent prepared in this embodiment is as follows: Figure 1 As shown, Figure 1 The display shows 3350cm. -1 A strong and broad absorption peak appears at 3050 cm⁻¹, which is attributed to the OH group in the boric acid group; -1 The peak appearing at 1650 cm⁻¹ belongs to CH on the aromatic ring; -1 and 1450cm-1 The absorption peak at 750 cm⁻¹ is attributed to the imidazole group; -1 and 690cm -1 The absorption peak at 550 cm⁻¹ is attributed to CH on the aromatic ring; in addition, the absorption peak at 550 cm⁻¹ is also attributed to CH on the aromatic ring. -1 The complete disappearance of the nearby characteristic absorption peaks indicates the absence of bromine atoms; these results indicate that 3-bromophenylboronic acid and 2-phenylbenzimidazole have reacted successfully. 2. Preparation of modified wear-resistant particles: Take 100g of alumina particles (average particle size 5μm), disperse them in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 3.0g of bridging agent, stir evenly, heat to 65℃, mechanically stir, and react for 1.5h; after the reaction, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate three times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; the chemical formula for the reaction of alumina particles and bridging agent is as follows: ; The ATR-FTIR image of the modified wear-resistant particles prepared in this embodiment is as follows: Figure 2 As shown; Figure 2 The display shows 3390cm -1 The characteristic absorption of OH is located at 3050 cm⁻¹. -1 The sharp peak at 1620 cm⁻¹ is attributed to the CH stretching vibration of the aromatic ring in the bridging agent. -1 and 1450cm -1 The absorption peak at 1340 cm⁻¹ is attributed to the skeletal vibration of the imidazole group in the bridging agent; -1 The absorption peak at 500 cm⁻¹ is attributed to the stretching vibration of BO, proving the formation of a boronic ester bond; while the absorption peak at 500 cm⁻¹ is attributed to the stretching vibration of BO, proving the formation of a boronic ester bond; -1 The broad absorption band in the vicinity is an intrinsic characteristic of alumina; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:20:40:80:1, stirred and mixed evenly, and dispersed at 1400rpm for 30min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 60 seconds, apply 120% glue, and dry it in a three-stage oven: first at 85℃ for 60 seconds, then at 110℃ for 120 seconds, and finally at 130℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 170℃, a pressure of 3.2MPa and a time of 270s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the high wear-resistant decorative panel.

[0022] Example 2: A process for preparing a high wear-resistant decorative panel, comprising the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.12 mol of 3-bromophenylboronic acid, 0.008 mol of cuprous iodide, 0.25 mol of cesium carbonate, and 150 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 130 °C and reacted for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 55 °C for 10 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of alumina particles (average particle size of 5μm), disperse them in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 5.0g of bridging agent, stir evenly, heat to 60℃, mechanically stir, and react for 1.0h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:10:50:70:2, stirred and mixed evenly, and dispersed at 1200rpm for 40min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 45 seconds, apply 115% glue, and perform three-stage oven drying: first, treat at 90℃ for 60 seconds, then at 100℃ for 120 seconds, and finally at 120℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 160℃, a pressure of 3.5MPa and a time of 240s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the high wear-resistant decorative panel.

[0023] Example 3: A process for preparing a high wear-resistant decorative panel, comprising the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.115 mol of 2-bromophenylboronic acid, 0.003 mol of cuprous iodide, 0.15 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 110 °C and reacted for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of silica (average particle size of 5μm), disperse it in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 1.0g of bridging agent, stir evenly, heat to 63℃, mechanically stir, and react for 1.5h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, water-soluble melamine-formaldehyde resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:30:30:90:0.8, stirred and mixed evenly, and dispersed at 1500 rpm for 20 min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 30 seconds, apply 125% glue, and dry it in a three-stage oven: first at 80℃ for 60 seconds, then at 105℃ for 120 seconds, and finally at 125℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 165℃, a pressure of 3.0MPa and a time of 300s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the high wear-resistant decorative panel.

[0024] Example 4: A process for preparing a high wear-resistant decorative panel, comprising the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.115 mol of 4-bromophenylboronic acid, 0.003 mol of cuprous iodide, 0.15 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 110 °C and reacted for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of silicon carbide (average particle size of 5μm), disperse it in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 1.0g of bridging agent, stir evenly, heat to 63℃, mechanically stir, and react for 1.5h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, alcohol-soluble melamine-formaldehyde resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:30:30:90:0.8, stirred and mixed evenly, and dispersed at 1500 rpm for 20 min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 30 seconds, apply 125% glue, and dry it in a three-stage oven: first at 80℃ for 60 seconds, then at 105℃ for 120 seconds, and finally at 125℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 165℃, a pressure of 3.0MPa and a time of 300s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 36 hours (temperature 25℃, relative humidity 50%) to obtain the high wear-resistant decorative panel.

[0025] Example 5: A process for preparing a high wear-resistant decorative panel, comprising the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.115 mol of 3-bromophenylboronic acid, 0.003 mol of cuprous iodide, 0.15 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 110 °C and reacted for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of zirconium oxide (average particle size of 5μm), disperse it in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 1.0g of bridging agent, stir evenly, heat to 63℃, mechanically stir, and react for 1.5h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, thermosetting phenolic liquid resin, modified wear-resistant particles, propylene glycol methyl ether, methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:30:30:90:0.8, stirred and mixed evenly, and dispersed at 1500 rpm for 20 min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 30 seconds, apply 125% glue, and dry it in a three-stage oven: first at 80℃ for 60 seconds, then at 105℃ for 120 seconds, and finally at 125℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 165℃, a pressure of 3.0MPa and a time of 300s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 48 hours (temperature 25℃, relative humidity 50%) to obtain the high wear-resistant decorative panel.

[0026] Comparative Example 1: A preparation process for a high wear-resistant decorative panel, differing from Example 1 in that the wear-resistant particles are not modified, and includes the following steps: 1. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:20:40:80:1, stirred and mixed evenly, and dispersed at 1400rpm for 30min using a high-speed disperser to obtain wear-resistant resin liquid; 2. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 60 seconds, apply 120% glue, and dry it in a three-stage oven: first at 85℃ for 60 seconds, then at 110℃ for 120 seconds, and finally at 130℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 3. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 170℃, a pressure of 3.2MPa and a time of 270s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the decorative panel.

[0027] Comparative Example 2: A preparation process for a high wear-resistant decorative panel, differing from Example 1 in that it uses KH-560 modified wear-resistant particles, including the following steps: 1. Preparation of silane hydrolysate: Take 3g of γ-glycidoxypropyltrimethoxysilane (KH-560), add 100mL of anhydrous ethanol, stir to dissolve, slowly add 5mL of deionized water, adjust the pH to 5.0 with glacial acetic acid, stir and hydrolyze at 25℃ for 30min to obtain silane hydrolysate. 2. Preparation of modified wear-resistant particles: Take 100g of alumina particles (average particle size of 5μm), disperse them in 500mL of anhydrous ethanol, and ultrasonically disperse for 30min; add silane hydrolysate, stir evenly, heat to 80℃, and mechanically stir for 2h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain KH-560 modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), KH-560 modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:20:40:80:1, stirred and mixed evenly, and dispersed at 1400rpm for 30min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 60 seconds, apply 120% glue, and dry it in a three-stage oven: first at 85℃ for 60 seconds, then at 110℃ for 120 seconds, and finally at 130℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 170℃, a pressure of 3.2MPa and a time of 270s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the decorative panel.

[0028] Comparative Example 3: A preparation process for a high-wear-resistant decorative panel, differing from Example 1 in that, in preparing the high-wear-resistant decorative panel, room-temperature pressing followed by high-temperature curing is used instead of hot pressing, including the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.11 mol of 3-bromophenylboronic acid, 0.005 mol of cuprous iodide, 0.2 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 120 °C and reacted for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of alumina particles (average particle size of 5μm), disperse them in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 3.0g of bridging agent, stir evenly, heat to 65℃, mechanically stir, and react for 1.5h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:20:40:80:1, stirred and mixed evenly, and dispersed at 1400rpm for 30min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 60 seconds, apply 120% glue, and dry it in a three-stage oven: first at 85℃ for 60 seconds, then at 110℃ for 120 seconds, and finally at 130℃ for 60 seconds; after drying, the volatile matter at the outlet is controlled at 5.0±0.5%, and the pre-curing degree is 45±5%, thus obtaining the wear-resistant surface layer; 5. Preparation of high wear-resistant decorative panels: The substrate layer, decorative layer, and wear-resistant surface layer are layered from bottom to top and fed into a cold press. The pressing is carried out at room temperature under the following conditions: pressing pressure of 3.2 MPa, pressing time of 30 min, and temperature of 25℃. After pressing, the panels are removed from the cold press and placed in a forced-air oven for high-temperature curing under the following conditions: curing temperature of 170℃ and curing time of 6 h. After curing, the panels are removed, allowed to cool naturally to room temperature, and then stacked for curing for 24 h (temperature of 25℃ and relative humidity of 50%) to obtain the decorative panels.

[0029] Comparative Example 4: A preparation process for a high wear-resistant decorative panel, differing from Example 1 in that a three-stage drying process is not used when preparing the wear-resistant surface layer, and includes the following steps: 1. Preparation of bridging agent: Under a nitrogen atmosphere, 0.1 mol of 2-phenylbenzimidazole, 0.11 mol of 3-bromophenylboronic acid, 0.005 mol of cuprous iodide, 0.2 mol of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a three-necked flask. After stirring and mixing, the mixture was heated to 120 °C and reacted for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the insoluble matter was removed by filtration. The mixture was then purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 10:1). The target component was collected, concentrated under reduced pressure, and dried under vacuum at 50 °C for 12 h to obtain the bridging agent. 2. Preparation of modified wear-resistant particles: Take 100g of alumina particles (average particle size of 5μm), disperse them in 500mL of anhydrous ethanol, ultrasonically disperse for 30min, add 3.0g of bridging agent, stir evenly, heat to 65℃, mechanically stir, and react for 1.5h; after the reaction is completed, centrifuge at 4000rpm for 10min, discard the supernatant, collect the precipitate, wash the precipitate 3 times with anhydrous ethanol, place the washed precipitate in a vacuum drying oven, and dry at 80℃ for 12h to obtain modified wear-resistant particles; 3. Preparation of wear-resistant resin liquid: In a 5L stainless steel container, liquid bisphenol A type epoxy resin (epoxy value 0.51eq / 100g), modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole are mixed in a mass ratio of 100:20:40:80:1, stirred and mixed evenly, and dispersed at 1400rpm for 30min using a high-speed disperser to obtain wear-resistant resin liquid; 4. Preparation of wear-resistant surface layer: Take the surface base paper, immerse it in wear-resistant resin liquid for 60s, apply 120% glue, and dry it in an oven under the following conditions: drying temperature of 110℃ and drying time of 240s; control the volatile matter at the outlet to 5.0±0.5% and the pre-curing degree to 45±5% to obtain the wear-resistant surface layer. 5. Preparation of high wear-resistant decorative panel: The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top and hot-pressed. A single-layer hot press is used for hot pressing at a temperature of 170℃, a pressure of 3.2MPa and a time of 270s. The cooling method is to hold the pressure and cool down to 60℃ before releasing the pressure. The pressed decorative panel is then removed and stacked for curing for 24 hours (temperature 25℃, relative humidity 50%) to obtain the decorative panel.

[0030] Performance testing 1. Abrasion resistance test The abrasion resistance test was conducted on the samples prepared in Examples 1-2 and Comparative Examples 1-4, and the results were determined in accordance with the national standard GB / T 17657-2022 "Test Methods for Physical and Chemical Properties of Wood-based Panels and Decorative Wood-based Panels".

[0031] Cut the decorative panels from Examples 1-2 and Comparative Examples 1-4 into 100mm × 100mm specimens, with 3 specimens per group. Place the specimens in an environment with a temperature of 25℃ and a relative humidity of 50% for 16 hours. Drill an 8mm diameter mounting hole in the center of each specimen and mount it on the abrasion tester turntable. Use an H-22 grinding wheel to perform the abrasion test and record the total number of revolutions until the abrasion layer on the surface of the specimen is worn through to reveal the decorative layer. Measure the initial abrasion value, i.e., after 100 revolutions, and weigh the specimen for mass loss. The mass loss value is the abrasion value (mg / 100r).

[0032] The experimental results are shown in Table 1: Table 1 Results of abrasion resistance test of the film Test sample Wear revolutions (r) Wear value (mg / 100r) Example 1 6500 35 Example 2 6300 37 Comparative Example 1 3600 93 Comparative Example 2 4800 51 Comparative Example 3 4200 72 Comparative Example 4 5000 45 As can be seen from Table 1, the wear resistance of the high wear-resistant decorative panels prepared in Examples 1 and 2 is significantly better than that of Comparative Examples 1 to 4, indicating that the decorative panels prepared by the present invention have excellent wear resistance.

[0033] Comparative Example 1 used unmodified wear-resistant particles, with a wear rotation speed lower than that of Examples 1 and 2, but a wear value higher than that of Examples 1 and 2. The results show that the interfacial bonding force between the unmodified wear-resistant particles and the resin matrix is ​​weak, and they are easy to fall off during friction, thus failing to effectively exert their wear-resistant effect. Comparative Example 2 used wear-resistant particles modified with silane coupling agents. Although the wear resistance was improved compared to Comparative Example 1, it was still inferior to Examples 1 and 2, indicating that the irreversible covalent bonds of the silane coupling agent could not achieve the gradient migration of particles, and the wear-resistant particles failed to accumulate on the surface, resulting in low wear resistance efficiency. Comparative Example 3 used room temperature pressing followed by high temperature curing, indicating that without the synergistic effect of hot pressing, although the borate ester bonds could be sufficiently broken during subsequent high temperature curing, without pressure drive, the particles could not migrate in a direction to form a gradient distribution, resulting in limited improvement in wear resistance. Comparative Example 4 used a single constant temperature drying process instead of a three-stage gradient drying process, indicating that the three-stage gradient drying process plays an important role in ensuring uniform resin distribution and avoiding local defects.

[0034] 2. Stability Test The stability of the samples prepared in Examples 1-2 and Comparative Examples 1-4 was tested by performing a thermal cycling test. The decorative panels of Examples 1-2 and Comparative Examples 1-4 were cut into 150mm×150mm specimens. The specimens were placed in a low-temperature test chamber and kept at -20℃ for 4 hours. After being removed, they were immediately placed in a high-temperature test chamber and kept at 60℃ for 2 hours. The alternation of hot and cold temperatures constituted one cycle. After the 5th cycle, the specimens were removed and observed under a magnifying glass in a well-lit area to check for microcracks on the surface. The number of cycles in which the first visible microcrack appeared was recorded. At least three specimens were tested in each group, and the average value was taken.

[0035] The experimental results are shown in Table 2: Table 2. Results of stability test experiments Test sample Number of microcracks Example 1 >30 times Example 2 >30 times Comparative Example 1 19 times Comparative Example 2 24 times Comparative Example 3 18 times Comparative Example 4 19 times As can be seen from Table 2, the high wear-resistant decorative panels prepared in Examples 1 and 2 did not show microcracks after 20 cycles in the hot and cold cycling test, demonstrating excellent crack resistance stability.

[0036] Comparative Example 1 developed microcracks after 19 cycles because the interface between the modified wear-resistant particles and the resin matrix was weak, and thermal stress easily caused cracks at the interface. Comparative Example 2 showed better crack resistance than Comparative Example 1, indicating that silane modification can enhance the interface bonding, but it is still inferior to the modification scheme of this invention. Comparative Example 3 developed microcracks after 18 cycles because the resin curing shrinkage during the high-temperature curing process after room temperature pressing was not compensated by pressure, resulting in large internal stress and easy cracking. Comparative Example 4 used a single constant temperature drying process, which reduced the uniformity of resin distribution and created stress concentration points in local areas, leading to decreased stability.

[0037] 3. Adhesion test Adhesion tests were conducted using samples prepared in Examples 1-2 and Comparative Examples 1-4, referring to the national standard GB / T9286-2021 "Cross-cut Test for Paints and Varnishes". The following experiments were performed: The decorative panels of Examples 1-2 and Comparative Examples 1-4 were cut into 250mm × 100mm specimens, with 3 specimens per group; the specimens were placed in an environment with a temperature of 23℃ and a relative humidity of 50% for 16 hours; using a single-edged cutting tool, with the blade perpendicular to the surface of the specimen, six parallel cutting lines were made at a uniform cutting rate, with a spacing of 2mm, and the cuts penetrated to the surface of the substrate; the above operation was repeated, and six more parallel cuts were made, intersecting the original cuts at 90° angles to form a grid pattern.

[0038] In a well-lit environment, use a magnifying glass to observe the cut area of ​​the sample and observe it from different directions, and rate the cut area of ​​the sample.

[0039] The ratings were conducted according to the grading table in the national standard GB / T 9286-2021, where level 0 represents the best performance and level 5 represents the worst performance. The rating results are shown in Table 3. Table 3 Adhesion test results Test sample Measurement and rating Example 1 Level 0 Example 2 Level 0 Comparative Example 1 Level 2 Comparative Example 2 Level 1 Comparative Example 3 Level 3 Comparative Example 4 Level 1 As shown in Table 3, the adhesion test rating of the high wear-resistant decorative panels prepared in Examples 1 and 2 was 0, which is the best level. The cut edges were completely smooth and there was no peeling. The adhesion rating of Comparative Example 1 was 2, with coating peeling at the cut intersection, affecting an area of ​​about 15%. This was because the unmodified wear-resistant particles and the resin matrix had weak interfacial bonding due to physical adsorption. The adhesion rating of Comparative Example 2 was 1, with a few cracks at the cut edges, affecting an area of ​​about 5%. This indicates that although silane modification can form covalent bonds, the improved adhesion performance is still not as good as the modification scheme of this invention. The adhesion rating of Comparative Example 3 was 3, with severe coating peeling. This was because the resin curing shrinkage during the high-temperature curing process after room temperature pressing was not compensated by pressure, resulting in a decrease in bonding strength. This result fully demonstrates the necessity of the hot pressing process. The adhesion rating of Comparative Example 4 was 1, indicating that although the single constant temperature drying affected the uniformity of resin distribution, its impact on adhesion was smaller than that of the pressing process. However, it was still inferior to the examples, indicating that the three-stage drying process can bring out the best properties of the wear-resistant layer.

[0040] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A high wear-resistant decorative panel, comprising, from bottom to top, a substrate layer, a decorative layer, and a wear-resistant surface layer, characterized in that, The wear-resistant surface layer contains modified wear-resistant particles, which are obtained by reacting the hydroxyl groups on the surface of the wear-resistant particles with a bridging agent through borate ester bonds. The bridging agent is obtained by reacting 2-phenylbenzimidazole and bromophenylboronic acid.

2. A manufacturing process for the high wear-resistant decorative panel according to claim 1, characterized in that, Includes the following steps: S1. Mix the resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, and disperse them at 1200~1500 rpm for 20~40 min using a high-speed disperser to obtain a wear-resistant resin liquid. S2. Take the surface paper, immerse it in the wear-resistant resin liquid for 30~60s, apply 115~125% glue, and dry it in three stages to obtain the wear-resistant surface layer. S3. The substrate layer, decorative layer and wear-resistant surface layer are stacked from bottom to top, hot-pressed and cured for 24~48 hours to obtain a high wear-resistant decorative panel.

3. The preparation process of the high wear-resistant decorative panel according to claim 2, characterized in that, The modified wear-resistant particles are prepared as follows: wear-resistant particles are taken, dispersed in anhydrous ethanol, and sonicated; a bridging agent is added, stirred evenly, and heated to 60~65℃ for 1~1.5h; after the reaction is completed, the particles are centrifuged, the precipitate is collected, washed with anhydrous ethanol, and vacuum dried to obtain the modified wear-resistant particles.

4. The preparation process of the high wear-resistant decorative panel according to claim 3, characterized in that, The bridging agent is prepared as follows: 2-phenylbenzimidazole, bromophenylboronic acid, cuprous iodide, cesium carbonate and N,N-dimethylformamide are mixed under a nitrogen atmosphere and stirred until homogeneous. The mixture is then reacted at 110-130℃ for 8-12 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered to remove insoluble matter, and the filtrate is purified by column chromatography. The components are collected, concentrated under reduced pressure, and dried under vacuum to obtain the bridging agent.

5. The preparation process of the high wear-resistant decorative panel according to claim 3, characterized in that, The mass ratio of the wear-resistant particles to the bridging agent is 100:1~5.

6. The preparation process of the high wear-resistant decorative panel according to claim 3, characterized in that, The wear-resistant particles are selected from any one of alumina, silicon dioxide, silicon carbide, or zirconium oxide.

7. The preparation process of the high wear-resistant decorative panel according to claim 4, characterized in that, The molar ratio of 2-phenylbenzimidazole, bromophenylboronic acid, cuprous iodide and cesium carbonate is 1:1.1~1.2:0.03~0.08:1.5~2.5; the bromophenylboronic acid is any one of 2-bromophenylboronic acid, 3-bromophenylboronic acid or 4-bromophenylboronic acid.

8. The preparation process of the high wear-resistant decorative panel according to claim 2, characterized in that, The resin is selected from any one of epoxy resin, melamine-formaldehyde resin, or phenolic resin; wherein the epoxy resin is a liquid bisphenol A type epoxy resin; the melamine-formaldehyde resin is a water-soluble or alcohol-soluble liquid resin; and the phenolic resin is a thermosetting methyl phenolic liquid resin.

9. The preparation process of the high wear-resistant decorative panel according to claim 2, characterized in that, In step S1, the mass ratio of the resin, modified wear-resistant particles, propylene glycol methyl ether, methyl hexahydrophthalic anhydride and 2-ethyl-4-methylimidazole is 100:10~30:30~50:70~90:0.8~2.

0.

10. The preparation process of the high wear-resistant decorative panel according to claim 2, characterized in that, In step S2, the three-stage drying process is: 80~90℃ for 60s, 100~110℃ for 120s, and 120~130℃ for 60s. In step S3, the hot pressing conditions are: temperature 160~170℃, pressure 3.0~3.5MPa, time 240~300s, and the cooling method is: pressure holding and cooling to below 60℃ and then depressurizing.

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