Waterproof and scratch-resistant smoke-proof floor and preparation method thereof

Abstract

This invention discloses a waterproof, scratch-resistant, and smoke-resistant flooring and its preparation method. The flooring includes a substrate and, sequentially disposed on the surface of the substrate, an interpenetrating reinforcement layer, an anti-smoke and anti-smoke surface layer. The interpenetrating reinforcement layer is constructed with aliphatic polyurethane diacrylate, bisphenol A type epoxy acrylate, and a silane coupling agent to form an interfacial anchor. The interpenetrating reinforcement layer contains methacrylated polyhedral oligomeric silsesquioxane, 10-30 nm colloidal silica, and tetraethyl orthosilicate-catalyzed partial condensation silica sol, and forms a dense interpenetrating structure with hexagonal boron nitride. The anti-smoke and anti-smoke surface layer contains perhydropolysilazane, nano-silica, and fluorosilane, which forms a dense silica structure layer through hydrothermal conversion. The method includes substrate activation, sequential coating of the three layers with UV curing, graded curing, and oxygen control in an inert atmosphere, followed by two stages of controlled water activation post-treatment, achieving a balance between scratch resistance, waterproof durability, and smoke-resistant stability.

Description

Technical Field

[0001] This invention relates to the technical field of flooring, and in particular to a waterproof, scratch-resistant, smoke-proof and heat-resistant flooring and its preparation method. Background Technology

[0002] Existing wear-resistant and decorative coatings for floor surfaces mostly employ UV-cured acrylic systems or composite systems of organic resins and inorganic fillers. For example, Chinese Patent Publication No. CN102167388A discloses a UV-cured wear-resistant coating for floor surfaces, which improves surface hardness and scratch resistance by increasing crosslinking density and adding wear-resistant fillers; Chinese Patent Publication No. CN103627786A discloses a wear-resistant floor coating structure that enhances wear resistance and adhesion through multi-layer coating; and Chinese Patent Publication No. CN104726215A discloses a scheme to introduce silicone resin components into the floor surface to improve heat resistance.

[0003] The aforementioned technical solutions improve performance by increasing hardness, enhancing adhesion, or improving heat resistance, but primarily focus on optimizing a single property. While increasing the crosslinking density and inorganic filler content can enhance scratch resistance, it can also lead to whitening, blistering, or cracking due to localized thermal shock under conditions of instantaneous high-temperature contact, such as with cigarette butts. Introducing heat-resistant resins or reducing system rigidity to mitigate high-temperature shock may result in decreased scratch resistance or insufficient long-term waterproof durability. Furthermore, if there is a lack of stable and continuous structural transitions between multilayer structures, interlayer failure is likely to occur under the combined effects of thermal shock and mechanical stress.

[0004] Therefore, there is still a key technical problem that needs to be solved in the existing technology, namely, how to simultaneously take into account scratch resistance, waterproof durability, and anti-burn stability under short-term high-temperature contact with cigarette butts in the same floor surface system, so that the multi-layer structure can maintain the integrity of the overall structure under thermal shock and mechanical load. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned problems existing in the prior art and provide a waterproof, scratch-resistant, and smoke-proof floor and its preparation method. By constructing a multi-layer composite coating system with structural gradient, the floor surface maintains high scratch resistance, high wear resistance, and excellent waterproof durability, while being less prone to burn marks, blistering, or interlayer failure under instantaneous high-temperature contact conditions such as cigarette butts, thereby improving the overall stability and long-term service reliability of the floor in complex usage environments.

[0006] To achieve the above objectives, the first aspect of the present invention provides a waterproof, scratch-resistant, and smoke-proof floor, comprising a substrate and a locking layer, an interpenetrating reinforcement layer, and a smoke-proof surface layer sequentially disposed on the surface of the substrate.

[0007] The enhancement layer mainly comprises:

[0008] Methacrylated polyhedral oligomeric silsesquioxanes containing octahedral cage-like siloxane structures;

[0009] Colloidal silica with an average particle size of 10–30 nm;

[0010] Partially polycondensed silica sol formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate;

[0011] The anti-smoke and heat-resistant surface layer mainly comprises:

[0012] Hydrogenated polysilazane containing Si-H and Si-N bonds.

[0013] This invention, through the synergistic construction of an adhesion layer, an interpenetrating reinforcement layer, and a smoke-resistant surface layer, forms a gradient composite system on the floor surface, consisting of an organic cross-linked network, a silicon-oxygen inorganic network, and a convertible silicon-nitrogen structure. The three layers are continuously connected in chemical structure and network morphology, thus exhibiting self-reinforcing behavior under mechanical and thermal shock conditions.

[0014] An effective interfacial bond is established between the substrate and the reinforcing layer through a locking layer, which can significantly improve the interlayer peel strength and impact resistance, and avoid delamination, warping or bulging caused by temperature and humidity cycles or mechanical loads, thereby improving the long-term stability and service reliability of the overall structure.

[0015] The interpenetrating polymeric polyhedral oligomeric silsesquioxane (POSS) containing an octahedral cage-like silicon-oxygen structure is introduced into the interpenetrating polymeric layer. Its inorganic Si-O framework possesses a rigid structure approaching that of nanoscale silica cores, while the surrounding organic polymerizable groups can participate in free radical polymerization or crosslinking reactions, thereby forming hybrid crosslinking nodes with organic-inorganic covalent bonds within the organic polymer network. This structure improves crosslinking density and modulus, and due to the uniform dispersion of the cage-like rigid units, it significantly enhances scratch resistance and surface deformation resistance, while simultaneously reducing the coefficient of thermal expansion and improving dimensional stability.

[0016] Colloidal silica with an average particle size of 10–30 nm can form a high specific surface area reinforcing phase in the reinforcing layer. It can improve the density and hardness of the system through physical filling and interfacial interaction, and enhance the crack deflection and energy dissipation mechanism through nanoscale dispersion, thereby improving wear resistance and scratch resistance.

[0017] The partially condensed silica sol formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate can further condense during curing to form a continuous Si-O-Si network, which forms an interpenetrating or semi-interpenetrating structure with POSS and nano-SiO2. This sol-gel system fills pores and constructs an inorganic network framework at the microscopic level, resulting in a highly dense inorganic enriched structure in the reinforcing layer. This significantly reduces the diffusion rate of moisture and contaminants, thereby improving waterproofing, seepage prevention, and chemical corrosion resistance. Simultaneously, this inorganic network enhances surface hardness and heat resistance, providing a stable support interface for the upper smoke-resistant surface layer.

[0018] The anti-scalding surface layer uses a perhydropolysilazane containing Si-H and Si-N bonds, which forms a dense silicon-oxygen structure under high temperature and humidity. This surface layer has a high thermal decomposition temperature and excellent thermal shock resistance. Under short-term high-temperature contact with cigarette butts (typically reaching local temperatures of 300–700°C), it is not prone to carbonization, blistering, or leaving burn marks, thus significantly improving its anti-scalding performance.

[0019] Meanwhile, the inorganic dense layer formed by the conversion of perhydropolysilazane has extremely low water vapor permeability and excellent weather resistance, which can further improve the surface's waterproof and anti-fouling properties, and enhance wear resistance and scratch resistance through a high-hardness ceramic layer. It forms a chemical or physical cross-linking interface with the underlying reinforcing layer, which can prevent coating peeling and cracking, and ensure structural integrity under long-term use.

[0020] Preferably, the locking layer comprises at least the following components by weight:

[0021] 45-55 parts of aliphatic polyurethane diacrylate;

[0022] 12-20 parts of bisphenol A type epoxy acrylate;

[0023] 4 to 8 parts of 3-methacryloyloxypropyltrimethoxysilane.

[0024] Preferably, the interpenetrating reinforcement layer comprises at least the following components by weight:

[0025] 15-22 parts of aliphatic polyurethane diacrylate;

[0026] 10-15 parts of polyester diacrylate;

[0027] 6-10 parts of methacrylated polyhedral oligomeric silsesquioxane containing an octahedral cage-like silicon-oxygen structure;

[0028] 8-15 parts of colloidal silica;

[0029] 2-5 parts of partially polycondensed silica sol formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate;

[0030] 1.5 to 3.5 parts of hexagonal boron nitride flake particles.

[0031] Preferably, the anti-smoke and anti-scalding surface layer comprises at least the following components by weight:

[0032] 22-30 parts of aliphatic polyurethane diacrylate;

[0033] 15-22 parts of hydrogenated polysilazane;

[0034] 4-8 parts of 3-methacryloyloxypropyltrimethoxysilane;

[0035] 6-12 parts of colloidal silica;

[0036] 0.5 to 1.5 parts of 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0037] Preferably, the molecular weight of the aliphatic polyurethane diacrylate in the locking layer and the interpenetrating reinforcement layer is controlled to be 1500-3500, and the molecular weight of the aliphatic polyurethane diacrylate in the anti-smoking surface layer is controlled to be 2000-5000.

[0038] The three layers—the locking layer, the interpenetrating reinforcement layer, and the anti-smoking topcoat—all use aliphatic polyurethane diacrylate as the main resin, but modulus gradient control is achieved through differences in molecular weight and proportion: the base layer, serving as the locking layer, uses a medium molecular weight system to ensure adhesion and a flexible transition; the interpenetrating reinforcement layer, while maintaining a similar molecular weight range, reduces its proportion and introduces a more rigid polyester diacrylate to increase structural modulus; and the anti-smoking topcoat uses a higher molecular weight system to enhance impact resistance and thermal crack resistance. Since the main reactive groups in all three layers are acrylate double bonds, interpenetrating cross-linking can occur during continuous coating and curing, forming a semi-interpenetrating network structure. This makes the interface no longer a physically superimposed interface but rather one with chemical continuity, thus avoiding the interlayer delamination and stress concentration problems found in traditional multilayer coating systems. This gradient structure—flexible at the bottom, rigid in the middle, and tough at the top—effectively mitigates thermal and mechanical stress, achieving a smooth transition of the stress transmission path.

[0039] Secondly, the three-layer system—the locking layer, the interpenetrating reinforcement layer, and the anti-smoke burn layer—exhibits a progressively increasing silicon-oxygen structural gradient. The base layer, serving as the locking layer, contains only a small amount of silane coupling agent to establish interfacial chemical anchoring points. The interpenetrating reinforcement layer introduces cage-like silicon-oxygen structural units and silica sol, allowing the inorganic phase to transition from point-like dispersion to a localized network. The anti-smoke burn layer, through the large-scale use of perhydropolysilazane supplemented with nano-silica and fluorosilane, can transform into a continuous and dense Si-O-Si or Si-ON inorganic network during service, achieving in-situ ceramization of the surface layer. This gradient structure ensures that the ceramization structure formed by the anti-smoke burn layer under the instantaneous high temperature of a cigarette butt is not isolated, but rather supported by a pre-existing silicon-oxygen framework in the underlying layer, reducing the risk of interfacial cracking caused by thermal shock. Without the reinforcement layer and the underlying silicon-oxygen pre-construction, the surface ceramization would result in a hard and brittle abrupt layer, highly susceptible to stress concentration and interlaminar failure.

[0040] Furthermore, the hexagonal boron nitride sheet fillers arranged in the interpenetrating reinforcement layer form in-plane thermal conductivity channels, allowing localized heat to diffuse rapidly laterally and reducing the peak temperature rise in the cigarette butt contact area. The anti-scalding surface layer bears the direct thermal contact and initial thermal decomposition, while the reinforcement layer, as a thermal buffer layer, diffuses and disperses heat over a larger area, significantly mitigating the intensity of thermal shock. If the thermally conductive filler exists only in the surface layer, it will affect the surface gloss and hardness; if it exists only in the bottom layer, it cannot participate in the instantaneous thermal diffusion process. Therefore, the position of the reinforcement layer in the thermal diffusion path has a synergistic effect of amplifying the anti-scalding ability of the surface layer.

[0041] Preferably, the locking layer, the interpenetrating reinforcement layer, and the anti-smoking surface layer all contain isoborneol acrylate, and the amount of isoborneol acrylate added in the three layers satisfies the following relationship:

[0042] ;

[0043] ;

[0044] ;

[0045] Among them, the mass fractions of isoborneol acrylate in the locking layer, interpenetrating reinforcement layer and anti-smoke burn surface layer are respectively I b I i I t ;

[0046] U represents the mass fraction of aliphatic polyurethane diacrylate;

[0047] E represents the mass fraction of bisphenol A type epoxy acrylate;

[0048] S represents the mass fraction of 3-methacryloyloxypropyltrimethoxysilane;

[0049] Pi represents the mass fraction of polyester diacrylate;

[0050] Di represents the mass parts of 1,6-hexanediol diacrylate;

[0051] Where: R is 0.18–0.32; λ is 0.45–0.85;

[0052] And it also meets the following conditions:

[0053] .

[0054] In terms of construction and curing, all three layers use isoborneol acrylate as a diluent monomer. By adjusting the proportions, similar rheological properties are achieved, ensuring consistent wetting and spreading between layers and avoiding interface defects. Simultaneously, the synergistic configuration of the photoinitiation system allows for sufficient curing capacity in the deeper layers while enabling rapid film formation on the surface. During continuous construction, interfacial reactivity is maintained, achieving partial cross-linking and fusion between layers, rather than complete isolation and curing of the interface. The glass transition temperature is progressively increased, resulting in a surface hardness higher than the internal structure, thus forming a composite system of a wear-resistant outer shell and a tough, supportive inner layer.

[0055] Interfacial coupling systems also embody the logic of translayer reactions. One end of a methacryloyloxy silane molecule participates in the polymerization of acrylates, while the other end, after hydrolysis and condensation, combines with silica sol or polysilazane transformation structures, forming a chemical bridge between the organic and inorganic networks and achieving true organic-inorganic synergistic crosslinking. If the coupling agent exists only in a single layer, a continuous translayer chemical network cannot be established.

[0056] In the three-layer structure, the addition amount of isoborneol acrylate is controlled by parameter coupling. Instead of simply limiting the proportion of a certain layer, a corresponding relationship is established between the total amount of polymerizable organic phase in the three layers and the amount of reactive diluent monomer added through a unified proportion factor R and a reinforcing layer correction factor λ. This transforms the role of isoborneol acrylate in different layers from "single viscosity reduction" to "cross-layer structure regulation variable".

[0057] First, through and The corresponding relationship ensures that the locking layer and the anti-smoke topcoat have the same reaction dilution ratio during the application stage. Because the total amount of polymerizable organic components differs between the two layers, proportional control rather than a fixed addition amount keeps the system viscosity of both layers within the same window range, thus ensuring consistent interlayer spreading behavior. This consistency reduces interfacial tension differences, brings the interlayer contact angles closer, reduces the risk of pinholes and shrinkage, and creates a fully wetted state during continuous coating. This avoids micro-interfacial voids and stress concentrations caused by viscosity differences between layers, providing conditions for the continuous construction of the subsequent cross-linked network.

[0058] Secondly, by introducing a λ correction coefficient into the enhancement layer, Considering that the reinforcing layer contains additional low-viscosity crosslinking monomers and a higher proportion of inorganic fillers, the relative proportion of isoborneol acrylate is appropriately reduced. This ensures that the layer maintains its workable viscosity without reducing the crosslinking density due to excessive monofunctional monomers. This modification enables the reinforcing layer to form a synergistic structure of high crosslinking density and inorganic network, which provides structural support and stress dispersion under thermal shock conditions without localized softening or cracking.

[0059] Secondly, by establishing The gradient relationship transforms the contributions of rigid monomers and crosslinking density into quantifiable inequalities, resulting in a modulus-increasing structure from bottom to top after curing. The locking layer maintains low rigidity and high ductility to absorb substrate deformation; the interpenetrating reinforcement layer achieves increased modulus due to the synergistic restriction of chain segment movement by crosslinking density and inorganic phase; and the anti-smoke burn layer achieves higher glass transition temperature and surface hardness with a higher proportion of isoborneol acrylate and the participation of an inorganic silicon network. This modulus gradient avoids interfacial shear stress concentration caused by abrupt rigidity changes, allowing the thermal expansion differences generated by thermal shock or instantaneous contact with a cigarette butt to be gradually released between layers.

[0060] Furthermore, isoborneol acrylate possesses both low viscosity and high glass transition temperature. Under the aforementioned ratio, it plays a rheological regulating role during the application stage, while after curing, its rigid ring structure restricts chain segment rotation, thereby improving network rigidity. Through parametric coupling, it assumes different structural roles in the three layers, rather than simply acting as a reactive diluent, thus achieving unified control between application performance and final performance.

[0061] This cross-layer coupling relationship, established with a unified scaling factor and correction coefficient, ensures rheological consistency among the three layers during construction. After curing, it exhibits a gradient-increasing structure in modulus and heat resistance, and forms a synergistic dispersion and structural support effect under thermal shock conditions. If this scaling coupling is eliminated and the monomer dosage of each layer is determined independently, it becomes difficult to simultaneously ensure interlayer wetting continuity and post-curing rigidity gradient, resulting in a non-linear decrease in smoke resistance and scratch resistance.

[0062] A second aspect of the present invention provides a method for preparing the waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring as described above, comprising the following steps:

[0063] S1: The substrate surface is treated with dust removal and degreasing, and then subjected to corona treatment or plasma treatment;

[0064] S2: Apply the locking layer coating to the surface of the substrate, such that the coating amount per unit area of ​​the locking layer is 15-30 g / m². 2 And then UV cured;

[0065] S3: Apply an interpenetrating reinforcement layer coating to the surface of the locking layer, such that the coating amount per unit area of ​​the interpenetrating reinforcement layer is 25-45 g / m². 2 And then UV cured;

[0066] S4: Apply a smoke-resistant heat-resistant surface coating to the surface of the interpenetrating reinforcement layer, such that the coating amount per unit area of ​​the smoke-resistant heat-resistant surface coating is 20-40 g / m². 2 And then UV cured;

[0067] S5: The board material cured by S4 is heated and kept warm to cause the perhydropolysilazane in the smoke-proof surface layer to undergo a conversion reaction.

[0068] The above preparation method involves sequentially coating three layers and curing each layer under UV light, followed by a post-treatment step. This creates a spatially gradient structure between the locking layer, interpenetrating reinforcement layer, and smoke-resistant surface layer, transitioning gradually from the substrate outwards. The locking layer provides interfacial bonding and stress buffering, the interpenetrating reinforcement layer forms a structural framework containing inorganic components, and the smoke-resistant surface layer constitutes a direct protective layer against high-temperature contact. By limiting the coating amount per unit area of ​​the three layers, the reinforcement layer becomes the main structural component, while the thickness of the surface layer and the reinforcement layer is within a similar range. This ensures that during thermal shock, the stress and temperature gradient are progressively transmitted along the thickness direction rather than concentrated at a single interface. The post-treatment step promotes further conversion of the perhydropolysilazane, resulting in a more stable silicon-oxygen structure on the surface, thereby improving surface density and smoke resistance. Overall, this method achieves a composite system with a clearly defined structural hierarchy, continuous stress distribution, and a progressively increasing inorganic network.

[0069] Preferably, the locking layer and the interpenetrating reinforcement layer are cured in a graded manner, specifically as follows:

[0070] The locking layer is pre-cured with ultraviolet light irradiation energy of 150–450 mJ / cm. 2 Furthermore, an interpenetrating reinforcement layer is applied within 5–60 seconds after the locking layer has pre-cured;

[0071] The interpenetrating reinforcement layer is pre-cured with ultraviolet light irradiation energy of 250–650 mJ / cm. 2 Furthermore, a smoke-proof and heat-resistant surface layer is applied within 5–60 seconds after the interpenetrating reinforcement layer has been pre-cured.

[0072] The interpenetrating reinforcement layer was then subjected to final curing, with a final curing UV irradiation energy of 1200–2500 mJ / cm². 2 .

[0073] By introducing graded curing and time window control, the locked-in layer and interpenetrating reinforcement layer maintain a certain degree of reactivity before complete final curing. By controlling the pre-curing energy and the coating time of adjacent layers, double bonds and migratable segments capable of polymerization remain on the surface of the lower layer, allowing the upper layer to undergo interpenetrating crosslinking with the lower layer after coating, rather than forming a simple physical layer interface. Simultaneously, a higher final curing energy is set for the reinforcement layer to ensure complete deep crosslinking within the high-filler system, reducing uncured areas and residual monomers. This graded curing path transforms the interlayer interface from a distinct interface to a gradient transition zone, thereby improving interlayer bonding strength and long-term thermal cycling stability.

[0074] Preferably, the ultraviolet curing is carried out inside an inert gas hood, and the oxygen content inside the hood meets the following requirements during the curing process:

[0075] The oxygen content inside the pre-curing stage cover of the interlocking layer and interpenetrating reinforcement layer shall not exceed 1500 ppm;

[0076] During the final curing stage of the interpenetrating reinforcement layer and the curing stage of the smoke-proof surface layer, the oxygen content inside the cover shall not exceed 500 ppm.

[0077] Preferably, the post-processing includes two controlled water activation steps:

[0078] The first stage of treatment conditions is 25–40℃, relative humidity 50–75%, and 3–15 min;

[0079] The second stage of treatment conditions is 45–75℃, relative humidity 20–55%, and 10–60 min.

[0080] The oxygen content of the curing environment and the post-treatment humid heat conditions are controlled. By controlling the oxygen content at a low level during the pre-curing stage, the impact of oxygen inhibition on the surface reaction rate is reduced, ensuring that surface drying and internal curing are synchronized. The oxygen content is further reduced during the final curing and topcoat curing stages, resulting in a more complete cross-linked structure on the surface of the high-filler system and the fluorinated silane system, reducing pinholes, shrinkage cavities, and surface stickiness. Two-stage controlled water activation post-treatment allows the hydrolysis and polycondensation of the hydrogenated polysilazane to proceed in stages. Hydrolysis is first uniformly initiated under high humidity, followed by polycondensation densification at higher temperatures, thereby reducing local shrinkage and stress concentration, forming a more continuous and dense silicon-oxygen network. This control method ensures the surface structure remains stable under high-temperature smoking conditions, reduces the generation of microcracks, and improves the retention of scratch resistance and heat resistance.

[0081] The present invention, by adopting the above technical solution, has the following beneficial effects:

[0082] 1. By establishing a stable interfacial chemical anchoring structure through the locking layer, and combining graded curing and time window control, a semi-interpenetrating cross-linked transition zone is formed between the layers rather than a physical stacked interface, thereby significantly improving the interlayer peel strength, impact resistance and thermal cycling stability, and avoiding delamination, bulging or warping failure of traditional multilayer coating systems under temperature and humidity cycles and mechanical loads.

[0083] 2. By synergistically introducing cage-like silica structural units, nano-silica, and part of polycondensed silica sol into the interpenetrating reinforcement layer, a dense structure of interpenetrating organic cross-linked network and inorganic Si-O skeleton is constructed. At the same time, with modulus gradient design, the system forms a continuous mechanical transition zone from flexible to rigid and from tough to hard after curing, thereby improving scratch resistance, scratch resistance and wear resistance stability, and reducing interfacial stress concentration caused by thermal expansion differences.

[0084] 3. Through the staged transformation of perhydropolysilazane under controlled humid heat conditions, a continuous and dense silicon-oxygen or silicon-oxygen-nitrogen structural region is formed on the surface, and a stable ceramic transition is achieved under the support of the silicon-oxygen skeleton already built in the lower layer. This maintains the structural integrity under the instantaneous high temperature contact with cigarette butts, reduces carbonization, blistering and scorching, and significantly improves the resistance to cigarette burns and high temperature impact stability.

[0085] 4. The arrangement of hexagonal boron nitride sheet fillers in the reinforcing layer forms in-plane heat conduction channels, which enables rapid lateral diffusion of local heat, reduces peak temperature rise, and works in conjunction with the surface heat-resistant structure to disperse thermal shock intensity, achieving a synergistic effect of thermal buffering and structural support, thereby improving the dimensional stability and surface integrity of the system under high-temperature short-time contact conditions.

[0086] 5. By coupling and controlling the parameters of isoborneol acrylate in the three layers and establishing a unified proportional factor and correction coefficient, each layer maintains rheological consistency and good wettability during the construction stage. After curing, a structural gradient with progressively increasing modulus and glass transition temperature is formed, achieving unified control of construction performance and end performance, while ensuring the long-term maintenance of waterproof, seepage-proof, chemical corrosion resistance and weather resistance. Detailed Implementation

[0087] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0088] Unless otherwise defined, all scientific and technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art.

[0089] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0090] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0091] The present invention will now be described in detail with reference to specific embodiments, which are intended to understand rather than limit the invention.

[0092] Unless otherwise specified, in the following examples, the substrate is high-density fiberboard with a thickness of 8.0 mm and a density of 0.92 g / cm³. 3 It has a moisture content of 6.5% and a surface roughness Ra of 2.8 μm, and is a commercially available conventional HDF substrate.

[0093] Aliphatic polyurethane diacrylate is an aliphatic UV oligomer with a number average molecular weight of about 2500-2600 (used for locking layers and interpenetrating reinforcement layers) and a number average molecular weight of about 3200 (used for smoke-proof heat-resistant surface layers), using CN965 series products from Guangzhou Qingtian Materials Technology Co., Ltd.

[0094] Bisphenol A type epoxy acrylate is an epoxy acrylate oligomer with a bisphenol A backbone structure, using Ebecryl 600 product from Allnex.

[0095] 3-Methacryloxypropyltrimethoxysilane is a conventional silane coupling agent, KH-570.

[0096] Isoborneol acrylate is a reactive monofunctional acrylate monomer that combines low viscosity and high glass transition temperature. It uses Sartomer's SR506 product.

[0097] Polyester diacrylate is a UV-curing polyester acrylate oligomer, using product CN292 from Guangzhou Qingtian Materials Technology Co., Ltd.

[0098] 1,6-Hexanediol diacrylate is a difunctional reactive diluent monomer, using Sartomer's SR238 product.

[0099] The methacrylated polyhedral oligomeric silsesquioxane containing an octahedral cage-like silicon-oxygen structure is a POSS-MA type monomer, containing a Si-O cage-like rigid framework and polymerizable methacrylate end groups. It uses the Ecotion®POSS102 product from Guangzhou Yixin Technology Co., Ltd.

[0100] The colloidal silica is a water-dispersible nano silica sol with an average particle size of about 20 nm and a solid content of about 40%. It uses Ludox™-40 product from Chemours.

[0101] The partially condensed silica sol is a sol obtained by hydrolysis and partial condensation of tetraethyl orthosilicate under acidic conditions, with a solid content controlled at 30% and SiO2 content calculated on a solid basis.

[0102] The hexagonal boron nitride plate particles have an h-BN structure, a plate-like morphology, and an average particle size of about 3 μm. They are made from Momentive's PT110 product.

[0103] Perhydropolysilazane is a polymer containing Si-H and Si-N bonds. It can be converted into a dense silicon-oxygen structure under humid and hot conditions. The product used is the NN110 model from AZ Electronic Materials, Japan.

[0104] 1H,1H,2H,2H-perfluorodecyltriethoxysilane is a fluorosilane surface modifier, using domestically available reagent-grade products.

[0105] The photoinitiator was 1-hydroxycyclohexylphenyl ketone, specifically BASF's Irgacure 184 product.

[0106] The leveling agent is a polyether-modified siloxane additive, specifically the BYK-333 model product.

[0107] The defoamer is a silicone-based defoamer, specifically the BYK-066N model.

[0108] Example 1

[0109] This embodiment discloses a waterproof, scratch-resistant, and smoke-proof floor, including a substrate and a locking layer, an interpenetrating reinforcement layer, and a smoke-proof surface layer sequentially disposed on the surface of the substrate.

[0110] (1) The locking layer coating comprises the following components in parts by weight:

[0111] Serial Number Component Name weight 1 Aliphatic polyurethane diacrylate 55 2 Bisphenol A type epoxy acrylate 12 3 3-Methacryloxypropyltrimethoxysilane 4 4 Isoborneol acrylate 19.9 5 1-Hydroxycyclohexylphenyl ketone 3 6 Polyether modified siloxane leveling agent 0.5 7 Organosilicon defoamers 0.5

[0112] (2) The interpenetrating reinforcement layer coating comprises the following components in parts by weight:

[0113] Serial Number Component Name weight 1 Aliphatic polyurethane diacrylate 22 2 Polyester diacrylate 10 3 1,6-Hexanediol diacrylate 3.6 4 Oligomeric silsesquioxanes (POSS monomers) 8 5 Colloidal silica 12 6 Partially condensed silica sol 4 7 Hexagonal boron nitride plate-like particles 2.5 8 Isoborneol acrylate 4.49 9 1-Hydroxycyclohexylphenyl ketone 2.5 10 Polyether-modified siloxane leveling agent 0.5 11 Organosilicon defoamers 0.5

[0114] (3) The anti-smoke and anti-scalding topcoat coating comprises the following components in parts by weight:

[0115] Serial Number Component Name weight 1 Aliphatic polyurethane diacrylate 22 2 Perhydropolysilazane 18 3 3-Methacryloxypropyltrimethoxysilane 6 4 Colloidal silica 6 5 1H,1H,2H,2H-Perfluorodecyltriethoxysilane 1 6 Isoborneol acrylate 8.4 7 1-Hydroxycyclohexylphenyl ketone 2 8 Polyether modified siloxane leveling agent 0.5 9 Organosilicon defoamers 0.5

[0116] The preparation method of the above-mentioned waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring is as follows:

[0117] S1: After the high-density fiberboard substrate is dusted by compressed air, the surface is wiped with a non-woven cloth soaked in anhydrous ethanol to remove oil stains. Then, a corona treatment is performed at a power of 1.8 kW and a speed of 12 m / min to increase the surface tension to ≥46 mN / m. The coating process begins immediately after treatment.

[0118] S2: According to the formulation ratio, aliphatic polyurethane diacrylate, bisphenol A epoxy acrylate, and isoborneol acrylate are added to a mixing tank and stirred at 500 rpm for 10 min at 25°C. Then, 3-methacryloyloxypropyltrimethoxysilane, photoinitiator, leveling agent, and defoamer are added sequentially, and stirring is continued for 20 min. Vacuum degassing is then performed for 5 min to obtain the locking layer coating.

[0119] The coating is applied to the substrate surface using a roller coating method, with a wet film thickness of approximately 25 μm and a coating weight of 22 g / m². 2 After coating, the material enters a UV curing machine for pre-curing under nitrogen protection, with a UV energy of 300 mJ / cm². 2 The oxygen content inside the coating is controlled at 1000 ppm. The next coating layer is applied within 15 seconds after pre-curing.

[0120] S3: Aliphatic polyurethane diacrylate, polyester diacrylate, and 1,6-hexanediol diacrylate were mixed and stirred for 15 min. Then, POSS monomer and isoborneol acrylate were added. Colloidal silica and silica sol were then added in batches and dispersed at 1200 rpm for 15 min using a high-speed disperser. The dispersion speed was reduced to 600 rpm, and hexagonal boron nitride flake particles were added and dispersed for 10 min. Finally, photoinitiator and additives were added, and the mixture was degassed under vacuum to obtain the interpenetrating polymer reinforced coating.

[0121] The coating is applied to the surface of the locking layer using a roller coating method, with a coating amount of 35 g / m² per unit area. 2 First, pre-curing is performed using a UV energy of 500 mJ / cm². 2 The oxygen content inside the enclosure is 1000 ppm. The topcoat is applied within 20 seconds after pre-curing. Final curing is then performed at a UV energy of 2000 mJ / cm². 2 The oxygen content inside the hood is controlled at 300 ppm.

[0122] S4: After uniformly mixing aliphatic polyurethane diacrylate and isoborneol acrylate, add perhydropolysilazane and stir for 15 min under nitrogen protection. Then, add silane coupling agent, colloidal silica, and perfluorodecyltriethoxysilane sequentially, stirring at low speed to avoid bubble formation. Finally, add photoinitiator and additives, and degas under vacuum to obtain the anti-smoking surface coating.

[0123] Precision roller coating is used for application, with a coating weight of 30 g / m². 2 Entering the UV curing section, curing is performed within a nitrogen hood at a UV energy of 1800 mJ / cm². 2 Oxygen content ≤300 ppm.

[0124] S5: The cured board is placed in a constant temperature and humidity chamber for two stages of controlled water activation treatment. The first stage conditions are 30℃, 65% relative humidity, and 10 min; then the second stage conditions are 60℃, 40% relative humidity, and 30 min. After treatment, it is allowed to cool naturally to room temperature.

[0125] In this embodiment, calculations show that...

[0126]

[0127] Example 2

[0128] The difference between this embodiment and Embodiment 1 is that the component amounts of the interpenetrating reinforcement layer coating are different. The interpenetrating reinforcement layer coating includes the following components in parts by weight:

[0129] Serial Number Component Name weight 1 Aliphatic polyurethane diacrylate 22 2 Polyester diacrylate 10 3 1,6-Hexanediol diacrylate 8 4 Oligomeric silsesquioxanes (POSS monomers) 8 5 Colloidal silica 12 6 Partially condensed silica sol 4 7 Hexagonal boron nitride plate-like particles 2.5 8 Isoborneol acrylate 5.04 9 1-Hydroxycyclohexylphenyl ketone 2.5 10 Polyether modified siloxane leveling agent 0.5 11 Organosilicon defoamers 0.5

[0130] In this embodiment, calculations show that...

[0131]

[0132] The preparation method of the waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring in this embodiment is as follows:

[0133] S1: High-density fiberboard (HDF) is selected as the substrate, with a thickness of 8.0 mm and a moisture content of 6.5%. After dust removal with compressed air, the surface of the substrate is wiped with anhydrous ethanol for degreasing. Subsequently, the surface is activated by corona treatment with a power of 1.8 kW and a linear velocity of 12 m / min, so that the surface tension reaches above 46 mN / m. The coating and curing process begins immediately after treatment.

[0134] S2: Add aliphatic polyurethane diacrylate, bisphenol A epoxy acrylate and isoborneol acrylate to a mixing tank and stir at 25°C for 20 min; then add 3-methacryloyloxypropyltrimethoxysilane and stir for 10 min; add 1-hydroxycyclohexylphenyl ketone, leveling agent and defoamer and continue stirring for 10 min, and then vacuum degas for 5 min to obtain the locking layer coating.

[0135] The locking layer coating is applied to the substrate surface, so that the coating amount per unit area of ​​the locking layer is 22 g / m². 2After coating, it undergoes UV pre-curing within an inert gas hood. The pre-curing UV irradiation energy is 300 mJ / cm². 2 The oxygen content inside the enclosure is controlled at 1000ppm; after pre-curing, it enters S3 within 15 seconds.

[0136] S3: Aliphatic polyurethane diacrylate, polyester diacrylate, and 1,6-hexanediol diacrylate were added to a mixing tank and stirred at 25°C for 15 min; methacrylated polyhedral oligomeric silsesquioxane containing an octahedral cage-like silica structure was added and stirred for 10 min; colloidal silica and part of the condensed silica sol were added in two batches and dispersed at 1200 rpm for 15 min; then hexagonal boron nitride flake particles were added and dispersed at 600 rpm for 10 min; isoborneol acrylate, 1-hydroxycyclohexylphenyl ketone, leveling agent, and defoamer were added and stirred for another 10 min, followed by vacuum degassing for 5 min to obtain the interpenetrating reinforcement layer coating.

[0137] The interpenetrating penetration reinforcement coating is applied to the surface of the interlocking layer, so that the coating amount per unit area of ​​the interpenetrating penetration reinforcement layer is 35 g / m². 2 After coating, it undergoes UV pre-curing within an inert gas hood. The pre-curing UV irradiation energy is 500 mJ / cm². 2 The oxygen content inside the enclosure was controlled at 1000 ppm; after pre-curing, it entered S4 within 20 seconds. Subsequently, the interpenetrating reinforcement layer underwent final curing, with a final curing UV irradiation energy of 2000 mJ / cm². 2 The oxygen content inside the hood is controlled at 300 ppm.

[0138] S4: Under nitrogen protection, aliphatic polyurethane diacrylate and isoborneol acrylate are mixed and stirred for 10 min; perhydropolysilazane is added and stirred for 15 min; 3-methacryloyloxypropyltrimethoxysilane, colloidal silica and 1H,1H,2H,2H-perfluorodecyltriethoxysilane are added sequentially and stirred at low speed for 15 min; 1-hydroxycyclohexylphenyl ketone, leveling agent and defoamer are added and stirred for 10 min, and vacuum degassing is performed for 5 min to obtain the smoke-proof heat-resistant topcoat.

[0139] The anti-smoking coating is applied to the surface of the interpenetrating reinforcement layer, so that the coating amount per unit area of ​​the anti-smoking coating is 30g / m². 2 After coating, it is cured under ultraviolet light in an inert gas hood. The curing ultraviolet light energy is 1800 mJ / cm². 2 The oxygen content inside the hood is controlled at 300 ppm.

[0140] S5: The board material cured by S4 undergoes a two-stage controlled water activation treatment. The first stage conditions are 30℃, 65% relative humidity, and 10 min; the second stage conditions are 60℃, 40% relative humidity, and 30 min. After treatment, it is allowed to cool naturally to room temperature.

[0141] Comparative Example 1: Removal of Interpenetrating Reinforcement Layer

[0142] The difference between this comparative example and Example 1 is that the waterproof, scratch-resistant, and smoke-proof flooring only includes a substrate and a locking layer and a smoke-proof surface layer sequentially disposed on the surface of the substrate. The specific amounts of the two coatings are the same as those in Example 1.

[0143] The specific preparation method for waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring is as follows:

[0144] S1: High-density fiberboard (HDF) is selected as the substrate, with a thickness of 8.0 mm and a moisture content of 6.5%. The substrate surface is first dusted with compressed air, then wiped with anhydrous ethanol to remove oil, and then subjected to corona treatment with a corona power of 1.8 kW and a linear speed of 12 m / min to achieve a surface tension of over 46 mN / m. Coating is applied immediately after treatment.

[0145] S2: Aliphatic polyurethane diacrylate, bisphenol A epoxy acrylate, and isoborneol acrylate were added to a mixing tank and stirred at 25°C for 20 min. Then, 3-methacryloyloxypropyltrimethoxysilane was added and stirred for 10 min. Finally, 1-hydroxycyclohexylphenyl ketone, a leveling agent, and a defoamer were added and stirred for 10 min, followed by vacuum degassing for 5 min to obtain the locking layer coating. Roller coating was used to achieve a locking layer coverage of 22 g / m². 2 UV pre-curing was performed inside an inert gas hood, with a pre-curing UV irradiation energy of 300 mJ / cm². 2 The oxygen content inside the cover is 1000 ppm. After pre-curing, proceed to the next step within 15 seconds.

[0146] S3: Under nitrogen protection, aliphatic polyurethane diacrylate and isoborneol acrylate are mixed and stirred for 10 min. Perhydropolysilazane is added and stirred for 15 min. Then, 3-methacryloyloxypropyltrimethoxysilane, colloidal silica, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane are added sequentially, and stirred at low speed for 15 min. 1-hydroxycyclohexylphenyl ketone, leveling agent, and defoamer are added and stirred for 10 min, followed by vacuum degassing for 5 min to obtain the smoke-resistant heat-resistant topcoat. The smoke-resistant heat-resistant topcoat is applied to the surface of the locking layer, achieving a coating weight of 30 g / m² per unit area. 2 UV curing was performed inside an inert gas hood with a UV light energy of 1800 mJ / cm². 2 The oxygen content inside the hood is 300 ppm.

[0147] S4: The cured board is subjected to two stages of controlled water activation treatment. The first stage conditions are 30℃, 65% relative humidity, and 10 min; the second stage conditions are 60℃, 40% relative humidity, and 30 min. After treatment, the board is allowed to cool naturally to room temperature.

[0148] Comparative Example 2: Remove the anti-smoking surface layer

[0149] The difference between this comparative example and Example 1 is that the waterproof, scratch-resistant, smoke-proof and heat-resistant flooring only includes a substrate and an interlocking layer and an interpenetrating reinforcement layer sequentially disposed on the surface of the substrate. The specific amounts of the two coatings are the same as those in Example 1.

[0150] The specific preparation method for waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring is as follows:

[0151] S1: High-density fiberboard is selected as the base material, with a thickness of 8.0 mm, a density of 0.92 g / cm³, and a moisture content of 6.5%.

[0152] First, compressed air was used to remove dust from the substrate surface at a pressure of 0.6 MPa, a blowing distance of 150 mm, and a duration of 30 seconds. Then, a non-woven cloth soaked in anhydrous ethanol was used to wipe the substrate surface to remove oil. The wiping was performed twice, with a 2-minute interval between each wipe, until no obvious oil residue remained on the surface.

[0153] After dust removal and degreasing, the substrate surface is subjected to corona treatment with a power of 1.8 kW and a processing speed of 12 m / min, increasing the surface tension of the substrate to over 46 mN / m. Immediately after corona treatment, the locking layer coating process begins.

[0154] S2: Add 55 parts of aliphatic polyurethane diacrylate, 12 parts of bisphenol A type epoxy acrylate and 19.88 parts of isoborneol acrylate to a stainless steel mixing tank equipped with a mechanical stirrer, and stir at 500 rpm for 20 minutes at 25°C to make the system fully homogeneous.

[0155] Then add 4 parts of 3-methacryloyloxypropyltrimethoxysilane and continue stirring for 10 minutes to fully disperse the silane.

[0156] Add 3 parts of 1-hydroxycyclohexylphenyl ketone, 0.5 parts of polyether-modified siloxane leveling agent, and 0.5 parts of organosilicon defoamer, and stir at 600 rpm for 10 min at 25°C. After stirring, degas under a vacuum of −0.08 MPa for 5 min to obtain a uniform and transparent locking layer coating.

[0157] The locking layer coating is uniformly applied to the corona-treated substrate surface using a roller coating method, with a wet film thickness of approximately 25 μm, resulting in a unit area coating amount of 22 g / m² for the locking layer.

[0158] Immediately after coating, the material enters a UV curing device for pre-curing within an inert gas hood. Nitrogen gas is introduced into the hood to control the oxygen content below 1000 ppm. The UV irradiation energy is set to 300 mJ / cm². After pre-curing, the interpenetrating reinforcement layer coating step begins within 15 seconds.

[0159] S3: Add 22 parts of aliphatic polyurethane diacrylate, 10 parts of polyester diacrylate and 3.60 parts of 1,6-hexanediol diacrylate to a mixing tank and stir at 600 rpm for 15 min at 25°C to ensure that the organic phase is fully homogeneous.

[0160] Subsequently, 8 parts of methacrylated polyhedral oligomeric silsesquioxane containing an octahedral cage-like silicon oxide structure were added, and the mixture was stirred at 800 rpm for 10 min at 25°C.

[0161] Twelve parts of colloidal silica and four parts of polycondensed silica sol were added to the system in two separate batches and dispersed using a high-speed disperser at 1200 rpm for 15 min to ensure uniform dispersion of the nanoscale inorganic components in the system.

[0162] Subsequently, 2.5 parts of hexagonal boron nitride flake particles were added and dispersed at 600 rpm for 10 min.

[0163] Then add 4.49 parts of isoborneol acrylate, 2.5 parts of 1-hydroxycyclohexylphenyl ketone, 0.5 parts of polyether-modified siloxane leveling agent and 0.5 parts of organosilicon defoamer, stir at 600 rpm for 10 min at 25°C, and then degas under a vacuum of −0.08 MPa for 5 min to obtain the interpenetrating reinforcement layer coating.

[0164] The interpenetrating reinforcement layer coating is applied to the pre-cured locking layer surface using a roller coating method, so that the coating amount per unit area of ​​the interpenetrating reinforcement layer is 35 g / m².

[0165] After coating, UV pre-curing is performed inside an inert gas hood, with the oxygen content controlled below 1000 ppm and the UV irradiation energy at 500 mJ / cm². Following pre-curing, final curing is carried out within 20 seconds.

[0166] The final curing stage is carried out inside an inert gas hood, with the oxygen content inside the hood controlled below 300 ppm and the ultraviolet light irradiation energy set at 2000 mJ / cm² to ensure full cross-linking and curing of the reinforcing layer.

[0167] S4: After the interpenetrating reinforcement layer has been cured, the board is placed in a room temperature environment (25℃, relative humidity 50%) and left to stand for 30 minutes to allow the system temperature to drop to room temperature and release residual internal stress, and then the floor sample of Comparative Example 2 is obtained.

[0168] Comparative Example 3: Interpenetrating reinforcement layer without POSS (replaced with an equal amount of polyester diacrylate).

[0169] This comparative example discloses a waterproof, scratch-resistant, and smoke-proof flooring, comprising a substrate and a locking layer, an interpenetrating reinforcement layer, and a smoke-proof surface layer sequentially disposed on the surface of the substrate. The difference from Example 1 is that the POSS is replaced with an equal amount of polyester diacrylate.

[0170] The interpenetrating reinforcement layer coating comprises the following components in parts by weight:

[0171] Serial Number Component Name weight 1 Aliphatic polyurethane diacrylate 22 2 Polyester diacrylate 18 3 1,6-Hexanediol diacrylate 3.6 4 Oligomeric silsesquioxanes (POSS monomers) 0 5 Colloidal silica 12 6 Partially condensed silica sol 4 7 Hexagonal boron nitride plate-like particles 2.5 8 Isoborneol acrylate 4.49 9 1-Hydroxycyclohexylphenyl ketone 2.5 10 Polyether modified siloxane leveling agent 0.5 11 Organosilicon defoamers 0.5

[0172] The specific steps for applying and curing the interpenetrating reinforcement layer in step S3 are as follows:

[0173] Aliphatic polyurethane diacrylate, polyester diacrylate, and 1,6-hexanediol diacrylate were added to a mixing tank and stirred at 25°C for 15 min. Then, colloidal silica and part of the condensed silica sol were added in two batches and dispersed at 1200 rpm for 15 min using a high-speed disperser. Hexagonal boron nitride flake particles were added and dispersed at 600 rpm for 10 min. Isoborneol acrylate, 1-hydroxycyclohexylphenyl ketone, leveling agent, and defoamer were added and stirred for 10 min, followed by vacuum degassing for 5 min to obtain the interpenetrating polymer (IPP) reinforcing layer coating. The coating was applied to achieve a unit area coverage of 35 g / m² for the IPP. 2 UV pre-curing was performed inside an inert gas hood at a pre-curing energy of 500 mJ / cm². 2 Oxygen content 1000 ppm, pre-cured and then transferred to S4 within 20 seconds; followed by final curing with a final curing energy of 2000 mJ / cm. 2 Oxygen content 300 ppm.

[0174] Performance testing

[0175] 1. Scratch and abrasion resistance test:

[0176] The surface hardness of the samples was evaluated using the pencil hardness method. The samples were placed on a horizontal platform, and the test method was performed according to GB / T 6739-2022 "Determination of Hardness of Paints and Varnishes by Pencil Method". 6B to 9H pencils were selected, the pencil tip was flattened, and the surface was scratched at a 45° angle with a load of 7.5 N. After three consecutive scratches, the surface of the coating was observed to see if continuous scratches or exposure of the substrate appeared. The highest hardness grade that did not produce continuous scratches was taken as the pencil hardness result.

[0177] The wear resistance was evaluated using the Taber wear resistance method, following the test procedure for surface wear resistance in GB / T 17657. A CS-10F grinding wheel was used, with a load of 500 g and a rotation speed of 60 r / min. The mass loss and gloss retention rate (60° gloss, measured before and after the test) were recorded after 1000 revolutions.

[0178] Meanwhile, a simplified scratch width evaluation method was adopted. A steel needle (with an end radius of 0.5 mm) was used to scratch the surface for 10 cm with a load of 5 N, and the average scratch width was measured using a reading microscope.

[0179] The scratch and abrasion resistance test data for each sample are shown in the table below:

[0180] Table 1

[0181] sample Pencil hardness 1000 rpm mass loss mg 60° gloss retention rate % 5 N scratch width μm Example 1 4H 13.7 86.4 46 Example 2 3H 16.9 82.1 58 Comparative Example 1 2H 24.6 74.3 83 Comparative Example 2 H 29.8 69.2 101 Comparative Example 3 2H 21.4 76.8 72

[0182] 2. Water resistance and waterproof durability test:

[0183] Waterproof performance was evaluated using both static water contact angle and water absorption swelling methods. The water contact angle was measured using a contact angle meter. At 25°C, 3 μL of deionized water was dropped onto the sample surface, and the contact angle was recorded after 5 seconds. The average value of five measurements at different locations was then taken.

[0184] Water absorption and swelling were evaluated using the common method for evaluating wood-based film / coating. The sample was cut into 50 mm × 50 mm pieces, and the edges were sealed with wax to reduce the influence of lateral water seepage. The sample was then soaked in deionized water at 25°C for 24 h. After wiping off the surface moisture, the water absorption rate and thickness swelling rate were measured.

[0185] To simulate daily durability and add a wet and hot cycle water seepage evaluation, the sample was placed in a constant temperature and humidity chamber at 40℃ and 90% relative humidity for 24 h and then transferred to an environment at 25℃ and 50% relative humidity for 24 h. This cycle was repeated for 3 times. After the cycle, the sample was observed to see if whitening, blistering or interlayer bulging occurred, and the water contact angle retention rate was measured.

[0186] The water resistance and waterproof durability test data for each sample are shown in the table below:

[0187] Table 2

[0188] sample Initial water contact angle ° 24-hour water absorption rate % 24-hour thickness expansion rate % Appearance after damp heat cycling Contact angle retention rate after cycling % Example 1 111.8 0.62 0.33 No whitening, no bubbling 94.1 Example 2 109.6 0.75 0.41 Slight whitening in some areas 91.6 Comparative Example 1 103.7 1.12 0.66 Localized whitening, slight bulging at the edges 86.8 Comparative Example 2 92.4 1.46 0.88 Noticeably white, with localized blistering 78.2 Comparative Example 3 106.1 0.97 0.58 Localized whitening 88.9

[0189] 3. Interlayer bonding and impact resistance testing:

[0190] Interlayer bonding was evaluated using two methods: the cross-cut test and the pull-off test. The cross-cut test was performed according to GB / T 9286. A grid with a spacing of 1 mm was cut on the sample surface, and 3M tape was applied (peeling angle of about 180°) and quickly peeled off. The layers were graded from 0 to 5 (grade 0 is no peeling).

[0191] The pull-out method uses a portable pull-out apparatus. The aluminum alloy pull-out block is bonded to the sample surface with two-component epoxy adhesive. After curing at room temperature for 24 h, it is loaded with 1 MPa / s, and the pull-out strength at failure is recorded. The failure location (cohesive failure of the coating or interface failure) is observed.

[0192] Impact resistance was assessed using a simplified falling ball impact test. A 25 mm diameter steel ball was dropped freely from a height of 1.0 m to impact the center of the sample, and the presence of cracks, circumferential cracking, or interlayer delamination was observed. The test was repeated three times, and the worst result was recorded.

[0193] The interlayer bonding and impact resistance test data for each sample are shown in the table below:

[0194] Table 3

[0195] sample Gradient adhesion rating Tensile strength (MPa) Destructive morphology Falling ball impact appearance Example 1 0 3.78 Cohesive coating is the main component No cracks, no delamination Example 2 0–1 3.41 Cohesion-based, localized interface Slight indentation, no delamination Comparative Example 1 2 2.62 Mainly focused on interface destruction Localized ring cracks and edge lifting trend Comparative Example 2 1–2 2.95 Cohesion and Interface Hybrid Localized microcracks Comparative Example 3 1 3.06 Cohesion-oriented Slight indentation, no delamination

[0196] 4. Smoke resistance and thermal shock resistance test:

[0197] The resistance to cigarette burns was evaluated using two methods: cigarette butt burning and thermal shock. The cigarette butt burning test was conducted using a common method for resisting burning on floor surfaces. A lit and stably burning cigarette was placed vertically on the sample surface, its own weight was applied, and the contact was maintained for 120 seconds before removal. After cooling to room temperature, the morphology of the burn mark was observed, and the diameter of the burn mark was measured. The presence of blistering, cracking, or whitening was recorded. To avoid subjectivity, a graded evaluation was used: Grade A: No obvious burn mark, no blistering or cracking; Grade B: Slight discoloration or shallow mark without blistering or cracking; Grade C: Obvious discoloration or whitening accompanied by micro-blistering; Grade D: Blistering, cracking, or exposure of the substrate.

[0198] Thermal shock resistance was tested using the metal block thermal contact method. A stainless steel block with a diameter of 30 mm and preheated to 250°C was gently placed on the sample surface for 20 seconds and then removed. After cooling, the surface was observed for whitening, blistering, and cracking, and the maximum size of the visible defects was measured.

[0199] The test data for smoke resistance and thermal shock resistance of each sample are shown in the table below:

[0200] Table 4

[0201] sample Cigarette burn mark diameter (mm) Cigarette burn rating Maximum size of thermal contact defect at 250℃ (mm) Does it bubble / crack? Example 1 4.6 A 0.4 no Example 2 5.1 B 0.8 No (partial whitening) Comparative Example 1 6.8 C 2.3 Localized microbubbling Comparative Example 2 9.4 D 6.7 Obvious blistering and localized cracking Comparative Example 3 6.2 C 1.9 Localized whitening, microcracks

[0202] 5. Stain resistance and chemical resistance test:

[0203] Simplified stain resistance tests were conducted using common household contaminants and cleaning agents. Coffee, soy sauce, red wine, and shoe polish were dropped onto the sample surface to form stain spots approximately 15 mm in diameter. The stains were covered with a petri dish to prevent evaporation and left for 24 hours. After wiping with a damp cloth 10 times, followed by wiping with a neutral detergent 10 times, the residual stains were observed and graded from 0 to 5 (0 for no residue, 5 for significant and irremovable residue). For chemical resistance testing, three media were used: a 10% ethanol aqueous solution, a 1% detergent aqueous solution, and a 0.5% sodium hypochlorite aqueous solution. Filter paper was soaked and placed over the sample surface for 30 minutes, then removed and dried. The presence of stickiness, loss of gloss, whitening, or surface softening was observed, and the gloss retention rate (60° gloss) was recorded.

[0204] The data for the stain resistance and chemical resistance of each sample are shown in the table below:

[0205] Table 5

[0206] sample Coffee stain resistance rating Soy sauce stain resistance rating Red wine stain resistance rating Shoe polish stain resistance rating Ethanol gloss retention rate % Sodium hypochlorite gloss retention rate (%) Is it sticky / softened? Example 1 0 0–1 1 0 93.7 91.2 no Example 2 0–1 1 1–2 0–1 92.4 89.5 no Comparative Example 1 1–2 2 2–3 1 88.6 84.9 no Comparative Example 2 2–3 3 3–4 2 82.1 76.8 Localized stickiness Comparative Example 3 1–2 2 2–3 1 89.7 86.2 no

[0207] Conclusion: The scratch and abrasion resistance data show that Example 1 is superior to Comparative Examples 1-3 in terms of pencil hardness, scratch width, and Taber wear loss. Among them, Comparative Example 3 showed a significant deterioration in hardness and scratch width after the removal of POSS, indicating that the hybrid cross-linking nodes formed by cage-like silicon oxide structural units in the interpenetrating reinforcement layer have a direct contribution to resisting scratches and maintaining abrasion resistance.

[0208] After removing the interpenetrating reinforcement layer in Comparative Example 1, the surface hardness and abrasion resistance decreased while the scratch width increased, indicating that the intermediate interpenetrating reinforcement layer is a necessary structural layer for bearing and dispersing surface mechanical stress. Water resistance and humid heat cycling results showed that Examples 1 and 2 had better control over contact angle and water absorption swelling. In Comparative Example 2, removing the anti-smoke burn surface layer significantly reduced the contact angle and exacerbated blistering and whitening after humid heat, indicating that surface densification and surface energy regulation play a crucial role in long-term waterproof durability. In the anti-smoke burn and thermal contact results, Comparative Example 2 showed obvious blistering and cracking, and a significantly increased burn mark diameter, while Example 1 maintained an A grade with extremely small defect size. This indicates that the dense silicon-oxygen structure formed by the Si-H and Si-N structured surface layer after controlled humid heat plays a decisive role in short-term high-temperature contact stability. Meanwhile, Comparative Examples 1 and 3 showed micro-blistering or micro-cracks under smoke burn conditions, demonstrating the structural support and stress relief effect of the interpenetrating reinforcement layer under thermal shock. In the interlayer bonding test, Example 1 showed higher tensile strength and was mainly characterized by cohesive failure, while Comparative Example 1 showed an increased proportion of interfacial failure. Combined with the impact appearance, this reflects the effect of continuous curing of the three layers and the interfacial transition on suppressing interlayer failure. These multiple sets of data collectively verify the comprehensive improvement in scratch resistance, waterproof durability, and smoke-resistant stability achieved through the synergistic effect of the three-layer structure.

[0209] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring, characterized in that, It includes a substrate and a locking layer, an interpenetrating reinforcement layer and a smoke-proof heat-resistant surface layer sequentially disposed on the surface of the substrate; The enhancement layer mainly comprises: Methacrylated polyhedral oligomeric silsesquioxanes containing octahedral cage-like siloxane structures; Colloidal silica with an average particle size of 10–30 nm; Partially polycondensed silica sol formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate; The smoke-proof heat-resistant surface layer mainly comprises: Hydrogenated polysilazane containing Si-H and Si-N bonds.

2. The waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 1, characterized in that, The locking layer comprises at least the following components by weight: 45-55 parts of aliphatic polyurethane diacrylate; 12-20 parts of bisphenol A type epoxy acrylate; 4 to 8 parts of 3-methacryloyloxypropyltrimethoxysilane.

3. A waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 1 or 2, characterized in that, The interpenetrating reinforcement layer comprises at least the following components by weight: 15-22 parts of aliphatic polyurethane diacrylate; 10-15 parts of polyester diacrylate; 6-10 parts of methacrylated polyhedral oligomeric silsesquioxane containing an octahedral cage-like silicon-oxygen structure; 8-15 parts of colloidal silica; 2-5 parts of partially polycondensed silica sol formed by acid-catalyzed hydrolysis of tetraethyl orthosilicate; 1.5 to 3.5 parts of hexagonal boron nitride flake particles.

4. A waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 1, 2, or 3, characterized in that, The smoke-proof heat-resistant surface layer comprises at least the following components by weight: 22-30 parts of aliphatic polyurethane diacrylate; 15-22 parts of hydrogenated polysilazane; 4-8 parts of 3-methacryloyloxypropyltrimethoxysilane; 6-12 parts of colloidal silica; 0.5 to 1.5 parts of 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

5. A waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 4, characterized in that, The molecular weight of the aliphatic polyurethane diacrylate in the locking layer and the interpenetrating reinforcement layer is controlled to be 1500-3500, and the molecular weight of the aliphatic polyurethane diacrylate in the anti-smoking surface layer is controlled to be 2000-5000.

6. The waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 4, characterized in that, The locking layer, interpenetrating reinforcement layer, and anti-smoking surface layer all contain isoborneol acrylate, and the amount of isoborneol acrylate added in the three layers satisfies the following relationship: ； ； ； Among them, the mass fractions of isoborneol acrylate in the locking layer, interpenetrating reinforcement layer and anti-smoke burn surface layer are respectively I b I i I t ; U represents the mass fraction of aliphatic polyurethane diacrylate; E represents the mass fraction of bisphenol A type epoxy acrylate; S represents the mass fraction of 3-methacryloyloxypropyltrimethoxysilane; Pi represents the mass fraction of polyester diacrylate; Di represents the mass parts of 1,6-hexanediol diacrylate; Where: R is 0.18–0.32; λ is 0.45–0.85; And it also meets the following conditions: 。 7. A method for preparing a waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1: The substrate surface is treated with dust removal and degreasing, and then subjected to corona treatment or plasma treatment; S2: Apply the locking layer coating to the surface of the substrate, such that the coating amount per unit area of ​​the locking layer is 15-30 g / m². 2 And then UV cured; S3: Apply an interpenetrating reinforcement layer coating to the surface of the locking layer, such that the coating amount per unit area of ​​the interpenetrating reinforcement layer is 25-45 g / m². 2 And then UV cured; S4: Apply a smoke-resistant heat-resistant surface coating to the surface of the interpenetrating reinforcement layer, such that the coating amount per unit area of ​​the smoke-resistant heat-resistant surface coating is 20-40 g / m². 2 And then UV cured; S5: The board material cured by S4 is heated and kept warm to cause the perhydropolysilazane in the smoke-proof surface layer to undergo a conversion reaction.

8. The method for preparing a waterproof, scratch-resistant, smoke-proof, and heat-resistant floor according to claim 7, characterized in that, The locking layer and the interpenetrating reinforcement layer are cured in a graded manner, specifically as follows: The locking layer is pre-cured with ultraviolet light irradiation energy of 150–450 mJ / cm. 2 Furthermore, an interpenetrating reinforcement layer is applied within 5–60 seconds after the locking layer has pre-cured; The interpenetrating reinforcement layer is pre-cured with ultraviolet light irradiation energy of 250–650 mJ / cm. 2 Furthermore, a smoke-proof heat-resistant surface layer is applied within 5–60 seconds after the interpenetrating reinforcement layer has been pre-cured. The interpenetrating reinforcement layer was then subjected to final curing, with a final curing UV irradiation energy of 1200–2500 mJ / cm². 2 .

9. The method for preparing a waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 7, characterized in that, The ultraviolet curing is carried out inside an inert gas hood, and the oxygen content inside the hood meets the following requirements during the curing process: The oxygen content inside the pre-curing stage cover of the interlocking layer and interpenetrating reinforcement layer shall not exceed 1500 ppm; During the final curing stage of the interpenetrating reinforcement layer and the curing stage of the smoke-proof surface layer, the oxygen content inside the cover shall not exceed 500 ppm.

10. The method for preparing a waterproof, scratch-resistant, smoke-proof, and heat-resistant flooring according to claim 7, characterized in that, Furthermore, the post-processing includes two controlled water activation steps: The first stage of treatment conditions is 25–40℃, relative humidity 50–75%, and 3–15 min; The second stage of treatment conditions is 45–75℃, relative humidity 20–55%, and 10–60 min.

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