Non-slip indoor floor and method for manufacturing the same

Abstract

This invention relates to the field of building decoration materials technology, specifically to an anti-slip indoor floor and its preparation method. The method includes: adding reactive anti-slip particles, fumed silica, a leveling agent, and a defoamer to a UV resin composition, stirring, and vacuum degassing to obtain an anti-slip and wear-resistant UV coating mixture; hot-pressing a mosaic texture onto the surface of a multi-layer PVC substrate and cooling it to set; corona-treating the embossed substrate, then roller-coating the mixture, leveling, and performing two-stage UV curing to form a 10-25 μm dry film anti-slip and wear-resistant UV-cured layer. The reactive anti-slip particles are angular alumina particles with methacrylate groups introduced through KH570 silanization, and their surface is loaded with nano-ZnO under the action of a dopamine layer, which can participate in the photocuring and resin network chemical bonding. The resulting floor possesses anti-slip, wear-resistant, strong adhesion, water resistance, and yellowing resistance properties.

Description

Technical Field

[0001] This invention belongs to the field of building decoration materials technology, specifically relating to an anti-slip indoor floor and its preparation method. Background Technology

[0002] As interior decoration materials develop towards safety, durability, and environmental friendliness, flooring surfaces not only need to possess excellent decorative effects but also need to consider comprehensive properties such as slip resistance, wear resistance, water resistance, aging resistance, and low volatile organic compound (VOC) emissions. Especially in indoor settings such as homes, hospitals, schools, nursing homes, and commercial spaces, the slip resistance of the flooring surface directly affects user safety, while wear resistance, yellowing resistance, and adhesion directly determine the product's lifespan and long-term appearance stability. Ultraviolet (UV) cured coatings, due to their advantages such as fast curing speed, low energy consumption, low VOC emissions, and suitability for continuous production, have become one of the important technical routes for interior flooring surface treatment.

[0003] In existing indoor anti-slip flooring technologies, a common approach is to directly incorporate inorganic anti-slip particles into the surface coating through physical blending to create a rough surface structure and increase the coefficient of friction. However, this approach typically suffers from the following problems: First, the bonding strength between the anti-slip particles and the resin matrix is ​​insufficient, leading to easy detachment under prolonged foot traffic and friction, resulting in a decline in anti-slip performance. Second, increasing the amount of particles added to improve anti-slip effects often sacrifices the smoothness, wear resistance, and transparency of the coating, making it difficult to achieve a balance between anti-slip properties and durability. Third, traditional polyurethane or acrylic flooring surfaces are prone to yellowing, loss of gloss, microcrack propagation, and decreased adhesion under long-term indoor sunlight, heat and humidity, and repeated mechanical stress, affecting the flooring's service life and decorative performance.

[0004] Therefore, there is an urgent need to provide a non-slip indoor floor and its preparation method to solve the problems in the existing technology, such as easy shedding of anti-slip particles, difficulty in achieving both anti-slip and wear resistance, insufficient resistance to ultraviolet aging, poor surface toughness and service stability, and insufficient adaptability to continuous preparation. Summary of the Invention

[0005] The purpose of this invention is to provide an anti-slip indoor floor and its preparation method, so as to achieve a synergistic improvement in the anti-slip properties, wear resistance, water resistance, UV aging resistance, adhesion strength and processing adaptability of the indoor floor surface.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing anti-slip indoor flooring, comprising the following steps:

[0008] Step (1) Add reactive anti-slip particles, fumed silica, leveling agent and defoamer to the UV resin composition, stir and then perform vacuum degassing to obtain an anti-slip and wear-resistant UV coating mixture.

[0009] Step (2) The PVC flooring substrate is subjected to surface embossing treatment, and after cooling and shaping, the PVC embossed flooring substrate is obtained;

[0010] Step (3) After corona treatment of the PVC embossed floor substrate surface, the anti-slip and wear-resistant UV coating mixture is roller coated onto the PVC embossed floor substrate surface, leveled, and then subjected to two-stage UV curing to obtain anti-slip indoor flooring.

[0011] Preferably, in step (1), the mass ratio of the UV resin composition, reactive anti-slip particles, fumed silica, leveling agent, and defoamer is 100:10-25:0.5-3.0:0.1-1.0:0.1-0.5; the stirring time is 10-30 min; the vacuum degassing time is 10-30 min; the viscosity of the anti-slip and wear-resistant UV coating mixture is 2000-6000 mPa·s; the leveling agent is selected from at least one of polymethylalkylsiloxane and organic modified polysiloxane; and the defoamer is selected from at least one of polydimethylsiloxane and polyether modified polysiloxane.

[0012] Preferably, in step (2), the embossing process is carried out by hot pressing; the embossing temperature is 120-170℃, the embossing pressure is 0.3-1.5MPa, the embossing time is 5-30s, the embossing depth is 20-150μm, and the embossing texture is a mosaic texture.

[0013] Preferably, in step (2), the PVC flooring substrate consists of, from top to bottom, a wear-resistant layer, a decorative film layer, a fireproof layer, a PVC panel layer, and a moisture-proof layer.

[0014] Preferably, the wear-resistant layer is a transparent PVC wear-resistant layer; the decorative film layer is a printed PVC decorative film; the fireproof layer is disposed below the decorative film, and the fireproof layer may be composed of PVC resin, ceramic fiber and / or glass fiber; the PVC panel layer is a solid PVC layer, and the PVC panel layer contains at least PVC resin, filler and stabilizer, and may add plasticizer, lubricant and / or impact modifier as needed; the moisture-proof layer is a polyvinyl chloride foam layer, containing PVC resin, foaming material, filler, plasticizer and stabilizer.

[0015] Preferably, the wear-resistant layer has a thickness of 0.05-0.70 mm, the decorative film layer has a thickness of 0.05-0.20 mm, the fireproof layer has a thickness of 0.2-1.5 mm, the PVC panel layer has a thickness of 2.0-6.0 mm, and the moisture-proof layer has a thickness of 0.2-3.0 mm.

[0016] Preferably, the PVC flooring substrate can be prepared by conventional mixing / open mixing or extrusion / calendering processes to obtain the PVC panel layer; then, a fireproof layer is set on the PVC panel layer by adhesive bonding or hot pressing, and a decorative film layer and a wear-resistant layer are sequentially bonded on the fireproof layer; at the same time, a moisture-proof layer is set on the PVC panel layer by adhesive bonding or hot pressing; after cooling and shaping, the PVC flooring substrate is obtained.

[0017] Preferably, the PVC flooring substrate is a multi-layer PVC composite board or roll substrate commonly used in the art.

[0018] Preferably, in step (3), the corona treatment conditions are as follows: the power supply frequency is 10-30kHz, and the surface tension of the PVC embossed floor substrate after corona treatment reaches 36-42dyn / cm; the wet film thickness of the anti-slip and wear-resistant UV coating mixture is controlled at 10-30μm; the leveling conditions are: the leveling temperature is 40-70℃, and the leveling time is 1-3min; the curing energy of the first stage in the two-stage UV curing is 400-800mJ / cm. 2 The curing energy for the second stage is 1000-1500 mJ / cm. 2 The dry film thickness of the anti-slip indoor flooring after UV curing is 10-25μm.

[0019] Preferably, the preparation method of the reactive anti-slip particles includes the following steps:

[0020] A1: Add alumina particles to a mixed solvent, then add 3-(methacryloyloxy)propyltrimethoxysilane, adjust the pH of the system, carry out hydrolysis and heating reactions, then filter, wash and dry to obtain silanized alumina particles.

[0021] A2: Disperse nano zinc oxide in ethanol, sonicate it, add the silanized alumina particles and stir, then add dopamine hydrochloride and adjust the pH of the system with Tris buffer. Stir at room temperature, then filter, wash and vacuum dry to obtain reactive anti-slip particles.

[0022] In the above process, nano zinc oxide is deposited and fixed on the surface of silanized alumina particles with the assistance of a dopamine layer. The dopamine layer can stabilize the ZnO deposition and enhance the aging resistance and wear resistance of the particles. By introducing methacrylate groups on the surface of reactive anti-slip particles through KH570, it can participate in the subsequent ultraviolet curing reaction and form a chemical bond with the resin network.

[0023] Preferably, in A1, the mass ratio of alumina particles, mixed solvent, and 3-(methacryloyloxy)propyltrimethoxysilane is 80-120:300-500:2-5; the pH of the system is 4.0-5.5; the hydrolysis temperature is 40-50℃, the hydrolysis time is 20-40 min; the heating reaction temperature is 65-75℃, the reaction time is 1-3 h; and the drying temperature is 70-90℃, the drying time is 4-8 h.

[0024] Preferably, in A1, the median particle size D50 of the alumina particles is 10-20 μm; the alumina particles have a prismatic or multi-faceted structure; the mixed solvent is composed of ethanol and water mixed in a mass ratio of 90:10-98:2.

[0025] Preferably, in A2, the mass ratio of nano zinc oxide, ethanol, silanized alumina particles, and dopamine hydrochloride is 0.2-2:60-120:100:0.2-1.0; the ultrasonic dispersion time is 10-30 min; the stirring time after adding silanized alumina particles is 0.5-2 h; the pH of the system is adjusted to 8.0-9.0 using Tris buffer; the stirring time at room temperature is 2-5 h; the vacuum drying temperature is 50-70℃, and the vacuum drying time is 6-10 h.

[0026] Preferably, the method for preparing the UV resin composition includes the following steps:

[0027] P1: Polycarbonate diol, isophorone diisocyanate (IPDI) and dibutyltin dilaurate are added to a reactor for reaction to obtain an isocyanate-terminated prepolymer; after cooling, a hydroxybenzoxazine monomer is added to continue the reaction, and then 2-hydroxyethyl methacrylate (HEMA) is added for end-capping to obtain a modified polyurethane acrylate prepolymer.

[0028] P2: Aliphatic polyurethane acrylate oligomer, modified polyurethane acrylate prepolymer, vanillin methacrylate, bis(2-hydroxyethyl) disulfide, ureidopyrimidinone methacrylate monomer, isoborneol acrylate (IBOA), 1,6-hexanediol diacrylate (HDDA), 1-hydroxycyclohexylphenyl ketone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and ultraviolet absorber are mixed evenly to obtain a UV resin composition.

[0029] Preferably, in P1, the mass ratio of polycarbonate diol, IPDI, dibutyltin dilaurate, hydroxybenzoxazine monomer, and HEMA is 20-35:8-18:0.02-0.10:4-8:2-6; the reaction temperature is 70-90℃, and the reaction time is 1-3h; the reaction temperature for further reaction is 50-70℃, and the reaction time is 1-3h; the capping time is 0.5-2h.

[0030] Preferably, in P2, the mass ratio of aliphatic polyurethane acrylate oligomer, modified polyurethane acrylate prepolymer, vanillin methacrylate, bis(2-hydroxyethyl) disulfide, ureidopyrimidinone methacrylate monomer, IBOA, HDDA, 1-hydroxycyclohexylphenyl ketone, TPO, and ultraviolet absorber is 25-45:10-20:5-15:2-8:1-5:8-18:5-12:1-4:0.5-2:0.1-1.0.

[0031] Preferably, in P2, the ultraviolet absorber is selected from at least one of UV-326 and UV-531.

[0032] Preferably, the method for preparing the hydroxybenzoxazine-containing monomer includes the following steps:

[0033] Paraformaldehyde was added to the reactor, and ethanolamine solution was added dropwise under low temperature conditions while stirring. Bisphenol A was then added and the temperature was increased to carry out the reaction. After the reaction was completed, the solvent and low-boiling substances were removed by vacuum distillation. The crude product was dissolved in dichloromethane and washed with potassium hydroxide aqueous solution, then washed with deionized water until neutral. Subsequently, it was dried, concentrated and recrystallized to obtain a hydroxybenzoxazine monomer.

[0034] Preferably, the molar ratio of ethanolamine, paraformaldehyde, and bisphenol A is (1.8-2.2):(3.6-4.4):1; the reaction temperature when adding the ethanolamine solution is 0-15℃; the stirring time after the addition is 15-40 min; the reaction temperature after adding bisphenol A is 85-105℃, and the reaction time is 4-10 h; the mass fraction of the potassium hydroxide aqueous solution is 5-10 wt%, and the number of washings is 1-3.

[0035] In the above process, ethanolamine, paraformaldehyde, and bisphenol A undergo a ring-closing reaction to generate a benzoxazine structure, which introduces a rigid aromatic ring into the subsequent polyurethane chain, thereby improving the surface layer's hardness and water resistance.

[0036] Preferably, the method for preparing the vanillin methacrylate includes the following steps:

[0037] Vanillin was mixed with methacrylic anhydride, heated, and then potassium acetate was added to react. After the reaction was completed, the byproduct methacrylic acid was removed by distillation. The distillate was extracted with water and dried with anhydrous sodium sulfate to obtain vanillin methacrylate.

[0038] Preferably, the molar ratio of vanillin to methacrylic anhydride is 1:(0.9-1.1); the reaction temperature is 60-80℃, the reaction time is 12-30h; and the amount of potassium acetate used is 1-5% of the vanillin quality.

[0039] In the above process, the phenolic hydroxyl groups in vanillin undergo esterification with methacrylic anhydride, introducing methacrylate double bonds into the molecule that can participate in UV curing, while retaining the aromatic structure, which is beneficial to improving the rigidity and UV aging resistance of the resin system.

[0040] Secondly, the present invention provides a non-slip indoor floor, which is prepared by the above-described preparation method.

[0041] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0042] 1. This invention modifies alumina particles by silanization and further loads nano-zinc oxide onto their surface, giving the anti-slip particles functional groups that can participate in the UV curing reaction. This allows the anti-slip particles to chemically anchor to the resin network during curing, improving particle bonding strength, reducing the risk of particle detachment, and enhancing the bonding strength and wear resistance of the anti-slip layer. The alumina particles can bear local friction loads, reducing direct wear on the resin matrix. Simultaneously, the use of prismatic and multi-faceted alumina particles to construct a micro-rough surface structure and the use of a two-stage UV curing process to suppress particle sedimentation facilitates the formation of a surface anti-slip layer and a dense underlying coating structure, thus achieving both anti-slip and wear-resistant performance.

[0043] 2. The polycarbonate soft segment of this invention is beneficial for providing hydrolysis resistance and toughness; the aliphatic polyurethane acrylate helps to improve light stability, while the introduction of hydroxybenzoxazine monomer and vanillin methacrylate, the hydroxybenzoxazine monomer helps to build a rigid aromatic structure and improve the hardness, water resistance and cohesive strength of the coating, and vanillin methacrylate can participate in the photocuring reaction and help to enhance the system's resistance to ultraviolet aging; at the same time, the surface active sites of nano ZnO are passivated under the coating of dopamine layer, which helps to reduce the risk of resin degradation caused by potential photocatalysis, and synergistically improves the yellowing resistance with ultraviolet absorbers; at the same time, the construction of dynamic interaction and multiple hydrogen bonding network in the resin system by bis(2-hydroxyethyl) disulfide and ureidopyrimidinone methacrylate monomer improves the energy dissipation capacity and interfacial adhesion, which is beneficial to improve the toughness, microcrack resistance and long-term service stability of the coating, making the floor surface less prone to brittleness and early failure when subjected to repeated trampling, friction and local stress impact.

[0044] 3. This invention pre-forms a mosaic embossed structure on the surface of a PVC flooring substrate, giving the resulting flooring the visual appearance and three-dimensional decorative effect of mosaic tiles. Simultaneously, an anti-slip and wear-resistant UV-cured functional layer is formed on the embossed substrate surface, combining decorative properties with anti-slip and wear-resistant characteristics. The UV curing process used has a fast curing speed, low volatile organic compound emissions, and is suitable for continuous roller coating production, making it suitable for industrial applications in indoor flooring. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0046] Figure 1 This is a photograph of the anti-slip indoor flooring of the present invention;

[0047] Figure 2 This is a broken line graph of the critical inclination angle of the anti-slip indoor floor using the shoe-wearing ramp method according to the present invention;

[0048] Figure 3 This is a bar chart showing the wear resistance performance of the anti-slip indoor flooring of this invention. Detailed Implementation

[0049] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0050] Example 1

[0051] This embodiment discloses a method for preparing reactive anti-slip particles, including the following steps:

[0052] A1: Weigh 100g of alumina particles and add them to 400g of mixed solvent. Add 3g of 3-(methacryloyloxy)propyltrimethoxysilane (KH570), adjust the pH to 4.5, stir and hydrolyze at 45℃ for 30min, then heat to 70℃ and react for 2h. Filter, wash and dry at 80℃ for 6h to obtain silanized alumina particles.

[0053] A2: Add 0.8g of nano ZnO to 80g of ethanol and sonicate for 20min. Then add 100g of silanized alumina particles and stir for 1h. Then add 0.5g of dopamine hydrochloride and Tris buffer to adjust the pH to 8.5. Stir at room temperature for 3h, filter, wash and vacuum dry at 60℃ for 8h to obtain reactive anti-slip particles.

[0054] Example 2

[0055] This embodiment discloses a method for preparing a hydroxybenzoxazine-containing monomer, comprising the following steps:

[0056] Add 12g of paraformaldehyde to the reactor, add 12.2g of ethanolamine solution dropwise at 5-10℃, stir for 20-30min, then add 22.8g of bisphenol A, react at 90-100℃ for 4-8h, distill under reduced pressure, dissolve the crude product in dichloromethane and wash 1-2 times with potassium hydroxide aqueous solution, then wash with deionized water until neutral, dry, concentrate and recrystallize to obtain a hydroxybenzoxazine monomer.

[0057] Example 3

[0058] This embodiment discloses a method for preparing vanillin methacrylate, including the following steps:

[0059] 152g vanillin and 154g methacrylic anhydride were heated to 70℃, and then 3g potassium acetate was added and reacted for 24h. The methacrylic acid was removed by distillation, and the distillation product was extracted with water and dried with anhydrous sodium sulfate to obtain vanillin methacrylate.

[0060] Example 4

[0061] This embodiment discloses a method for preparing a UV resin composition, including the following steps:

[0062] P1: 25g polycarbonate diol, 12g IPDI and 0.05g dibutyltin dilaurate were reacted at 80℃ for 2h to obtain an isocyanate-terminated prepolymer; after cooling to 60℃, 6g of the hydroxybenzoxazine monomer prepared in Example 2 was added, and the reaction was carried out for 2h. Then, 4g of 2-hydroxyethyl methacrylate (HEMA) was added for end-capping for 1h to obtain a benzene-modified polyurethane acrylate prepolymer.

[0063] P2: 35g of aliphatic polyurethane acrylate oligomer, 15g of prepolymer, 10g of vanillin methacrylate prepared in Example 3, 4g of bis(2-hydroxyethyl) disulfide, 2g of ureidopyrimidinone methacrylate monomer, 12g of IBOA, 8g of HDDA, 2g of 1-hydroxycyclohexylphenyl ketone, 1g of TPO, and 0.4g of UV-326 were stirred evenly to obtain a UV resin composition.

[0064] Optional implementation methods for the substrate structure:

[0065] In one optional embodiment, the fireproof layer in the PVC flooring substrate can be made by composite of PVC resin and inorganic heat-resistant fibers, wherein the inorganic heat-resistant fibers are ceramic fibers and / or glass fibers; wherein the mass ratio of PVC resin to the inorganic heat-resistant fibers can be (40-85):(5-40), and may further include fillers and stabilizers. The moisture-proof layer can be a PVC foam layer, wherein the PVC resin, foaming agent, filler, plasticizer, and stabilizer can be selected according to conventional formulations in the art, and obtained through mixing / extrusion / calendering and foaming. The wear-resistant layer, decorative film layer, fireproof layer, PVC panel layer, and moisture-proof layer can also be obtained by directly composited with commercially available multi-layer PVC composite flooring substrate finished products or semi-finished products in the art, and the present invention can be implemented provided that the layer sequence and thickness range described in this application are met.

[0066] Example 5

[0067] This embodiment discloses a method for preparing anti-slip indoor flooring, including the following steps:

[0068] Step (1) Add 18g of reactive anti-slip particles prepared in Example 1, 1.5g of fumed silica, 0.5g of polymethylalkylsiloxane and 0.3g of polydimethylsiloxane to the UV resin composition prepared in Example 4, stir for 20min and then degas under vacuum for 15min to obtain an anti-slip and wear-resistant UV coating mixture.

[0069] The viscosity of the anti-slip and wear-resistant UV coating mixture is 3000-5000 mPa·s;

[0070] Step (2) Select a multi-layer PVC composite board commonly used in this field as the PVC flooring substrate. Its structure from top to bottom consists of a wear-resistant layer, a decorative film layer, a fireproof layer, a solid PVC panel layer, and a moisture-proof layer. Use hot pressing to emboss the surface to obtain a mosaic texture. After cooling and shaping, obtain the PVC embossed flooring substrate. The embossing temperature is 150℃, the embossing pressure is 0.8MPa, the embossing time is 15s, and the embossing depth is 80μm.

[0071] Step (3) The surface of the PVC embossed floor substrate is corona treated to a surface tension of ≥38dyn / cm and the wet film thickness is controlled at 20μm. The anti-slip and wear-resistant UV coating mixture is applied by roller coating. First, it is leveled at 60℃ for 2min, and then two-stage UV curing is performed. The dry film thickness is 16μm, and the anti-slip indoor floor is obtained.

[0072] UV curing stage 1: 600 mJ / cm 2 The second segment is 1200 mJ / cm 2 .

[0073] Example 6

[0074] This embodiment is basically the same as Example 5, except that: in the preparation of the UV resin composition, the amount of hydroxybenzoxazine monomer in step P1 of Example 4 is reduced to 5g; at the same time, in step (3) of Example 5, the wet film thickness of the anti-slip and wear-resistant UV coating mixture is adjusted to 25-30μm. The remaining steps and process parameters are the same as in Example 5.

[0075] Example 7

[0076] This embodiment is basically the same as Example 5, except that in the preparation of the UV resin composition, in step P2 of Example 4, the amount of vanillin methacrylate is reduced to 8g, and the amount of bis(2-hydroxyethyl) disulfide is increased to 5g. The remaining steps and process parameters are the same as in Example 5.

[0077] Example 8

[0078] The preparation method of the anti-slip indoor floor in this embodiment is basically the same as that in Example 5, except that in step (1) of Example 5, the amount of reactive anti-slip particles is increased to 20g and the amount of fumed silica is adjusted to 1g. The remaining steps and process parameters are the same as those in Example 5.

[0079] Example 9

[0080] This embodiment is basically the same as embodiment 5, except that in step (3) of embodiment 5, the two-stage UV curing energy is adjusted to 500 mJ / cm for the first stage. 2 The second segment is 1300 mJ / cm 2 The remaining steps and process parameters are the same as in Example 5.

[0081] Comparative Example 1

[0082] Compared with Example 5, Comparative Example 1 uses unmodified alumina particles instead of reactive anti-slip particles, and the rest is the same as Example 5.

[0083] Comparative Example 2

[0084] Compared with Example 5, Comparative Example 2 uses alumina particles that have only undergone KH570 silanization treatment and are not loaded with ZnO and dopamine layers instead of the reactive anti-slip particles of Example 1, while the rest is the same as Example 5.

[0085] Comparative Example 3

[0086] Compared with Example 5, Comparative Example 3 did not include hydroxybenzoxazine monomer, vanillin methacrylate, bis(2-hydroxyethyl) disulfide and ureidopyrimidinone methacrylate monomer in the UV resin composition. Instead, it was made up with an equal mass of IBOA / HDDA (mass ratio 2:1). The rest was the same as in Example 5.

[0087] Comparative Example 4

[0088] Comparative Example 4 is the same as Example 5 except that it does not undergo mosaic embossing.

[0089] Comparative Example 5

[0090] Compared with Example 5, Comparative Example 5 changed the two-stage UV curing in step (3) of Example 5 to single-stage curing, and the total curing energy was 1800 mJ / cm. 2 The rest is the same as in Example 5.

[0091] Performance testing and results analysis:

[0092] Performance tests were conducted on Examples 5-9 and Comparative Examples 1-5.

[0093] (1) Anti-slip performance: Tested according to Appendix B of DIN EN 16165:2023-02 (shoe-wearing ramp method): The sample is fixed on a ramp device with continuously adjustable inclination angle; SAE 10W-30 engine oil is used as the test liquid and evenly spread on the sample surface; the tester wears test shoes that meet the standard requirements and walks with the prescribed gait, and records the critical inclination angle when slippage occurs; the average value of different testers / repetitions is taken as the final inclination angle. The R grade is calculated and determined based on the critical inclination angle obtained according to Appendix B of DIN EN 16165:2023-02, with reference to the R grade inclination angle range specified in DIN 51130; when the inclination angle is near the grade boundary value, the grade is determined by the unrounded average inclination angle, and the angles in the table are rounded values ​​for display.

[0094] (2) Wear resistance: The mass loss of the sample was measured by rotating rubber grinding wheel under a load of 750g and a rotation speed of 1000r. The smaller the value, the better the wear resistance.

[0095] (3) Adhesion: The adhesion was tested by the pull-off method on the simultaneously prepared flat PVC witness sample, and the result is expressed in MPa.

[0096] (4) Water resistance: The test sample was immersed in deionized water at 23±2℃ for 168h, then removed, dried and left for 2h before testing the adhesion by pull-off method. The adhesion retention rate was calculated as the adhesion after immersion / the adhesion before immersion × 100%.

[0097] (5) Resistance to artificial aging: Xenon arc aging for 500 hours was used, followed by measurement of the overall color difference ΔE and 60° gloss retention rate; at the same time, it was observed whether blistering, cracking, powdering and peeling occurred.

[0098] The test results are shown in Table 1:

[0099] Table 1

[0100] Group Shoe-wearing ramp method, angle ° Shoe-wearing ramp method, grade <![CDATA[Wear loss / mg·1000r -1 > Pull-off adhesion / MPa Adhesion retention rate after water resistance / % ΔE Gloss retention rate / % Example 5 19 R10 28 4.1 92 1.6 88 Example 6 17 R10 33 3.7 85 2.1 82 Example 7 19 R10 31 3.9 88 2.0 84 Example 8 22 R11 35 3.6 87 1.8 80 Example 9 20 R11 26 4.0 90 1.7 86 Comparative Example 1 13 R10 43 2.7 71 2.9 74 Comparative Example 2 15 R10 38 3.2 79 2.6 77 Comparative Example 3 14 R10 41 3.0 73 3.4 70 Comparative Example 4 11 R10 32 3.8 88 1.9 85 Comparative Example 5 14 R10 37 3.3 80 2.2 78

[0101] According to Table 1 and the test results of Examples 5-9 and Comparative Examples 1-5, the anti-slip indoor flooring prepared in the embodiments of the present invention has good anti-slip properties, wear resistance, adhesion, water resistance and anti-aging properties.

[0102] As can be seen from the comparison of Comparative Examples 1 and 2 and Examples 5-9, when the reactive anti-slip particles of the present invention are not used, or only insufficiently reactive modified anti-slip particles are used, the interfacial bonding force between the particles and the UV resin matrix is ​​insufficient. This makes it easier for particles to detach and for the surface to wear off during use, resulting in decreased wear resistance and reduced adhesion. Simultaneously, because the particles are difficult to stably fix to the coating surface, the frictional characteristics of the floor surface are weakened, and the anti-slip performance decreases; furthermore, unstable interfacial bonding also affects the structural stability of the coating after immersion in water, reducing water resistance.

[0103] As can be seen from the comparison between Comparative Example 3 and Examples 5-9, when the UV resin system lacks the synergistic system composed of hydroxybenzoxazine monomer, vanillin methacrylate and dynamic monomers (bis(2-hydroxyethyl) disulfide, ureidopyrimidinone methacrylate monomer), the cohesive strength and structural stability of the cured resin network decrease, which leads to a decrease in water retention rate and a deterioration in resistance to artificial aging (increased ΔE, decreased gloss retention rate). At the same time, the interfacial load-bearing capacity and abrasion resistance decrease, which manifests as increased abrasion weight loss and reduced overall durability.

[0104] As can be seen from the comparison of Comparative Example 4 and Examples 5-9, when the PVC flooring substrate is not treated with mosaic embossing, the flooring surface lacks an effective composite rough structure, resulting in a decrease in anti-slip performance.

[0105] The comparison between Comparative Example 5 and Examples 5-9 shows that changing the two-stage UV curing to a single-stage curing process is not conducive to the stable distribution and fixation of anti-slip particles in the coating, nor is it conducive to the formation of a uniform, anti-slip surface and dense bottom layer of the cured layer. This results in a decrease in wear resistance, adhesion and water resistance. This indicates that the two-stage UV curing process plays an important role in improving the overall performance of the coating.

[0106] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0107] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing anti-slip indoor flooring, characterized in that, Includes the following steps: Step (1) Add reactive anti-slip particles, fumed silica, leveling agent and defoamer to the UV resin composition, stir and then perform vacuum degassing to obtain an anti-slip and wear-resistant UV coating mixture; wherein, the reactive anti-slip particles are alumina particles with methacrylate groups on the surface, and the nano zinc oxide loaded on the surface of the particles is coated and fixed on the surface of the alumina particles by a dopamine layer. Step (2) The PVC flooring substrate is subjected to surface embossing treatment, and after cooling and shaping, the PVC embossed flooring substrate is obtained; Step (3) After corona treatment of the PVC embossed floor substrate surface, the anti-slip and wear-resistant UV coating mixture is roller coated onto the PVC embossed floor substrate surface, leveled, and then subjected to two-stage UV curing to obtain anti-slip indoor flooring.

2. The method for preparing anti-slip indoor flooring according to claim 1, characterized in that, In step (1), the mass ratio of UV resin composition, reactive anti-slip particles, fumed silica, leveling agent, and defoamer is 100:10-25:0.5-3.0:0.1-1.0:0.1-0.5; the stirring time is 10-30 min; the vacuum degassing time is 10-30 min; the viscosity of the anti-slip and wear-resistant UV coating mixture is 2000-6000 mPa·s; the leveling agent is selected from at least one of polymethylalkylsiloxane and organic modified polysiloxane; the defoamer is selected from at least one of polydimethylsiloxane and polyether modified polysiloxane; in step (2), the embossing process is carried out by hot pressing embossing. The process is as follows: embossing temperature is 120-170℃, embossing pressure is 0.3-1.5MPa, embossing time is 5-30s; embossing depth is 20-150μm; embossing texture is mosaic texture; in step (3), the corona treatment conditions are: power frequency is 10-30kHz, and the surface tension of the PVC embossed floor substrate after corona treatment reaches 36-42dyn / cm; the wet film thickness of the anti-slip and wear-resistant UV coating mixture is controlled at 10-30μm; leveling conditions are: leveling temperature is 40-70℃, leveling time is 1-3min; the curing energy of the first stage in the two-stage UV curing is 400-800mJ / cm. 2 The curing energy for the second stage is 1000-1500 mJ / cm. 2 The dry film thickness of the anti-slip indoor flooring after UV curing is 10-25μm.

3. The method for preparing anti-slip indoor flooring according to claim 1, characterized in that, The preparation method of the reactive anti-slip particles includes the following steps: A1: Add alumina particles to a mixed solvent, then add 3-(methacryloyloxy)propyltrimethoxysilane, adjust the pH of the system, carry out hydrolysis and heating reactions, then filter, wash and dry to obtain silanized alumina particles. A2: Disperse nano zinc oxide in ethanol, sonicate it, add the silanized alumina particles and stir, then add dopamine hydrochloride and adjust the pH of the system with Tris buffer. Stir at room temperature, then filter, wash and vacuum dry to obtain reactive anti-slip particles.

4. The method for preparing anti-slip indoor flooring according to claim 3, characterized in that, In the A1 formulation, the mass ratio of alumina particles, mixed solvent, and 3-(methacryloyloxy)propyltrimethoxysilane is 80-120:300-500:2-5; the system pH is 4.0-5.5; the hydrolysis temperature is 40-50℃, and the hydrolysis time is 20-40 min; the reaction temperature is 65-75℃, and the reaction time is 1-3 h; the drying temperature is 70-90℃, and the drying time is 4-8 h; the median particle size D50 of the alumina particles is 10-20 μm; the alumina particles have a prismatic or multi-faceted structure; the mixed solvent... The mixture is composed of ethanol and water at a mass ratio of 90:10-98:2; in A2, the mass ratio of nano zinc oxide, ethanol, silanized alumina particles and dopamine hydrochloride is 0.2-2:60-120:100:0.2-1.0; the ultrasonic dispersion time is 10-30 min; the stirring time after adding silanized alumina particles is 0.5-2 h; the pH of the system is adjusted to 8.0-9.0 using Tris buffer; the stirring time at room temperature is 2-5 h; the vacuum drying temperature is 50-70℃, and the vacuum drying time is 6-10 h.

5. The method for preparing anti-slip indoor flooring according to claim 1, characterized in that, The method for preparing the UV resin composition includes the following steps: P1: Polycarbonate diol, IPDI and dibutyltin dilaurate are added to a reactor for reaction to obtain an isocyanate-terminated prepolymer; after cooling, a hydroxybenzoxazine monomer is added to continue the reaction, and then HEMA is added for end-capping to obtain a modified polyurethane acrylate prepolymer. P2: The aliphatic polyurethane acrylate oligomer, modified polyurethane acrylate prepolymer, vanillin methacrylate, bis(2-hydroxyethyl) disulfide, ureidopyrimidinone methacrylate monomer, IBOA, HDDA, 1-hydroxycyclohexylphenyl ketone, TPO and ultraviolet absorber are mixed evenly to obtain a UV resin composition.

6. The method for preparing anti-slip indoor flooring according to claim 5, characterized in that, In P1, the mass ratio of polycarbonate diol, IPDI, dibutyltin dilaurate, hydroxybenzoxazine-containing monomer, and HEMA is 20-35:8-18:0.02-0.10:4-8:2-6; the reaction temperature is 70-90℃, and the reaction time is 1-3 hours; the reaction temperature for further reaction is 50-70℃, and the reaction time is 1-3 hours; the capping time is 0.5-2 hours; in P2, aliphatic polyurethane acrylate oligomer, modified polyurethane acrylate... The mass ratio of acrylate prepolymer, vanillin methacrylate, bis(2-hydroxyethyl) disulfide, ureidopyrimidinone methacrylate monomer, IBOA, HDDA, 1-hydroxycyclohexylphenyl ketone, TPO, and ultraviolet absorber is 25-45:10-20:5-15:2-8:1-5:8-18:5-12:1-4:0.5-2:0.1-1.0; the ultraviolet absorber is selected from at least one of UV-326 and UV-531.

7. The method for preparing anti-slip indoor flooring according to claim 5, characterized in that, The method for preparing the hydroxybenzoxazine monomer includes the following steps: Paraformaldehyde was added to the reactor, and ethanolamine solution was added dropwise under low temperature conditions while stirring. Bisphenol A was then added and the temperature was increased to carry out the reaction. After the reaction was completed, the solvent and low-boiling substances were removed by vacuum distillation. The crude product was dissolved in dichloromethane and washed with potassium hydroxide aqueous solution, then washed with deionized water until neutral. Subsequently, it was dried, concentrated and recrystallized to obtain a hydroxybenzoxazine monomer.

8. The method for preparing anti-slip indoor flooring according to claim 7, characterized in that, The molar ratio of ethanolamine, paraformaldehyde, and bisphenol A is (1.8-2.2):(3.6-4.4):1; the reaction temperature during the addition of ethanolamine solution is 0-15℃; the stirring time after the addition is 15-40 min; the reaction temperature after the addition of bisphenol A is 85-105℃, and the reaction time is 4-10 h; the mass fraction of potassium hydroxide aqueous solution is 5-10 wt%, and the number of washings is 1-3.

9. The method for preparing anti-slip indoor flooring according to claim 5, characterized in that, The method for preparing the vanillin methacrylate includes the following steps: Vanillin was mixed with methacrylic anhydride, heated, and then potassium acetate was added to react. After the reaction was completed, the byproduct methacrylic acid was removed by distillation. The distillate was extracted with water and dried with anhydrous sodium sulfate to obtain vanillin methacrylate. The molar ratio of vanillin to methacrylic anhydride is 1:(0.9-1.1); the reaction temperature is 60-80℃, and the reaction time is 12-30h; the amount of potassium acetate used is 1-5% of the vanillin quality.

10. A non-slip indoor floor, characterized in that, The product includes a PVC embossed flooring substrate and an anti-slip and wear-resistant UV-curable coating disposed on the upper surface of the PVC embossed flooring substrate; the upper surface of the PVC embossed flooring substrate has a mosaic embossed texture; the anti-slip and wear-resistant UV-curable coating comprises a resin network formed by UV curing of a UV resin composition and reactive anti-slip particles and fumed silica dispersed therein, wherein the surface of the reactive anti-slip particles contains methacrylate groups and forms a chemical bond with the resin network, and the reactive anti-slip particles are alumina particles with nano-zinc oxide loaded on the surface, wherein the nano-zinc oxide is coated with a dopamine layer and fixed on the surface of the alumina particles.

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