Antiskid wear-resistant PVC floor and preparation method thereof

Abstract

The present application relates to the technical field of PVC material, in particular to a kind of anti-skid wear-resistant PVC floor and preparation method thereof.The floor is five-layer composite structure, from bottom to top includes successively: PVC base material layer, glass fiber reinforced layer, PVC plastic sol layer, wear-resistant layer and UV curing coating layer;The PVC base material layer includes PVC resin, calcium-zinc composite stabilizer, calcium carbonate, rutile titanium dioxide, lubricant and functional composite plasticizing system, the functional composite plasticizing system is composed of bio-based plasticizer and tung oil-DOPO amide ester.The present application provides mechanics and flame-retardant basis by the functional plasticizing system of PVC base layer, glass fiber layer enhances dimensional stability, plastic sol layer buffers stress, transparent wear-resistant layer integrates anti-skid particles and decorative texture, UV coating provides surface protection, five-layer structure function is complementary, synergistic, finally realizes the unity of high anti-skid, high wear-resistant, high flame-retardant, high environmental protection and high decorative.

Description

Technical Field

[0001] This invention belongs to the field of PVC material technology, specifically relating to a non-slip and wear-resistant PVC flooring and its preparation method. Background Technology

[0002] Due to its excellent overall performance, polyvinyl chloride (PVC) resilient flooring has expanded its application from traditional indoor spaces to semi-outdoor and high-traffic public areas with higher requirements for durability, safety, and functionality, such as school corridors, public restaurants, poolside areas, high-speed rail / subway platforms, and airport bridges. These application scenarios present unprecedented challenges to flooring: while meeting basic commercial requirements such as high strength, high wear resistance, and weather resistance, it must also possess excellent and durable anti-slip safety, and take into account aesthetic decorative effects.

[0003] Currently, the anti-slip function of PVC flooring used in the above-mentioned scenarios is mainly achieved through the following technical approaches: 1) Surface embossing: Pressing raised and recessed textures onto the wear-resistant layer to increase friction. However, traditional embossed textures (such as simple dots and squares) have limited anti-slip effect and are prone to wear and dirt accumulation under long-term high-frequency stepping and cleaning, leading to a rapid decline in anti-slip performance. 2) Adding anti-slip particles: Incorporating hard particles such as corundum and silicon carbide into the surface coating. Although this method can improve the anti-slip level in the short term, the particles are easy to fall off, the surface is rough and easily traps dirt, making cleaning difficult, and seriously affecting the aesthetics and gloss of the floor, as well as the feel underfoot. 3) Using highly elastic, rough surface materials: such as some rubber flooring, which has good anti-slip properties, but has disadvantages such as poor wear resistance, easy aging and discoloration, and limited decorative textures.

[0004] These existing technological solutions share a common core flaw: it's difficult to achieve a good balance between anti-slip performance, aesthetic appeal, and long-term durability. Pursuing high anti-slip properties often comes at the cost of aesthetics and ease of cleaning; conversely, a smooth surface focused on aesthetics may not meet the stringent anti-slip requirements of wet environments. More importantly, in semi-outdoor and high-traffic environments, the flooring's anti-slip performance must possess excellent durability and not fail rapidly due to daily wear and tear. Furthermore, to meet the decorative needs of high-end public spaces, the flooring must possess realistic, three-dimensional textures reminiscent of natural stone (such as granite and marble). Traditional printing techniques can only present patterns on a flat surface, lacking the crystalline texture and three-dimensional feel of natural stone, resulting in a monotonous and dull visual effect that fails to meet the modern architectural aesthetics' requirements for material "texture."

[0005] Therefore, there is an urgent need in this field for an innovative PVC flooring manufacturing technology that can fundamentally integrate structural anti-slip properties, durability and wear resistance, and highly realistic three-dimensional decorative effects, to develop a high-performance anti-slip decorative flooring that is both safe and reliable, as well as beautiful and durable, specifically designed for semi-outdoor and high-requirement areas. Summary of the Invention

[0006] The purpose of this invention is to provide a non-slip and wear-resistant PVC flooring and its preparation method, which solves the technical problems of insufficient non-slip properties, poor flame retardancy, low dimensional stability, poor environmental protection, and limited decorative features of existing PVC flooring in semi-outdoor or high-traffic areas.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a non-slip and wear-resistant PVC flooring, the flooring having a five-layer composite structure, comprising, from bottom to top: a PVC substrate layer, a glass fiber reinforcement layer, a PVC plastisol layer, a wear-resistant layer, and a UV-cured coating.

[0009] Furthermore, the PVC substrate layer comprises PVC resin, calcium-zinc composite stabilizer, calcium carbonate, rutile titanium dioxide, lubricant, and functional composite plasticizing system.

[0010] Furthermore, the functional composite plasticizing system is composed of a bio-based plasticizer and tung oil-DOPO amide ester.

[0011] Furthermore, the wear-resistant layer has an embossed pattern on its surface with a texture depth of 0.2-0.4 mm.

[0012] Through the above technical solutions, the diagonal angles of the embossed pattern are staggered, and together with the embossing depth, it provides the floor with excellent anti-slip function and design effect.

[0013] Furthermore, the wear-resistant layer is made of a blend of high-transparency PVC resin and three-phase functional particles, which include colored quartz sand particles, nylon 6 microspheres and flake silicates.

[0014] Through the above technical solutions, the three-phase functional granules and PVC resin are melt-extruded together by a twin-screw extruder. Various granules are uniformly coated by PVC resin to form a whole, which not only creates a special texture, but also effectively prevents the granules from being scratched off and losing their anti-slip and decorative functions. It provides continuous and stable anti-slip and wear-resistant effects throughout the entire service life of the floor.

[0015] Furthermore, the thickness of the UV-cured coating is 0.01-0.03 mm; the thickness of the wear-resistant layer is 0.5-0.7 mm; the thickness of the PVC plastisol layer is 0.15-0.2 mm; the thickness of the glass fiber reinforced layer is 0.09-0.11 mm; and the thickness of the PVC substrate layer is 1.2-2.5 mm.

[0016] Furthermore, the preparation method of the tung oil-DOPO amide ester includes the following steps:

[0017] S1: Mix 260-322g of methyl tung oil, 105-129g of diethanolamine and 1.9-2.3g of KOH, and carry out the amidation reaction by vacuum stirring at 75-85℃ for 3.5-4.5h. Then extract with ethyl acetate and wash with saturated NaCl solution 2-3 times. Finally, dry the organic phase with MgSO4, filter, and vacuum distill to obtain tung oil diethanolamide.

[0018] In the above process, methyl tungate reacts with the imino group of diethanolamine.

[0019] S2: Dissolve 70-120g of tung oil diethanolamide in 600-1000mL of dichloroethane, add 40-70g of butyl levulinate and 2.8-4.8g of p-toluenesulfonic acid (PTSA), and stir and reflux at 82-86℃ for 3.5-4.5h under a nitrogen atmosphere. After the reaction is completed, cool to room temperature, neutralize to pH 7-8 with saturated potassium carbonate aqueous solution, separate the liquid and liquid phases, and distill the organic phase under reduced pressure to obtain butyl levulinate of tung oil.

[0020] In the above process, the intramolecular cyclization of dihydroxyl groups and ketone carbonyl groups forms a thermodynamically stable heterocyclic structure, which effectively masks the activity of hydroxyl groups.

[0021] S3: Mix 30-40g of tung oil butyl acetate and 19-24g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), heat to 150-160℃ under a nitrogen atmosphere, stir and react for 5-6h, cool to room temperature, recrystallize with hot ethanol at 50-60℃, cool to 0-5℃ and stand, filter, wash 3-5 times with cold ethanol, and vacuum dry at 55-65℃ for 10-14h to obtain tung oil-DOPO amide ester.

[0022] In the above process, the double bond of tung oil diethanolamide undergoes an addition reaction with the pH bond of DOPO.

[0023] Furthermore, the method for preparing the bio-based plasticizer includes the following steps:

[0024] P1: Add 24-30g L-lactic acid, 52-64g butyl carbitol, and 0.75-0.95g catalyst p-toluenesulfonic acid monohydrate to 130-170mL cyclohexane. Reflux the mixture at 125-135℃ for 3.5-4.5h under a nitrogen atmosphere. Collect water during the reaction, while continuously refluxing cyclohexane into the flask to form an azeotrope with water. Cool to 45-55℃ and wash successively with 4-6% NaHCO3 solution, deionized water, and saturated NaCl solution until neutral. Dry the organic phase with anhydrous MgSO4 and remove the solvent by rotary evaporation to obtain carbitol lactate.

[0025] P2: Add 30-40g of carbitol lactate to 150-200mL of tetrahydrofuran, add 21-28g of pyridine, and slowly add 22-28g of acetic anhydride dropwise over 30-45min under ice-water bath and mechanical stirring. After the addition is complete, remove the ice bath and move to room temperature to continue stirring for 12-24h. After the reaction is complete, pour the reaction solution into ice water, wash 2-3 times with 1mol / L dilute hydrochloric acid, then wash with saturated sodium bicarbonate solution until no bubbles are generated, and finally wash once with saturated sodium chloride solution. After drying the organic phase with anhydrous magnesium sulfate for 25-35min, filter. Remove the solvent by rotary evaporation under reduced pressure below 40℃ to obtain the bio-based plasticizer.

[0026] In the above process, the acetylation reaction converts the terminal hydroxyl group into a stable acetate bond under mild conditions, eliminating the potential interference of free hydroxyl groups on the thermal stability of PVC. The acid value of the product is significantly reduced, and the thermal stability and hydrolysis resistance are significantly enhanced.

[0027] Secondly, the present invention also provides a method for preparing anti-slip and wear-resistant PVC flooring, comprising the following steps:

[0028] Step (1) Add 100g of PVC resin, 3.6-4.4g of calcium-zinc composite stabilizer, 200-300g of calcium carbonate and 2.7-3.3g of rutile titanium dioxide to a high-speed mixer. First, mix at 100-120℃ and 800-1200rpm for 4.5-5.5min. After cooling to 54-66℃, add 40-50g of bio-based plasticizer, 10.8-13.2g of tung oil-DOPO amide ester and 1.08-1.32g of lubricant. Then mix at 200-400rpm for 2.7-3.3min. Discharge the material at 40.5-49.5℃. Plasticize and extrude the mixture in a twin-screw extruder at temperature zones of 150℃, 165℃, 175℃, 180℃ and 175℃, with a screw speed of 200-350rpm, to obtain PVC base sheet.

[0029] Through the above technical solutions, the bio-based plasticizer is an acetate derivative obtained by further acetylation of the residual hydroxyl groups after esterification of lactic acid and butyl carbitol; a functional composite plasticizing system composed of tung oil-DOPO amide ester and bio-based plasticizer is adopted. Among them, tung oil-DOPO amide ester has both flame retardant and interfacial reactive activity; bio-based plasticizer provides flexibility and plasticization.

[0030] Step (2) The PVC base sheet is fed into a two-roll calender. The temperature of the upper roll is set to 160℃ and the temperature of the lower roll is set to 150℃. Calendering is carried out by gradually adjusting the roll gap. The linear speed is controlled at 10-16m / min to obtain the PVC base layer. Then, 20-70g / m 2The glass fiber mat is hot-pressed onto one side of the PVC substrate layer at a temperature of 139.5-170.5℃ and a pressure of 0.45-0.55MPa, and then shaped by a 40℃ cooling roller to obtain a composite substrate with a glass fiber reinforced layer.

[0031] Step (3) Take 34-36g of PVC paste resin, 18-22g of plasticizer, 36-38.5g of stone powder, 2.5-3g of titanium dioxide, 2-3g of viscosity reducer, 0.5-1g of dispersant, and 1-2g of calcium-zinc composite stabilizer, stir evenly to obtain PVC plasticized paste, and then apply it at 150-250g / m 2 The coating amount is evenly applied to the outer surface of the glass fiber mat, and then heated and cured at 160-200℃ for 1-3 minutes to obtain a PVC plastisol layer.

[0032] Step (4) Print the pattern on the surface of the PVC plastisol layer using water-based environmentally friendly ink, and dry it at 108-132℃ for 27-33s to obtain the printed pattern layer;

[0033] Step (5) Mix 68-70g of high-transparency PVC resin, 26-28g of DOTP, 0.08-0.12g of lubricant, 2-4g of calcium-zinc composite stabilizer, 1-3g of colored quartz sand particles, 0.5-1.5g of nylon 6 microspheres and 0.5-1.5g of flake silicate evenly, melt extrude in a twin-screw extruder at 170-190℃, and thermally bond it to the surface of the printed layer at a temperature of 150-170℃ and a pressure of 0.27-0.33MPa to obtain a wear-resistant layer of mixed colored sand and silicate particles;

[0034] Step (6) Use a steel plate embossing roller with a texture depth of 0.2-0.4mm to hot press the wear-resistant layer at a temperature of 148-181℃ and a pressure of 0.54-0.66MPa to obtain the embossed pattern, with a linear speed of 10-16m / min.

[0035] Step (7) Apply UV-curable polyurethane acrylate coating at 15-30 g / m 2 The wet film is evenly roller-coated onto the surface of the wear-resistant layer, and then immediately enters the nitrogen-protected UV curing channel at an irradiation intensity of 800-1200 mJ / cm². 2 Expose for 3-6 seconds to obtain a UV-cured coating, then cool, cut, inspect, package, palletize, and store to obtain anti-slip and wear-resistant PVC flooring.

[0036] Furthermore, in step (3), the plasticizer is dioctyl terephthalate (DOTP); the viscosity reducer is naphtha; and the dispersant is acid ester 1148.

[0037] Furthermore, in step (5), the colored quartz sand particles have a particle size of 0.3-0.55 mm; the nylon 6 microspheres have a particle size of approximately 0.3-0.55 mm; and the flake silicate is synthetic mica particles with a particle size of 1-4 mm.

[0038] Furthermore, in step (6), the embossed pattern is a design-oriented steel plate pattern, a wheat ear diagonal pattern, or a triangular geometric pattern.

[0039] Furthermore, the lubricant is calcium stearate and PE wax in a mass ratio of 1:1.

[0040] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0041] 1. This invention employs a three-tiered anti-slip mechanism: Colored quartz sand embedded in the wear-resistant layer forms evenly distributed micro-protrusions with nylon 6 microspheres, providing initial frictional resistance; the sheet-like synthetic mica, due to its hexagonal atomic arrangement structure, exhibits a natural metallic luster and sheet-like step effect, enhancing anisotropic friction; the embossed pattern promotes the directional expulsion of water and oil along the embossed texture, preventing liquid film lubrication, and also forms aesthetically pleasing raised and recessed points on the surface, enhancing the anti-slip effect. The synergistic effect of these three elements gives the floor excellent anti-slip properties.

[0042] 2. The phosphaphenanthrene structure in the tung oil-DOPO amide ester prepared by this invention promotes char formation and releases free radical scavengers during combustion, resulting in significant flame retardancy. Simultaneously, the residual double bonds in its molecule can undergo interfacial reactions with PVC chains, enhancing compatibility. The bio-based plasticizer, after acetylation treatment, converts the terminal hydroxyl groups into stable acetate bonds, completely eliminating the catalytic effect of free hydroxyl groups on the thermal degradation of PVC, thus improving processing stability and long-term heat resistance.

[0043] 3. This invention utilizes a functional composite plasticizing system of bio-based plasticizers and tung oil-DOPO amide esters. The bio-based plasticizer has highly flexible molecular chains, effectively improving the ductility and impact resistance of the PVC matrix. Meanwhile, tung oil-DOPO amide esters possess a rigid polycyclic skeleton and reactive double bonds, providing not only flame retardancy but also interfacial anchoring with PVC, inhibiting molecular chain slippage, thereby synergistically enhancing abrasion resistance and dimensional stability. A balance is achieved between flexibility and rigidity, enhancing the flooring's impact resistance and abrasion resistance. Simultaneously, the rigid skeleton of tung oil-DOPO amide esters inhibits plasticizer migration and thermal expansion, ensuring the flooring remains flat and crack-free in semi-outdoor environments with drastic temperature and humidity changes over the long term.

[0044] 4. This invention achieves high performance while maintaining excellent environmental friendliness. The differences in color, gloss, and morphology of the three-phase particles in the transparent wear-resistant layer produce a shimmering and layered effect similar to natural stone under light. Combined with the stone-like texture printed with water-based ink, it achieves a natural aesthetic effect for industrial materials. The UV-cured PUR coating on the surface further enhances its anti-fouling, scratch-resistant, and weather-resistant properties, facilitating daily maintenance. In summary, this invention provides a mechanical and flame-retardant foundation through the functional plasticizing system of the PVC base layer, enhances dimensional stability through the glass fiber layer, buffers stress through the plasticized sol layer, integrates anti-slip particles and decorative textures through the transparent wear-resistant layer, and provides surface protection through the UV coating. The five-layer structure complements each other and works synergistically to ultimately achieve a unity of high anti-slip, high wear resistance, high flame retardancy, high environmental friendliness, and high decorative appeal. 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 partial enlarged view of the steel plate texture design on the surface of the anti-slip and wear-resistant PVC flooring of the present invention;

[0047] Figure 2 This is a partial enlarged view of the wheat ear diagonal pattern on the surface of the anti-slip and wear-resistant PVC flooring of the present invention;

[0048] Figure 3 This is a partial enlarged view of the triangular geometric pattern on the surface of the anti-slip and wear-resistant PVC flooring of the present invention;

[0049] Figure 4 This is a line graph showing the wear resistance of the anti-slip and wear-resistant PVC flooring of the present invention.

[0050] Figure 5 This is a bar chart showing the impact resistance of the anti-slip and wear-resistant PVC flooring of the present invention. Detailed Implementation

[0051] 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.

[0052] If the manufacturers of the reagents or instruments used are not specified, they are all conventional products that can be purchased on the market.

[0053] Example 1

[0054] This embodiment discloses a method for preparing a bio-based plasticizer, including the following steps:

[0055] P1: In a 1000 mL three-necked flask equipped with a Dean-Stark water separator, mechanical stirrer, condenser, and nitrogen inlet tube, 27 g L-lactic acid, 58 g butyl carbitol, 0.85 g p-toluenesulfonic acid monohydrate, and 150 mL cyclohexane were added sequentially as a dehydrating agent. Under nitrogen protection, stirring was started and the mixture was heated to an oil bath temperature of 130 °C while maintaining reflux. The water generated during the reaction formed an azeotrope with cyclohexane and was separated and collected using a Dean-Stark water separator. The reaction continued for 4 hours until no water droplets were separated from the separator, indicating that the esterification reaction was basically complete. Heating was then stopped, and the reaction mixture was cooled to 50 °C. The mixture was washed sequentially in a separatory funnel with 5% sodium bicarbonate aqueous solution, deionized water, and saturated sodium chloride aqueous solution until the aqueous phase was neutral. The organic phase was then dried overnight with anhydrous magnesium sulfate. The filtrate was distilled under reduced pressure in a rotary evaporator at a water bath temperature of 50 °C to remove cyclohexane and residual low-boiling substances, yielding carbitol lactate.

[0056] P2: 35g of carbitol lactate was added to 175mL of tetrahydrofuran dried through a 4A molecular sieve, followed by 25g of pyridine. In an ice-water bath, under mechanical stirring, 25g of acetic anhydride was slowly added dropwise over 40min via a constant-pressure dropping funnel. After the addition was complete, the ice bath was removed, the reaction mixture was moved to room temperature, and the reaction was continued with stirring for 18h. After the reaction was complete, the reaction solution was slowly poured into a beaker containing 200g of crushed ice and washed three times with 1mol / L dilute hydrochloric acid to completely remove pyridine. The separated organic phase was then washed with saturated sodium bicarbonate aqueous solution until no bubbles were generated to neutralize residual acetic acid. Finally, it was washed once with saturated sodium chloride aqueous solution, and the organic phase was dried over anhydrous magnesium sulfate for 30min. The mixture was filtered, and the filtrate was concentrated under reduced pressure using a rotary evaporator in a 40℃ water bath to remove the solvent, yielding a bio-based plasticizer. The acid value of the product was determined to be 0.3mg KOH / g, and the hydroxyl value was ≤5mg KOH / g by titration.

[0057] Example 2

[0058] This embodiment discloses a method for preparing tung oil-DOPO amide ester, including the following steps:

[0059] S1: In a three-necked flask, add 292g methyl tung oil, 117.2g diethanolamine, and 2.1g KOH. Start stirring and heat to 80℃, while simultaneously turning on the vacuum pump to maintain the system pressure at -0.095MPa. Under these conditions, react for 4 hours, continuously distilling off methanol byproducts. After the reaction is complete, cool to room temperature, transfer the reactants to a separatory funnel, add 500mL ethyl acetate and 300mL deionized water, shake thoroughly to extract, allow to stand and separate into layers, and collect the organic phase. Wash the organic phase three times with saturated sodium chloride aqueous solution to remove residual diethanolamine. Dry the organic phase overnight with anhydrous magnesium sulfate, filter, and remove ethyl acetate from the filtrate under reduced pressure at 60℃ using a rotary evaporator to obtain tung oil diethanolamide.

[0060] S2: Add 100g of tung oil diethanolamide, 800mL of dichloroethane, 55g of butyl levulinate and 3.8g of p-toluenesulfonic acid monohydrate to a three-necked flask. Under nitrogen protection, heat to an oil bath temperature of 84℃ and reflux. Remove the water generated in the reaction by azeotropic extraction using a Dean-Stark water separator. After 4 hours of reaction, no more water drips from the water separator. Stop heating and cool to room temperature. Add 100mL of saturated potassium carbonate aqueous solution to the reaction solution and stir for 15 minutes to neutralize the catalyst. Allow to stand and separate the layers. Separate the organic phase and wash it with deionized water until neutral. Dichloroethane is removed from the organic phase by vacuum evaporation at 50℃ using a rotary evaporator to obtain butyl levulinate of tung oil.

[0061] S3: 35g of tung oil butyl levulinate and 21.6g of DOPO were added to a three-necked flask. Under continuous nitrogen purging, the oil bath temperature was raised to 155℃, and the mixture was vigorously stirred at this temperature for 5.5h. After the reaction was completed, heating was stopped, and the temperature was allowed to drop to 80℃. The viscous reactant was poured into a beaker while still hot. After cooling to room temperature, the product solidified. To remove unreacted DOPO, 150mL of ethanol preheated to 55℃ was added, and the mixture was stirred to disperse the product. Then, the mixture was placed in an ice-water bath at 0℃ and allowed to stand for 2h. The precipitated solid was filtered through a Buchner funnel, and the filter cake was washed four times with pre-cooled ethanol and dried under vacuum at 60℃ for 12h to obtain tung oil-DOPO amide ester. The acid value was 0.5mg KOH / g.

[0062] Example 3

[0063] This embodiment discloses a method for preparing anti-slip and wear-resistant PVC flooring, including the following steps:

[0064] Step (1) Weigh 100g of PVC resin, 4g of calcium-zinc composite stabilizer, 250g of calcium carbonate and 3g of rutile titanium dioxide, and put them into a high-speed mixer. First, mix at 1100 rpm and 110°C for 5 minutes to initially plasticize the material and remove moisture. Then, circulate cooling water to cool the material to 60°C. Add 45g of the bio-based plasticizer prepared in Example 1, 12g of the tung oil-DOPO amide ester prepared in Example 2 and 1.2g of the lubricant obtained by premixing calcium stearate and PE wax in a 1:1 mass ratio to the mixer. Adjust the speed to 300 rpm. Mix at low speed for 3 minutes to ensure the liquid components uniformly wet the powder. Control the discharge temperature below 45℃ to obtain a uniform dry mix. Feed the dry mix into a twin-screw extruder and set the temperatures of the five temperature zones of the extruder as follows: Zone 1 150℃, Zone 2 165℃, Zone 3 175℃, Zone 4 180℃, and Die Head 175℃. Set the screw speed to 250 rpm. After plasticizing, melting, and homogenizing, the material is extruded and then traction and cooled by a three-roll calender to obtain a PVC base sheet with a thickness of 2mm and a width of 600mm. The sheet is then wound up for later use.

[0065] Step (2) The above-mentioned PVC base sheet is fed into a two-roll calender. The upper roll temperature is set to 160℃ and the lower roll temperature is set to 150℃. The sheet is calendered from an initial 3mm to 2.8mm through gradually adjusted roll gaps. The linear speed is controlled at 13m / min. Subsequently, the sheet is immediately fed into the hot pressing composite unit, and a 50g / m² layer is coated on the calendered smooth surface of the sheet. 2 The fiberglass mat is hot-pressed and laminated at a composite roller temperature of 155℃ and a pressure of 0.5MPa, so that the fiberglass mat is embedded in the semi-molten PVC surface layer; the composite board is immediately shaped by a set of cooling rollers at 40℃ to obtain a composite substrate with a smooth surface and a tight structure.

[0066] Step (3): 35g PVC paste resin, 20g plasticizer, 37.7g stone powder, 2.7g titanium dioxide, 2.4g naphtha (viscosity reducer), 0.7g dispersant 1148, and 1.5g calcium-zinc composite stabilizer are stirred at 800rpm for 10min to obtain a uniform plasticized paste with suitable viscosity. The plasticized paste is then mixed at 200g / m³. 2 The wet film coating amount is uniformly coated on the glass fiber surface of the composite substrate obtained in step (2). Then the board is heated and cured by steel roller at 175°C. The rotation speed of the steel roller is controlled so that the entire heating process lasts for about 1 minute, so that the PVC paste resin is completely gelled and partially melted, forming a dense PVC plasticizer layer that is firmly bonded to the glass fiber.

[0067] Step (4) Using a four-plate printing press, environmentally friendly water-based PVC ink is used to print a background pattern imitating natural stone texture on the smooth sol layer obtained in step (3). After printing, it is dried at 120°C for 30 seconds to allow the ink to solidify and form a clear and wear-resistant printed pattern layer.

[0068] Step (5) Mix 69.4g of high-transparency PVC resin, 27.5g of DOTP, 0.1g of lubricant, 3g of calcium-zinc composite stabilizer, 2g of colored quartz sand particles, 1g of nylon 6 microspheres and 0.9g of flake silicate evenly in a high-speed mixer. Extrude the mixture in a twin-screw extruder at 170-190℃ to melt-extrude a wear-resistant film of mixed colored sand and silicate particles with a thickness of 0.7mm. This wear-resistant film is immediately laminated online onto the surface of the printed layer in step (4) through a hot press roller at a temperature of 160℃ and a pressure of 0.3MPa. After cooling, a strong bond is formed.

[0069] Step (6) The composite board is fed into the embossing machine unit. A steel embossing roller with a design-featured steel plate pattern is used to hot press the wear-resistant layer surface at a roller temperature of 165℃ and a linear pressure of 0.6MPa. The linear speed is 12m / min. After embossing, the floor surface has a texture with excellent anti-slip effect and three-dimensional decorative feel.

[0070] Step (7) Mix 70g of aliphatic polyurethane acrylate, 25g of trimethylolpropane triacrylate and 5g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide evenly, at 22g / m 2 The wet film is evenly roller-coated onto the embossed wear-resistant layer surface. The coated board immediately enters a UV curing channel filled with high-purity nitrogen, with an irradiation intensity of 900 mJ / cm². 2 The board passes through at a speed of 12m / min and is exposed for 4 seconds. The coating is instantly cured, forming a transparent protective layer with a thickness of about 0.01mm. Finally, it is cooled to room temperature in the cooling section, cut to the predetermined size, and after passing manual visual inspection and instrument inspection, it is dustproof packaged, stacked and palletized to obtain non-slip and wear-resistant PVC flooring.

[0071] Example 4

[0072] The preparation method in this embodiment is exactly the same as that in Example 3, except that the formulation in step (1) is adjusted: the amount of bio-based plasticizer is reduced to 40g, while the amount of tung oil-DOPO amide ester is increased to 13.2g; the embossing roller in step (6) is replaced with a wheat ear twill embossing roller. The remaining steps and process parameters are completely consistent with those in Example 3.

[0073] Example 5

[0074] The preparation method of this embodiment is exactly the same as that of Example 3, except that the formulation in step (1) is adjusted: the amount of bio-based plasticizer is increased to 50g, and the amount of tung oil-DOPO amide ester is reduced to 10.8g; the embossing roller in step (6) is replaced with a triangular geometric embossing roller. The remaining steps and process parameters are completely consistent with those of Example 3.

[0075] Comparative Example 1: Flooring containing only bio-based plasticizers

[0076] This comparative example was used to verify the effect of using bio-based plasticizers alone. The preparation method was basically the same as in Example 3, but in step (1), tung oil-DOPO amide ester was not used, and the amount of bio-based plasticizer was increased to 57g. The remaining steps and process parameters were the same as in Example 3.

[0077] Comparative Example 2: Flooring containing only tung oil-DOPO amide ester

[0078] This comparative example was used to verify the effect of using tung oil-DOPO amide ester alone. The preparation method was basically the same as in Example 3, but in step (1), no bio-based plasticizer was used, and the amount of tung oil-DOPO amide ester was increased to 57g. The remaining steps and process parameters were the same as in Example 3.

[0079] Comparative Example 3: It does not contain three-phase functional anti-slip particles and has a traditional dot embossed pattern. The remaining structure and process parameters are the same as those in Example 3.

[0080] Comparative Example 4: Flooring using carbitol lactate

[0081] The preparation method of this comparative example is basically the same as that of Example 3, except that in step (1), 45g of carbitol lactate is used instead of the bio-based plasticizer. The remaining steps and process parameters are the same as those in Example 3. This comparative example is used to verify the negative impact of free hydroxyl groups on the thermal stability of PVC, highlighting the technical effect of acetylation modification in this invention.

[0082] Performance testing:

[0083] Abrasion resistance: Tested according to EN 660-2, with a load of (1±0.01) kg per abrasion wheel and a drop rate of (21±3) g / min. The abrasion value and abrasion resistance level are tested per 100 revolutions. Impact strength: Tested according to GB / T 1043-1993. According to EN ISO 24343-1:2012, the test sample is placed on a flat surface, and a ring-shaped load is placed on the test sample. A total force of 500 N is slowly applied to the sample surface over 2 seconds. After 150 minutes, the applied force is removed, and after another 150 minutes, the final thickness of the sample is measured using appropriate instruments, accurate to 0.01 mm. Dimensional stability (%) is tested according to EN 434 standard. Limiting oxygen index (LOI) is tested according to GB / T 2406.2-2009 standard. VOC emissions over 28 days are tested according to ISO 16000-6 standard. Anti-slip properties are tested according to DIN 51130.

[0084] The test results are shown in Table 1:

[0085] Table 1

[0086] Wear resistance mm 3 / 100 revolutions <![CDATA[Impact strength / KJ / m 2 > Indentation resistance / mm Dimensional stability / % Flame retardancy / % <![CDATA[Environmental friendliness / μg / m 3 > Anti-slip properties Example 3 1.63, T-class 14.2 0.04 0.032 32.5 <100 R11 Example 4 1.51, T-class 12.8 0.06 0.028 34.2 <100 R11 Example 5 1.70, T-class 15.5 0.03 0.036 30.8 <100 R11 Comparative Example 1 1.47, T-class 16.8 0.045 0.105 26.5 <100 R11 Comparative Example 2 1.90, T-class 8.6 0.15 0.040 35.0 <100 R11 Comparative Example 3 2.45, P grade 12.0 0.09 0.038 32.1 <100 R9 Comparative Example 4 1.67, T-class 13.9 0.05 0.081 31.8 <100 R11

[0087] According to Table 1 and the results from Examples 3-5 and Comparative Examples 1-4, the anti-slip and wear-resistant PVC flooring prepared by this invention exhibits excellent comprehensive performance in terms of anti-slip properties, flame retardancy, dimensional stability, impact resistance, and environmental friendliness. A comparison between Comparative Example 1 and Examples 3-5 shows that while using bio-based plasticizers alone can improve the flexibility of the material, the lack of rigid flame-retardant components results in insufficient flame retardancy and poor dimensional stability under temperature variations. In contrast, this invention, by introducing tung oil-DOPO amide ester, not only significantly improves flame retardancy but its rigid molecular structure also effectively inhibits thermal expansion, thereby greatly improving dimensional stability. A comparison between Comparative Example 2 and Examples 3-5 shows that while using tung oil-DOPO amide esters alone provides good flame retardancy, the excessive rigidity and insufficient flexibility of the material lead to decreased impact resistance, making it prone to damage under heavy loads or impacts. In contrast, this invention, through synergistic compounding with bio-based plasticizers, maintains high flame retardancy while imparting sufficient toughness to the substrate, achieving a balance between rigidity and flexibility. A comparison of Comparative Example 3 and Example 3 shows that the absence of three-phase functional anti-slip particles and the use of a traditional dot embossed pattern, coupled with a lack of directional flow-guiding structure, leads to decreased wear resistance and anti-slip properties. A comparison of Comparative Example 4 and Example 3 shows that the unacetylated bio-based intermediate, containing free hydroxyl groups, interferes with the thermal stability system of PVC, affecting the long-term performance of the material. In contrast, this invention, through acetylation modification of the bio-based plasticizer, effectively passivates active groups, significantly enhancing thermal stability and processing reliability.

[0088] 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.

[0089] 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 non-slip and wear-resistant PVC flooring, characterized in that, The anti-slip and wear-resistant PVC flooring has a five-layer composite structure, which includes, from bottom to top: a PVC substrate layer, a glass fiber reinforcement layer, a PVC plastisol layer, a wear-resistant layer, and a UV-cured coating. The PVC substrate layer specifically includes the following components: 100 parts by weight of PVC resin, 3.6-4.4 parts by weight of calcium-zinc composite stabilizer, 200-300 parts by weight of calcium carbonate, 2.7-3.3 parts by weight of rutile titanium dioxide, 40-50 parts by weight of bio-based plasticizer, 10.8-13.2 parts by weight of tung oil-DOPO amide ester, and 1.08-1.32 parts by weight of lubricant.

2. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The thickness of the UV-curable coating is 0.01-0.03 mm; the thickness of the wear-resistant layer is 0.5-0.7 mm; the thickness of the PVC plastisol layer is 0.15-0.2 mm; the thickness of the glass fiber reinforced layer is 0.09-0.11 mm; and the thickness of the PVC substrate layer is 1.2-2.5 mm.

3. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The wear-resistant layer has an embossed pattern on its surface with a texture depth of 0.2-0.4 mm.

4. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The wear-resistant layer is made of a blend of high-transparency PVC resin and three-phase functional particles, including colored quartz sand particles, nylon 6 microspheres and flake silicates; the colored quartz sand particles have a particle size of 0.3-0.55 mm; the nylon 6 microspheres have a particle size of 0.3-0.55 mm; and the flake silicates are synthetic mica particles with a particle size of 1-4 mm.

5. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The lubricant is a mixture of calcium stearate and PE wax in a mass ratio of 1:

1.

6. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The preparation method of the tung oil-DOPO amide ester includes the following steps: S1: Methyl tung oil, diethanolamine and KOH are mixed and stirred at 75-85℃ under vacuum of -0.095MPa for 3.5-4.5h. After removing impurities, drying, filtering and vacuum distillation are carried out to obtain tung oil diethanolamide. S2: Dissolve tung oil diethanolamide in dichloroethane, add butyl levulinate and p-toluenesulfonic acid, and stir and reflux at 82-86℃ for 3.5-4.5h under nitrogen atmosphere. After the reaction is completed, cool to room temperature, neutralize to pH 7-8 with saturated potassium carbonate aqueous solution, separate the liquid and liquid phases, and distill the organic phase under reduced pressure to obtain butyl levulinate of tung oil. S3: Mix tung oil butyl levulinate and DOPO, heat to 150-160℃ under a nitrogen atmosphere, stir and react for 5-6 hours, cool to room temperature, then recrystallize with hot ethanol at 50-60℃, cool to 0-5℃ and stand, filter, wash and dry to obtain tung oil-DOPO amide ester.

7. The anti-slip and wear-resistant PVC flooring according to claim 6, characterized in that, In step S1, the ratio of methyl tung oil, diethanolamine, and KOH is 260-322g:105-129g:1.9-2.3g; the impurity removal method is extraction with ethyl acetate and washing 2-3 times with saturated NaCl solution; the drying method is drying the organic phase with MgSO4. In step S2, the ratio of tung oil diethanolamide, dichloroethane, butyl levulinate, and p-toluenesulfonic acid is 70-120g:600-1000mL:40-70g:2.8-4.8g. In step S3, the ratio of butyl levulinate and DOPO is 30-40g:19-24g; the washing and drying method is washing 3-5 times with cold ethanol and vacuum drying at 55-65℃ for 10-14h.

8. The anti-slip and wear-resistant PVC flooring according to claim 1, characterized in that, The preparation method of the bio-based plasticizer includes the following steps: P1: L-lactic acid, butyl carbitol and p-toluenesulfonic acid monohydrate are added to cyclohexane and refluxed at 125-135℃ for 3.5-4.5h under a nitrogen atmosphere. After cooling to 45-55℃ and removing impurities, carbitol lactate is obtained. P2: Add carbitol lactate to tetrahydrofuran, add pyridine, and slowly add acetic anhydride dropwise over 30-45 minutes under ice-water bath and mechanical stirring. After the addition is complete, remove the ice bath, move to room temperature and continue stirring for 12-24 hours. After the reaction is complete, pour the reaction solution into ice water to remove impurities and obtain the bio-based plasticizer.

9. The anti-slip and wear-resistant PVC flooring according to claim 8, characterized in that, In step P1, the ratio of L-lactic acid, butyl carbitol, p-toluenesulfonic acid monohydrate, and cyclohexane is 24-30g:52-64g:0.75-0.95g:130-170mL. The impurity removal method involves washing sequentially with 4-6% NaHCO3 solution, deionized water, and saturated NaCl solution until neutral. The organic phase is dried over anhydrous MgSO4 and then the solvent is removed by rotary evaporation. In step P2, the ratio of carbitol lactate, tetrahydrofuran, pyridine, and acetic anhydride is 30-40g:150-200mL:21-28g:22-28g. The impurity removal method involves washing 2-3 times with 1mol / L dilute hydrochloric acid, then washing with saturated sodium bicarbonate solution until no bubbles are generated, and finally washing once with saturated sodium chloride solution. The organic phase is dried over anhydrous magnesium sulfate for 25-35 minutes and then filtered. The filtrate is then evaporated under reduced pressure at below 40℃ to remove the solvent.

10. A method for preparing anti-slip and wear-resistant PVC flooring according to any one of claims 1-9, characterized in that, Includes the following steps: Step (1) Put PVC resin, calcium-zinc composite stabilizer, calcium carbonate and rutile titanium dioxide into a high-speed mixer. First, mix at 100-120℃ and 800-1200 rpm for 4.5-5.5 min. After cooling to 54-66℃, add bio-based plasticizer, tung oil-DOPO amide ester and lubricant. Then mix at 200-400 rpm for 2.7-3.3 min. Discharge at 40.5-49.5℃. Plasticize and extrude the mixture in a twin-screw extruder at temperature zones of 150℃, 165℃, 175℃, 180℃ and 175℃. The screw speed is 200-350 rpm to obtain PVC base sheet. Step (2) Feed the PVC base sheet into a two-roll calender. Set the temperature of the upper roll to 160℃ and the lower roll to 150℃. Calender by gradually adjusting the roll gap, and control the linear speed at 10-16m / min. Then, calender the PVC base sheet with a thickness of 20-70g / m 2 The fiberglass mat is hot-pressed onto one side of the PVC substrate at a temperature of 139.5-170.5℃ and a pressure of 0.45-0.55MPa, and then shaped by a 40℃ cooling roller to obtain a composite substrate. Step (3) Take PVC paste resin, DOTP, stone powder, titanium dioxide, viscosity reducer, dispersant and calcium-zinc composite stabilizer, stir evenly to obtain PVC plasticized paste, and then apply it at 150-250g / m 2 The coating amount is evenly applied to the outer surface of the glass fiber mat, and then heated and cured at 160-200℃ for 1-3 minutes to obtain a PVC plastisol layer. Step (4) Print the pattern on the surface of the PVC plastisol layer using water-based environmentally friendly ink, and dry it at 108-132℃ for 27-33s to obtain the printed pattern layer; Step (5) After mixing the high-transparency PVC resin, plasticizer, lubricant, calcium-zinc stabilizer, colored quartz sand particles, nylon 6 microspheres and flake silicate particles evenly, the mixture is melt-extruded in a twin-screw extruder at 170-190℃ and then thermally bonded to the surface of the printed layer at a temperature of 150-170℃ and a pressure of 0.27-0.33MPa to obtain a wear-resistant layer of mixed colored sand and silicate particles. Step (6) Use a steel plate embossing roller with a texture depth of 0.2-0.4mm to hot press the wear-resistant layer at a temperature of 148-181℃ and a pressure of 0.54-0.66MPa to obtain a combined pattern, with a linear speed of 10-16m / min. Step (7) Apply UV-curable polyurethane acrylate coating at 15-30 g / m 2 The wet film is evenly roller-coated onto the surface of the wear-resistant layer, and then immediately enters the nitrogen-protected UV curing channel at an irradiation intensity of 800-1200 mJ / cm². 2 Expose for 3-6 seconds to obtain a UV-cured coating, then cool, cut, inspect, package, palletize, and store to obtain anti-slip and wear-resistant PVC flooring.

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