Flooring film and method of making same

Abstract

This invention relates to the field of floor membrane technology, and discloses a floor membrane and its preparation method. The floor membrane provided by this invention includes a wear-resistant layer, a transition layer, and a resilience layer stacked sequentially: the density of the wear-resistant layer > the density of the transition layer > the density of the resilience layer; the density of the transition layer is 0.5 g / cm³. 3 -0.7g / cm 3 In this invention, the wear-resistant layer is dense and hard, dispersing the initial impact force and preventing local collapse, thus improving wear resistance, scratch resistance, and weather resistance; the transition layer disperses impact energy, balances and buffers, provides support, and prevents stress concentration; the rebound layer provides efficient impact energy absorption and rebound, offering cushioning. The floor membrane of this invention is integrally molded, solving the problem of interlayer delamination, extending service life, and does not use adhesives, resulting in lower costs and no VOC emissions.

Description

Technical Field

[0001] This invention relates to the field of floor membrane technology, and more specifically to a floor membrane and its preparation method. Background Technology

[0002] In existing technologies, floor membranes include those with a single-density foam layer structure and those with a multi-layer composite structure. Floor membranes with a single-density foam layer structure mainly achieve uniform foaming through chemical foaming agents or physical foaming, and are widely used in packaging, floor mats, decorative materials, sports floor mats, and building vibration damping. However, they cannot simultaneously meet the requirements of high impact absorption and surface abrasion resistance. Impact energy cannot be effectively dispersed, easily leading to local stress concentration, unsatisfactory shock absorption effect, and a decline in shock absorption effect after long-term use. Floor membranes with a multi-layer composite structure include a wear-resistant layer and a foam layer, bonded together with an adhesive. After long-term stress or changes in temperature and humidity, the interlayer adhesive strength weakens, easily leading to delamination and bubbles. Furthermore, the adhesive itself may age and become brittle, further weakening the structural integrity. At the same time, the adhesives used in the composite process often contain volatile organic compounds (VOCs), which are detrimental to indoor air quality and environmental protection requirements. Multi-layer composites require multiple molding, gluing, bonding, and curing processes, resulting in a long process flow, high energy consumption, large equipment investment, and high cost. In addition, regardless of whether it is a single-density or simple composite structure floor membrane, it is prone to plastic deformation under repeated impacts, resulting in decreased resilience and a significant reduction in shock absorption effect. Summary of the Invention

[0003] This invention provides a floor membrane to solve the problems of poor shock absorption, easy formation of delamination bubbles, and poor resilience in the prior art.

[0004] In a first aspect, the present invention provides a floor membrane comprising a wear-resistant layer, a transition layer, and a resilience layer stacked sequentially: The density of the wear-resistant layer is greater than the density of the transition layer, which is greater than the density of the resilience layer. The density of the transition layer is 0.5 g / cm³. 3 -0.7g / cm 3 .

[0005] In one optional embodiment, the density of the wear-resistant layer is 0.8 g / cm³. 3 -1.2g / cm 3 .

[0006] In one optional embodiment, the density of the resilience layer is 0.1 g / cm³. 3 -0.3g / cm 3 .

[0007] In one optional embodiment, the wear-resistant layer comprises, by weight percentage: 80wt%-90wt% thermoplastic polyurethane elastomer, 3wt%-12wt% first filler, 0.3wt%-1.5wt% antioxidant, 0.5wt%-2.5wt% lubricant, 0.5wt%-1.5wt% ultraviolet absorber, and 1wt%-3wt% pigment.

[0008] In one alternative embodiment, the raw material composition of the transition layer, by mass percentage, includes: 75wt%-87wt% of a mixture of ethylene-vinyl acetate copolymer and polyolefin elastomer, 3wt%-8wt% of a first foaming agent, 0.2wt%-1wt% of a crosslinking agent, 5wt%-15wt% of a second filler, and 0.5wt%-2wt% of a first coupling agent.

[0009] In one alternative embodiment, the mass ratio of the ethylene-vinyl acetate copolymer to the polyolefin elastomer in the mixture is 4-7:3-6.

[0010] In one optional embodiment, the raw material composition of the rebound layer, by mass percentage, includes: 60wt%-75wt% polyolefin elastomer, 2wt%-5wt% second foaming agent, 10wt%-15wt% non-polyolefin elastomer, 0.5wt%-2wt% first activator, 8wt%-15wt% third filler, and 0.5wt%-3wt% second coupling agent.

[0011] In one alternative embodiment, the first filler includes at least one of silicon dioxide, silicon carbide, alumina, and titanium dioxide.

[0012] In one alternative embodiment, the antioxidant comprises at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl)phosphite, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and N,N'-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine.

[0013] In one alternative embodiment, the lubricant comprises at least one of zinc stearate, calcium stearate, polyethylene wax, and ethylene bis-stearamide.

[0014] In one optional embodiment, the ultraviolet absorber includes at least one selected from 2-[2-hydroxy-3,5-bis(1,1-dimethylpropylphenyl)]-2H-benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol), 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylamidinium.

[0015] In one alternative embodiment, the pigment includes at least one of titanium dioxide, carbon black, phthalocyanine blue, and iron oxide red.

[0016] In one alternative embodiment, the first blowing agent includes at least one of 4,4'-oxobisbenzenesulfonyl hydrazine and azodicarbonamide.

[0017] In an optional embodiment, when the first foaming agent is azodicarbonamide, the transition layer further includes a second activator.

[0018] In one alternative embodiment, the content of the second activator in the transition layer is 0.2wt%-1wt%.

[0019] In one alternative embodiment, the second activator includes at least one of zinc oxide, stearic acid, and magnesium oxide.

[0020] In one alternative embodiment, the crosslinking agent includes at least one selected from dicumyl peroxide, 1,1-di-tert-butylperoxycyclohexane, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0021] In one alternative embodiment, the second filler and the third filler are each independently selected from at least one of calcium carbonate, talc, wollastonite, and aluminum hydroxide.

[0022] In one alternative embodiment, the first coupling agent and the second coupling agent are each independently selected from at least one of γ-aminopropyltriethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and aluminate.

[0023] In one optional embodiment, the second foaming agent includes at least one of azodicarbonamide, sodium bicarbonate, and azobisisobutyronitrile.

[0024] In one alternative embodiment, the non-polyolefin elastomer includes at least one of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, and styrene-ethylene-butene-styrene block copolymer.

[0025] In one alternative embodiment, the first activator includes at least one of zinc oxide, zinc stearate, magnesium oxide, and stearic acid.

[0026] In one alternative embodiment, the thickness of the wear-resistant layer is 0.3mm-0.5mm.

[0027] In one alternative embodiment, the thickness of the transition layer is 1.0 mm to 1.5 mm.

[0028] In one alternative embodiment, the thickness of the rebound layer is 2mm-3mm.

[0029] In a second aspect, the present invention provides a method for preparing the floor membrane described in the first aspect, comprising the following steps: (1) The raw materials of the wear-resistant layer are mixed and melted for the first time to obtain a first molten material; the raw materials of the transition layer are mixed and melted for the second time to obtain a second molten material; the raw materials of the resilience layer are mixed and melted for the third time to obtain a third molten material; (2) The first molten material, the second molten material and the third molten material are extruded and merged in parallel to form a wear-resistant layer, a transition layer and a resilience layer stacked in sequence, and then cast and cooled to obtain the final product.

[0030] In one alternative embodiment, the temperature of the first melt is 180°C-200°C.

[0031] In one alternative embodiment, the temperature of the second melting point is 150°C-170°C.

[0032] In one alternative embodiment, the temperature of the third melting point is 130°C-150°C.

[0033] In one alternative embodiment, the extrusion rate of the first molten material is 8 m / min to 12 m / min.

[0034] In one optional embodiment, the extrusion rate of the second molten material is 10 m / min to 15 m / min.

[0035] In one optional embodiment, the extrusion rate of the third molten material is 12 m / min to 18 m / min.

[0036] In one alternative embodiment, the mass ratio of the first molten material, the second molten material, and the third molten material is 1:2-3:3-5.

[0037] The technical solution of this invention has the following advantages: 1. The floor membrane provided by the present invention comprises a wear-resistant layer, a transition layer, and a resilience layer stacked sequentially: the density of the wear-resistant layer > the density of the transition layer > the density of the resilience layer; the density of the transition layer is 0.5 g / cm³. 3 -0.7g / cm 3 In this invention, the wear-resistant layer is dense and hard, dispersing the initial impact force and preventing local collapse, thus improving wear resistance, scratch resistance, and weather resistance. The transition layer disperses impact energy, balances and buffers, provides support, and prevents stress concentration. The rebound layer provides efficient impact energy absorption and rebound, offering cushioning. The floor membrane of this invention is integrally molded, solving the problem of interlayer delamination, extending service life, and does not use adhesives, resulting in lower costs and no VOC emissions. By controlling the density of the wear-resistant layer > the transition layer > the rebound layer, impact energy is gradually attenuated and uniformly dispersed, avoiding stress concentration, enhancing shock absorption performance, and improving fatigue resistance. The density of the transition layer is controlled at 0.5 g / cm³. 3 -0.7g / cm 3 This balances the hardness of the wear-resistant layer with the softness and elasticity of the resilience layer, preventing stress concentration. If the density is >0.7g / cm³ 3 The stress buffer disappears, and the damping performance drops sharply; if the density is <0.1g / cm³ 3 Insufficient support can lead to localized collapses or even deformation.

[0038] 2. The method for preparing the floor membrane provided by the present invention includes the following steps: (1) mixing the raw materials of the wear-resistant layer and melting them for the first time to obtain a first molten material; mixing the raw materials of the transition layer and melting them for the second time to obtain a second molten material; mixing the raw materials of the resilience layer and melting them for the third time to obtain a third molten material; (2) extruding the first molten material, the second molten material and the third molten material and merging them side by side to form a wear-resistant layer, a transition layer and a resilience layer stacked in sequence, casting and cooling to obtain the final product. The present invention adopts a three-layer co-extrusion casting one-step molding process. The three layers of raw materials are melted and bonded in the die head, and the interface is a mutual penetration and entanglement of molecular chains. After cooling, they form a whole. Detailed Implementation

[0039] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0040] Unless otherwise specified, all experimental steps or conditions in the examples were performed according to conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0041] To address the problems existing in the aforementioned related technologies, according to a first aspect of the present invention, the present invention provides a floor membrane comprising a wear-resistant layer, a transition layer, and a resilience layer sequentially stacked: The density of the wear-resistant layer is greater than the density of the transition layer, which is greater than the density of the resilience layer. The density of the transition layer is 0.5 g / cm³. 3 -0.7g / cm 3 .

[0042] In this invention, the wear-resistant layer is dense and hard, dispersing the initial impact force and preventing local collapse, thus improving wear resistance, scratch resistance, and weather resistance. The transition layer disperses impact energy, balances and buffers, provides support, and prevents stress concentration. The rebound layer provides efficient impact energy absorption and rebound, offering cushioning. The floor membrane of this invention is integrally molded, solving the problem of interlayer delamination, extending service life, and does not use adhesives, resulting in lower costs and no VOC emissions. By controlling the density of the wear-resistant layer > the transition layer > the rebound layer, impact energy is gradually attenuated and uniformly dispersed, avoiding stress concentration, enhancing shock absorption performance, and improving fatigue resistance. The density of the transition layer is controlled at 0.5 g / cm³. 3 -0.7g / cm 3 This balances the hardness of the wear-resistant layer with the softness and elasticity of the resilience layer, preventing stress concentration. If the density is >0.7g / cm³ 3 The stress buffer disappears, and the damping performance drops sharply; if the density is <0.1g / cm³ 3 Insufficient support can lead to localized collapses or even deformation.

[0043] In one optional embodiment, the density of the wear-resistant layer is 0.8 g / cm³. 3 -1.2g / cm 3 The density of the wear-resistant layer is controlled at 0.8 g / cm³. 3 -1.2g / cm 3 This ensures the wear-resistant layer has sufficient hardness to resist wear and scratches, disperse initial impact force, prevent local collapse, and maintain a certain degree of toughness to avoid brittleness. If the density is >1.2g / cm³ 3 This can lead to an overly hard abrasion layer, reduced toughness, easy cracking upon impact, and a stiff feel underfoot; if the density is <0.8g / cm³ 3 It lacks hardness and wear resistance, making it difficult to resist friction and impact, and it is prone to scratches and dents.

[0044] In one optional embodiment, the density of the resilience layer is 0.1 g / cm³. 3 -0.3g / cm 3 The density of the rebound layer was controlled at 0.1 g / cm³. 3 -0.3g / cm3 This allows the rebound layer to form a sufficiently porous structure, providing efficient impact energy absorption and rebound performance; at the same time, it ensures a certain level of support to prevent collapse due to excessive compression. If the density is >0.3 g / cm³ 3 The resilience and shock absorption capacity decrease significantly; if the density is <0.1g / cm³ 3 It will be over-compressed when subjected to impact, with insufficient support, and the microporous structure is easily damaged and cannot be repaired.

[0045] In one optional embodiment, the wear-resistant layer comprises, by weight percentage: 80wt%-90wt% thermoplastic polyurethane elastomer (TPU), 3wt%-12wt% first filler, 0.3wt%-1.5wt% antioxidant, 0.5wt%-2.5wt% lubricant, 0.5wt%-1.5wt% UV absorber, and 1wt%-3wt% pigment. Adding fillers can improve wear resistance and effectively disperse impact.

[0046] In one alternative embodiment, the raw material composition of the transition layer, by mass percentage, includes: 75wt%-87wt% of a mixture of ethylene-vinyl acetate copolymer (EVA) and polyolefin elastomer (POE), 3wt%-8wt% of a first foaming agent, 0.2wt%-1wt% of a crosslinking agent, 5wt%-15wt% of a second filler, and 0.5wt%-2wt% of a first coupling agent.

[0047] In one alternative embodiment, the mass ratio of the ethylene-vinyl acetate copolymer to the polyolefin elastomer in the mixture is 4-7:3-6.

[0048] In one optional embodiment, the raw material composition of the rebound layer, by weight percentage, includes: 60wt%-75wt% polyolefin elastomer, 2wt%-5wt% second foaming agent, 10wt%-15wt% non-polyolefin elastomer, 0.5wt%-2wt% first activator, 5wt%-15wt% third filler, and 0.5wt%-3wt% second coupling agent.

[0049] In this invention, the TPU in the wear-resistant layer can enhance wear resistance; the EVA and POE in the transition layer provide balanced support and transition; and the POE and elastomer in the resilience layer achieve ultra-high resilience.

[0050] In one alternative embodiment, the first filler includes at least one of silicon dioxide, silicon carbide, alumina, and titanium dioxide.

[0051] In one optional embodiment, the antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and N,N'-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine (antioxidant 1098). Adding antioxidants can inhibit the oxidative degradation of the wear-resistant layer raw materials during melt processing and use, improve the aging resistance of the floor membrane, and extend its service life.

[0052] In one optional embodiment, the lubricant includes at least one of zinc stearate, calcium stearate, polyethylene wax, and ethylene bis-stearamide; adding lubricant can reduce the viscosity of the molten material, improve processing fluidity, reduce material adhesion in the extruder, ensure smooth processing, and improve the surface finish of the floor film.

[0053] It should be noted that, in this invention, the molecular weight of polyethylene wax is 2000-4000.

[0054] In one optional embodiment, the ultraviolet absorber includes at least one of 2-[2-hydroxy-3,5-bis(1,1-dimethylpropylphenyl)]-2H-benzotriazole (UV-328), 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol) (UV-360), 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-326), and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylamidine (UV-1); provided that the ultraviolet absorber can prevent photoaging of the floor film when used outdoors, avoid fading, cracking and other problems, and improve weather resistance.

[0055] In one optional embodiment, the pigment includes at least one of titanium dioxide, carbon black, phthalocyanine blue, and iron oxide red; thereby giving the floor film different colors to meet different decorative needs, while some pigments (such as titanium dioxide and carbon black) also have a certain ultraviolet shielding effect, which helps to improve weather resistance.

[0056] In one alternative embodiment, the first foaming agent includes at least one of 4,4'-oxobis(benzenesulfonyl hydrazine) (OBSH) and azodicarbonamide (AC foaming agent); thereby decomposing to generate gas during melt processing, forming a microporous structure, reducing the density of the transition layer, and improving resilience and shock absorption performance.

[0057] In an optional embodiment, when the first foaming agent is azodicarbonamide, the transition layer further includes a second activator.

[0058] In one alternative embodiment, the content of the second activator in the transition layer is 0.2wt%-1wt%.

[0059] In one alternative embodiment, the second activator includes at least one of zinc oxide, stearic acid, and magnesium oxide.

[0060] In one optional embodiment, the crosslinking agent includes at least one of dicumyl peroxide (DCP), 1,1-di-tert-butyl peroxide cyclohexane, di-tert-butyl peroxide (DTBP), and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; thereby causing the raw materials of the transition layer to undergo a crosslinking reaction, forming a three-dimensional network structure, improving the strength, heat resistance, and dimensional stability of the transition layer, and preventing deformation.

[0061] In one alternative embodiment, the second and third fillers are each independently selected from at least one of calcium carbonate, talc, wollastonite, and aluminum hydroxide; thereby reducing production costs while improving rigidity, wear resistance, and dimensional stability, and reducing shrinkage deformation.

[0062] In one optional embodiment, the first coupling agent and the second coupling agent are each independently selected from at least one of γ-aminopropyltriethoxysilane (KH-550), γ-(methacryloyloxy)propyltrimethoxysilane (KH-570), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560), and aluminate; thereby improving the interfacial compatibility between the inorganic filler and the mixed matrix of ethylene-vinyl acetate copolymer and polyolefin elastomer, increasing the bonding force between the two, enhancing the mechanical properties of the transition layer, and reducing filler agglomeration.

[0063] In one alternative embodiment, the second foaming agent includes at least one of azodicarbonamide (AC foaming agent), sodium bicarbonate, and azobisisobutyronitrile (AIBN); thereby decomposing to generate gas during melt processing, forming a microporous structure, reducing the density of the rebound layer, and improving resilience and shock absorption performance.

[0064] In one alternative embodiment, the non-polyolefin elastomer includes at least one of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, and styrene-ethylene-butene-styrene block copolymer (SEBS); in synergy with POE, it further enhances the resilience and impact absorption properties of the rebound layer, while improving the toughness and fatigue resistance of the rebound layer.

[0065] In one alternative embodiment, the first activator includes at least one of zinc oxide, zinc stearate, magnesium oxide, and stearic acid; thereby promoting the decomposition of the second foaming agent, reducing the decomposition temperature of the second foaming agent, and improving the foaming efficiency.

[0066] In one alternative embodiment, the wear-resistant layer has a thickness of 0.3mm-0.5mm; this allows the wear-resistant layer to have sufficient wear resistance and service life, without excessively increasing the overall thickness and weight of the floor membrane.

[0067] In one optional embodiment, the thickness of the transition layer is 1.0mm-1.5mm; this allows the transition layer to effectively disperse impact energy, balance and buffer, provide support, and prevent stress concentration.

[0068] In one optional embodiment, the thickness of the rebound layer is 2mm-3mm; this allows the rebound layer to have sufficient impact energy absorption and rebound performance, providing a good cushioning effect.

[0069] In a second aspect, the present invention provides a method for preparing the floor membrane described in the first aspect, comprising the following steps: (1) The raw materials of the wear-resistant layer are mixed and melted for the first time to obtain a first molten material; the raw materials of the transition layer are mixed and melted for the second time to obtain a second molten material; the raw materials of the resilience layer are mixed and melted for the third time to obtain a third molten material; (2) The first molten material, the second molten material and the third molten material are extruded and merged in parallel to form a wear-resistant layer, a transition layer and a resilience layer stacked in sequence, and then cast and cooled to obtain the final product.

[0070] In one alternative embodiment, the temperature of the first melt is 180°C-200°C.

[0071] In one alternative embodiment, the temperature of the second melting point is 150°C-170°C.

[0072] In one alternative embodiment, the temperature of the third melting point is 130°C-150°C.

[0073] It is understood that the present invention controls the first melting temperature to be 180℃-200℃, the second melting temperature to be 150℃-170℃, and the third melting temperature to be 130℃-150℃, so that each layer of material is fully melted and plasticized, and maintains a suitable melt viscosity. This ensures that each layer of material can be well bonded in the die head, while avoiding material degradation.

[0074] In one alternative embodiment, the extrusion rate of the first molten material is 8 m / min to 12 m / min.

[0075] In one optional embodiment, the extrusion rate of the second molten material is 10 m / min to 15 m / min.

[0076] In one optional embodiment, the extrusion rate of the third molten material is 12 m / min to 18 m / min.

[0077] In one alternative embodiment, the mass ratio of the first molten material, the second molten material, and the third molten material is 1:2-3:3-5.

[0078] Furthermore, this invention controls the three molten material streams to be jointly introduced into a T-shaped multilayer co-extrusion die. By independently adjusting the melt flow rate and thickness ratio of each layer within the die, the three layers of melt are brought together in parallel at the die exit, forming a gradient structure with density continuously decreasing from the surface to the bottom layer before cooling.

[0079] In one optional embodiment, the cooling step includes drawing the extruded film onto a segmented, temperature-controlled cooling roller assembly for casting cooling. The cooling roller assembly employs a segmented gradient cooling method, dividing the film into three temperature zones along the film's travel direction: the first zone has a temperature of 70℃-80℃, allowing the film to initially set and release internal stress; the second zone has a temperature of 50℃-70℃, allowing heat to be slowly dissipated from the film, stabilizing the cell structure and locking the density gradient of each layer; the third zone has a temperature of 30℃-50℃, cooling the film to below room temperature for final setting. The temperature difference between adjacent rollers is controlled within 10℃-20℃. The linear speed of the cooling rollers is matched to the extrusion rate, and the draw ratio is controlled at 1.2-1.5:1, ensuring uniform cooling and solidification of the film from the surface inwards.

[0080] Furthermore, the cooling temperature and speed are matched with the extrusion rate, allowing the film to cool and solidify uniformly from the surface inwards, locking in the gradient structure, and ultimately forming a continuous, gradient density floor film.

[0081] In this invention, the thermoplastic polyurethane elastomer was purchased from BASF, model TPU 1185A, with a density of 1.12 g / cm³. 3 The polyolefin elastomer was purchased from Dow Chemical, model number ENGAGE. TM 8150, density is 0.868 g / cm³ 3 The ethylene-vinyl acetate copolymer was purchased from DuPont, model number Elvax. ® 260, vinyl acetate content is 28%; polyethylene wax purchased from Honeywell, model AC. ®6A, molecular weight 2000-4000; talc powder purchased from Guangyuan Chemical, model HS-358; wollastonite purchased from Guangyuan Chemical, model 1250 mesh; aluminate purchased from Shandong Shoucheng Chemical, model DL-411; natural rubber purchased from Hainan Natural Rubber Industry Group, model SCR WF; styrene-butadiene rubber purchased from Sinopec Qilu Petrochemical, model SBR 1502; butadiene rubber purchased from Sinopec Yanshan Petrochemical, model BR 9000; styrene-ethylene-butene-styrene block copolymer purchased from Sinopec Baling Petrochemical, model YH-503, styrene content 33%; polyurethane adhesive purchased from Fujian Kangda New Materials, model WD8969.

[0082] Example 1 This embodiment provides a floor membrane, comprising a wear-resistant layer, a transition layer, and a resilience layer; wherein: By weight percentage, the wear-resistant layer consists of: 89.7 wt% TPU, 6 wt% silica, 0.5 wt% antioxidant 1010, 1 wt% zinc stearate, 0.8 wt% UV-328, and 2 wt% titanium dioxide. The raw material composition of the transition layer, by mass percentage, includes: 83.5 wt% EVA and POE mixture (EVA and POE mass ratio of 1:1), 5 wt% OBSH, 0.5 wt% DCP, 10 wt% calcium carbonate, and 1 wt% KH-550; The raw material composition of the rebound layer, by mass percentage, includes: 71wt% POE, 3wt% sodium bicarbonate, 12wt% natural rubber powder, 1.5wt% zinc oxide, 12wt% calcium carbonate, and 0.5wt% KH-550.

[0083] This embodiment provides a method for preparing a floor membrane, including the following steps: (1) After drying the above raw materials, weigh 100g of wear-resistant layer raw material, 250g of transition layer raw material and 350g of resilience layer raw material according to the above ratio, mix them separately and then transport them to a co-extrusion extruder with a three-channel structure. (2) The three channels of the extruder are divided into independent temperature control zones. The barrel temperature of the wear-resistant layer is 190℃, the barrel temperature of the transition layer is 160℃, and the barrel temperature of the springback layer is 140℃. The materials of each layer are fully melted and plasticized under the conveying and shearing of their respective screws, and the molten materials of the wear-resistant layer, the molten materials of the transition layer and the molten materials of the springback layer are obtained respectively. (3) The wear-resistant layer molten material, the transition layer molten material and the elastic layer molten material are fed into a T-shaped multi-layer co-extrusion die. The extrusion rates are 10 m / min, 12 m / min and 15 m / min, respectively. The three layers of melt are merged in parallel at the die outlet. The extruded film is drawn onto a segmented temperature-controlled cooling roller group for casting and cooling. The cooling roller passes through three temperature zones, namely 80℃, 60℃ and 40℃. The linear speed of the cooling roller is matched with the extrusion rate and the draw ratio is 1.3:1. The floor film is prepared. The thickness of the wear-resistant layer is 0.42 mm, the thickness of the transition layer is 1.18 mm and the thickness of the elastic layer is 2.47 mm.

[0084] Example 2 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the transition layer includes: 86.9 wt% EVA / POE mixture (the mass ratio of EVA to POE is 7:3), 7 wt% OBSH, 0.3 wt% DCP, 5 wt% calcium carbonate, and 0.8 wt% KH-550; and by mass percentage, the raw material composition of the rebound layer includes: 70 wt% POE, 5 wt% sodium bicarbonate, 15 wt% natural rubber powder, 1 wt% zinc oxide, 8 wt% calcium carbonate, and 1 wt% KH-550. The barrel temperature of the transition layer is 170°C, and the barrel temperature of the rebound layer is 150°C. The extrusion rates of the molten material in the transition layer and the molten material in the rebound layer are 10 m / min and 12 m / min, respectively, with a draw ratio of 1.2:1. The thickness of the transition layer is 1.02 mm, and the thickness of the rebound layer is 2.98 mm.

[0085] Example 3 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the transition layer includes: 79wt% EVA / POE mixture (mass ratio of EVA to POE is 4:6), 4wt% OBSH, 0.8wt% DCP, 15wt% calcium carbonate, and 1.2wt% KH-550; and by mass percentage, the raw material composition of the rebound layer includes: 68wt% POE, 2wt% sodium bicarbonate, 10wt% natural rubber powder, 2wt% zinc oxide, 15wt% calcium carbonate, and 3wt% KH-550. The barrel temperature of the transition layer is 150℃, and the barrel temperature of the rebound layer is 130℃. The extrusion rates of the molten material in the transition layer and the molten material in the rebound layer are 15m / min and 18m / min, respectively, with a draw ratio of 1.5:1. The thickness of the transition layer is 1.48mm, and the thickness of the rebound layer is 2.03mm.

[0086] Example 4 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the wear-resistant layer includes: 80.5wt% TPU, 12wt% silica, 0.8wt% antioxidant 1010, 2.5wt% zinc stearate, 1.2wt% UV-328, and 3wt% titanium dioxide; wherein, the barrel temperature of the wear-resistant layer is 200℃, and the thickness of the wear-resistant layer is 0.32mm.

[0087] Example 5 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the wear-resistant layer includes: 90wt% TPU, 5.7wt% silica, 0.3wt% antioxidant 1010, 0.5wt% zinc stearate, 0.5wt% UV-328, and 3wt% titanium dioxide; wherein, the barrel temperature of the wear-resistant layer is 180℃, and the thickness of the wear-resistant layer is 0.58mm.

[0088] Example 6 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the wear-resistant layer includes: TPU 80.5wt%, silicon carbide 12wt%, antioxidant 1076 0.8wt%, ethylene bis-stearamide 2.5wt%, UV-326 1.2wt%, and phthalocyanine blue 3wt%; the thickness of the wear-resistant layer is 0.34mm.

[0089] Example 7 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the wear-resistant layer includes: TPU 80.5wt%, alumina 12wt%, antioxidant 10980.8wt%, polyethylene wax 2.5wt%, UV-1 1.2wt%, and iron oxide red 3wt%; the thickness of the wear-resistant layer is 0.36mm.

[0090] Example 8 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the transition layer includes: 78wt% of a mixture of EVA and POE (the mass ratio of EVA and POE is 1:1), 8wt% of AC foaming agent, 1wt% of zinc oxide, 1wt% of DTBP, 10wt% of wollastonite, and 2wt% of aluminate; the thickness of the transition layer is 1.33mm.

[0091] Example 9 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the transition layer includes: 81wt% of a mixture of EVA and POE (the mass ratio of EVA and POE is 1:1), 6wt% of AC foaming agent, 0.2wt% of stearic acid, 0.2wt% of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 12wt% of aluminum hydroxide, and 0.5wt% of KH-570; the thickness of the transition layer is 1.31mm.

[0092] Example 10 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the resilience layer includes: 67wt% POE, 5wt% AIBN, 14wt% SEBS, 2wt% stearic acid, 10wt% talc, and 2wt% KH-560; the thickness of the resilience layer is 2.68mm.

[0093] Example 11 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the raw material composition of the rebound layer includes: 75wt% POE, 4.5wt% sodium bicarbonate, 13wt% styrene-butadiene rubber powder, 0.5wt% magnesium oxide, 5wt% aluminum hydroxide, and 2wt% aluminate; the thickness of the rebound layer is 2.61mm.

[0094] Example 12 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the mass of the transition layer raw material is 300g and the mass of the rebound layer raw material is 400g; the thickness of the transition layer is 1.50mm and the thickness of the rebound layer is 2.78mm.

[0095] Example 13 This embodiment provides a method for preparing a floor membrane, which is basically the same as the steps in Embodiment 1, except that, by mass percentage, the mass of the transition layer raw material is 200g and the mass of the rebound layer raw material is 500g; the thickness of the transition layer is 1.00mm and the thickness of the rebound layer is 3.00mm.

[0096] Comparative Example 1 This comparative example provides a method for preparing a floor membrane, which is basically the same as the steps in Example 1, except that the transition layer and the resilience layer are omitted, and only the wear-resistant layer is retained.

[0097] Comparative Example 2 This comparative example provides a method for preparing a floor membrane, which omits the transition layer and directly bonds the wear-resistant layer and the resilience layer with polyurethane adhesive.

[0098] Comparative Example 3 This comparative example provides a method for preparing a floor membrane, which is basically the same as the steps in Example 1, except that, by mass percentage, the raw material composition of the transition layer includes: 85wt% of a mixture of EVA and POE (the mass ratio of EVA and POE is 1:1), 1.5wt% of OBSH, 0.5wt% of DCP, 12.5wt% of calcium carbonate, and 0.5wt% of KH-550; the barrel temperature of the transition layer is 155℃, and the thickness of the transition layer is 1.16mm.

[0099] Experimental Example Density tests were performed on the wear-resistant layer, transition layer, and resilience layer prepared in Examples 1-13 and Comparative Examples 1-3, respectively. The results are shown in Table 1.

[0100] Table 1. Test results of the density of the wear-resistant layer, transition layer, and resilience layer in each embodiment and comparative example.

[0101] Experiment Example 2 Impact absorption rate, resilience, interlaminar peel strength, compression set, and volatile matter content of the floor membranes prepared in Examples 1-13 and Comparative Examples 1-3 were tested respectively. The results are shown in Table 2. Impact absorption rate: The impact absorption rate was tested according to Appendix B of GB / T 14833-2020 "Synthetic Materials for Sports Field Surface Layers"; Rebound rate: The rebound rate was tested according to the falling ball rebound method specified in GB / T 6670-2008 "Determination of rebound performance of flexible foam polymer materials".

[0102] Interlayer peel strength test: According to GB / T 8808-1988 "Peel Test Method for Flexible Composite Plastic Materials", the sample width is 30 mm and the peel speed is 200 mm / min. If no separation occurs between the layers during the peeling process, it is recorded as "no delamination". Compression set test: According to GB / T 6669-2008 "Determination of compression set of flexible foam polymer materials", the sample was compressed to 50% of its initial thickness and kept at a constant temperature of 23℃ for 22 hours to test the compression set. Volatile content: VOC content was tested according to GB 18586-2001 "Limits of Hazardous Substances in Polyvinyl Chloride Roll Flooring for Interior Decoration and Renovation".

[0103] Table 2. Performance test results of floor membranes in each embodiment and comparative example.

[0104] As can be seen from Tables 1 and 2, Example 1 achieves optimal overall performance by absorbing energy in stages and dispersing it evenly. The gradient structure effectively disperses stress and resists fatigue, achieving the best balance between impact absorption, resilience, and durability. Example 2 enhances the resilience of the rebound layer, resulting in excellent shock absorption and a comfortable feel, but its support and deformation resistance may be slightly weaker, making it suitable for applications requiring high comfort and shock absorption. Example 3 increases the density of the transition and rebound layers, achieving stronger support, resistance to compressive deformation, and durability, but at the cost of some shock absorption and softness, making it suitable for applications requiring high load-bearing capacity. In applications requiring specific surface conditions; Example 4, by reducing the density of the wear-resistant layer, improves the overall flexibility of the floor membrane while maintaining wear resistance, achieving a balance between flexibility and wear resistance, suitable for applications requiring both surface softness and wear resistance; Example 5, by increasing the density of the wear-resistant layer, enhances its wear resistance and rigidity, suitable for applications requiring the highest surface scratch and abrasion resistance, and applicable to applications requiring high surface hardness; Example 6, using silicon carbide filler in the wear-resistant layer, increases hardness but slightly decreases toughness; Example 7, using alumina and polyethylene wax in the wear-resistant layer, improves processing fluidity but slightly reduces resilience. Example 8: The transition layer has strong cushioning but slightly weak support, while the rebound layer has good support, balancing rebound and durability, suitable for occasions with high daily usage frequency; Example 9: The transition layer has strong cushioning, and the rebound layer has excellent resilience, providing a soft feel and excellent softness and resilience, suitable for occasions with extremely high comfort requirements; Example 10: The rebound layer uses AIBN foaming agent and SEBS, resulting in good resilience and impact absorption performance; Example 11: The rebound layer uses sodium bicarbonate foaming agent and styrene-butadiene rubber, with slightly lower foaming efficiency and slightly weaker overall performance; Example 12: By increasing the thickness of the transition layer and rebound layer... To further improve the buffering performance, Example 13 increased the thickness of the rebound layer and thinned the transition layer, enhancing support while maintaining good rebound. Comparative Example 1 omitted the transition layer and rebound layer, using only a single-density wear-resistant layer, which could not achieve gradient energy absorption, resulting in poor shock absorption performance, easy stress concentration, low durability, easy plastic deformation, and rapid rebound decay. Comparative Example 2 omitted the transition layer, and the high-hardness wear-resistant layer and high-resilience rebound layer were directly bonded together with adhesive, lacking stress buffering, resulting in poor impact absorption rate, and due to the sudden change in hardness, fatigue damage was easily caused at the interface, posing a very high risk of delamination. In Comparative Example 3, the density of the transition layer was too high, resulting in an uneven transition and a decrease in impact absorption rate.

[0105] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A floor membrane, characterized in that, It includes a wear-resistant layer, a transition layer, and a resilience layer stacked sequentially: The density of the wear-resistant layer is greater than the density of the transition layer, which is greater than the density of the resilience layer. The density of the transition layer is 0.5 g / cm³. 3 -0.7g / cm 3 .

2. The floor membrane according to claim 1, characterized in that, The density of the wear-resistant layer is 0.8 g / cm³. 3 -1.2g / cm 3 ; And / or, the density of the resilience layer is 0.1 g / cm³. 3 -0.3g / cm 3 .

3. The floor membrane according to claim 1 or 2, characterized in that, By weight percentage, the raw material composition of the wear-resistant layer includes: 80wt%-90wt% thermoplastic polyurethane elastomer, 3wt%-12wt% first filler, 0.3wt%-1.5wt% antioxidant, 0.5wt%-2.5wt% lubricant, 0.5wt%-1.5wt% ultraviolet absorber, and 1wt%-3wt% pigment; And / or, by mass percentage, the raw material composition of the transition layer includes: 75wt%-87wt% of a mixture of ethylene-vinyl acetate copolymer and polyolefin elastomer, 3wt%-8wt% of a first foaming agent, 0.2wt%-1wt% of a crosslinking agent, 5wt%-15wt% of a second filler, and 0.5wt%-2wt% of a first coupling agent; Optionally, in the mixture of ethylene-vinyl acetate copolymer and polyolefin elastomer, the mass ratio of ethylene-vinyl acetate copolymer to polyolefin elastomer is 4-7:3-6; And / or, by mass percentage, the raw material composition of the rebound layer includes: 60wt%-75wt% polyolefin elastomer, 2wt%-5wt% second foaming agent, 10wt%-15wt% non-polyolefin elastomer, 0.5wt%-2wt% first activator, 8wt%-15wt% third filler, and 0.5wt%-3wt% second coupling agent.

4. The floor membrane according to claim 3, characterized in that, The first filler includes at least one of silicon dioxide, silicon carbide, alumina, and titanium dioxide; And / or, the antioxidant comprises at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl)phosphite, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and N,N'-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine; And / or, the lubricant comprises at least one of zinc stearate, calcium stearate, polyethylene wax, and ethylene bis-stearamide; And / or, the ultraviolet absorber comprises at least one of 2-[2-hydroxy-3,5-bis(1,1-dimethylpropylphenyl)]-2H-benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol), 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylamidinium; And / or, the pigment includes at least one of titanium dioxide, carbon black, phthalocyanine blue, and iron oxide red.

5. The floor membrane according to claim 3, characterized in that, The first blowing agent includes at least one of 4,4'-oxobisbenzenesulfonyl hydrazine and azodicarbonamide; Optionally, when the first blowing agent is azodicarbonamide, the transition layer further includes a second activator; Optionally, in the transition layer, the content of the second activator is 0.2wt%-1wt%; Optionally, the second activator includes at least one of zinc oxide, stearic acid, and magnesium oxide; And / or, the crosslinking agent includes at least one of dicumyl peroxide, 1,1-di-tert-butylperoxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; And / or, the second filler and the third filler are each independently selected from at least one of calcium carbonate, talc, wollastonite, and aluminum hydroxide; And / or, the first coupling agent and the second coupling agent are each independently selected from at least one of γ-aminopropyltriethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and aluminate.

6. The floor membrane according to claim 3, characterized in that, The second foaming agent includes at least one of azodicarbonamide, sodium bicarbonate, and azobisisobutyronitrile; And / or, the non-polyolefin elastomer includes at least one of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, and styrene-ethylene-butene-styrene block copolymer; And / or, the first activator includes at least one of zinc oxide, zinc stearate, magnesium oxide, and stearic acid.

7. The floor membrane according to claim 1, characterized in that, The thickness of the wear-resistant layer is 0.3mm-0.5mm; And / or, the thickness of the transition layer is 1.0mm-1.5mm; And / or, the thickness of the rebound layer is 2mm-3mm.

8. A method for preparing a floor membrane according to any one of claims 1-7, characterized in that, Includes the following steps: (1) The raw materials of the wear-resistant layer are mixed and melted for the first time to obtain a first molten material; the raw materials of the transition layer are mixed and melted for the second time to obtain a second molten material; the raw materials of the resilience layer are mixed and melted for the third time to obtain a third molten material; (2) The first molten material, the second molten material and the third molten material are extruded and merged in parallel to form a wear-resistant layer, a transition layer and a resilience layer stacked in sequence, and then cast and cooled to obtain the final product.

9. The method for preparing the floor membrane according to claim 8, characterized in that, The temperature of the first melt is 180℃-200℃; And / or, the temperature of the second melt is 150°C-170°C; And / or, the temperature of the third melting point is 130°C-150°C; And / or, the extrusion rate of the first molten material is 8 m / min-12 m / min; And / or, the extrusion rate of the second molten material is 10 m / min-15 m / min; And / or, the extrusion rate of the third molten material is 12 m / min-18 m / min.

10. The method for preparing the floor membrane according to claim 8 or 9, characterized in that, The mass ratio of the first molten material, the second molten material, and the third molten material is 1:2-3:3-5.

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