An environmentally friendly Non-PVC floor and its preparation method

Abstract

The present invention belongs to the technical field of plastic floors, and particularly relates to an environmentally friendly Non-PVC floor and a preparation method thereof. The floor is sequentially provided with a transparent sheet layer, a color film layer, a base material layer, and a floor cushion layer from top to bottom; the base material layer includes PET, PETG, calcium carbonate powder, plasticizer, toughening agent, external lubricant, internal lubricant, and oxidized wax. The transparent sheet layer and the floor cushion layer adopt quaternized chitosan-coated nano-zinc oxide loaded with trivalent titanium as an antibacterial material, which has excellent dispersibility and antibacterial properties. The floor cushion layer modified with cork particles and nano-silica white carbon black using ramie fiber as a substrate improves the sound insulation effect and mechanical properties through hot pressing and bonding with PP and PE.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic floors, and particularly relates to an environmentally friendly Non-PVC floor and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC) is the third-largest synthetic polymer plastic in the world in terms of production volume and is widely used in fields such as chemical engineering, materials, textiles, and construction. However, PVC has poor thermal stability and is prone to decomposing to produce toxic gases at high temperatures, which is harmful to the environment and the human body. With the increasing global emphasis on sustainable development, more and more consumers and enterprises are starting to pay attention to the environmental performance of products. Producing floors without polyvinyl chloride (Non-PVC) and using environmentally friendly materials such as polyethylene terephthalate-1,4-cyclohexanedimethanol ester (PETG) helps to promote the sustainable development of the industry.

[0003] The Chinese invention patent with the publication number CN118958623A discloses a flame-retardant and deformation-resistant PETG floor and a preparation method thereof. The floor includes a UV coating, a wear-resistant layer, a color film layer, a base material layer, and a sound insulation cushion layer from top to bottom. The base material layer specifically includes the following components in parts by weight: 40-70 parts of PETG resin, 30-55 parts of PET resin, 60-120 parts of PET recycled material, 10-20 parts of modified PET, 10-40 parts of toughening agent, 0-1.5 parts of lubricant, 200-300 parts of stone powder, 3-5 parts of antioxidant, 1-3 parts of flame retardant, 0-1 part of chain extender, and 0-1 part of polyamide. This invention prepares a flame-retardant and deformation-resistant PETG floor with good flame retardancy, mechanical properties, and deformation resistance through the blending of PET, PETG, and modified PET and the addition of a multi-element synergistic flame retardant. However, the existing technology has the technical problem that the UV coating and antibacterial properties of the floor are not combined and modified to improve the wear resistance and antibacterial ability of the floor. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly Non-PVC floor and a preparation method thereof to solve the technical problem in the existing technology that the UV coating and antibacterial properties of the floor are not combined and modified to improve the wear resistance and antibacterial ability of the floor.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] An environmentally friendly Non-PVC floor is provided with a transparent sheet layer, a color film layer, a bottom layer, and a floor cushion layer from top to bottom. The thickness of the transparent sheet is 0.1-0.76 mm, the thickness of the floor cushion is 0.5-5.0 mm, and the total thickness of the transparent sheet, color film, and bottom layer is 1.5-6.0 mm.

[0007] The base material layer, by mass parts, comprises the following raw materials: 20 - 30 parts of PET, 70 - 80 parts of PETG, 200 - 600 parts of calcium carbonate powder, 20 - 60 parts of plasticizer, 10 - 40 parts of toughening agent, 0 - 2 parts of external lubricant, 0 - 2 parts of internal lubricant, and 0 - 2 parts of oxidized wax.

[0008] Preferably, the transparent sheet layer, by mass parts, comprises the following raw materials: 20 - 30 parts of PET, 70 - 80 parts of PETG, 2 - 5 parts of nano antibacterial material, 0.5 - 2 parts of ultraviolet absorber, 0.5 - 2 parts of antioxidant, 20 - 60 parts of plasticizer, 10 - 40 parts of toughening agent, and 1 - 2 parts of lubricant;

[0009] The color film layer, by mass parts, comprises the following raw materials: 100 - 110 parts of PETG, 2 - 8 parts of masterbatch, 0.5 - 2 parts of ultraviolet absorber, 0.5 - 2 parts of antioxidant, 20 - 60 parts of plasticizer, 10 - 40 parts of toughening agent, and 0.5 - 2 parts of lubricant;

[0010] The floor cushion layer, by mass parts, comprises the following raw materials: 10 - 20 parts of PP, 4 - 8 parts of PE, 80 - 90 parts of cork particles, 2 - 5 parts of nano antibacterial material, 10 - 20 parts of modified hemp fiber, and 0.5 - 2 parts of lubricant.

[0011] Preferably, the total mass parts of PET and PETG in the transparent sheet layer and the base material layer are both 100 parts, and the mass ratio of PET to PETG is both 2 - 3:7 - 8; the ultraviolet absorbers in the transparent sheet layer and the color film layer are both one or more combinations of UV - 234, UV - 405, and UV - 1300; the antioxidants in the transparent sheet layer and the color film layer are both one or more combinations of 168, 1010, and 1076; the average particle size of the cork particles in the floor cushion layer is 10 - 20 mesh; the plasticizers in the transparent sheet layer, the color film layer, and the base material layer are both one or more combinations of epoxidized soybean oil, epoxidized linseed oil, and dioctyl epoxy tetrahydrophthalate, and the toughening agents are both one or more combinations of BET, ABS, and EEA; the lubricants in the transparent sheet layer, the color film layer, the base material layer, and the floor cushion layer are both one or more combinations of polyethylene wax, butyl stearate, and polyethylene glycol - 600.

[0012] Preferably, the preparation method of the nano antibacterial material comprises the following steps:

[0013] S21. By mass parts, add 3 - 5 parts of nano zinc oxide into 30 - 50 parts of isopropanol, ultrasonically disperse for 30 - 40 min, and then add 0.5 - 1 part of surfactant to obtain a dispersion liquid;

[0014] S22. Add 0.3 - 0.6 parts by mass of titanium trichloride to 30 - 50 parts of isopropanol. After mixing evenly, add the dispersion liquid, and stir at 300 - 500 rpm for 30 - 40 min under a nitrogen atmosphere;

[0015] S23. Heat the system to 180 - 200 °C, keep it warm for 12 - 24 h, cool it down to 40 - 50 °C, centrifuge and filter to collect the solid, wash it successively with deionized water and ethanol, dry it in vacuum at 60 - 70 °C, and grind it to obtain nano - zinc oxide loaded with trivalent titanium;

[0016] S24. Add 1.5 - 3 parts by mass of quaternized chitosan - 100k to 50 parts of deionized water, add 5 - 6 parts of nano - zinc oxide loaded with trivalent titanium, disperse it by ultrasonic for 30 - 40 min, stir at 300 - 500 rpm for 12 - 24 h, centrifuge and filter to collect the solid, dry it at 60 - 70 °C, and grind it to obtain the nano - antibacterial material.

[0017] Preferably, the surfactant in S21 is one or a combination of more than one of pentadecyl glycoside, polyvinylpyrrolidone, and polyethylene glycol - 200.

[0018] Preferably, the preparation method of the modified hemp fiber includes the following steps:

[0019] S31. Soak 20 - 30 parts by mass of hemp fiber in 50 - 100 parts of 5 - 10 wt% sodium hydroxide solution for 2 - 4 h, rinse it with deionized water until neutral, and dry it at 80 - 100 °C to obtain alkali - treated hemp fiber;

[0020] S32. Add 3 - 8 parts by mass of kh - 590 silane coupling agent to 100 - 150 parts of deionized water, stir at 500 - 600 rpm at 40 - 50 °C for 30 - 40 min, add 10 - 20 parts of alkali - treated hemp fiber and 1 - 3 parts of nano - silica, stir for 1 - 2 h, filter and dry to obtain the modified hemp fiber.

[0021] A preparation method of an environmentally friendly Non - PVC floor includes the following steps:

[0022] S1. Weigh the raw materials required for each layer, pass the cork particles through steam at 300 - 350 °C for 0.5 - 1 h, dry them at 80 - 100 °C to control the water content to be 6 - 8% for pretreatment, and set aside after cooling;

[0023] S2. Prepare the transparent sheet layer and the color film layer: After mixing the raw materials of the transparent sheet layer and the color film layer evenly, successively obtain the transparent sheet layer and the color film layer through an extruder;

[0024] S3. Preparation of the base layer: After the raw materials of the base layer are evenly mixed, the base layer is obtained through a kneader, an open mill, and calendering.

[0025] S4. Preparation of the cushion layer: The raw materials of the cushion layer are evenly mixed and then hot-pressed at 150 - 170 °C for 10 - 15 min by a hot press to obtain the cushion layer.

[0026] S5. Bonding of the Non-PVC floor substrate: The transparent sheet layer, the color film layer, and the base layer are hot-pressed at 210 - 230 °C for 10 - 15 min by a hot press to obtain a plastic layer. Glue is coated on the cushion layer, and the plastic layer is bonded to obtain the Non-PVC floor substrate.

[0027] S6. Surface treatment: A UV wear-resistant primer with a thickness of 150 - 200 μm is coated on the surface of the Non-PVC floor substrate, irradiated with ultraviolet light for curing for 30 - 90 s, and then die-cut and milled to obtain the Non-PVC floor.

[0028] In the preparation method of the present invention, the transparent sheet layer, the color film layer, and the base layer can also obtain the Non-PVC floor substrate through a co-extrusion process.

[0029] Preferably, in S2, the temperature at the feed inlet of the extruder is 210 - 220 °C, and the temperature at the discharge outlet is 230 - 250 °C.

[0030] Preferably, in S3, the mixing temperature of the kneader is 230 °C - 250 °C, the mixing interval is 5 min, the single mixing time is 10 - 15 min, and the open mill temperature of the open mill is 190 °C - 220 °C.

[0031] Preferably, in S5, the glue is any one of AB glue or PUR glue.

[0032] Preferably, the preparation method of the UV wear-resistant primer includes the following steps:

[0033] S11. By mass, add 10 - 15 parts of epoxy palm oil to 50 - 80 parts of n-heptane, then dropwise add 20 - 30 parts of isopropanolamine. After introducing nitrogen, react at 70 - 100 °C for 4 - 6 h to obtain palm oil amide polyol.

[0034] S12. By mass, react 10 - 15 parts of palm oil amide polyol with 40 - 50 parts of isophorone diisocyanate under nitrogen protection at 70 - 80 °C for 1 - 3 h. Then lower the temperature to 40 - 50 °C, add 10 - 15 parts of hydroxyethyl acrylate and 0.3 - 0.5 parts of p-hydroxyanisole, and continue to react for 2 - 4 h. Then carry out vacuum distillation to obtain modified polyurethane acrylate.

[0035] S13. By mass, add 2 - 3 parts of photoinitiator, 0.5 - 1 part of BYK-333 leveling agent, 30 - 40 parts of polyester acrylate, 10 - 20 parts of modified polyurethane acrylate, and 30 - 40 parts of isobornyl acrylate to 30 - 50 parts of absolute ethanol, and stir evenly to obtain the UV wear-resistant primer.

[0036] Preferably, in S13, the photoinitiator is any one or a combination of benzoyl formate, 2,2-dimethoxy-2-phenylacetophenone, and benzoyldimethylpyrrolidone.

[0037] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0038] 1. On the basis of the existing technology, the present invention improves the preparation process and components of each layer of the floor. The environmentally friendly Non-PVC floor prepared by the co-extrusion process or the hot pressing process has excellent sound insulation, antibacterial, and wear-resistant properties. The UV wear-resistant primer prepared by using modified polyurethane acrylate as a raw material has excellent wear resistance, flexibility, and adhesion. The transparent sheet layer and the floor cushion layer use quaternized chitosan-coated nano-zinc oxide loaded with trivalent titanium as an antibacterial material, which has excellent dispersibility and antibacterial properties. The floor cushion layer modified with cork particles and nano-silica white carbon black as a base material and bonded by hot pressing of PP and PE improves the sound insulation effect and mechanical properties.

[0039] 2. The UV wear-resistant primer of the present invention uses epoxy palm oil to prepare palm oil amide polyol, and then reacts with isophorone diisocyanate and hydroxyethyl acrylate to obtain modified polyurethane acrylate, which has excellent wear resistance and flexibility.

[0040] 3. The present invention hydrothermally reacts nano-zinc oxide and titanium trichloride in the presence of a surfactant to prepare nano-zinc oxide loaded with trivalent titanium, which reduces the band gap of nano-zinc oxide, increases its absorption range of visible light, and enhances its antibacterial ability. Coating nano-zinc oxide loaded with trivalent titanium with quaternized chitosan can significantly reduce the agglomeration phenomenon of nano-particles and improve the lifespan of the nano-antibacterial material.

[0041] 4. The present invention treats ramie fiber with sodium hydroxide solution and then modifies it with nano-silica white carbon black to form a uniform network structure on the surface of the ramie fiber, which can effectively disperse and absorb external stress, improve the mechanical strength of plant fiber, and enhance the interfacial bonding force between the ramie fiber and cork particles and plastics, thereby improving the impact resistance of the floor cushion layer. Description of the Drawings

[0042] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0043] Figure 1 It is a schematic diagram of the hierarchical structure of the environmentally friendly Non-PVC floor of the present invention.

[0044] Explanation of reference numerals: 1 - transparent sheet layer, 2 - color film layer, 3 - base material layer, 4 - floor cushion layer. Specific embodiments

[0045] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0046] Embodiment 1, referring to Figure 1 As shown, an environmentally friendly Non-PVC floor of this embodiment is provided with a transparent sheet layer 1, a color film layer 2, a base material layer 3, and a floor cushion layer 4 from top to bottom in sequence;

[0047] The transparent sheet layer, by mass, includes the following raw materials: 30 parts of PET, 70 parts of PETG, 4 parts of nano antibacterial material, 1 part of ultraviolet absorber, 1 part of antioxidant, 60 parts of plasticizer, 40 parts of toughening agent, and 2 parts of lubricant;

[0048] The color film layer, by mass, includes the following raw materials: 100 parts of PETG, 5 parts of color masterbatch, 1 part of ultraviolet absorber, 1 part of antioxidant, 60 parts of plasticizer, 40 parts of toughening agent, and 1 part of lubricant;

[0049] The base material layer, by mass, includes the following raw materials: 30 parts of PET, 70 parts of PETG, 600 parts of calcium carbonate powder, 60 parts of plasticizer, 40 parts of toughening agent, and 2 parts of lubricant;

[0050] The floor cushion layer, by mass, includes the following raw materials: 20 parts of PP, 8 parts of PE, 80 parts of cork particles, 2 parts of nano antibacterial material, 20 parts of modified hemp fiber, and 1 part of lubricant.

[0051] The thickness of the transparent sheet is 0.5 mm, the thickness of the floor mat is 3.0 mm, and the total thickness of the three layers of the transparent sheet, color film, and base material is 3.5 mm.

[0052] The UV absorbers of the transparent sheet layer and the color film layer are both UV-234; the antioxidants of the transparent sheet layer and the color film layer are both 168; the average particle size of the cork particles in the cushion layer is 12 mesh; the plasticizers of the transparent sheet layer, the color film layer and the base layer are all epoxy soybean oil, and the toughening agents are all BET; the lubricants of the transparent sheet layer, the color film layer, the base layer and the cushion layer are all polyethylene wax.

[0053] A preparation method of an environmentally friendly Non-PVC floor in this embodiment includes the following steps:

[0054] S1. Weigh the raw materials required for each layer. Pass the cork particles through steam at 350 °C for 0.5 h, dry them at 100 °C to control the moisture content to be 6% for pretreatment, and set aside after cooling.

[0055] S2. Prepare the transparent sheet layer and the color film layer: After mixing the raw materials of the transparent sheet layer and the color film layer evenly, pass them through an extruder in sequence. The temperature of the feed inlet of the extruder is 220 °C, and the temperature of the discharge outlet is 240 °C to obtain the transparent sheet layer and the color film layer.

[0056] S3. Prepare the base layer: After mixing the raw materials of the base layer evenly, obtain the base layer through a kneader, a roll mill, and calendering. The kneading temperature of the kneader is 230 °C, the kneading interval is 5 min, and the single kneading time is 15 min. The rolling temperature of the roll mill is 220 °C.

[0057] S4. Prepare the cushion layer: Mix the raw materials of the cushion layer evenly, and prepare the cushion layer by hot pressing at 170 °C for 10 min through a hot press.

[0058] S5. Bond the Non-PVC floor substrate: Obtain a plastic layer by hot pressing the transparent sheet layer, the color film layer and the base layer at 230 °C for 10 min through a hot press. Coat the cushion layer with PUR glue and bond the plastic layer to obtain the Non-PVC floor substrate.

[0059] S6. Surface treatment: Coat a UV wear-resistant primer with a thickness of 200 μm on the surface of the Non-PVC floor substrate, cure it by ultraviolet irradiation for 60 s, and then perform punching and milling to obtain the Non-PVC floor.

[0060] A preparation method of the UV wear-resistant primer in this embodiment includes the following steps:

[0061] S11. By mass, add 15 parts of epoxy palm oil to 60 parts of n-heptane, then dropwise add 30 parts of isopropanolamine. After introducing nitrogen, react at 100 °C for 5 h to obtain palm oil amide polyol.

[0062] S12. By mass, react 15 parts of palm oil amide polyol with 45 parts of isophorone diisocyanate at 80 °C for 2 h under nitrogen protection. Then lower the temperature to 40 °C, add 10 parts of hydroxyethyl acrylate and 0.4 part of p-hydroxyanisole, and continue to react for 2 h. Then perform vacuum distillation to obtain the modified polyurethane acrylate.

[0063] S13. By mass, add 3 parts of benzoyl formate photoinitiator, 1 part of BYK-333 leveling agent, 40 parts of polyester acrylate, 20 parts of modified polyurethane acrylate, and 40 parts of isobornyl acrylate to 50 parts of absolute ethanol, and stir evenly to obtain the UV wear-resistant primer.

[0064] The preparation method of the nano antibacterial material in this example includes the following steps:

[0065] S21. By mass, add 3 parts of nano zinc oxide to 40 parts of isopropanol. After ultrasonic dispersion for 40 min, add 0.7 part of polyvinylpyrrolidone to obtain a dispersion.

[0066] S22. By mass, add 0.6 part of titanium trichloride to 50 parts of isopropanol, mix evenly, then add the dispersion, and stir at 400 rpm for 40 min under a nitrogen atmosphere.

[0067] S23. Heat the system to 200 °C, keep it warm for 24 h, cool it down to 50 °C, centrifuge and filter to collect the solid, wash it successively with deionized water and ethanol, dry it in vacuum at 70 °C, and grind it to obtain nano zinc oxide loaded with trivalent titanium.

[0068] S24. By mass, dissolve 3 parts of quaternized chitosan-100k in 50 parts of deionized water, add 5 parts of nano zinc oxide loaded with trivalent titanium, perform ultrasonic dispersion for 30 min, stir at 500 rpm for 24 h, centrifuge and filter to collect the solid, dry it at 60 °C, and grind it to obtain the nano antibacterial material.

[0069] The preparation method of the modified hemp fiber in this example includes the following steps:

[0070] S31. By mass, soak 20 parts of hemp fiber in 50 parts of 10 wt% sodium hydroxide solution for 2 h, rinse it with deionized water until neutral, and dry it at 80 °C to obtain alkali-treated hemp fiber.

[0071] S32. By mass, add 3 parts of kh-590 silane coupling agent to 100 parts of deionized water, stir at 500 rpm at 40 °C for 30 min, add 15 parts of alkali-treated hemp fiber and 3 parts of nano silica, stir for 2 h, filter and dry to obtain the modified hemp fiber.

[0072] Example 2, refer to Figure 1As shown in the figure, an environmentally friendly Non-PVC floor of this embodiment is provided with a transparent sheet layer, a color film layer, a base material layer, and a floor mat layer from top to bottom in sequence;

[0073] The transparent sheet layer, by mass, comprises the following raw materials: 20 parts of PET, 80 parts of PETG, 3 parts of nano antibacterial material, 0.5 part of ultraviolet absorber, 1 part of antioxidant, 30 parts of plasticizer, 20 parts of toughening agent, and 1 part of lubricant;

[0074] The color film layer, by mass, comprises the following raw materials: 110 parts of PETG, 8 parts of masterbatch, 1 part of ultraviolet absorber, 1 part of antioxidant, 30 parts of plasticizer, 20 parts of toughening agent, and 1 part of lubricant;

[0075] The base material layer, by mass, comprises the following raw materials: 20 parts of PET, 80 parts of PETG, 300 parts of calcium carbonate powder, 30 parts of plasticizer, 20 parts of toughening agent, and 1 part of lubricant;

[0076] The floor mat layer, by mass, comprises the following raw materials: 20 parts of PP, 8 parts of PE, 80 parts of cork particles, 2 parts of nano antibacterial material, 20 parts of modified hemp fiber, and 1 part of lubricant.

[0077] The thickness of the transparent sheet is 0.1 mm, the thickness of the floor mat is 5.0 mm, and the total thickness of the three layers of the transparent sheet, color film, and base material is 1.5 mm.

[0078] The ultraviolet absorbers of the transparent sheet layer and the color film layer are both UV-405; the antioxidants of the transparent sheet layer and the color film layer are both 1010; the average particle size of the cork particles of the floor mat layer is 20 mesh; the plasticizers of the transparent sheet layer, color film layer, and base material layer are all epoxy linseed oil, and the toughening agents are all ABS; the lubricants of the transparent sheet layer, color film layer, base material layer, and floor mat layer are all polyethylene glycol-600.

[0079] A preparation method of an environmentally friendly Non-PVC floor of this embodiment comprises the following steps:

[0080] S1. Weigh the raw materials required for each layer, pass the cork particles through steam at 350 °C for 1 h, dry them at 100 °C to control the water content to be 8% for pretreatment, and cool them for later use;

[0081] S2. Prepare the transparent sheet layer and the color film layer: After mixing the raw materials of the transparent sheet layer and the color film layer evenly, pass them through an extruder in sequence. The temperature of the feed inlet of the extruder is 210 °C, and the temperature of the discharge outlet is 230 °C to obtain the transparent sheet layer and the color film layer;

[0082] S3. Prepare the base layer: After the raw materials of the base layer are evenly mixed, the base layer is obtained through a kneader, an open mill, and calendering. The kneading temperature of the kneader is 230°C, the kneading interval is 5 minutes, the single kneading time is 15 minutes, and the open mill temperature of the open mill is 215°C;

[0083] S4. Prepare the underlayment: The raw materials of the underlayment are evenly mixed and the underlayment is prepared by hot pressing at 170°C for 10 minutes through a hot press;

[0084] S5. Bond the Non-PVC floor substrate: The transparent sheet layer, the color film layer, and the base layer are hot pressed at 220°C for 10 minutes through a hot press to obtain a plastic layer. The underlayment is coated with PUR glue to bond the plastic layer to obtain the Non-PVC floor substrate;

[0085] S6. Surface treatment: Coat a UV wear-resistant primer with a thickness of 200 μm on the surface of the Non-PVC floor substrate, cure it by ultraviolet irradiation for 60 seconds, and then perform punching and milling to obtain the Non-PVC floor.

[0086] The preparation methods of the UV wear-resistant primer and the modified hemp fiber in this example are the same as those in Example 1.

[0087] The difference between the nano antibacterial material in this example and that in Example 1 is that the surfactant is replaced with pentadecyl glucoside.

[0088] Example 3, refer to Figure 1 As shown, an environmentally friendly Non-PVC floor in this example is provided with a transparent sheet layer, a color film layer, a base layer, and an underlayment from top to bottom;

[0089] The transparent sheet layer, by mass, includes the following raw materials: 25 parts of PET, 75 parts of PETG, 4 parts of nano antibacterial material, 0.5 part of ultraviolet absorber, 1 part of antioxidant, 60 parts of plasticizer, 40 parts of toughening agent, and 2 parts of lubricant;

[0090] The color film layer, by mass, includes the following raw materials: 110 parts of PETG, 5 parts of color masterbatch, 1 part of ultraviolet absorber, 1 part of antioxidant, 60 parts of plasticizer, 40 parts of toughening agent, and 2 parts of lubricant;

[0091] The base layer, by mass, includes the following raw materials: 25 parts of PET, 75 parts of PETG, 200 parts of calcium carbonate powder, 60 parts of plasticizer, 40 parts of toughening agent, and 2 parts of lubricant;

[0092] The underlayment, by mass, includes the following raw materials: 20 parts of PP, 8 parts of PE, 80 parts of cork particles, 2 parts of nano antibacterial material, 20 parts of modified hemp fiber, and 2 parts of lubricant.

[0093] The thickness of the transparent sheet is 0.76 mm, the thickness of the floor mat is 1.0 mm, and the total thickness of the three layers of the transparent sheet, color film and base material is 5.5 mm.

[0094] The UV absorbers in the transparent sheet layer and the color film layer are both UV-1300; the antioxidants in the transparent sheet layer and the color film layer are both 1076; the average particle size of the cork particles in the floor mat layer is 16 mesh; the plasticizers in the transparent sheet layer, color film layer and base material layer are all dioctyl epoxy tetrahydrophthalate, and the toughening agents are all EEA; the lubricants in the transparent sheet layer, color film layer, base material layer and floor mat layer are all butyl stearate.

[0095] A preparation method of an environmentally friendly Non-PVC floor in this embodiment includes the following steps:

[0096] S1. Weigh the raw materials required for each layer, pass the cork particles through steam at 300 °C for 1 h, dry them at 90 °C to control the water content to 8% for pretreatment, and set aside after cooling;

[0097] S2. Prepare the transparent sheet layer and the color film layer: After mixing the raw materials of the transparent sheet layer and the color film layer evenly, pass them through an extruder in sequence. The temperature of the feed inlet of the extruder is 215 °C, and the temperature of the discharge outlet is 235 °C to obtain the transparent sheet layer and the color film layer;

[0098] S3. Prepare the base material layer: After mixing the raw materials of the base material layer evenly, obtain the base material layer through a kneader, an open mill and calendering. The kneading temperature of the kneader is 235 °C, the kneading interval is 5 min, the single kneading time is 15 min, and the open milling temperature of the open mill is 220 °C;

[0099] S4. Prepare the floor mat layer: Mix the raw materials of the floor mat layer evenly, and prepare the floor mat layer by hot pressing at 170 °C for 10 min through a hot press;

[0100] S5. Bond the Non-PVC floor substrate: Obtain a plastic layer by hot pressing the transparent sheet layer, the color film layer and the base material layer at 215 °C for 15 min through a hot press. Coat the floor mat layer with AB glue and bond the plastic layer to obtain the Non-PVC floor substrate;

[0101] S6. Surface treatment: Coat the surface of the Non-PVC floor substrate with a UV wear-resistant primer with a thickness of 180 μm, cure it by ultraviolet irradiation for 90 s, and punch and mill the edges to obtain the Non-PVC floor.

[0102] The preparation method of the nano antibacterial material in this embodiment is the same as that in Embodiment 1.

[0103] The difference between the UV wear-resistant primer in this embodiment and that in Embodiment 1 is that the photoinitiator is replaced by benzoyldimethylpyrrolidone.

[0104] The modified hemp fiber in this example is different from that in Example 1 in that the alkali treatment process in S31 is replaced by soaking in 100 parts of 5wt% sodium hydroxide solution for 4 hours.

[0105] Comparative Example 1. The difference between this comparative example and Example 1 is that palm oil amide polyol is replaced by polycaprolactone polyol.

[0106] Comparative Example 2. The difference between this comparative example and Example 1 is that quaternized chitosan - 100k is replaced by polyacrylamide.

[0107] Comparative Example 3. The difference between this comparative example and Example 1 is that the hemp fiber is not soaked and treated with sodium hydroxide solution.

[0108] Performance Test

[0109] According to GB50118 - 2010 "Code for Sound Insulation Design of Civil Buildings", a reference floor slab is established. Hollow blocks are used as the reference floor slab, the thickness of the reference floor slab is set to 150 mm, and each side is covered with environmentally friendly Non - PVC flooring. The weighted impact sound pressure level of the hollow blocks without the environmentally friendly Non - PVC flooring covered is 86 dB, and the weighted impact sound pressure levels of the floors prepared in each example and comparative example are measured.

[0110] According to GB3960 - 83 "Test Method for Sliding Friction and Wear of Plastics", the wear rates of the floors prepared in each example and comparative example are measured.

[0111] According to GB / T 1040.2 - 2022 "Determination of Tensile Properties of Plastics - Part 2: Test Conditions for Moulded and Extruded Plastics", the tensile strength and elongation at break of the floors prepared in each example and comparative example are measured.

[0112] According to GB / T 21866 - 2008 "Determination Method and Antibacterial Effect of Antibacterial Coatings (Paint Films)", using the floor sample containing only PETG as the blank control group, the floor sample is sterilized by ultraviolet irradiation for 3 hours; the Escherichia coli strain is activated and prepared into a bacterial suspension with a concentration of 3×10 4 cfu / ml; the sample is placed in the bacterial suspension, shaken at 300 r / min for 5 minutes at room temperature, 1 ml of the bacterial suspension is diluted 100 times, 1 ml of the diluted bacterial suspension is evenly smeared on the sample and then placed in a sterilized petri dish, and cultured for 24 hours under the conditions of 38℃ and relative humidity greater than 90%. Then, it is washed repeatedly with the washing solution, the washing solution is inoculated into the nutrient agar medium, and cultured for another 24 hours at 38℃ for colony counting, and the antibacterial rate is calculated by the following formula.

[0113]

[0114] R - antibacterial rate, %;

[0115] B——Average number of colonies in the blank control group;

[0116] C——Average number of colonies in the sample.

[0117] The test results are shown in Table 1 below:

[0118] Table 1

[0119]

[0120] It can be seen from the data in the table that in Comparative Example 1, replacing palm oil amide polyol with polycaprolactone polyol results in poor abrasion resistance of the UV-resistant primer. In Comparative Example 2, replacing quaternized chitosan-100k with polyacrylamide inhibits the antibacterial performance of the nano antibacterial material, and the antibacterial rate is only 61.3%. In Comparative Example 3, the ramie fiber is not alkali-treated, resulting in a weakened bonding force with the cushion layer, so there is a slight downward trend in both the tensile strength and the elongation at break. This shows that the environmentally friendly Non-PVC floor prepared by the present invention has excellent sound insulation, antibacterial, and abrasion resistance properties.

[0121] As mentioned above, it is only the preferred specific embodiment of the present invention. However, the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent replacements or changes, should be covered within the protection scope of the present invention.

[0122] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principle and practical application of the present invention, so that those skilled in the art in the relevant technical field can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. An environmentally friendly Non-PVC floor, characterized in that, A transparent sheet layer, a color film layer, a base layer, and a floor mat layer are sequentially arranged from top to bottom; The transparent sheet layer, by mass, comprises the following raw materials: 20-30 parts of PET, 70-80 parts of PETG, 2-5 parts of nano antibacterial material, 0.5-2 parts of ultraviolet absorber, 0.5-2 parts of antioxidant, 20-60 parts of plasticizer, 10-40 parts of toughening agent, and 1-2 parts of lubricant; The color film layer, by mass, comprises the following raw materials: 100-110 parts of PETG, 2-8 parts of masterbatch, 0.5-2 parts of ultraviolet absorber, 0.5-2 parts of antioxidant, 20-60 parts of plasticizer, 10-40 parts of toughening agent, and 0.5-2 parts of lubricant; The base layer, by mass, comprises the following raw materials: 20-30 parts of PET, 70-80 parts of PETG, 200-600 parts of filler, 20-60 parts of plasticizer, 10-40 parts of toughening agent, and 0.5-2 parts of lubricant; The floor mat layer, by mass, comprises the following raw materials: 10-20 parts of PP, 4-8 parts of PE, 80-90 parts of cork particles, 2-5 parts of nano antibacterial material, 10-20 parts of modified hemp fiber, and 0.5-2 parts of lubricant; The preparation method of the nano antibacterial material comprises the following steps: S21. By mass, add 3-5 parts of nano zinc oxide into 30-50 parts of isopropanol, ultrasonically disperse for 30-40 min, and then add 0.5-1 part of surfactant to obtain a dispersion; S22. By mass, add 0.3-0.6 part of titanium trichloride into 30-50 parts of isopropanol, mix evenly, then add the dispersion, and stir at 300-500 rpm for 30-40 min under a nitrogen atmosphere; S23. Heat the system to 180-200 °C, keep warm for 12-24 h, cool down to 40-50 °C, centrifuge and filter to collect the solid, wash it successively with deionized water and ethanol, dry it in vacuum at 60-70 °C, and grind it to obtain nano zinc oxide loaded with trivalent titanium; S24. By mass, dissolve 1.5-3 parts of quaternized chitosan-100k in 50 parts of deionized water, add 5-6 parts of nano zinc oxide loaded with trivalent titanium, ultrasonically disperse for 30-40 min, stir at 300-500 rpm for 12-24 h, centrifuge and filter to collect the solid, dry it at 60-70 °C, and grind it to obtain the nano antibacterial material.

2. The environmentally friendly Non-PVC floor according to claim 1, wherein The thickness of the transparent sheet is 0.1-0.76 mm, the thickness of the floor mat is 0.5-5.0 mm, and the total thickness of the three layers of the transparent sheet, color film, and base is 1.5-6.0 mm.

3. An environmentally friendly Non-PVC floor according to claim 1, characterized in that, The total mass parts of PET and PETG in the transparent sheet layer and the base layer are both 100 parts, and the mass ratio of PET to PETG is both 2 - 3:7 - 8; the ultraviolet absorbers in the transparent sheet layer and the color film layer are one or more combinations of UV-234, UV-405, and UV-1300; the antioxidants in the transparent sheet layer and the color film layer are one or more combinations of 168, 1010, and 1076; the filler in the base layer is one or more combinations of montmorillonite, calcium carbonate powder, and magnesium hydroxide powder; the average particle size of the cork particles in the floor cushion layer is 10 - 20 mesh; the plasticizers in the transparent sheet layer, the color film layer, and the base layer are one or more combinations of epoxidized soybean oil, epoxidized linseed oil, and dioctyl epoxytetrahydrophthalate, and the toughening agents are one or more combinations of BET, ABS, and EEA; the lubricants in the transparent sheet layer, the color film layer, the base layer, and the floor cushion layer are one or more combinations of polyethylene wax, butyl stearate, and polyethylene glycol - 600.

4. An environmentally friendly Non-PVC floor according to claim 1, characterized in that, The surfactant in S21 is one or more combinations of pentadecyl glycoside, polyvinylpyrrolidone, and polyethylene glycol - 200.

5. An environmentally friendly Non-PVC floor according to claim 1, characterized in that, The preparation method of the modified hemp fiber includes the following steps: S31. By mass, soak 20 - 30 parts of hemp fiber in 50 - 100 parts of 5 - 10wt% sodium hydroxide solution for 2 - 4h, rinse with deionized water until neutral, and dry at 80 - 100°C to obtain alkali-treated hemp fiber; S32. By mass, add 3 - 8 parts of kh-590 silane coupling agent to 100 - 150 parts of deionized water, stir at 40 - 50°C at 500 - 600 rpm for 30 - 40 min, add 10 - 20 parts of alkali-treated hemp fiber and 1 - 3 parts of nano silica white carbon black and stir for 1 - 2 h, filter and dry to obtain modified hemp fiber.

6. The preparation method of an environmentally friendly Non-PVC floor according to any one of claims 1-5, characterized in that, It includes the following steps: S1. Weigh the raw materials required for each layer, pass the cork particles through steam at 300 - 350°C for 0.5 - 1 h, dry at 80 - 100°C to control the water content to be 6 - 8% for pretreatment, and cool for later use; S2. Prepare the transparent sheet layer and the color film layer: After mixing the raw materials of the transparent sheet layer and the color film layer evenly, successively obtain the transparent sheet layer and the color film layer through an extruder; S3. Prepare the base layer: After mixing the raw materials of the base layer evenly, obtain the base layer through a kneader, an open mill, and calendering; S4. Prepare the floor cushion layer: Mix the raw materials of the floor cushion layer evenly, and prepare the floor cushion layer by hot pressing at 150 - 170°C for 10 - 15 min through a hot press; S5. Bond the Non-PVC floor substrate: Obtain a plastic layer by hot pressing the transparent sheet layer, the color film layer, and the base layer at 210 - 230°C for 10 - 15 min through a hot press, coat glue on the floor cushion layer, and bond the plastic layer to obtain the Non-PVC floor substrate; S6. Surface treatment: Coat a UV wear-resistant primer with a thickness of 150 - 200 μm on the surface of the Non-PVC floor substrate, cure by ultraviolet irradiation for 30 - 90 s, and punch and mill the edges to obtain the Non-PVC floor; The UV wear-resistant primer comprises the following raw materials: photoinitiator, BYK-333 leveling agent, polyester acrylate, modified polyurethane acrylate, isobornyl acrylate and absolute ethanol; The preparation method of the modified polyurethane acrylate comprises the following steps: S11. By mass, add 10-15 parts of epoxy palm oil into 50-80 parts of n-heptane, then dropwise add 20-30 parts of isopropanolamine. After introducing nitrogen, react at 70-100 °C for 4-6 h to obtain palm oil amide polyol; S12. By mass, react 10-15 parts of palm oil amide polyol with 40-50 parts of isophorone diisocyanate at 70-80 °C for 1-3 h under nitrogen protection. Lower the temperature to 40-50 °C, add 10-15 parts of hydroxyethyl acrylate and 0.3-0.5 part of p-hydroxyanisole and continue to react for 2-4 h. Carry out vacuum distillation to obtain the modified polyurethane acrylate.

7. The preparation method of an environmentally friendly Non-PVC floor according to claim 6, characterized in that, In step S2, the temperature of the feed inlet of the extruder is 200-220 °C, and the temperature of the discharge outlet is 230-250 °C; in step S3, the mixing temperature of the internal mixer is 230 °C-250 °C, the mixing interval is 5-10 min, and the single mixing time is 10-20 min. The kneading temperature of the open mill is 190 °C-220 °C; in step S5, the glue is any one of AB glue or PUR glue.

8. The preparation method of an environmentally friendly Non-PVC floor according to claim 6, characterized in that, The preparation method of the UV wear-resistant primer comprises the following steps: By mass, add 2-3 parts of photoinitiator, 0.5-1 part of BYK-333 leveling agent, 30-40 parts of polyester acrylate, 10-20 parts of modified polyurethane acrylate and 30-40 parts of isobornyl acrylate into 30-50 parts of absolute ethanol, and stir evenly to obtain the UV wear-resistant primer.

9. The preparation method of an environmentally friendly Non-PVC floor according to claim 8, characterized in that, In step S13, the photoinitiator is any one or a combination of benzoylformate, 2,2-dimethoxy-2-phenylacetophenone, benzoyldimethylpyrrolidone.

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