A flame-retardant and anti-deformation PETG floor and its preparation method

Abstract

The present invention relates to the technical field of floor materials, and particularly relates to a flame-retardant and anti-deformation PETG floor and a preparation method thereof. The floor comprises a UV coating, a wear-resistant layer, a color film layer, a substrate layer and a sound insulation cushion layer from top to bottom. Specifically, the substrate layer comprises 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. The present invention prepares a flame-retardant and anti-deformation PETG floor with good flame retardancy, mechanical properties and anti-deformation ability by blending PET, PETG and modified PET and adding a multi-element synergistic flame retardant.

Description

Technical Field

[0001] The present invention belongs to the technical field of floor materials, and particularly relates to a flame-retardant and deformation-resistant PETG floor and a preparation method thereof. Background Art

[0002] Most of the existing floors are made of PVC material. PVC elastic floors cannot be recycled multiple times and also contain halogens. Incineration treatment will produce dioxin, polluting the environment. PET material is non-toxic, odorless, has good hygienic safety, excellent mechanical properties and chemical stability. PET (polyethylene terephthalate) can be processed by injection molding, blow molding, extrusion and other processes, with relatively low cost, and is an environmentally friendly recyclable material. PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester) is a modified material of PET, with better impact resistance. It adds cyclohexanedimethanol on the basis of PET, improving the toughness and chemical resistance of the material. However, the heating length change rate of PET material is relatively large, and its flame retardancy needs to be improved. Summary of the Invention

[0003] The purpose of the present invention is to provide a flame-retardant and deformation-resistant PETG floor and a preparation method thereof, which are used to solve the technical problems of poor flame retardancy and deformation resistance of floors in the prior art.

[0004] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0005] The technical solutions provided by the present invention are as follows:

[0006] In the first aspect, the present invention provides a flame-retardant and deformation-resistant PETG floor. The floor includes 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.

[0007] Preferably, the antioxidant includes at least one of antioxidant DLTP and antioxidant 1076.

[0008] Preferably, the flame retardant is compounded by aluminum hydroxide, magnesium hydroxide, aluminum borate and modified DOPO in a mass ratio of 1-2:0.5-1:0.5-1:1.

[0009] Preferably, the toughening agent includes at least one of thermoplastic polyurethane (TPU), ethylene-ethyl acrylate copolymer (EEA), SEBS and rubber powder.

[0010] Preferably, the stone powder is calcium silicate.

[0011] Preferably, the lubricant includes at least one of stearic acid, polyethylene wax, and EBS.

[0012] Preferably, the chain extender includes at least one of chain extender PBT-GS, diethylaminoethanol, and N,N-dihydroxy(diisopropyl)aniline.

[0013] Preferably, the preparation method of the modified DOPO includes the following steps:

[0014] P1: Under a nitrogen atmosphere, dissolve 100 - 110 g of DOPO in toluene, heat to 90 - 100 °C, then add a tetrahydrofuran solution containing 40 - 50 g of maleic anhydride, keep stirring and reacting for 20 - 24 h, remove the solvent, wash with xylene, and dry to obtain the maleic anhydride-grafted DOPO;

[0015] P2: Mix 28.1 - 56 g of maleic anhydride-grafted DOPO, 12.3 - 25 g of naringenin, 0.39 - 0.8 g of p-toluenesulfonic acid, and 20 - 40 mL of N,N-dimethylformamide, add 10.4 - 20 g of diethanolamine dropwise in 3 portions, then react at 115 - 125 °C for 5 - 6 h, wash with ether 3 - 5 times, and then obtain the intermediate by rotary evaporation;

[0016] P3: Mix 10 - 20 g of the intermediate, 7.3 - 15 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 0.017 - 0.034 g of benzyltriethylammonium chloride, heat at 105 - 111 °C for 10 - 14 h to obtain the modified DOPO.

[0017] Preferably, the structural formula of the modified DOPO is as follows:

[0018]

[0019] Preferably, the preparation method of the modified PET includes the following steps:

[0020] Mix 166 - 332 g of terephthalic acid, 74.5 - 150 g of ethylene glycol, 51.5 - 102 g of 2,5-dihydroxymethyltetrahydrofuran, and 1.5 - 3 g of isosorbide, stir and heat to 230 - 270 °C, then control the pressure at 200 - 400 kPa by removing water during the reaction, react for 2 - 3 h, then reduce the pressure to atmospheric pressure, and then reduce the pressure to 10 - 200 Pa, heat to 270 - 280 °C within 0.5 - 1.5 h, react for 3 - 5 h, and then introduce N2 to increase the pressure to 0.15 - 0.25 MPa to obtain the modified PET.

[0021] The structural formula of PET is as follows:

[0022]

[0023] Preferably, the preparation method of the base material layer includes the following steps:

[0024] After uniformly mixing 60 - 120 parts of PET recycled material, 1 - 3 parts of flame retardant, and 3 - 5 parts of antioxidant, add 40 - 70 parts of PETG resin, 30 - 55 parts of PET resin, 10 - 20 parts of modified PET, 10 - 40 parts of toughening agent, 0 - 1.5 parts of lubricant, 200 - 300 parts of stone powder, 0 - 1 part of chain extender, and 0 - 1 part of polyamide and continue to blend. Extrude through a conical twin-screw extruder at 160 - 250 °C, then form through die technology, and then control the thickness through a thickness control roller to obtain the base material layer.

[0025] Preferably, the thickness of the base material layer is 3 - 4 mm.

[0026] Preferably, the upper surface of the base material layer is a color film layer; the color film layer includes one of PET color film, PETG color film, and TPU color film; the thickness of the color film layer is 0.05 - 0.15 mm.

[0027] Preferably, the upper surface of the color film layer is a wear-resistant layer; the wear-resistant layer includes one of PET film, PETG film, and TPU film; the thickness of the wear-resistant layer is 0.1 - 0.2 mm; the wear-resistant layer is preferably transparent.

[0028] Preferably, the upper surface of the wear-resistant layer is a UV coating; the UV coating is composed of an acrylate / acrylate copolymer with a crosslinking degree of 1 - 30%, ethyl acrylate with a molecular weight of 10,000 - 200,000, a UV-crosslinkable acrylate monomer, an acrylic resin, and a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, a leveling agent BYK-306, and a dispersant DISPERBYK-110; the mass ratio of the acrylate / acrylate copolymer, ethyl acrylate, and the UV-crosslinkable acrylate monomer and acrylic resin is 10 - 20:12 - 17:30 - 40.

[0029] Preferably, the thickness of the UV coating is 0.1 - 0.76 mm.

[0030] Preferably, the lower surface of the base material layer includes a sound insulation cushion layer, and the sound insulation cushion layer includes one of PE foam and EVA foam; the thickness of the sound insulation cushion layer is 1 - 2 mm.

[0031] In a second aspect, the present invention also provides a preparation method of a flame retardant and deformation-resistant PETG floor, including the following steps:

[0032] Step (1): Feed the color film layer and the wear-resistant layer onto the substrate layer in sequence through the unwinding device. Then, heat the wear-resistant layer and the color film layer to 60 - 90 °C by infrared, and make the wear-resistant layer and the color film layer adhere evenly to the substrate through the embossing roller. Cool and cut it into semi-finished products during the traction process.

[0033] Step (2): Uniformly coat the semi-finished product with a UV coating through a UV device and cure it to obtain a product with a surface coating. Then, perform slicing and grooving. For the grooved product, bond the sound insulation cushion layer to the lower surface of the substrate layer with PUR hot melt adhesive to obtain a flame-retardant and deformation-resistant PETG floor.

[0034] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0035] 1. In the present invention, by blending PET, PETG, and modified PET, a flame-retardant and deformation-resistant PETG floor with good flame retardancy, mechanical properties, and deformation resistance is prepared. The cyclic monomers of modified PET exhibit a higher steric effect than the linear structure monomers. The benzene ring is a conjugated system with high stability, and the increased rigidity of isosorbide increases the rigidity of the molecular chain. The prepared modified PET has good heat resistance and mechanical properties, and has good compatibility with PET and PETG. After blending, it improves the mechanical properties and heat resistance of the flame-retardant and deformation-resistant PETG floor, and can improve the processing performance, improve the melt fluidity and reduce the melt viscosity, making the production stable and efficient; the high content of aromatic rings in the modified DOPO molecule increases the rigidity of the floor molecular chain, synergistically improving the mechanical properties and deformation resistance of the floor.

[0036] 2. In the present invention, a modified DOPO flame retardant with multiple flame retardant elements is generated by reacting biomass naringenin with DOPO and 3-(2,3-epoxypropoxy)propyltrimethoxysilane. After being compounded with aluminum hydroxide, it has a good flame retardant effect. The modified DOPO thermally decomposes in the gas phase to generate phosphorus-containing free radicals, including PO2˙ and PO˙, which capture combustion free radicals and reduce combustible hydrocarbons. At the same time, the flame retardant toughening agent also decomposes to generate incombustible gases, which play a flame retardant role in the gas phase. In the condensed phase, the flame retardant toughening agent thermally decomposes to generate phosphoric acid derivatives, promoting the development of the expanded carbon layer. The P and Si elements promote the formation of a continuous and dense hybrid carbon layer during the combustion of the flame retardant high-insulating epoxy composite, effectively hindering the combustion in the condensed phase; the synergistic flame retardancy of the P, N, and Si elements enhances the gas-phase and condensed-phase flame retardancy; aluminum hydroxide and magnesium hydroxide release water vapor when PET burns, absorb heat, reduce the flame temperature, and delay the flame spread rate, achieving a flame retardant effect. Aluminum hydroxide is dispersed in the matrix in the form of solid particles and can form a protective layer during combustion, slowing down the flame propagation speed. Moreover, the high specific surface area of aluminum hydroxide can promote the carbonization reaction of PET during combustion, forming a carbon layer that covers the material surface and plays a role in heat insulation, insulation, and flame retardancy; borate aluminum undergoes a chemical reaction during combustion to generate boron- and aluminum-containing gas-phase compounds, which inhibit the free radical reaction during combustion, slow down the flame spread rate, and can form a protective film on the material surface to prevent air and heat from entering the material interior, thereby reducing the oxygen supply during combustion and achieving a flame retardant effect. It synergistically acts with the modified DOPO to improve the flame retardancy of the floor.

[0037] 3. In the present invention, adding stone powder provides rigidity, improves the support performance of the floor. At the same time, the chemical properties of the stone powder are relatively inactive, improving the thermal stability of the floor and having a flame retardant effect. It synergistically acts with the flame retardant to improve the flame retardancy of the floor; the chain extender reacts with the functional groups on the polymer chain to expand the molecular chain and increase the molecular weight, increasing the chain length, which can improve the flatness of the floor, strengthen the mixing, contact, and reaction between PET, PETG, and other components, increase the proportion of other added components, and improve the performance of the floor. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order 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.

[0039] Figure 1 It is the process flow chart for the preparation of the flame retardant and deformation-resistant PETG floor of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0040] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0041] Example 1

[0042] This example discloses a preparation method of modified DOPO, including the following steps:

[0043] P1: Under a nitrogen atmosphere, 105 g of DOPO is dissolved in toluene, and after heating to 95 °C, a tetrahydrofuran solution containing 45 g of maleic anhydride is added. After maintaining the temperature and stirring for reaction for 22 h, the solvent is removed, washed with xylene, and dried to obtain the maleic anhydride-grafted DOPO;

[0044] P2: 42 g of maleic anhydride-grafted DOPO, 18 g of naringenin, 0.6 g of p-toluenesulfonic acid, and 30 mL of N,N-dimethylformamide are mixed. After dropwise adding 15 g of diethanolamine in 3 portions, the reaction is carried out at 120 °C for 5.5 h, washed 4 times with ether, and then the intermediate is obtained by rotary evaporation;

[0045] P3: 15 g of the intermediate, 10.5 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 0.026 g of benzyltriethylammonium chloride are mixed and heated at 108 °C for 12 h to obtain the modified DOPO.

[0046] Example 2

[0047] This example discloses a preparation method of modified PET, including the following steps:

[0048] 249 g of terephthalic acid, 112.5 g of ethylene glycol, 75 g of 2,5-bis(hydroxymethyl)tetrahydrofuran, and 2.2 g of isosorbide are stirred and heated to 250 °C. Then, by removing water during the reaction, the pressure is controlled at 300 kPa, and the reaction is carried out for 2.5 h. Then the pressure is reduced to atmospheric pressure, and then the pressure is reduced to 100 Pa, and heated to 275 °C within 1 h. After reacting for 4 h, N2 is introduced to increase the pressure to 0.2 MPa to obtain the modified PET.

[0049] Example 3

[0050] This example discloses a preparation method of a substrate layer, including the following steps:

[0051] After uniformly mixing 90 g of recycled PET material, 2 g of flame retardant, and 4 g of antioxidant, 55 g of PETG resin, 42 g of PET resin, 15 g of modified PET prepared in Example 2, 20 g of toughening agent, 1 g of lubricant, 250 g of stone powder, 0.5 g of chain extender, and 0.5 g of polyamide were added for continued blending. The mixture was extruded through a conical twin-screw extruder at 200 °C, then formed by die technology, and then the thickness was controlled by a thickness control roller to obtain a substrate layer.

[0052] The antioxidant is antioxidant DLTP.

[0053] The flame retardant is composed of aluminum hydroxide, magnesium hydroxide, aluminum borate, and modified DOPO prepared in Example 1, compounded in a mass ratio of 1.5:0.75:0.75:1.

[0054] The toughening agent is TPU; the stone powder is calcium silicate; the lubricant is stearic acid; the chain extender is chain extender PBT-GS.

[0055] Example 4

[0056] This example discloses a method for preparing a substrate layer, including the following steps:

[0057] After uniformly mixing 60 g of recycled PET material, 3 g of flame retardant, and 3 g of antioxidant, 70 g of PETG resin, 30 g of PET resin, 20 g of modified PET prepared in Example 2, 10 g of toughening agent, 1.5 g of lubricant, 200 g of stone powder, and 1 g of chain extender were added for continued blending. The mixture was extruded through a conical twin-screw extruder at 250 °C, then formed by die technology, and then the thickness was controlled by a thickness control roller to obtain a substrate layer.

[0058] The antioxidant is antioxidant 1076.

[0059] The flame retardant is composed of aluminum hydroxide, magnesium hydroxide, aluminum borate, and modified DOPO prepared in Example 1, compounded in a mass ratio of 1:1:0.5:1.

[0060] The toughening agent is EEA; the stone powder is calcium silicate; the lubricant is polyethylene wax; the chain extender is N,N-dihydroxy(diisopropyl)aniline.

[0061] Example 5

[0062] This example discloses a method for preparing a substrate layer, including the following steps:

[0063] After mixing 70 g of recycled PET material, 2.5 g of flame retardant, and 3.5 g of antioxidant evenly, 60 g of PETG resin, 35 g of PET resin, 18 g of modified PET prepared in Example 2, 20 g of toughening agent, 1.2 g of lubricant, 250 g of stone powder, 0.8 g of chain extender, and 0.3 g of polyamide were added for further blending. The mixture was extruded through a conical twin-screw extruder at 220 °C, then formed by die technology, and then the thickness was controlled by a thickness control roller to obtain the substrate layer.

[0064] The antioxidant is antioxidant 1076.

[0065] The flame retardant is prepared by compounding aluminum hydroxide, magnesium hydroxide, aluminum borate, and modified DOPO prepared in Example 1 in a mass ratio of 2:0.5:1:1.

[0066] The toughening agent is SEBS; the stone powder is calcium silicate; the lubricant is EBS; the chain extender is diethylaminoethanol.

[0067] Example 6

[0068] This example discloses a method for preparing a substrate layer, which includes the following steps:

[0069] After mixing 120 g of recycled PET material, 1 g of flame retardant, and 5 g of antioxidant evenly, 40 g of PETG resin, 55 g of PET resin, 10 g of modified PET prepared in Example 2, 40 g of toughening agent, 300 g of stone powder, and 1 g of polyamide were added for further blending. The mixture was extruded through a conical twin-screw extruder at 160 °C, then formed by die technology, and then the thickness was controlled by a thickness control roller to obtain the substrate layer.

[0070] The antioxidant includes at least one of antioxidant DLTP and antioxidant 1076.

[0071] The flame retardant is prepared by compounding aluminum hydroxide, magnesium hydroxide, aluminum borate, and modified DOPO prepared in Example 1 in a mass ratio of 1.2:0.9:0.6:1.

[0072] The toughening agent is rubber powder; the stone powder is calcium silicate; the lubricant is stearic acid; the chain extender is diethylaminoethanol.

[0073] Example 7

[0074] After uniformly mixing 110 g of recycled PET material, 1.2 g of flame retardant, and 4.5 g of antioxidant, 50 g of PETG resin, 50 g of PET resin, 12 g of modified PET prepared in Example 2, 30 g of toughening agent, 0.3 g of lubricant, 280 g of stone powder, 0.3 g of chain extender, and 0.8 g of polyamide were added for further blending. The mixture was extruded through a conical twin-screw extruder at 170 °C, then formed by die technology, and then the thickness was controlled by a thickness fixing roller to obtain a substrate layer.

[0075] The antioxidant is antioxidant DLTP.

[0076] The flame retardant is prepared by compounding aluminum hydroxide, magnesium hydroxide, aluminum borate, and modified DOPO prepared in Example 1 in a mass ratio of 1.8:0.6:0.8:1.

[0077] The toughening agent is polyurethane; the stone powder is calcium silicate; the lubricant is polyethylene wax; the chain extender is N,N-dihydroxy(diisopropyl)aniline.

[0078] Example 8

[0079] Refer to Figure 1 As shown, this example discloses a preparation method of a flame-retardant and deformation-resistant PETG floor, including the following steps:

[0080] Step (1): The color film layer and the wear-resistant layer are sequentially conveyed onto the substrate layer prepared in Example 3 through a unwind device. Then, the wear-resistant layer and the color film layer are heated to 75 °C by infrared heating, and then the wear-resistant layer and the color film layer are uniformly adhered to the substrate through an embossing roller, and cooled and cut into semi-finished products during the traction process.

[0081] Step (2): The semi-finished products are uniformly coated with a UV coating through a UV device and cured to obtain products with a surface coating. Then, they are sliced and grooved. For the grooved products, a sound insulation cushion layer is adhered to the lower surface of the substrate layer through PUR hot melt adhesive to obtain a flame-retardant and deformation-resistant PETG floor.

[0082] The color film layer is a PET color film; the wear-resistant layer is a PET film; the UV coating is composed of acrylate / acrylate copolymer, thermoplastic ethyl acrylate, UV-crosslinkable acrylate monomer, acrylic resin, and photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, leveling agent BYK-306, and dispersant DISPERBYK-110; the mass ratio of acrylate / acrylate copolymer, thermoplastic ethyl acrylate, and UV-crosslinkable acrylate monomer and acrylic resin is 15:15:35; the sound insulation cushion layer is a PE foam.

[0083] Example 9

[0084] Refer to Figure 1As shown in the figure, this embodiment discloses a preparation method of a flame-retardant and anti-deformation PETG floor, which includes the following steps:

[0085] Step (1): Convey the color film layer and the wear-resistant layer to the substrate layer prepared in Example 4 in sequence through a unwinding device. Then, after infrared heating the wear-resistant layer and the color film layer to 60°C, make the wear-resistant layer and the color film layer adhere to the substrate evenly through an embossing roller, and cool and cut it into semi-finished products through the traction process;

[0086] Step (2): Uniformly coat the semi-finished product with a UV coating through a UV device and cure it to obtain a product with a surface coating. Then, perform slicing and grooving. For the grooved product, bond the sound insulation cushion layer to the lower surface of the substrate layer through PUR hot melt adhesive to obtain a flame-retardant and anti-deformation PETG floor.

[0087] The color film layer is a PETG color film; the wear-resistant layer is a PETG film; the UV coating is composed of acrylate / acrylate copolymer, ethyl acrylate of thermoplasticity, acrylate monomer cross-linkable by UV, acrylic resin, and photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, leveling agent BYK-306, and dispersant DISPERBYK-110; the mass ratio of acrylate / acrylate copolymer, ethyl acrylate of thermoplasticity, and acrylate monomer cross-linkable by UV and acrylic resin is 20:12:40; the sound insulation cushion layer is an EVA foam.

[0088] Example 10

[0089] Refer to Figure 1 As shown in the figure, this embodiment discloses a preparation method of a flame-retardant and anti-deformation PETG floor, which includes the following steps:

[0090] Step (1): Convey the color film layer and the wear-resistant layer to the substrate layer prepared in Example 5 in sequence through a unwinding device. Then, after infrared heating the wear-resistant layer and the color film layer to 90°C, make the wear-resistant layer and the color film layer adhere to the substrate evenly through an embossing roller, and cool and cut it into semi-finished products through the traction process;

[0091] Step (2): Uniformly coat the semi-finished product with a UV coating through a UV device and cure it to obtain a product with a surface coating. Then, perform slicing and grooving. For the grooved product, bond the sound insulation cushion layer to the lower surface of the substrate layer through PUR hot melt adhesive to obtain a flame-retardant and anti-deformation PETG floor.

[0092] The color film layer is a TPU color film; the wear-resistant layer is a TPU film; the UV coating is composed of acrylate / acrylate copolymer, ethyl acrylate thermoplastic, UV-crosslinkable acrylate monomer, acrylic resin, photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, leveling agent BYK-306, and dispersant DISPERBYK-110; the mass ratio of acrylate / acrylate copolymer, ethyl acrylate thermoplastic, and UV-crosslinkable acrylate monomer and acrylic resin is 10:17:30; the sound insulation cushion layer is a PE foam.

[0093] Example 11

[0094] Refer to Figure 1 As shown, this example discloses a preparation method of a flame-retardant and deformation-resistant PETG floor, including the following steps:

[0095] Step (1): Feed the color film layer and the wear-resistant layer onto the substrate layer prepared in Example 6 in sequence through a unwind device, then heat the wear-resistant layer and the color film layer to 65°C by infrared heating, and then make the wear-resistant layer and the color film layer adhere to the substrate evenly through an embossing roller, and cool and cut into semi-finished products during the traction process;

[0096] Step (2): Uniformly coat the UV coating on the semi-finished product through a UV device and cure it to obtain a product with a surface coating, then perform slicing and grooving. For the grooved product, bond the sound insulation cushion layer to the lower surface of the substrate layer through PUR hot melt adhesive to obtain a flame-retardant and deformation-resistant PETG floor.

[0097] The color film layer is a PET color film, a PETG color film, and a TPU color film; the wear-resistant layer is a PET film, a PETG film, and a TPU film; the UV coating is composed of acrylate / acrylate copolymer with a crosslinking degree, ethyl acrylate thermoplastic, UV-crosslinkable acrylate monomer, acrylic resin, photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, leveling agent BYK-306, and dispersant DISPERBYK-110; the mass ratio of acrylate / acrylate copolymer, ethyl acrylate thermoplastic, and UV-crosslinkable acrylate monomer and acrylic resin is 18:13:38; the sound insulation cushion layer is an EVA foam.

[0098] Example 12

[0099] Refer to Figure 1 As shown, this example discloses a preparation method of a flame-retardant and deformation-resistant PETG floor, including the following steps:

[0100] Step (1): The color film layer and the wear-resistant layer are successively conveyed onto the substrate layer prepared in Example 7 through a unwind device. Then, after heating the wear-resistant layer and the color film layer to 85°C by infrared heating, the wear-resistant layer and the color film layer are evenly adhered to the substrate through an embossing roller, and are cooled and cut into semi-finished products during the traction process.

[0101] Step (2): The semi-finished product is evenly coated with a UV coating through a UV device and cured to obtain a product with a surface coating. Then, it is sliced and grooved. For the grooved product, a sound-absorbing cushion layer is adhered to the lower surface of the substrate layer through PUR hot melt adhesive to obtain a flame-retardant and deformation-resistant PETG floor.

[0102] The color film layer is a PET color film, a PETG color film, and a TPU color film; the wear-resistant layer is a PET film, a PETG film, and a TPU film; the UV coating is composed of an acrylate / acrylate copolymer, ethyl thermoplastic acrylate, a UV-crosslinkable acrylate monomer, an acrylic resin, and a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, a leveling agent BYK-306, and a dispersant DISPERBYK-110; the mass ratio of the acrylate / acrylate copolymer, ethyl thermoplastic acrylate, and the UV-crosslinkable acrylate monomer and the acrylic resin is 12:15:35; the sound-absorbing cushion layer is a PE foam.

[0103] Comparative Example 1

[0104] Compared with Example 8, in the process of preparing the flame-retardant and deformation-resistant PETG floor in Comparative Example 1, no flame retardant was added to the substrate layer, and other conditions remained unchanged.

[0105] Comparative Example 2

[0106] Compared with Example 8, in the process of preparing the flame-retardant and deformation-resistant PETG floor in Comparative Example 2, no modified PET was added, and other conditions remained unchanged.

[0107] Experimental Example

[0108] The properties of the flame-retardant and deformation-resistant PETG floors prepared in Examples 8 - 12 and Comparative Examples 1 - 2 were tested, and the test results are shown in Table 1:

[0109] Table 1

[0110]

[0111]

[0112] As can be seen from the test results in Table 1, the flame-retardant and deformation-resistant PETG floors prepared in Examples 8-12 of the present invention have excellent physical and chemical properties, and have good flame retardancy and deformation resistance. By comparing Comparative Example 1 with Example 8, it can be seen that adding a flame retardant can enhance the flame retardancy of the flame-retardant and deformation-resistant PETG floor; by comparing Comparative Example 2 with Example 8, it can be seen that adding modified PET can enhance the physical and chemical properties of the flame-retardant and deformation-resistant PETG floor.

[0113] As mentioned above, the above are only the preferred specific embodiments of the present invention, but 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 substitutions or changes, should be covered within the protection scope of the present invention.

[0114] 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. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A flame-retardant and anti-deformation PETG floor, characterized in that, The floor from top to bottom includes a UV coating, a wear-resistant layer, a color film layer, a base material layer and a sound insulation cushion layer; the base material layer specifically includes the following components 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, 0-1 part of polyamide; The flame retardant is compounded by aluminum hydroxide, magnesium hydroxide, aluminum borate and modified DOPO in a mass ratio of 1-2:0.5-1:0.5-1:1; The preparation method of the modified DOPO includes the following steps: P1: Under a nitrogen atmosphere, dissolve 100-110 g of DOPO in toluene, heat to 90-100 °C, then add a tetrahydrofuran solution containing 40-50 g of maleic anhydride, keep warm and stir for reaction for 20-24 h, remove the solvent, wash with xylene, and dry to obtain maleic anhydride grafted DOPO; P2: Mix 28.1-56 g of maleic anhydride grafted DOPO, 12.3-25 g of naringenin, 0.39-0.8 g of p-toluenesulfonic acid and 20-40 mL of N,N-dimethylformamide, add 10.4-20 g of diethanolamine dropwise in 3 times, and react at 115-125 °C for 5-6 h, wash with ether 3-5 times, and then obtain the intermediate through rotary evaporation; P3: Mix 10-20 g of the intermediate, 7.3-15 g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane and 0.017-0.034 g of benzyltriethylammonium chloride, heat at 105-111 °C for 10-14 h to obtain modified DOPO.

2. The flame-retardant and anti-deformation PETG floor according to claim 1, wherein The antioxidant includes at least one of antioxidant DLTP and antioxidant 1076; the toughening agent includes at least one of thermoplastic polyurethane (TPU), ethylene-ethyl acrylate copolymer (EEA), SEBS and rubber powder; the stone powder is calcium silicate; the lubricant includes at least one of stearic acid, polyethylene wax and EBS; the chain extender includes at least one of chain extender PBT-GS, diethylaminoethanol and N,N-dihydroxy(diisopropyl)aniline.

3. The flame-retardant and deformation-resistant PETG floor according to claim 1, wherein The preparation method of the modified PET includes the following steps: Mix 166-332 g of terephthalic acid, 74.5-150 g of ethylene glycol, 51.5-102 g of 2,5-dihydroxymethyltetrahydrofuran and 1.5-3 g of isosorbide, stir and heat to 230-270 °C, then control the pressure at 200-400 kPa by removing water during the reaction, react for 2-3 h, then reduce the pressure to atmospheric pressure, then reduce the pressure to a vacuum of 10-200 Pa, heat to 270-280 °C within 0.5-1.5 h, react for 3-5 h, and then introduce N2 to increase the pressure to 0.15-0.25 MPa to obtain modified PET.

4. The flame-retardant and deformation-resistant PETG floor according to claim 1, wherein The preparation method of the base material layer includes the following steps: After uniformly mixing 60 - 120 parts of PET recycled material, 1 - 3 parts of flame retardant, and 3 - 5 parts of antioxidant, add 40 - 70 parts of PETG resin, 30 - 55 parts of PET resin, 10 - 20 parts of modified PET, 10 - 40 parts of toughening agent, 0 - 1.5 parts of lubricant, 200 - 300 parts of stone powder, 0 - 1 part of chain extender, and 0 - 1 part of polyamide for further blending. Extrude through a conical twin - screw extruder at 160 - 250 °C, then form through die technology, and then control the thickness through a thickness - fixing roller to obtain the substrate layer.

5. The flame-retardant and deformation-resistant PETG floor according to claim 4, characterized in that, The thickness of the substrate layer is 3 - 4 mm.

6. The flame-retardant and deformation-resistant PETG floor according to claim 1, wherein, The color film layer includes one of PET color film, PETG color film, and TPU color film; the thickness of the color film layer is 0.05 - 0.15 mm; the wear - resistant layer includes one of PET film, PETG film, and TPU film; the thickness of the wear - resistant layer is 0.1 - 0.2 mm.

7. The flame-retardant and deformation-resistant PETG floor according to claim 1, wherein The UV coating is composed of an acrylate / acrylate copolymer with a cross - linking degree of 1 - 30%, ethyl acrylate with a molecular weight of 10000 - 200000, a UV - crosslinkable acrylate monomer, an acrylic resin, and a photoinitiator 2,4,6 - trimethylbenzoyl - diphenylphosphine oxide, a leveling agent BYK - 306, and a dispersant DISPERBYK - 110; the mass ratio of the acrylate / acrylate copolymer, ethyl acrylate, and the UV - crosslinkable acrylate monomer and acrylic resin is 10 - 20:12 - 17:30 - 40; the thickness of the UV coating is 0.1 - 0.76 mm.

8. The flame-retardant and deformation-resistant PETG floor according to claim 1, wherein The sound - proof cushion layer includes one of PE foam and EVA foam; the thickness of the sound - proof cushion layer is 1 - 2 mm.

9. A method for preparing a flame-retardant and anti-deformation PETG floor according to any one of claims 1-8, characterized in that, It includes the following steps: Step (1): Convey the color film layer and the wear - resistant layer to the substrate layer in sequence through a unwinding device. Then, heat the wear - resistant layer and the color film layer to 60 - 90 °C through infrared heating, and make the wear - resistant layer and the color film layer adhere to the substrate evenly through an embossing roller. Cool and cut it into semi - finished products during the traction process. Step (2): Uniformly coat the semi - finished product with a UV coating through a UV device and cure it to obtain a product with a surface coating. Then, perform slicing and grooving. For the grooved product, bond the sound - proof cushion layer to the lower surface of the substrate layer through PUR hot - melt adhesive to obtain the flame - retardant and deformation - resistant PETG floor.

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