Hard multilayer SPC floor and production process thereof

Abstract

The invention discloses a hard multilayer SPC floor and a production process thereof.After a color film layer and a wear-resistant layer are sequentially pressed on a base material layer, the surface of the wear-resistant layer is coated with a reinforced coating, ultraviolet irradiation is conducted, the hard multilayer SPC floor is prepared, the reinforced coating can form a grid cross-linked structure under the action of a modified monomer when ultraviolet curing is conducted, and the surface of the wear-resistant layer is coated with the reinforced coating; meanwhile, the modified monomer contains a large amount of fluoroalkane and organic silicon chain segments, so that the coating film has a very good stain-resistant effect, and the surface of the modified filler contains unprotected double bonds and can participate in curing of the coating, so that the surface of the reinforced filler is coated with a polyacrylate molecular net, and the hardness of the coating film is improved. The core-shell structure is matched with molybdenum disulfide, silicon dioxide and aluminum oxide, so that the wear-resisting effect of a coating film can be well improved, meanwhile, the self-lubricating effect of the core-shell structure is matched with the rebound resilience of cage-shaped backboard siloxane inside, and the service life of the floor is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of SPC floor preparation, and particularly relates to a rigid multi-layer SPC floor and its production process. Background Art

[0002] The rigid multi-layer SPC floor is a composite floor with stone powder and thermoplastic polymer materials as the core base materials. Its name comes from the English abbreviation, which is translated into Chinese as "stone plastic composite material", combining the decorative properties of wood and the stability of plastic. The main raw materials include calcium powder, polyvinyl chloride resin and stabilizers, and a multi-layer structure is formed through high-temperature extrusion and composite processes. A UV coating is provided on the surface to enhance wear resistance, prevent fading, and provide the gloss of the floor. However, the strength of the current UV coating is insufficient, and obvious wear phenomena still occur during use. At the same time, when stains adhere to the floor for a long time, the colors of some stains will penetrate into the wear-resistant layer of the floor, seriously affecting the beauty of the floor. Summary of the Invention

[0003] The purpose of the present invention is to provide a rigid multi-layer SPC floor and its production process, which solves the problems of wear and scratches that occur during the use of SPC floors at the present stage, and at the same time, the problem of color bleeding will occur when stains adhere for a long time.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A production process of a rigid multi-layer SPC floor specifically includes the following steps:

[0006] Weigh the following raw materials in parts by weight: 80-100 parts of PVC masterbatch, 160-180 parts of calcium carbonate, 6-8 parts of calcium-zinc stabilizer, 1-1.5 parts of PE wax, and 2-3 parts of ACR plasticizer. Mix the raw materials evenly under the condition of a temperature of 125-135°C, and then add them into a twin-screw extruder. Under the condition of a temperature of 180-200°C, extrude and form to obtain a base material layer. After successively pressing a color film layer and a wear-resistant layer above the base material layer, apply a strengthening coating on the surface of the wear-resistant layer, and irradiate it with 365nm ultraviolet light for 5-8s to obtain a rigid multi-layer SPC floor.

[0007] Further, the wear-resistant layer is made of the following raw materials in parts by weight: 100 parts of PVC masterbatch, 30 parts of silicon carbide, 25 parts of dioctyl phthalate, and 2 parts of epoxidized soybean oil.

[0008] Further, the strengthening coating is made by the following steps:

[0009] Step A1: Mix octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(oxiranylmethoxy)propyl]disiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide. Introduce nitrogen for protection and react for 10 - 12 h under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 90 - 95 °C to obtain pretreated polysiloxane;

[0010] Step A2: Mix the pretreated polysiloxane, diethanolamine, and DMF evenly. React for 6 - 8 h under the conditions of a rotation speed of 120 - 150 r / min, a temperature of 40 - 50 °C, and a pH value of 11 - 12 to obtain modified polysiloxane. Mix the modified polysiloxane, acryloyl chloride, triethylamine, and DMF evenly and react for 3 - 5 h under the conditions of a rotation speed of 300 - 500 r / min and a temperature of 20 - 25 °C to obtain a modified monomer;

[0011] Step A3: Weigh the following raw materials by weight: 25 - 30 parts of butyl acrylate, 25 - 30 parts of methyl methacrylate, 12 - 15 parts of 2-hydroxyethyl methacrylate, 20 - 25 parts of the modified monomer, 8 - 10 parts of reinforcing filler, 4 - 6 parts of molybdenum disulfide, 1 - 3 parts of silicon dioxide, 3 - 5 parts of alumina, and 3 - 5 parts of photoinitiator. Mix the raw materials evenly to obtain the reinforcing coating.

[0012] Furthermore, the molar ratio of octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(oxiranylmethoxy)propyl]disiloxane, and tetramethylammonium hydroxide described in Step A1 is 1.4:1:1:2.

[0013] Furthermore, the molar ratio of the pretreated polysiloxane and diethanolamine described in Step A2 is 1:2, and the molar ratio of the modified polysiloxane, acryloyl chloride, and triethylamine is 1:6:6.1.

[0014] Furthermore, the reinforcing filler is prepared by the following steps:

[0015] Step B1: Mix hexagonal boron nitride, sodium hydroxide, and deionized water evenly. Under the conditions of a frequency of 20 - 30 kHz and a temperature of 25 - 30 °C, perform ultrasonic treatment for 1 - 1.5 h, raise the temperature to 120 - 125 °C, perform reflux treatment for 20 - 25 h, cool to room temperature and wash until neutral to obtain hydroxylated hexagonal boron nitride. Mix the hydroxylated hexagonal boron nitride, 3-isocyanatopropylmethyldichlorosilane, dibutyltin dilaurate, and toluene. Introduce nitrogen for protection and react for 3 - 5 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 40 - 50 °C to obtain modified boron nitride;

[0016] Step B2: Mix cetyltrimethoxysilane, isopropanol, deionized water, and sodium hydroxide evenly. React under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 85 - 90 °C for 3 - 5 h, then cool down to 20 - 25 °C and react for 10 - 15 h to obtain sodium hexadecylcyclotetrasiloxanetetrasilanolate. Mix sodium hexadecyltetrasilanolate, triethylamine, and tetrahydrofuran evenly, introduce nitrogen protection, stir and add modified boron nitride under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 0 - 3 °C, react for 3 - 5 h, raise the temperature to 20 - 25 °C, react for 10 - 15 h, then add 3-(methyldichlorosilyl)propyl (alcohol) acrylate and continue to react for 8 - 10 h to obtain the reinforced filler.

[0017] Further, the dosage ratio of hexagonal boron nitride, sodium hydroxide, and deionized water in Step B1 is 1 mmol: 0.5 mmol: 100 mL. The molar ratio of the hydroxyl groups on hydroxylated hexagonal boron nitride to 3-isocyanatopropylmethyldichlorosilane is 1:1. The dosage of dibutyltin dilaurate is 1% of the mass of 3-isocyanatopropylmethyldichlorosilane.

[0018] Further, the dosage ratio of cetyltrimethoxysilane, isopropanol, deionized water, and sodium hydroxide in Step B2 is 120 mmol: 120 mL: 2.5 g: 80 mmol. The dosage ratio of sodium hexadecyltetrasilanolate, triethylamine, tetrahydrofuran, modified boron nitride, and 3-(methyldichlorosilyl)propyl (alcohol) acrylate is 18 g: 5 g: 30 mL: 3 g: 5 g.

[0019] Advantages of the present invention: A rigid multi-layer SPC floor prepared by the present invention, after successively pressing a color film layer and a wear-resistant layer above the substrate layer, a reinforcing coating is applied on the surface of the wear-resistant layer and irradiated with ultraviolet light to obtain a rigid multi-layer SPC floor. The reinforcing coating comprises the following raw materials: butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, modified monomer, reinforced filler, molybdenum disulfide, silicon dioxide, aluminum oxide, and photoinitiator. The modified monomer is prepared by ring-opening polymerization using octamethylcyclotetrasiloxane and tetramethyltris(3-trifluoropropyl)cyclotetrasiloxane as raw materials and then end-capping with 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane to form an epoxy group-terminated pretreated polysiloxane. React the pretreated polysiloxane with diethanolamine so that the epoxy groups on the pretreated polysiloxane react with the imines on diethanolamine to obtain a modified polysiloxane. React the modified polysiloxane with acryloyl chloride so that the hydroxyl groups on the modified polysiloxane react with the acyl chlorides on acryloyl chloride to obtain the modified monomer.

[0020] The reinforcing filler is made of cubic boron nitride and treated with sodium hydroxide to obtain hydroxylated boron nitride. The hydroxylated boron nitride is reacted with 3-isocyanatopropylmethyldichlorosilane, so that the hydroxyl groups on the surface of the hydroxylated boron nitride react with the isocyanate groups on 3-isocyanatopropylmethyldichlorosilane to obtain modified boron nitride. Cetyltrimethoxysilane is hydrolyzed and condensed to form sodium cetylcyclotetrasiloxanetetrasilanol. The sodium cetylcyclotetrasiloxanetetrasilanol is reacted with the modified boron nitride, so that the sodium silanol on the sodium cetylcyclotetrasiloxanetetrasilanol reacts with the chlorine atom sites on the modified boron nitride. Then, 3-(methyldichlorosilyl)propyl (alcohol) acrylate is added to react with the remaining sodium silanol to obtain the reinforcing filler.

[0021] When the reinforcing coating is cured by ultraviolet light, under the action of the modified monomer, a network cross-linked structure can be formed, thereby enhancing the hardness of the coating film. At the same time, the modified monomer contains a large amount of fluoroalkane and organosilicon segments, so that the coating film has a good antifouling effect, and even if stains adhere for a long time, there will be no bleeding phenomenon. The surface of the modified filler contains unprotected double bonds, which can participate in the curing of the coating, so that the polyacrylate molecular network coats the surface of the reinforcing filler, thereby forming a stable core-shell structure. When combined with molybdenum disulfide, silicon dioxide and alumina, it can well increase the wear resistance of the coating film. At the same time, the self-lubricating effect of itself cooperates with the resilience of the internal cage-shaped backplane siloxane, so that when the floor is subjected to an external force, the surface coating film will undergo slight deformation to offset the acting force, thereby increasing the service life of the floor. Detailed implementation mode

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0023] Example 1, a production process of a hard multi-layer SPC floor, specifically includes the following steps:

[0024] Weigh the following raw materials in parts by weight: 80 parts of PVC masterbatch, 160 parts of calcium carbonate, 6 parts of calcium-zinc stabilizer, 1 part of PE wax and 2 parts of ACR plasticizer. Mix the raw materials evenly at a temperature of 125 °C, and then add them to a twin-screw extruder and extrude and form at a temperature of 180 °C to obtain a base material layer. After successively pressing a color film layer and a wear-resistant layer above the base material layer, a reinforcing coating is applied on the surface of the wear-resistant layer and irradiated with 365 nm ultraviolet light for 5 s to obtain a hard multi-layer SPC floor.

[0025] The wear-resistant layer is made of the following raw materials by weight: 100 parts of PVC masterbatch, 30 parts of silicon carbide, 25 parts of dioctyl phthalate, and 2 parts of epoxidized soybean oil. The PVC masterbatch used for the substrate layer and the wear-resistant layer is of the SG-5 type, the calcium-zinc stabilizer is of the CZ758 type, the PE wax is of the LP1020P type, and the ACR plasticizer is of the ACR401 type.

[0026] The strengthening coating is prepared by the following steps:

[0027] Step A1: Mix octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide, introduce nitrogen protection, and react for 10 h under the conditions of a rotation speed of 120 r / min and a temperature of 90 °C to obtain pretreated polysiloxane;

[0028] Step A2: Mix the pretreated polysiloxane, diethanolamine, and DMF evenly, and react for 6 h under the conditions of a rotation speed of 120 r / min, a temperature of 40 °C, and a pH value of 11 to obtain modified polysiloxane. Mix the modified polysiloxane, acryloyl chloride, triethylamine, and DMF evenly, and react for 3 h under the conditions of a rotation speed of 300 r / min and a temperature of 20 °C to obtain a modified monomer;

[0029] Step A3: Weigh the following raw materials by weight: 25 parts of butyl acrylate, 25 parts of methyl methacrylate, 12 parts of 2-hydroxyethyl methacrylate, 20 parts of modified monomer, 8 parts of strengthening filler, 4 parts of molybdenum disulfide, 1 part of silicon dioxide, 3 parts of alumina, and 3 parts of photoinitiator. Mix the raw materials evenly to obtain the strengthening coating.

[0030] The molar ratio of octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, and tetramethylammonium hydroxide described in Step A1 is 1.4:1:1:2.

[0031] The molar ratio of the pretreated polysiloxane and diethanolamine described in Step A2 is 1:2, and the molar ratio of the modified polysiloxane, acryloyl chloride, and triethylamine is 1:6:6.1.

[0032] The particle size of the molybdenum disulfide described in Step A3 is 5 μm, the particle size of the silicon dioxide is 30 nm, the particle size of the alumina is 50 μm, and the photoinitiator is 1173.

[0033] The strengthening filler is prepared by the following steps:

[0034] Step B1: Mix hexagonal boron nitride, sodium hydroxide, and deionized water evenly. Under the conditions of a frequency of 20 kHz and a temperature of 25 °C, perform ultrasonic treatment for 1 h, then raise the temperature to 120 °C, carry out reflux treatment for 20 h, cool down to room temperature, and wash until neutral to obtain hydroxylated hexagonal boron nitride. Mix the hydroxylated hexagonal boron nitride, 3-isocyanatopropylmethyldichlorosilane, dibutyltin dilaurate, and toluene, introduce nitrogen protection, and react at a rotation speed of 200 r / min and a temperature of 40 °C for 3 h to obtain modified boron nitride;

[0035] Step B2: Mix cetyltrimethoxysilane, isopropyl alcohol, deionized water, and sodium hydroxide evenly. React at a rotation speed of 150 r / min and a temperature of 85 °C for 3 h, then cool down to 20 °C and react for 10 h to obtain sodium cetylcyclotetrasiloxanetetrasilanol. Mix sodium cetyltetrasilanol, triethylamine, and tetrahydrofuran evenly, introduce nitrogen protection, stir and add modified boron nitride at a rotation speed of 200 r / min and a temperature of 0 °C, react for 3 h, raise the temperature to 20 °C, react for 10 h, then add 3-(methyldichlorosilyl)propyl methacrylate and continue to react for 8 h to obtain the reinforced filler.

[0036] The dosage ratio of the hexagonal boron nitride, sodium hydroxide, and deionized water described in Step B1 is 1 mmol: 0.5 mmol: 100 mL. The molar ratio of the hydroxyl groups on the hydroxylated hexagonal boron nitride to 3-isocyanatopropylmethyldichlorosilane is 1:1, and the dosage of dibutyltin dilaurate is 1% of the mass of 3-isocyanatopropylmethyldichlorosilane.

[0037] The dosage ratio of the cetyltrimethoxysilane, isopropyl alcohol, deionized water, and sodium hydroxide described in Step B2 is 120 mmol: 120 mL: 2.5 g: 80 mmol. The dosage ratio of sodium cetyltetrasilanol, triethylamine, tetrahydrofuran, modified boron nitride, and 3-(methyldichlorosilyl)propyl methacrylate is 18 g: 5 g: 30 mL: 3 g: 5 g.

[0038] Example 2, a production process for a rigid multi-layer SPC floor, specifically includes the following steps:

[0039] Weigh the following raw materials in parts by weight: 90 parts of PVC masterbatch, 170 parts of calcium carbonate, 7 parts of calcium-zinc stabilizer, 1.3 parts of PE wax, and 2.5 parts of ACR plasticizer. Mix the raw materials evenly under the condition of a temperature of 130 °C, then add them into a twin-screw extruder and extrude and form under the condition of a temperature of 190 °C to obtain the base material layer. After successively pressing a color film layer and a wear-resistant layer above the base material layer, apply a reinforced coating on the surface of the wear-resistant layer and irradiate it with 365 nm ultraviolet light for 7 s to obtain the rigid multi-layer SPC floor.

[0040] The described wear-resistant layer is made of the following raw materials in parts by weight: 100 parts of PVC masterbatch, 30 parts of silicon carbide, 25 parts of dioctyl phthalate, and 2 parts of epoxidized soybean oil. The PVC masterbatch used for the substrate layer and the wear-resistant layer is of the SG-5 type, the calcium-zinc stabilizer is of the CZ758 type, the PE wax is of the LP1040F type, and the ACR plasticizer is of the ACR401 type.

[0041] The described strengthening coating is made by the following steps:

[0042] Step A1: Mix octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide, introduce nitrogen protection, and react for 10 h under the conditions of a rotation speed of 120 r / min and a temperature of 95 °C to obtain pretreated polysiloxane;

[0043] Step A2: Mix the pretreated polysiloxane, diethanolamine, and DMF evenly, and react for 7 h under the conditions of a rotation speed of 150 r / min, a temperature of 45 °C, and a pH value of 11 to obtain modified polysiloxane. Mix the modified polysiloxane, acryloyl chloride, triethylamine, and DMF evenly, and react for 4 h under the conditions of a rotation speed of 300 r / min and a temperature of 25 °C to obtain a modified monomer;

[0044] Step A3: Weigh the following raw materials in parts by weight: 28 parts of butyl acrylate, 28 parts of methyl methacrylate, 12 parts of 2-hydroxyethyl methacrylate, 23 parts of modified monomer, 9 parts of strengthening filler, 5 parts of molybdenum disulfide, 2 parts of silicon dioxide, 4 parts of alumina, and 4 parts of photoinitiator. Mix the raw materials evenly to obtain the strengthening coating.

[0045] The molar ratio of octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, and tetramethylammonium hydroxide described in Step A1 is 1.4:1:1:2.

[0046] The molar ratio of the pretreated polysiloxane and diethanolamine described in Step A2 is 1:2, and the molar ratio of the modified polysiloxane, acryloyl chloride, and triethylamine is 1:6:6.1.

[0047] The particle size of the molybdenum disulfide described in Step A3 is 5 μm, the particle size of the silicon dioxide is 30 nm, the particle size of the alumina is 50 μm, and the photoinitiator is 907.

[0048] The described strengthening filler is made by the following steps:

[0049] Step B1: Mix hexagonal boron nitride, sodium hydroxide, and deionized water evenly. Under the conditions of a frequency of 25 kHz and a temperature of 25 °C, perform ultrasonic treatment for 1.5 h, then raise the temperature to 120 °C, carry out reflux treatment for 25 h, cool down to room temperature, and wash until neutral to obtain hydroxylated hexagonal boron nitride. Mix hydroxylated hexagonal boron nitride, 3-isocyanatopropylmethyldichlorosilane, dibutyltin dilaurate, and toluene, introduce nitrogen protection, and carry out a reaction for 4 h under the conditions of a rotation speed of 200 r / min and a temperature of 45 °C to obtain modified boron nitride;

[0050] Step B2: Mix cetyltrimethoxysilane, isopropanol, deionized water, and sodium hydroxide evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 85 °C, carry out a reaction for 4 h, then cool down to 25 °C and carry out a reaction for 10 h to obtain sodium cetylcyclotetrasiloxanetetrasilanol. Mix sodium cetyltetrasilanol, triethylamine, and tetrahydrofuran evenly, introduce nitrogen protection, stir and add modified boron nitride under the conditions of a rotation speed of 300 r / min and a temperature of 0 °C, carry out a reaction for 4 h, raise the temperature to 20 °C, carry out a reaction for 15 h, then add 3-(methyldichlorosilyl)propyl methacrylate and continue the reaction for 9 h to obtain the reinforced filler.

[0051] The dosage ratio of the hexagonal boron nitride, sodium hydroxide, and deionized water described in Step B1 is 1 mmol:0.5 mmol:100 mL. The molar ratio of the hydroxyl groups on the hydroxylated hexagonal boron nitride to 3-isocyanatopropylmethyldichlorosilane is 1:1. The dosage of dibutyltin dilaurate is 1% of the mass of 3-isocyanatopropylmethyldichlorosilane.

[0052] The dosage ratio of the cetyltrimethoxysilane, isopropanol, deionized water, and sodium hydroxide described in Step B2 is 120 mmol:120 mL:2.5 g:80 mmol. The dosage ratio of sodium cetyltetrasilanol, triethylamine, tetrahydrofuran, modified boron nitride, and 3-(methyldichlorosilyl)propyl methacrylate is 18 g:5 g:30 mL:3 g:5 g.

[0053] Example 3, a production process of a rigid multi-layer SPC floor, specifically includes the following steps:

[0054] Weigh the following raw materials in parts by weight: 100 parts of PVC masterbatch, 180 parts of calcium carbonate, 8 parts of calcium-zinc stabilizer, 1.5 parts of PE wax, and 3 parts of ACR plasticizer. Mix the raw materials evenly under the condition of a temperature of 135 °C, then add them into a twin-screw extruder and extrude and form under the condition of a temperature of 200 °C to obtain a base material layer. After successively pressing a color film layer and a wear-resistant layer above the base material layer, apply a reinforced coating on the surface of the wear-resistant layer and irradiate it with 365 nm ultraviolet light for 8 s to obtain a rigid multi-layer SPC floor.

[0055] The wear-resistant layer is made of the following raw materials by weight: 100 parts of PVC masterbatch, 30 parts of silicon carbide, 25 parts of dioctyl phthalate, and 2 parts of epoxidized soybean oil. The PVC masterbatch used for the substrate layer and the wear-resistant layer is of the SG-5 type, the calcium-zinc stabilizer is of the CZ759 type, the PE wax is of the LP1040F type, and the ACR plasticizer is of the PA-40 type.

[0056] The strengthening coating is made by the following steps:

[0057] Step A1: Mix octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide, introduce nitrogen protection, and react at a rotation speed of 150 r / min and a temperature of 95 °C for 12 h to obtain pretreated polysiloxane;

[0058] Step A2: Mix the pretreated polysiloxane, diethanolamine, and DMF evenly, and react at a rotation speed of 150 r / min, a temperature of 50 °C, and a pH value of 12 for 8 h to obtain modified polysiloxane. Mix the modified polysiloxane, acryloyl chloride, triethylamine, and DMF evenly, and react at a rotation speed of 500 r / min and a temperature of 25 °C for 5 h to obtain a modified monomer;

[0059] Step A3: Weigh the following raw materials by weight: 30 parts of butyl acrylate, 30 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 25 parts of modified monomer, 10 parts of strengthening filler, 6 parts of molybdenum disulfide, 3 parts of silicon dioxide, 5 parts of alumina, and 5 parts of photoinitiator. Mix the raw materials evenly to obtain the strengthening coating.

[0060] The molar ratio of octamethylcyclotetrasiloxane, tetramethyltris(3,3,3-trifluoropropyl)cyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(epoxyethylmethoxy)propyl]disiloxane, and tetramethylammonium hydroxide in Step A1 is 1.4:1:1:2.

[0061] The molar ratio of the pretreated polysiloxane and diethanolamine in Step A2 is 1:2, and the molar ratio of the modified polysiloxane, acryloyl chloride, and triethylamine is 1:6:6.1.

[0062] The particle size of the molybdenum disulfide in Step A3 is 5 μm, the particle size of the silicon dioxide is 30 nm, the particle size of the alumina is 50 μm, and the photoinitiator is 184.

[0063] The strengthening filler is made by the following steps:

[0064] Step B1: Mix hexagonal boron nitride, sodium hydroxide, and deionized water evenly. Under the conditions of a frequency of 30 kHz and a temperature of 30 °C, perform ultrasonic treatment for 1.5 h, then raise the temperature to 125 °C, carry out reflux treatment for 25 h, cool down to room temperature, and wash until neutral to obtain hydroxylated hexagonal boron nitride. Mix hydroxylated hexagonal boron nitride, 3-isocyanatopropylmethyldichlorosilane, dibutyltin dilaurate, and toluene, introduce nitrogen protection, and react at a rotation speed of 300 r / min and a temperature of 50 °C for 5 h to obtain modified boron nitride.

[0065] Step B2: Mix cetyltrimethoxysilane, isopropyl alcohol, deionized water, and sodium hydroxide evenly. React at a rotation speed of 200 r / min and a temperature of 90 °C for 5 h, then cool down to 25 °C and react for 15 h to obtain sodium cetylcyclotetrasiloxanetetrasilanol. Mix sodium cetyltetrasilanol, triethylamine, and tetrahydrofuran evenly, introduce nitrogen protection, stir and add modified boron nitride at a rotation speed of 300 r / min and a temperature of 3 °C, react for 5 h, raise the temperature to 25 °C, react for 15 h, then add 3-(methyldichlorosilyl)propyl methacrylate and continue to react for 10 h to obtain the reinforced filler.

[0066] The dosage ratio of hexagonal boron nitride, sodium hydroxide, and deionized water in Step B1 is 1 mmol:0.5 mmol:100 mL. The molar ratio of hydroxyl groups on hydroxylated hexagonal boron nitride to 3-isocyanatopropylmethyldichlorosilane is 1:1, and the dosage of dibutyltin dilaurate is 1% of the mass of 3-isocyanatopropylmethyldichlorosilane.

[0067] The dosage ratio of cetyltrimethoxysilane, isopropyl alcohol, deionized water, and sodium hydroxide in Step B2 is 120 mmol:120 mL:2.5 g:80 mmol. The dosage ratio of sodium cetyltetrasilanol, triethylamine, tetrahydrofuran, modified boron nitride, and 3-(methyldichlorosilyl)propyl methacrylate is 18 g:5 g:30 mL:3 g:5 g.

[0068] Comparative Example 1: Compared with Example 1, in this comparative example, octamethylcyclotetrasiloxane, tetramethyltris(3-trifluoropropyl)cyclotetrasiloxane, 1,3-divinyltetramethyldisiloxane, tetramethylammonium hydroxide, and dimethyl sulfoxide are mixed, nitrogen protection is introduced, and the reaction is carried out at a rotation speed of 120 r / min and a temperature of 90 °C for 10 h to obtain a product, which is used to replace the modified monomer, and the remaining steps are the same.

[0069] Comparative Example 2: Compared with Example 1, in this comparative example, tetramethyltris(3-trifluoropropyl)cyclotetrasiloxane is not added, and the remaining steps are the same.

[0070] Comparative Example 3: Compared with Example 1, hexagonal boron nitride was used to replace the strengthening filler in this comparative example, and the remaining steps were the same.

[0071] Comparative Example 4: Compared with Example 1, methyltrimethoxysilane was used to replace cetyltrimethoxysilane in this comparative example, and the remaining steps were the same.

[0072] Comparative Example 5: Compared with Example 1, dimethyldichlorosilane was used to replace 3-(methyldichlorosilyl)propyl (alcohol) acrylate in this comparative example, and the remaining steps were the same.

[0073] For the SPC floors prepared in Examples 1-3 and Comparative Examples 1-5, the thickness of the strengthening coating was 30 μm. The wear resistance effect was detected according to the standard of GB / T 3960-2016. The following raw materials with mass percentages were weighed: 0.05% toluidine blue and 0.5% Triton X-100 surfactant, and the balance was pure water. A treatment solution was prepared. The treatment solution was coated on the surface of the strengthening coating. After maintaining for 30 min, the SPC floor was cleaned and observed for bleeding. The detection results are shown in Table 1 below.

[0074] Table 1

[0075]

[0076] It can be seen from Table 1 above that this application has good wear resistance and anti-bleeding effects.

[0077] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A production process for a hard multi-layer SPC floor, characterized by: The specific steps include: The raw materials are mixed evenly at a temperature of 125-135°C, and then added into a twin-screw extruder for extrusion molding to obtain a base layer. A color film layer and a wear-resistant layer are pressed in sequence on the base layer, and a strengthening coating is applied on the surface of the wear-resistant layer, and irradiated with ultraviolet light to obtain a hard multi-layer SPC floor.

2. The production process of a hard multi-layer SPC floor according to claim 1, characterized in that: The substrate layer is made of the following raw materials in parts by weight: 80-100 parts of PVC masterbatch, 160-180 parts of calcium carbonate, 6-8 parts of calcium zinc stabilizer, 1-1.5 parts of PE wax and 2-3 parts of ACR plasticizer.

3. The production process of a hard multi-layer SPC floor according to claim 1, characterized in that: The wear-resistant layer is made of the following raw materials in parts by weight: 100 parts of PVC masterbatch, 30 parts of silicon carbide, 25 parts of dioctyl phthalate and 2 parts of epoxidized soybean oil.

4. The production process of a hard multi-layer SPC floor according to claim 1, characterized in that: The reinforced coating is prepared by the following steps: Step A1: octamethylcyclotetrasiloxane, tetramethyltri-3-trifluoropropylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-di[3-(oxiranylmethoxy)propyl]disiloxane, tetramethylammonium hydroxide and dimethyl sulfoxide are mixed, nitrogen is introduced for protection, and a reaction is carried out to prepare a pretreated polysiloxane; Step A2: mixing and reacting the pretreated polysiloxane, diethanolamine and DMF to obtain a modified polysiloxane, and mixing and reacting the modified polysiloxane, acryloyl chloride, triethylamine and DMF to obtain a modified monomer; Step A3: Weigh the following raw materials in parts by weight: 25-30 parts of butyl acrylate, 25-30 parts of methyl methacrylate, 12-15 parts of hydroxyethyl methacrylate, 20-25 parts of modified monomer, 8-10 parts of reinforcing filler, 4-6 parts of molybdenum disulfide, 1-3 parts of silicon dioxide, 3-5 parts of aluminum oxide and 3-5 parts of photoinitiator, mix the raw materials evenly to prepare a reinforced coating.

5. The production process of a hard multi-layer SPC floor according to claim 4 is characterized in that: The molar ratio of octamethylcyclotetrasiloxane, tetramethyltri-3-trifluoropropylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-bis[3-(oxiranylmethoxy)propyl]disiloxane and tetramethylammonium hydroxide described in step A1 is 1.4:1:1:

2.

6. The production process of a hard multi-layer SPC floor according to claim 4, characterized in that: The molar ratio of the pretreated polysiloxane to diethanolamine in step A2 is 1:2, and the molar ratio of the modified polysiloxane, acryloyl chloride and triethylamine is 1:6:6.

1.

7. The production process of a hard multi-layer SPC floor according to claim 4, characterized in that: The reinforcing filler is prepared by the following steps: Step B1: After mixing hexagonal boron nitride, sodium hydroxide and deionized water, ultrasonic treatment is performed, and then the temperature is raised and refluxed, the temperature is cooled to room temperature and washed to neutrality to obtain hydroxylated hexagonal boron nitride, and hydroxylated hexagonal boron nitride, 3-isocyanatopropylmethyldichlorosilane, dibutyltin dilaurate and toluene are mixed, nitrogen protection is introduced, and the reaction is carried out to obtain modified boron nitride; Step B2: After hexadecyltrimethoxysilane, isopropanol, deionized water and sodium hydroxide are mixed for reaction, the temperature is lowered and the reaction is continued to obtain sodium hexadecylcyclotetrasiloxane tetrasiliconate, sodium hexadecyltetrasiliconate, triethylamine and tetrahydrofuran are evenly mixed, nitrogen is introduced for protection, modified boron nitride is added with stirring, and after the reaction, 2-methylacrylate-3-(methyldichlorosilyl)propane (alcohol) ester is added, and the reaction is continued to obtain a reinforced filler.

8. The production process of a hard multi-layer SPC floor according to claim 7, characterized in that: The amount ratio of hexagonal boron nitride, sodium hydroxide and deionized water in step B1 is 1 mmol:0.5 mmol:100 mL, and the molar ratio of the hydroxyl group on the hydroxylated hexagonal boron nitride to 3-isocyanatopropylmethyldichlorosilane is 1:

1.

9. The production process of a hard multi-layer SPC floor according to claim 7, characterized in that: The amount ratio of hexadecyltrimethoxysilane, isopropanol, deionized water and sodium hydroxide described in step B2 is 120mmol:120mL:2.5g:80mmol, and the amount ratio of hexadecyl sodium tetrasiliconate, triethylamine, tetrahydrofuran, modified boron nitride and 2-methacrylate-3-(methyldichlorosilyl)propane(ol) ester is 18g:5g:30mL:3g:5g.

10. A hard multi-layer SPC floor, characterized by: Prepared according to any one of claims 1 to 9.

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