A high-gloss, high-hardness, ultra-flat diamond glaze tile and its preparation process

Abstract

The invention relates to the technical field of layered composite materials, and discloses a high-gloss, high-hardness, ultra-flat diamond glaze tile and a preparation process thereof. The high-gloss, high-hardness, ultra-flat diamond glaze tile comprises a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate and a coating material, and the preparation process comprises: mixing brick blank raw materials, dispersants, and water, ball milling, pressing and molding, drying and sintering to obtain a brick blank, spraying glaze on the surface of the brick blank to form a glaze surface, and polishing after firing to obtain a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate; compounding the coating material with the high-gloss, high-hardness, ultra-flat diamond glaze tile substrate, and the obtained high-gloss, high-hardness, ultra-flat diamond glaze tile has anti-slip and antibacterial properties.

Description

Technical Field

[0001] The invention relates to the technical field of layered composite materials, and in particular to a high-gloss, high-hardness, ultra-flat diamond glaze ceramic tile and a preparation process thereof. Background Art

[0002] As the most common floor decoration building material, ceramic tiles can effectively reduce safety hazards and improve safety by improving their anti-slip and antibacterial properties. At present, the methods to improve the anti-slip performance of ceramic tiles include: adjusting the ceramic glaze formula to increase the granularity of the tile surface; using molds to make grooves on the tile surface to make the tile surface have uneven levels and increase friction; enhancing the water permeability of ceramic tiles; using the suction cup principle to make an anti-slip agent layer on the tile surface, etc.

[0003] Prior art such as Chinese patent CN206605858U discloses an easy-to-clean ceramic tile. A transition layer is set on the surface of the tile substrate to improve the bonding performance between the coating material and the substrate. The resulting ceramic tile is easy to clean, but the setting of the intermediate layer affects the gloss of the tile, and the resulting ceramic tile is insufficient in anti-slip and antibacterial properties. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-gloss and high-hardness ultra-flat diamond glaze tile and its preparation process. The ultra-flat diamond glaze tile matrix has high gloss and high hardness, and the ultra-flat diamond glaze tile made from the ultra-flat diamond glaze tile matrix has anti-slip and antibacterial properties.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate comprises the following steps:

[0007] Step 1: Mix the raw materials for bricks, dispersants and water and grind them into a ball mill to obtain a green mud, put the green mud into a mold, press it into shape, dry it, sinter it and keep it warm to obtain a brick;

[0008] Step 2: Mix the frit, raw material, sodium carboxymethyl cellulose and water and grind them into a ball mill to obtain a glaze; spray the glaze onto the surface of the brick to form a glaze surface, dry it, and burn it; after burning, polish it to obtain a high-gloss, high-hardness and ultra-flat diamond glaze tile matrix.

[0009] Preferably, in step 1, the mass ratio of the raw material of the brick, the dispersant and the water is 10:0.2-0.3:7-8; the sintering conditions are: sintering at a temperature of 1160-1200° C. for 30-40 min and the heat preservation time is 2-2.5 h.

[0010] Preferably, in the step 1: the raw materials for the brick are prepared by mixing the following raw materials in the following mass ratios: 30-40 parts of clay, 5-10 parts of cristobalite, 5-10 parts of potassium feldspar, 18-22 parts of kaolin, 5-8 parts of sepiolite, and 20-30 parts of diopside;

[0011] Preferably, the dispersant in step 1 is prepared by the following steps:

[0012] Alkali lignin, phenol and water are mixed and dissolved, a regulator is added to adjust the pH value, sodium p-aminobenzenesulfonate is added, and the reaction is carried out. After the reaction is completed, a formaldehyde aqueous solution is added dropwise, and the reaction is continued after the addition is completed, and the dispersant is cooled.

[0013] Preferably, the mass ratio of alkali lignin, phenol, water, sodium p-aminobenzenesulfonate and 37wt% formaldehyde aqueous solution is 19.7-20.2:8.4-8.6:100-110:17.3-17.8:20-20.5; the reaction conditions are: react at a pH value of 10-10.5 and a temperature of 90-95°C for 2-3h; the dropwise addition time of the formaldehyde aqueous solution is 50-60min; and the continued reaction conditions are reacting at a temperature of 90-95°C for 1-2h.

[0014] Preferably, the regulator includes a 1 mol / L sodium hydroxide aqueous solution.

[0015] Preferably, in the step 2: the raw material is prepared by mixing the following raw materials in the following mass ratio: 15-20 parts of quartz, 6-8 parts of kaolin, 30-40 parts of potassium feldspar, 6-8 parts of corundum powder, 3-6 parts of zinc oxide, 2-5 parts of barium carbonate, and 1-3 parts of wollastonite; the frit is prepared by mixing the following raw materials in the following mass ratio: 15-20 parts of Al2O3, 50-60 parts of SiO2, 10-15 parts of CaO, 3-5 parts of K2O, 5-6 parts of MgO, 6-10 parts of BaO, 3-6 parts of ZnO, 0.1-0.2 parts of TiO2, 2-3 parts of Fe2O3, and 1-3 parts of Na2O.

[0016] Preferably, in step 2, the mass ratio of frit, raw material, sodium carboxymethyl cellulose and water is 15-20:80-85:0.5-1:40; the glaze amount is 1000-1200g / m 2 ; Firing conditions: firing at 1150-1250℃ for 40-60min.

[0017] Preferably, a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate is prepared by the method for preparing a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate as described above.

[0018] The present invention discloses a preparation process for preparing high-gloss, high-hardness and super-flat diamond glaze ceramic tiles by using the above-mentioned high-gloss, high-hardness and super-flat diamond glaze ceramic tile matrix, comprising the following steps:

[0019] Step (1), mixing polyethylene glycol diacrylate with glass microbeads, ultrasonically dispersing, adding 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol, reacting, after the reaction is completed, adding methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator, continuing the reaction, after the reaction is completed, filtering, washing, and drying to obtain modified glass microbeads;

[0020] The modified glass microbeads are mixed with water, ultrasonically dispersed, and a sodium hypochlorite aqueous solution is added to perform a chlorination reaction. After the chlorination is completed, the mixture is centrifuged, filtered, washed, and dried to obtain an antibacterial additive;

[0021] Step (2), mixing polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate, reacting, adding 1,4-butanediol and 1,2-propylene glycol after the reaction, continuing the reaction, adding pentaerythritol triacrylate, reacting again, cooling to room temperature after the reaction, and obtaining polyurethane acrylate;

[0022] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, an antibacterial additive, acetone, and a photoinitiator 1173 to obtain a coating material;

[0023] Step (3), coating the coating material on the side of the high-gloss, high-hardness, ultra-flat diamond glaze tile substrate having the glaze layer, and light curing to obtain the high-gloss, high-hardness, ultra-flat diamond glaze tile.

[0024] Preferably, in the step (1), the mass ratio of polyethylene glycol diacrylate, glass beads, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 15-20:8-10:9-10:4-4.5:0.5-0.6:80-100:6.5-7:6-6.5:0.2-0.3, and the first initiator and the second initiator are both potassium persulfate; the reaction conditions are: react at a temperature of 70-80°C for 3-4h; and the continued reaction conditions are: continue the reaction at a temperature of 70-80°C for 3-4h.

[0025] Preferably, in the step (1), the mass ratio of the modified glass microspheres, water and sodium hypochlorite aqueous solution is 1:10-20:40-50, the sodium hypochlorite aqueous solution is 10-10.5wt% sodium hypochlorite aqueous solution; and the chlorination reaction conditions are: chlorination reaction at room temperature for 6-8h.

[0026] Preferably, in the step (2), the molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 2.5-3:5.6:1-1.2:1-1.2:0.5-0.6, and the amount of dibutyltin dilaurate added is 0.4-0.5% of the polycarbonate diol; the reaction conditions are: reacting for 4-5 hours in a nitrogen atmosphere at a temperature of 70-80°C; continuing the reaction conditions are: continuing the reaction for 3-4 hours in a nitrogen atmosphere at a temperature of 60-70°C; and the second reaction conditions are: reacting again for 0.5-1 hour in a nitrogen atmosphere at a temperature of 50-60°C.

[0027] Preferably, in the step (2), the mass ratio of polyurethane acrylate, γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, antibacterial additive, acetone, and photoinitiator 1173 is 100:10-12:8-10:5-6:20-30:30-35:10-15:2-3.

[0028] Preferably, in step (3), the coating thickness is 1.5-1.8 mm; the light curing conditions are: in a nitrogen atmosphere, the irradiation intensity is 30-36 mW / cm 2 Light cure for 3-4 minutes under the conditions.

[0029] Preferably, a high-gloss, high-hardness, ultra-flat diamond glaze tile is prepared using the preparation process of the high-gloss, high-hardness, ultra-flat diamond glaze tile as described above.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The present invention prepares a lignin-modified dispersant through copolymerization modification, adds the dispersant into green mud, obtains a green brick after sintering, sprays glaze on the surface of the green brick, and obtains an ultra-flat diamond glaze tile substrate having high gloss and high hardness after sintering; a coating material containing raw materials such as polyurethane acrylate, γ-methacryloxypropyltrimethoxysilane, and antibacterial additives is coated on the surface of the ultra-flat diamond glaze tile substrate, and a coating with anti-skid and antibacterial functions is formed after light curing, so that the obtained ultra-flat diamond glaze tile has anti-skid and antibacterial properties.

[0032] Alkali lignin is an anionic surfactant, which has a certain dispersing effect on the particles of the raw materials of the brick. The present invention uses alkali lignin to replace part of phenol and introduces it as a functional monomer into the preparation of the aminosulfonic acid series dispersant, so that the obtained dispersant has a better dispersing effect. The dispersant is mixed with the raw materials of the brick and water, ball milled, pressed into shape, and sintered to obtain the brick; a glaze prepared from frit, raw material, sodium carboxymethyl cellulose and water is sprayed on the surface of the brick, and sintered again to obtain an ultra-flat diamond glaze tile matrix with high gloss and high hardness; wherein, the quartz in the glaze can improve the mechanical strength, whiteness, transparency and chemical stability of the glaze surface, and reduce the expansion coefficient of the glaze surface; kaolin and corundum powder can improve the hardness and stability of the glaze surface; potassium feldspar, zinc oxide and barium carbonate can all improve the gloss of the glaze surface; during the sintering process, the materials in the glaze are compounded to form a mullite phase, which gives the ultra-flat diamond glaze tile matrix high gloss and high hardness.

[0033] Adding glass microbeads to organic polymer materials can effectively improve the fluidity, wear resistance and glossiness of the materials; the present invention uses an in-situ polymerization method and a free radical polymerization reaction of carbon-carbon double bonds to mix glass microbeads with polyethylene glycol diacrylate, and then reacts and polymerizes with 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, methacryloylethyl sulfobetaine, and methyl methacrylate to form a polymer containing a halamine precursor on the surface of the glass microbeads to obtain modified glass microbeads, which are then chlorinated with a sodium hypochlorite aqueous solution to construct a halamine antibacterial structure. The obtained antibacterial additive not only has excellent antibacterial performance, but also has good compatibility with the base resin in the coating material and is easy to disperse, thereby effectively improving the antibacterial ability and anti-slip performance of the coating material;

[0034] Among them, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin is a hydantoin derivative, which can form a haloamine structure with N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide after chlorination, and synergistically with the antibacterial monomer methacryloylethyl sulfobetaine to give the material high-efficiency antibacterial properties. At the same time, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide has a catechol group, which has a positive addition effect on the adhesion of the coating material on the surface of the ultra-flat diamond glaze tile substrate.

[0035] The present invention adds polycarbonate diol with excellent optical properties during the preparation process of polyurethane acrylate, and evenly mixes the polycarbonate diol as a matrix resin with γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, ethyl acrylate, active diluent trimethylolpropane trimethacrylate, antibacterial additives, solvent acetone, and a photoinitiator, and then coats the mixture on the surface of an ultra-flat diamond glaze tile matrix. After photocuring, a cross-linked network structure is formed, and the obtained high-gloss and high-hardness ultra-flat diamond glaze tile has anti-slip and antibacterial properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a process flow chart for preparing high-gloss, high-hardness and ultra-flat diamond glaze tiles in the present invention;

[0037] Figure 2 It is a schematic structural diagram of a high-gloss, high-hardness, ultra-flat diamond glaze tile prepared in the present invention;

[0038] Figure 3 It is a bar graph of the antibacterial rate test results of the super flat diamond glaze ceramic tiles prepared in the embodiment and the comparative example of the present invention in the performance test;

[0039] Figure 4 It is a bar graph of the test results of the friction coefficient of the ultra-flat diamond glaze ceramic tile prepared in the embodiment and the comparative example of the present invention in the performance test;

[0040] Figure 5 It is a bar graph of the wear test results of the ultra-flat diamond glaze tiles prepared in the embodiments and comparative examples of the present invention in the performance test;

[0041] In the figure:

[0042] 1. Ultra-flat diamond glaze tile substrate; 101. Brick; 102. Glaze; 2. Coating material. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0044] Example 1

[0045] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate, comprising the following steps:

[0046] Step 1: Mix the raw materials for bricks, dispersant and water in a mass ratio of 10:0.2:7 and grind them to obtain green mud, put the green mud into a mold for pressing, dry at room temperature for 40 hours, sinter at 1160°C for 40 minutes, and keep warm for 2 hours to obtain a brick;

[0047] The raw materials for the bricks are prepared by mixing the following raw materials in the following mass ratios: 30 parts of clay, 5 parts of cristobalite, 5 parts of potassium feldspar, 18 parts of kaolin, 5 parts of sepiolite, and 20 parts of diopside;

[0048] The dispersant is prepared by the following steps:

[0049] Alkali lignin, phenol and water were mixed and dissolved, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10, sodium p-aminobenzenesulfonate was added, and the mixture was reacted at 90° C. for 3 h. After the reaction was completed, 37 wt % formaldehyde aqueous solution was added dropwise for 50 min. After the addition was completed, the mixture was reacted for 1 h, and the mixture was cooled to room temperature to obtain a dispersant. The mass ratio of alkali lignin, phenol, water, sodium p-aminobenzenesulfonate and 37 wt % formaldehyde aqueous solution was 19.7:8.4:100:17.3:20.

[0050] Step 2: Mix the frit, raw material, sodium carboxymethyl cellulose and water in a mass ratio of 15:85:0.5:40 and ball-mill to obtain a glaze; spray the glaze on the surface of the brick to form a glaze surface, with a glaze amount of 1000g / m 2 , dried in a drying kiln at 70°C to a water content of 1wt%, placed in a firing kiln at 1150°C for 60min, and polished after firing to obtain a high-gloss, high-hardness, ultra-flat diamond glaze tile matrix;

[0051] Among them, the raw material is prepared by mixing the following raw materials in the following mass ratio: 15 parts of quartz, 6 parts of kaolin, 30 parts of potassium feldspar, 6 parts of corundum powder, 3 parts of zinc oxide, 2 parts of barium carbonate, and 1 part of wollastonite; the frit is prepared by mixing the following raw materials in the following mass ratio: 15 parts of Al2O3, 50 parts of SiO2, 10 parts of CaO, 3 parts of K2O, 5 parts of MgO, 6 parts of BaO, 3 parts of ZnO, 0.1 parts of TiO2, 2 parts of Fe2O3, and 1 part of Na2O.

[0052] Example 2

[0053] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze ceramic tile substrate, comprising the following steps:

[0054] Step 1: Mix the raw materials for bricks, dispersant and water in a mass ratio of 10:0.25:7.5 and grind them to obtain green mud, put the green mud into a mold for pressing, dry at room temperature for 44 hours, sinter at 1180°C for 35 minutes, and keep warm for 2.3 hours to obtain a brick;

[0055] The raw materials for the bricks are prepared by mixing the following raw materials in the following mass ratios: 35 parts of clay, 8 parts of cristobalite, 8 parts of potassium feldspar, 20 parts of kaolin, 6 parts of sepiolite, and 25 parts of diopside;

[0056] The dispersant is prepared by the following steps:

[0057] Alkali lignin, phenol and water were mixed and dissolved, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10.3, sodium p-aminobenzenesulfonate was added, and the mixture was reacted at 93°C for 2.5 hours. After the reaction, 37 wt% formaldehyde aqueous solution was added dropwise for 55 minutes. After the addition was completed, the mixture was reacted for 1.5 hours, and the mixture was cooled to room temperature to obtain a dispersant. The mass ratio of alkali lignin, phenol, water, sodium p-aminobenzenesulfonate and 37 wt% formaldehyde aqueous solution was 20:8.5:105:17.5:20.3.

[0058] Step 2: Mix the frit, raw material, sodium carboxymethyl cellulose and water in a mass ratio of 18:83:0.8:40 and ball-mill to obtain a glaze; spray the glaze on the surface of the brick to form a glaze surface, with a glaze amount of 1100 g / m 2 , dried in a drying kiln at 75°C to a water content of 0.8wt%, placed in a firing kiln and fired at 1200°C for 50 minutes, and polished after firing to obtain a high-gloss, high-hardness, ultra-flat diamond glaze tile matrix;

[0059] Among them, the raw material is prepared by mixing the following raw materials in the following mass ratio: 18 parts of quartz, 7 parts of kaolin, 35 parts of potassium feldspar, 7 parts of corundum powder, 5 parts of zinc oxide, 4 parts of barium carbonate, and 2 parts of wollastonite; the frit is prepared by mixing the following raw materials in the following mass ratio: 18 parts of Al2O3, 55 parts of SiO2, 12 parts of CaO, 4 parts of K2O, 5 parts of MgO, 8 parts of BaO, 4 parts of ZnO, 0.1 parts of TiO2, 2 parts of Fe2O3, and 2 parts of Na2O.

[0060] Example 3

[0061] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile substrate, comprising the following steps:

[0062] Step 1: Mix the raw materials for bricks, dispersants and water in a mass ratio of 10:0.3:8 and grind them to obtain green mud, put the green mud into a mold for pressing, dry at room temperature for 48 hours, sinter at 1200°C for 30 minutes, and keep warm for 2.5 hours to obtain a brick;

[0063] The raw materials for the bricks are prepared by mixing the following raw materials in the following mass ratios: 40 parts of clay, 10 parts of cristobalite, 10 parts of potassium feldspar, 22 parts of kaolin, 8 parts of sepiolite, and 30 parts of diopside;

[0064] The dispersant is prepared by the following steps:

[0065] Alkali lignin, phenol and water were mixed and dissolved, 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH value to 10.5, sodium p-aminobenzenesulfonate was added, and the mixture was reacted at 95°C for 2 hours. After the reaction, 37 wt% formaldehyde aqueous solution was added dropwise for 60 minutes. After the addition was completed, the mixture was reacted for 2 hours, and the mixture was cooled to room temperature to obtain a dispersant. The mass ratio of alkali lignin, phenol, water, sodium p-aminobenzenesulfonate and 37 wt% formaldehyde aqueous solution was 20.2:8.6:110:17.8:20.5.

[0066] Step 2: Mix the frit, raw material, sodium carboxymethyl cellulose and water in a mass ratio of 20:80:1:40 and ball-mill to obtain a glaze; spray the glaze on the surface of the brick to form a glaze surface, with a glaze amount of 1200g / m 2 , dried in a drying kiln at 80°C to a water content of 0.6wt%, placed in a firing kiln and fired at 1250°C for 40 minutes, and polished after firing to obtain a high-gloss, high-hardness, ultra-flat diamond glaze tile matrix;

[0067] Among them, the raw material is prepared by mixing the following raw materials in the following mass ratio: 20 parts of quartz, 8 parts of kaolin, 40 parts of potassium feldspar, 8 parts of corundum powder, 6 parts of zinc oxide, 5 parts of barium carbonate, and 3 parts of wollastonite; the frit is prepared by mixing the following raw materials in the following mass ratio: 20 parts of Al2O3, 60 parts of SiO2, 15 parts of CaO, 5 parts of K2O, 6 parts of MgO, 10 parts of BaO, 6 parts of ZnO, 0.2 parts of TiO2, 3 parts of Fe2O3, and 3 parts of Na2O.

[0068] Example 4

[0069] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile, comprising the following steps:

[0070] Step (1), mixing polyethylene glycol diacrylate with glass microbeads, ultrasonically dispersing, adding 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol, reacting at 70°C for 4 hours, adding methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator after the reaction, and continuing to react at 70°C for 4 hours. After the reaction is completed, filtering, taking the filter cake, adding water 5 times the mass of the filter cake for washing, and drying at 50°C for 24 hours to obtain modified glass microbeads;

[0071] The mass ratio of polyethylene glycol diacrylate, glass beads, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 15:8:9:4:0.5:80:6.5:6.5:0.2, and both the first initiator and the second initiator are potassium persulfate;

[0072] The modified glass microspheres were mixed with water, ultrasonically dispersed for 5 minutes, and a 10 wt% sodium hypochlorite aqueous solution was added, wherein the mass ratio of the modified glass microspheres, water, and the sodium hypochlorite aqueous solution was 1:10:40, and the chlorination reaction was carried out at room temperature for 6 hours. After the chlorination was completed, the mixture was centrifuged and filtered to obtain a filter cake, and water 5 times the mass of the filter cake was added to wash the mixture until it was neutral, and the mixture was dried at 40°C for 18 hours to obtain an antibacterial additive;

[0073] Step (2), polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate are mixed, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 5 h. After the reaction is completed, 1,4-butanediol and 1,2-propylene glycol are added, and the mixture is further reacted in a nitrogen atmosphere at a temperature of 60° C. for 4 h. After the reaction is completed, pentaerythritol triacrylate is added, and the mixture is reacted again in a nitrogen atmosphere at a temperature of 50° C. for 1 h. After the reaction is completed, the mixture is cooled to room temperature to obtain polyurethane acrylate;

[0074] The molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 2.5:5.6:1.2:1.2:0.5, and the amount of dibutyltin dilaurate added is 0.4% of the polycarbonate diol;

[0075] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, an antibacterial additive, acetone, and a photoinitiator 1173 in a light-proof environment at a mass ratio of 100:10:10:6:20:30:10:2 to obtain a coating material;

[0076] Step (3), coating the coating material on the side of the high gloss, high hardness, ultra-flat diamond glaze tile substrate prepared in Example 1 with a glaze layer, with a coating thickness of 1.5 mm, in a nitrogen atmosphere, with an irradiation intensity of 30 mW / cm 2 After light curing for 4 minutes under the conditions of , high gloss, high hardness and ultra-flat diamond glaze tiles were obtained.

[0077] Example 5

[0078] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile, comprising the following steps:

[0079] Step (1), mixing polyethylene glycol diacrylate with glass microbeads, ultrasonically dispersing, adding 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol, reacting at 75°C for 3.5 hours, after the reaction is completed, adding methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator, and continuing to react at 75°C for 3.5 hours, after the reaction is completed, filtering, taking the filter cake, adding water 6 times the mass of the filter cake for washing, and drying at 55°C for 20 hours to obtain modified glass microbeads;

[0080] The mass ratio of polyethylene glycol diacrylate, glass beads, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 18:9:9.5:4.3:0.55:90:6.8:6.3:0.25, and both the first initiator and the second initiator are potassium persulfate;

[0081] The modified glass microspheres were mixed with water, ultrasonically dispersed for 6 minutes, and a 10.3 wt% sodium hypochlorite aqueous solution was added, wherein the mass ratio of the modified glass microspheres, water, and the sodium hypochlorite aqueous solution was 1:15:45, and the chlorination reaction was carried out at room temperature for 7 hours. After the chlorination was completed, the mixture was centrifuged and filtered to obtain a filter cake, and water 6 times the mass of the filter cake was added to wash the mixture until it was neutral, and the mixture was dried at 45°C for 16 hours to obtain an antibacterial additive;

[0082] Step (2), polycarbonate diol, isophorone diisocyanate, and dibutyltin dilaurate are mixed, and the mixture is reacted in a nitrogen atmosphere at a temperature of 75° C. for 4.5 hours. After the reaction is completed, 1,4-butanediol and 1,2-propylene glycol are added, and the mixture is further reacted in a nitrogen atmosphere at a temperature of 65° C. for 3.5 hours. After the reaction is completed, pentaerythritol triacrylate is added, and the mixture is reacted again in a nitrogen atmosphere at a temperature of 55° C. for 0.8 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain polyurethane acrylate;

[0083] The molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 2.8:5.6:1.1:1.1:0.55, and the amount of dibutyltin dilaurate added is 0.4% of the polycarbonate diol;

[0084] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, an antibacterial additive, acetone, and a photoinitiator 1173 in a light-proof environment at a mass ratio of 100:11:9:5.5:25:33:13:2.5 to obtain a coating material;

[0085] Step (3), coating the coating material on the side of the high gloss, high hardness, ultra-flat diamond glaze tile substrate prepared in Example 2 with a glaze layer, with a coating thickness of 1.65 mm, in a nitrogen atmosphere, with an irradiation intensity of 34 mW / cm 2 After light curing for 3.5 minutes under the conditions of , high gloss, high hardness and ultra-flat diamond glaze tiles were obtained.

[0086] Example 6

[0087] This embodiment discloses a preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile, comprising the following steps:

[0088] Step (1), mixing polyethylene glycol diacrylate with glass microbeads, ultrasonically dispersing, adding 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol, reacting at 80° C. for 3 hours, adding methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator after the reaction, and continuing to react at 80° C. for 3 hours. After the reaction is completed, filtering, taking the filter cake, adding water 8 times the mass of the filter cake for washing, and drying at 60° C. for 18 hours to obtain modified glass microbeads;

[0089] The mass ratio of polyethylene glycol diacrylate, glass beads, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 20:10:10:4.5:0.6:100:7:6:0.3, and both the first initiator and the second initiator are potassium persulfate;

[0090] The modified glass microspheres were mixed with water, ultrasonically dispersed for 8 minutes, and a 10.5 wt% sodium hypochlorite aqueous solution was added, wherein the mass ratio of the modified glass microspheres, water, and the sodium hypochlorite aqueous solution was 1:20:50, and the reaction was chlorinated at room temperature for 8 hours. After the chlorination was completed, the mixture was centrifuged and filtered to obtain a filter cake, and water 8 times the mass of the filter cake was added to wash the mixture until it was neutral, and the mixture was dried at 50° C. for 12 hours to obtain an antibacterial additive;

[0091] Step (2), polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate are mixed, and the mixture is reacted in a nitrogen atmosphere at 80°C for 4 hours. After the reaction is completed, 1,4-butanediol and 1,2-propylene glycol are added, and the mixture is reacted in a nitrogen atmosphere at 70°C for 3 hours. After the reaction is completed, pentaerythritol triacrylate is added, and the mixture is reacted again in a nitrogen atmosphere at 60°C for 0.5 hours. After the reaction is completed, the mixture is cooled to room temperature to obtain polyurethane acrylate;

[0092] The molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 3:5.6:1:1:0.6, and the amount of dibutyltin dilaurate added is 0.5% of the polycarbonate diol;

[0093] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, an antibacterial additive, acetone, and a photoinitiator 1173 in a light-proof environment at a mass ratio of 100:12:8:5:30:35:15:3 to obtain a coating material;

[0094] Step (3), coating the coating material on the side of the high gloss, high hardness, ultra-flat diamond glaze tile substrate prepared in Example 3 with a glaze layer, with a coating thickness of 1.8 mm, in a nitrogen atmosphere, with an irradiation intensity of 36 mW / cm 2 After light curing for 3 minutes under the conditions of , high gloss, high hardness and ultra-flat diamond glaze tiles were obtained.

[0095] Comparative Example 1

[0096] This comparative example discloses a preparation process of an ultra-flat diamond glaze tile, comprising the following steps:

[0097] Step (1), adding 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol to polyethylene glycol diacrylate, reacting at 70°C for 4 hours, adding methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator, and continuing to react at 70°C for 4 hours, filtering, taking a filter cake, adding water 5 times the mass of the filter cake for washing, and drying at 50°C for 24 hours to obtain a crude antibacterial additive;

[0098] Wherein, the mass ratio of polyethylene glycol diacrylate, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 15:9:4:0.5:80:6.5:6.5:0.2, and the first initiator and the second initiator are both potassium persulfate;

[0099] The crude antibacterial additive was mixed with water, ultrasonically dispersed for 5 minutes, and a 10 wt% sodium hypochlorite aqueous solution was added, wherein the mass ratio of the crude antibacterial additive, water, and the sodium hypochlorite aqueous solution was 1:10:40, and the reaction was chlorinated at room temperature for 6 hours. After the chlorination was completed, the reaction was centrifuged and filtered to obtain a filter cake, and water 5 times the mass of the filter cake was added to wash the filter cake until it was neutral, and the filter cake was dried at 40° C. for 18 hours to obtain an antibacterial additive;

[0100] Step (2), polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate are mixed, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 5 h. After the reaction is completed, 1,4-butanediol and 1,2-propylene glycol are added, and the mixture is further reacted in a nitrogen atmosphere at a temperature of 60° C. for 4 h. After the reaction is completed, pentaerythritol triacrylate is added, and the mixture is reacted again in a nitrogen atmosphere at a temperature of 50° C. for 1 h. After the reaction is completed, the mixture is cooled to room temperature to obtain polyurethane acrylate;

[0101] The molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 2.5:5.6:1.2:1.2:0.5, and the amount of dibutyltin dilaurate added is 0.4% of the polycarbonate diol;

[0102] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, an antibacterial additive, acetone, and a photoinitiator 1173 in a light-proof environment at a mass ratio of 100:10:10:6:20:30:10:2 to obtain a coating material;

[0103] Step (3), coating the coating material on the side of the high gloss, high hardness, ultra-flat diamond glaze tile substrate prepared in Example 1 with a glaze layer, with a coating thickness of 1.5 mm, in a nitrogen atmosphere, with an irradiation intensity of 30 mW / cm 2 After light curing for 4 minutes under the conditions of , ultra-flat diamond glaze tiles were obtained.

[0104] Comparative Example 2

[0105] This comparative example discloses a preparation process of an ultra-flat diamond glaze tile, comprising the following steps:

[0106] Step (1), mixing polyethylene glycol diacrylate and glass microspheres in a mass ratio of 15:8, and ultrasonically dispersing to obtain modified glass microspheres;

[0107] Step (2), polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate are mixed, and the mixture is reacted in a nitrogen atmosphere at a temperature of 70° C. for 5 h. After the reaction is completed, 1,4-butanediol and 1,2-propylene glycol are added, and the mixture is further reacted in a nitrogen atmosphere at a temperature of 60° C. for 4 h. After the reaction is completed, pentaerythritol triacrylate is added, and the mixture is reacted again in a nitrogen atmosphere at a temperature of 50° C. for 1 h. After the reaction is completed, the mixture is cooled to room temperature to obtain polyurethane acrylate;

[0108] The molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol and pentaerythritol triacrylate is 2.5:5.6:1.2:1.2:0.5, and the amount of dibutyltin dilaurate added is 0.4% of the polycarbonate diol;

[0109] Mixing polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, modified glass microspheres, methacryloylethyl sulfobetaine, acetone, and photoinitiator 1173 in a light-proof environment at a mass ratio of 100:10:10:6:20:30:3.9:10:2 to obtain a coating material;

[0110] Step (3), coating the coating material on the side of the high gloss, high hardness, ultra-flat diamond glaze tile substrate prepared in Example 1 with a glaze layer, with a coating thickness of 1.5 mm, in a nitrogen atmosphere, with an irradiation intensity of 30 mW / cm 2 After light curing for 4 minutes under the conditions of , ultra-flat diamond glaze tiles were obtained.

[0111] In the above embodiments and comparative examples: alkali lignin comes from Sigma-Aldrich Company, CAS No.: 8068-05-1; polyethylene glycol diacrylate comes from Jiangsu Haolong Chemical Co., Ltd., with an average molecular weight of 600, CAS No.: 26570-48-9; glass beads come from Hebei Huanhe Mineral Products Co., Ltd., with a specification of 35-45 μm; 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin comes from Shandong Xingshun New Materials Co., Ltd., CAS No.: 292621-62-6; N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide comes from Shanghai Lanke Chemical Co., Ltd., CAS No.: 201610-44-8; polycarbonate diol comes from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., with an average molecular weight of 2000, CAS No.: 29862-10-0.

[0112] Test example

[0113] The performance test was conducted on the ultra-flat diamond glaze ceramic tile substrates prepared in Examples 1-3; the performance test was conducted on the ultra-flat diamond glaze ceramic tiles prepared in Examples 4-6 and Comparative Examples 1-2. The specific results are shown in Tables 1 and 2:

[0114] Table 1

[0115] Example 1 Example 2 Example 3 Glossiness ＞90 ＞90 ＞90 Mohs hardness (grade) 6 6 6

[0116] Table 2

[0117] Antibacterial rate (%) Friction coefficient Wear amount (mg) Example 4 99.9 1.06 28 Example 5 99.9 1.07 26 Example 6 99.9 1.08 25 Comparative Example 1 99.9 0.62 33 Comparative Example 2 89.7 1.05 28

[0118] In the indicators in Table 1 and Table 2, the glossiness is measured with reference to GB / T13891-2008 "Measurement method for mirror gloss of building finishing materials"; the antibacterial rate is measured with reference to JC / T897-2002 "Antibacterial properties of antibacterial ceramic products", in which the bacteria species selected is Escherichia coli; the friction coefficient is measured by dry method, referring to the static friction coefficient measurement method in GB / T10006-1988 "Measurement method for friction coefficient of plastic films and sheets"; the wear amount is measured with reference to GB / T1768-2006 "Determination of wear resistance of paints and varnishes - rotating rubber grinding wheel method".

[0119] It can be seen from the test results of Table 1 and Table 2 that the super-flat diamond glaze tile substrate prepared by the present invention has high gloss and high hardness, and the super-flat diamond glaze tile made from the super-flat diamond glaze tile substrate has anti-slip and antibacterial properties.

[0120] Polyurethane acrylate is mixed evenly with γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, ethyl acrylate, active diluent trimethylolpropane trimethacrylate, antibacterial additive, solvent acetone and photoinitiator, and coated on the surface of super-flat diamond glaze tile substrate. After photocuring, a cross-linked network structure is formed, which gives the super-flat diamond glaze tile anti-slip and antibacterial properties. Among them, wear-resistant glass microbeads are introduced in the preparation process of the antibacterial additive, and the functional monomer 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin is a hydantoin derivative, which can form a haloamine structure with N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide after chlorination, and synergistically with the antibacterial monomer methacryloylethyl sulfobetaine to give the material high-efficiency antibacterial properties. The obtained antibacterial additive not only has excellent antibacterial properties, but also has good compatibility with the matrix resin in the coating material and is easy to disperse, thereby effectively improving the antibacterial ability and anti-slip properties of the coating material.

[0121] In Comparative Example 1, no glass beads were added, the wear resistance of the coating material was reduced, the wear amount was increased, and the friction coefficient was reduced, so the anti-slip performance of Comparative Example 1 was lower than that of the embodiment;

[0122] In Comparative Example 2, the surface of the glass microbeads does not contain polymerized antibacterial monomers 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide and methacryloylethyl sulfonobetaine, and only methacryloylethyl sulfonobetaine is added to the coating material as an antibacterial component. Due to the lack of the enhancement effect of the halamine structure on the antibacterial performance, the antibacterial performance of Comparative Example 2 is lower than that of the embodiment.

[0123] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation process for high-gloss, high-hardness, ultra-flat diamond glaze tiles, characterized in that: The following steps are involved: Step 1: polyurethane acrylate, γ-methacryloxypropyl trimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, antibacterial additives, acetone, and a photoinitiator are mixed to obtain a coating material; Among them, antibacterial additives The method comprises the following steps: The polyethylene glycol diacrylate is mixed with glass microbeads, and ultrasonic dispersion is performed. 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, a first initiator, and ethanol are added to react. After the reaction is completed, methacryloylethyl sulfobetaine, methyl methacrylate, and a second initiator are added to continue the reaction. After the reaction is completed, the modified glass microbeads are obtained by filtering, washing, and drying. The modified glass microbeads are mixed with water, ultrasonically dispersed, and a sodium hypochlorite aqueous solution is added to perform a chlorination reaction. After the chlorination is completed, the mixture is centrifuged, filtered, washed, and dried to obtain an antibacterial additive; Step 2: spray the glaze on the surface of the brick to form a glaze surface, and then dry, burnish and polish to obtain a high-gloss, high-hardness and ultra-flat diamond glaze tile matrix; The coating material is applied to the side of the high-gloss, high-hardness, ultra-flat diamond glaze tile substrate having the glaze layer, and light-cured to obtain the high-gloss, high-hardness, ultra-flat diamond glaze tile.

2. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 1, characterized in that: In the step 1, when preparing the antibacterial additive: When preparing modified glass microbeads, the mass ratio of polyethylene glycol diacrylate, glass microbeads, 3-[(4-vinylphenyl)methyl]-5,5-dimethylhydantoin, N-[2-(3,4-dihydroxyphenyl)ethyl]-2-acrylamide, the first initiator, ethanol, methacryloylethyl sulfobetaine, methyl methacrylate, and the second initiator is 15-20:8-10:9-10:4-4.5:0.5-0.6:80-100:6.5-7:6-6.5:0.2-0.3, and the first initiator and the second initiator are both potassium persulfate; the reaction conditions are: react at a temperature of 70-80°C for 3-4h; the continued reaction conditions are: continue to react at a temperature of 70-80°C for 3-4h; When preparing the antibacterial additive, the mass ratio of the modified glass microspheres, water and sodium hypochlorite aqueous solution is 1:10-20:40-50, and the sodium hypochlorite aqueous solution is 10-10.5wt% of sodium hypochlorite aqueous solution; the chlorination reaction conditions are: chlorination reaction at room temperature for 6-8h.

3. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 1, characterized in that: In the step 1, the polyurethane acrylate is prepared by the following steps: Mixing polycarbonate diol, isophorone diisocyanate and dibutyltin dilaurate, reacting, adding 1,4-butanediol and 1,2-propylene glycol after the reaction, continuing the reaction, adding pentaerythritol triacrylate, reacting again, cooling to room temperature after the reaction, and obtaining polyurethane acrylate; Among them, the molar ratio of polycarbonate diol, isophorone diisocyanate, 1,4-butanediol, 1,2-propylene glycol, and pentaerythritol triacrylate is 2.5-3:5.6:1-1.2:1-1.2:0.5-0.6, and the amount of dibutyltin dilaurate added is 0.4-0.5% of the polycarbonate diol; the reaction conditions are: reacting for 4-5 hours at a temperature of 70-80°C in a nitrogen atmosphere; the continued reaction conditions are: continuing to react for 3-4 hours at a temperature of 60-70°C in a nitrogen atmosphere; and the second reaction conditions are: reacting again for 0.5-1 hour at a temperature of 50-60°C in a nitrogen atmosphere.

4. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 1, characterized in that: In the step 1, the mass ratio of polyurethane acrylate, γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, ethyl acrylate, trimethylolpropane trimethacrylate, antibacterial additive, acetone, and photoinitiator is 100:10-12:8-10:5-6:20-30:30-35:10-15:2-3.

5. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 1, characterized in that: In the step 2, the high gloss, high hardness and ultra-flat diamond glaze ceramic tile substrate is prepared by the following steps: Step (1), mixing a raw material for a brick, a dispersant and water, and ball-milling the mixture to obtain a green mud, placing the green mud into a mold, pressing and molding the green mud, drying, sintering and heat-insulating the green mud to obtain a brick; Step (2), mixing the frit, raw material, sodium carboxymethyl cellulose and water with a ball mill to obtain a glaze; spraying the glaze on the surface of the brick to form a glaze surface, drying, firing, and polishing after firing to obtain a high-gloss, high-hardness, ultra-flat diamond glaze tile matrix.

6. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 5, characterized in that: In the step (1), the mass ratio of the raw material of the brick, the dispersant and the water is 10:0.2-0.3:7-8; the sintering conditions are: sintering at a temperature of 1160-1200°C for 30-40 minutes and a heat preservation time of 2-2.5 hours; the raw material of the brick is prepared by mixing the raw materials in the following mass ratios: 30-40 parts of clay, 5-10 parts of cristobalite, 5-10 parts of potassium feldspar, 18-22 parts of kaolin, 5-8 parts of sepiolite and 20-30 parts of diopside.

7. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 5, characterized in that: In step (1), the dispersant is prepared by the following steps: Alkali lignin, phenol and water are mixed and dissolved, a regulator is added to adjust the pH value, sodium p-aminobenzenesulfonate is added, and the reaction is carried out. After the reaction is completed, a formaldehyde aqueous solution is added dropwise, and the reaction is continued after the addition is completed, and the dispersant is cooled. Among them, the mass ratio of alkali lignin, phenol, water, sodium p-aminobenzenesulfonate and 37wt% formaldehyde aqueous solution is 19.7-20.2:8.4-8.6:100-110:17.3-17.8:20-20.5; the reaction conditions are: react at a pH value of 10-10.5 and a temperature of 90-95°C for 2-3h; the dropwise addition time of the formaldehyde aqueous solution is 50-60min; and the continued reaction conditions are reacting at a temperature of 90-95°C for 1-2h.

8. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 5, characterized in that: In the step (2), the raw material is prepared by mixing the following raw materials in the following mass ratio: 15-20 parts of quartz, 6-8 parts of kaolin, 30-40 parts of potassium feldspar, 6-8 parts of corundum powder, 3-6 parts of zinc oxide, 2-5 parts of barium carbonate, and 1-3 parts of wollastonite; the frit is prepared by mixing the following raw materials in the following mass ratio: 15-20 parts of Al2O3, 50-60 parts of SiO2, 10-15 parts of CaO, 3-5 parts of K2O, 5-6 parts of MgO, 6-10 parts of BaO, 3-6 parts of ZnO, 0.1-0.2 parts of TiO2, 2-3 parts of Fe2O3, and 1-3 parts of Na2O; the mass ratio of the frit, the raw material, sodium carboxymethyl cellulose, and water is 15-20:80-85:0.5-1:40; and the glaze amount is 1000-1200g / m 2 ; Firing conditions: firing at 1150-1250℃ for 40-60min.

9. The preparation process of a high-gloss, high-hardness, ultra-flat diamond glaze tile according to claim 1, characterized in that: In step 2, the coating thickness is 1.5-1.8 mm; the light curing conditions are: in a nitrogen atmosphere, the irradiation intensity is 30-36 mW / cm 2 Light cure for 3-4 minutes under the conditions.

10. A high-gloss, high-hardness, ultra-flat diamond glaze tile prepared by the preparation process of the high-gloss, high-hardness, ultra-flat diamond glaze tile as described in any one of claims 1 to 9.

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