A microcrystalline colored rock board and its production process

Abstract

The present invention relates to the field of rock slab technology, and specifically discloses a microcrystalline colored rock slab and its production process, comprising the following steps: S1, cooling the pressed green body and then applying a base glaze; S2, inkjet printing a pattern layer on the base glaze layer, printing digital glue after positioning, applying colored crystal dry particles, removing excess dry particles and drying, spraying fixing protective glue and then applying transparent microcrystalline dry particles, spraying the fixing protective glue and then drying; S3, firing and polishing. The present invention makes the rock slab present a diamond-like luster through the high refractive index of the colored crystal particles, while the microcrystalline dry particles can achieve a delicate texture and high gloss. By applying the fixing protective glue on the microcrystalline dry particles and the colored crystal dry particles, it can not only fix the dry particles, but also improve the wear resistance and anti-fouling properties.

Description

Technical Field

[0001] The present invention relates to the technical field of rock slabs, and in particular to a microcrystalline colored rock slab and a production process thereof. Background Art

[0002] Stone slabs are made from carefully selected natural mineral raw materials such as kaolin, quartz, feldspar, and oxides. After being blended in a specific ratio, they are dry-pressed using ultra-high pressure in a press to form an extremely dense green body. This is then uniformly sintered for a long time at temperatures exceeding 1200°C, resulting in ultra-large, ultra-thin porcelain slabs. Essentially a highly sintered, densified ceramic, stone slabs achieve a significant leap in physical and chemical properties through a unique formula and rigorous manufacturing process. Advanced inkjet technology not only creates a luxurious texture and feel comparable to natural stone, but also boasts exceptional Mohs hardness, exceptional impact and flexural strength, and excellent wear, scratch, and high-temperature resistance. These exceptional properties have significantly expanded the application of stone slabs, extending their reach from traditional wall and floor coverings to furniture finishes such as kitchen countertops, bathroom cabinets, dining tables, cabinet doors, and wardrobe panels. They are also finding their way into demanding applications such as commercial spaces, making them a preferred high-end finishing material that combines decorative, functional, safe, and environmentally friendly qualities.

[0003] In order to enrich the application scenarios of stone slabs and meet the various finishing requirements of consumers, stone slabs can be customized with different glazes to show individual needs of matte, glossy, uneven and patterned. In the field of stone slabs, microcrystalline refers specifically to a structural layer or structural feature composed of extremely small crystals formed on the surface or inside the stone slab through a special process; its core lies in the use of specially formulated microcrystalline frit dry particles or microcrystalline glazes to melt and recrystallize on the surface during the high-temperature sintering stage of the stone slab, or through a special formula to precipitate uniformly distributed nano to micron crystals from the matrix during the cooling process; these microcrystalline structures are small in size and densely arranged, giving the stone slab surface an excellent performance improvement, achieving a highly smooth and delicate texture like a mirror and a transparent and warm gloss. Color crystal represents the decorative technology system of brilliant colors and lifelike patterns on the surface of rock slabs. Its core includes not only high-precision digital inkjet printing using inorganic ceramic ink to directly draw patterns, but also the use of pre-colored colored ceramic dry particles as the key decorative means. The color crystal dry particle process precisely spreads or positions fine ceramic particles of different colors on the surface of the blank. After high-temperature sintering, they melt and color to form a highly saturated and extremely stable decorative layer. This dry particle color crystal technology is particularly good at expressing materials with strong three-dimensional sense and rich texture, such as natural mineral crystals, metal rust or relief effects. Whether it is inkjet color crystal or dry particle color crystal, it is finally cured at high temperature in the kiln and permanently combined with the substrate, presenting a decorative effect with rich layers, lifelike details and never fading.

[0004] Patent publication number CN118754439A discloses an innovative microcrystalline glaze and its preparation method, as well as microcrystalline colored ceramic tiles and their preparation method. The microcrystalline glaze is composed of 65-70% microcrystalline ultrafine glaze powder, 0.8-1.2% zirconium silicate, 0.1-0.3% carboxymethyl cellulose, 0.2-0.5% sodium tripolyphosphate, and the rest is water, in terms of weight percentage. Among them, the microcrystalline ultrafine glaze powder is composed of 15-21 parts of microcrystalline dry particles, 8-15 parts of aluminum-containing quartz stone, 5-8 parts of feldspar, 10-15 parts of silicon-containing clay, and 8-12 parts of cerium-containing fluoride vanadate complex, in terms of weight percentage. This microcrystalline glaze can randomly split under the protective glaze, not only ensuring that the surface of the microcrystalline colored ceramic tiles has excellent wear resistance and static friction performance, but also clearly showing the three-dimensional ice crack effect under the glaze, and the tiles have good stability and durability.

[0005] Patent publication number CN115838245A discloses a micro-crystallized, micro-gloss glaze, a micro-gloss ceramic slab with an ultra-smooth, fine glaze surface, and a method for preparing the same. The micro-gloss ceramic slab is formed by stacking and firing a base layer, a base glaze layer, a patterned layer, and a dry granular glaze layer from bottom to top. The dry granular glaze layer is prepared from a micro-gloss glaze. The micro-gloss glaze comprises, by weight, 100-160 parts of a transparent protective glaze slurry, 25-55 parts of dry granular powder, and 20-50 parts of a suspending agent. The dry granular powder is prepared from, by weight, 20-40 parts of potassium feldspar, 10-30 parts of sodium feldspar, 5-20 parts of nepheline feldspar, 5-10 parts of kaolin, 10-20 parts of barium carbonate, 5-10 parts of wollastonite, 3-8 parts of zinc oxide, 5-15 parts of strontium carbonate, 5-10 parts of calcite, and 2-8 parts of aluminum oxide. The micro-gloss ceramic rock slabs produced by this technology have a glossiness controlled between 10-15 degrees, and their surface has an ultra-smooth and delicate fine-grained touch.

[0006] Slate is a new material widely used in high-frequency usage scenarios such as architectural decoration, kitchen countertops, and bathroom walls and floors. Scratches can easily occur on kitchen countertops due to operations such as cutting vegetables and placing pots. Oil, sauce, and other stains can cause discoloration if they seep into the material. Bathroom floors are subject to long-term friction from shoe soles, and walls are prone to water stains. However, its wear-resistant properties prevent scratches and abrasions from frequent use, while its anti-fouling properties prevent stains from penetrating, ensuring the material maintains its beauty over time. From a maintenance cost perspective, if a slate has a long service life, it does not require frequent replacement, and daily cleaning is simple, reducing both financial and energy costs. Furthermore, wear and stain resistance can maintain the surface texture of the slate, so improving its wear and stain resistance is crucial. Summary of the Invention

[0007] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a microcrystalline colored crystal rock plate and a production process thereof.

[0008] The present invention makes the rock slab present a diamond-like luster through the high refractive index of the colored crystal particles, while the microcrystalline dry particles can achieve a highly smooth and delicate texture like a mirror and a transparent and warm gloss. The two together make the rock slab present a unique aesthetic effect. In order to improve the wear resistance of the rock slab, the present invention provides a fixing protective glue, which is applied to the microcrystalline dry particles and colored crystal dry particles. It can not only play the role of fixing the dry particles, but also greatly improve the wear resistance of the surface by forming a rigid layer on the outermost layer. Zirconia is a rigid particle with a high filling density and a dense coating. The hardness is further improved after the hydrolysis and cross-linking of zirconium oxide and tetraisopropyl titanate to form a covalent bond. After high-temperature ceramicization, a dense protective layer is formed on the surface of the rock slab, making the rock slab more durable.

[0009] To achieve the above object, the present invention provides a production process of microcrystalline colored crystal rock slabs, comprising the following steps:

[0010] S1. Cool the pressed green body from 80-90℃ to 50-55℃ and apply bottom glaze.

[0011] S2. Inkjet print the pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, remove excess dry particles and dry at 160-170℃, spray fixed protective glue and apply transparent microcrystalline dry particles, spray fixed protective glue and dry at 130-140℃;

[0012] S3. After firing at 1200~1300℃ and polishing, you can get microcrystalline colored crystal rock plate.

[0013] Furthermore, the base glaze is composed of the following raw materials in parts by weight: 25-35 parts of potassium feldspar, 10-15 parts of wollastonite, 5-10 parts of dolomite, 20-25 parts of quartz sand, 8-12 parts of kaolin, 12-18 parts of zirconium silicate, 0.8-1.2 parts of carboxymethyl cellulose, 2-4 parts of calcined alumina and 1-3 parts of zinc oxide.

[0014] Furthermore, the colored crystal dry particles are composed of the following raw materials in parts by weight: 20-30 parts of zircon sand, 30-40 parts of quartz sand, 15-25 parts of potassium feldspar, 10-20 parts of calcite, 2-6 parts of dolomite, 0.5-1.5 parts of carboxymethyl cellulose and 0.1-0.3 parts of titanium dioxide.

[0015] Furthermore, the microcrystalline dry particles are composed of the following raw materials in parts by weight: 40-60 parts of quartz sand, 6-10 parts of borax, 10-20 parts of potassium feldspar, 15-25 parts of calcite, 2-4 parts of soda ash, 2-4 parts of kaolin, 0.5-1 part of polyvinyl alcohol and 0.2-0.4 part of zinc oxide.

[0016] The preparation method of the fixing protective glue comprises the following steps:

[0017] X1. Add tetraisopropyl titanate to anhydrous ethanol under an inert atmosphere, add acetylacetone and stir evenly, then add water dropwise for hydrolysis, then add acid-activated zirconium oxide, stir for 1-2 hours, then heat and stir for 1-2 hours, centrifuge, wash, and dry to obtain modified zirconium oxide;

[0018] X2. Add modified zirconium oxide to ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose, and mix evenly.

[0019] Furthermore, the mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, and acid-activated zirconia is 1:2-3:0.1-0.2:0.2-0.3:0.6-1.

[0020] Furthermore, the temperature range of the heating is 40-50°C.

[0021] Furthermore, the mass ratio of the modified zirconium oxide, ethanol aqueous solution, zinc oxide, and hydroxypropyl methylcellulose is 1:2-3:0.2-0.4:0.1-0.3.

[0022] Preferably, the preparation method of the fixing protective glue comprises the following steps:

[0023] X1. Tetraisopropyl titanate is added to anhydrous ethanol under an inert atmosphere, followed by the addition of acetylacetone, followed by dropwise addition of water for hydrolysis, followed by the addition of acid-activated zirconium oxide, and the mixture is stirred for 1-2 hours. Dodecyldimethylamine betaine is then added, and the mixture is heated to 40-50° C. and stirred for 1-2 hours. The mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, acid-activated zirconium oxide, and dodecyldimethylamine betaine is 1:2-3:0.1-0.2:0.2-0.3:0.6-1:1-1.5. The mixture is centrifuged, washed, and dried to obtain modified zirconium oxide.

[0024] X2. Add modified zirconium oxide to ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose. The mass ratio of modified zirconium oxide, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:2~3:0.2~0.4:0.1~0.3. Mix evenly.

[0025] More preferably, the preparation method of the fixing protective glue comprises the following steps:

[0026] X1. Tetraisopropyl titanate is added to anhydrous ethanol under an inert atmosphere. After adding acetylacetone, water is added dropwise for hydrolysis. Then, acid-activated zirconium oxide is added. After stirring for 1 to 2 hours, dodecyldimethylamine betaine is added and stirred at a temperature of 1 to 2 hours. After centrifugation, the mixture is washed and dried to obtain modified zirconium oxide.

[0027] X2. Polycondense pentaerythritol with 3-aminopropionic acid and dibutyltin dilaurate at 160-180° C. for 6-10 hours, add hexamethylenediamine and toluene, and stir at 100-120° C. for 4-8 hours to terminate the amino groups. The mass ratio of pentaerythritol to 3-aminopropionic acid, dibutyltin dilaurate, hexamethylenediamine, and toluene is 1:6-7:0.01-0.03:1-3:5-10 to obtain an amino-terminated hyperbranched polymer.

[0028] X3. Add modified zirconium oxide and amino-terminated hyperbranched polymer to ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose. The mass ratio of modified zirconium oxide, amino-terminated hyperbranched polymer, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:0.8~1:2~3:0.2~0.4:0.1~0.3, and mix evenly.

[0029] The present invention also provides a microcrystalline colored rock plate produced by the above production process.

[0030] Beneficial effects of the present invention:

[0031] 1. Compared with the existing technology, the high refractive index of the colored crystal particles in the present invention makes the rock plate present a diamond-like luster, while the microcrystalline dry particles can achieve a highly smooth and delicate texture and a transparent and warm gloss like a mirror. The two together make the rock plate present a unique aesthetic effect.

[0032] 2. The present invention applies a fixing protective glue to the microcrystalline dry particles and colored crystal dry particles, which not only fixes the dry particles, but also greatly improves the wear resistance of the surface by forming a rigid layer on the outermost layer. Zirconium oxide is a rigid particle with a high filling density and a dense coating. The hardness is further improved after the zirconium oxide and tetraisopropyl titanate are hydrolyzed and cross-linked to form a covalent bond. After high-temperature ceramicization, a dense protective layer is formed on the surface of the rock plate, making the rock plate more durable. DETAILED DESCRIPTION

[0033] The acid-activated zirconium oxide is prepared by adding 10 parts by weight of zirconium oxide to 50 parts by weight of water, ultrasonically dispersing the mixture for 10 minutes at an ultrasonic power of 200 W and a frequency of 40 kHz to form a uniform suspension, adding 0.5 parts by weight of 40 wt% hydrofluoric acid dropwise, stirring at 60° C. for 30 minutes, centrifuging, washing with water to a pH of 6.5, and drying.

[0034] Dodecyldimethylaminoethyl lactone, CAS number: 683-10-3.

[0035] Polyvinyl alcohol, model: A205, Kuraray, Japan.

[0036] Example 1

[0037] A production process of microcrystalline colored rock slabs comprises the following steps, calculated in parts by weight:

[0038] S1. Cooling the pressed green body from 85° C. to 52° C. and applying a base glaze, the base glaze comprising 30 parts of potassium feldspar, 12 parts of wollastonite, 8 parts of dolomite, 22 parts of quartz sand, 10 parts of kaolin, 15 parts of zirconium silicate, 1 part of carboxymethyl cellulose, 3 parts of calcined alumina, and 2 parts of zinc oxide;

[0039] S2. Inkjet print a pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, including 25 parts of zircon sand, 35 parts of quartz sand, 20 parts of potassium feldspar, 15 parts of calcite, 4 parts of dolomite, 1 part of carboxymethyl cellulose and 0.2 parts of titanium dioxide, remove excess dry particles and dry at 165°C, spray fixative protective glue and apply transparent microcrystalline dry particles, including 50 parts of quartz sand, 8 parts of borax, 15 parts of potassium feldspar, 20 parts of calcite, 3 parts of soda ash, 3 parts of kaolin, 0.8 parts of polyvinyl alcohol and 0.3 parts of zinc oxide, spray fixative protective glue and dry at 135°C;

[0040] S3. After firing at 1250℃ and polishing, you can get the microcrystalline colored crystal rock plate.

[0041] The preparation method of the fixing protective glue comprises the following steps:

[0042] X1. Tetraisopropyl titanate was added to anhydrous ethanol under a nitrogen atmosphere, acetylacetone was added and stirred evenly, water was added dropwise for hydrolysis, and acid-activated zirconia was added. The mixture was stirred for 1 hour, then heated to 45° C. and stirred for 1 hour. The mixture was centrifuged, washed, and dried to obtain modified zirconia; the mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, and acid-activated zirconia was 1:2.5:0.15:0.25:0.8;

[0043] X2. Add modified zirconium oxide to 70 wt% ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose and mix evenly; the mass ratio of modified zirconium oxide, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:2.5:0.3:0.2.

[0044] Example 2

[0045] It is basically the same as Example 1, the only difference is the fixing protective glue;

[0046] The preparation method of the fixing protective glue comprises the following steps:

[0047] X1. Tetraisopropyl titanate was added to anhydrous ethanol under a nitrogen atmosphere, acetylacetone was added and stirred evenly, water was added dropwise for hydrolysis, acid-activated zirconia was added, and the mixture was stirred for 1 hour. Dodecyldimethylamine betaine was added, the temperature was raised to 45° C., and stirred for 1 hour. The mixture was centrifuged, washed, and dried to obtain modified zirconia; the mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, acid-activated zirconia, and dodecyldimethylamine betaine was 1:2.5:0.15:0.25:0.8:1.2;

[0048] X2. Add modified zirconium oxide to 70 wt% ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose, and mix evenly; the mass ratio of modified zirconium oxide, ethanol aqueous solution, zinc oxide, and hydroxypropyl methylcellulose is 1:2.5:0.3:0.2.

[0049] Example 3

[0050] It is basically the same as Example 1, the only difference is the fixing protective glue;

[0051] The preparation method of the fixing protective glue comprises the following steps:

[0052] X1. Tetraisopropyl titanate was added to anhydrous ethanol under a nitrogen atmosphere, acetylacetone was added and stirred evenly, water was added dropwise for hydrolysis, acid-activated zirconia was added, and the mixture was stirred for 1 hour. Dodecyldimethylamine betaine was added, the temperature was raised to 45° C., and stirred for 1 hour. The mixture was centrifuged, washed, and dried to obtain modified zirconia; the mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, acid-activated zirconia, and dodecyldimethylamine betaine was 1:2.5:0.15:0.25:0.8:1.2;

[0053] X2. Polycondense pentaerythritol with 3-aminopropionic acid and dibutyltin dilaurate at 170° C. for 8 h, add hexamethylenediamine and toluene, and stir at 110° C. for 6 h to terminate the amino group to obtain an amino-terminated hyperbranched polymer; the mass ratio of pentaerythritol to 3-aminopropionic acid, dibutyltin dilaurate, hexamethylenediamine, and toluene is 1:6.5:0.02:2:8;

[0054] X3. Add modified zirconium oxide and amino-terminated hyperbranched polymer to 70 wt % ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose and mix evenly; the mass ratio of modified zirconium oxide, amino-terminated hyperbranched polymer, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:0.9:2.5:0.3:0.2.

[0055] Comparative Example 1

[0056] A production process of microcrystalline colored rock slabs comprises the following steps, calculated in parts by weight:

[0057] S1. Cooling the pressed green body from 85° C. to 52° C. and applying a base glaze, the base glaze comprising 30 parts of potassium feldspar, 12 parts of wollastonite, 8 parts of dolomite, 22 parts of quartz sand, 10 parts of kaolin, 15 parts of zirconium silicate, 1 part of carboxymethyl cellulose, 3 parts of calcined alumina, and 2 parts of zinc oxide;

[0058] S2. Inkjet print a pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, including 25 parts of zircon sand, 35 parts of quartz sand, 20 parts of potassium feldspar, 15 parts of calcite, 4 parts of dolomite, 1 part of carboxymethyl cellulose and 0.2 parts of titanium dioxide, remove excess dry particles and dry at 165°C, spray fixative protective glue and apply transparent microcrystalline dry particles, including 50 parts of quartz sand, 8 parts of borax, 15 parts of potassium feldspar, 20 parts of calcite, 3 parts of soda ash, 3 parts of kaolin, 0.8 parts of polyvinyl alcohol and 0.3 parts of zinc oxide, spray fixative protective glue and dry at 135°C;

[0059] S3. After firing at 1250℃ and polishing, you can get the microcrystalline colored crystal rock plate.

[0060] The fixing and protecting glue is a 3 wt % hydroxypropyl methylcellulose aqueous solution.

[0061] Comparative Example 2

[0062] A production process of microcrystalline colored rock slabs comprises the following steps, calculated in parts by weight:

[0063] S1. Cooling the pressed green body from 85° C. to 52° C. and applying a base glaze, the base glaze comprising 30 parts of potassium feldspar, 12 parts of wollastonite, 8 parts of dolomite, 22 parts of quartz sand, 10 parts of kaolin, 15 parts of zirconium silicate, 1 part of carboxymethyl cellulose, 3 parts of calcined alumina, and 2 parts of zinc oxide;

[0064] S2. Inkjet print a pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, including 25 parts of zircon sand, 35 parts of quartz sand, 20 parts of potassium feldspar, 15 parts of calcite, 4 parts of dolomite, 1 part of carboxymethyl cellulose and 0.2 parts of titanium dioxide, remove excess dry particles and dry at 165°C, spray fixative protective glue and apply transparent microcrystalline dry particles, including 50 parts of quartz sand, 8 parts of borax, 15 parts of potassium feldspar, 20 parts of calcite, 3 parts of soda ash, 3 parts of kaolin, 0.8 parts of polyvinyl alcohol and 0.3 parts of zinc oxide, spray fixative protective glue and dry at 135°C;

[0065] S3. After firing at 1250℃ and polishing, you can get the microcrystalline colored crystal rock plate.

[0066] The preparation method of the fixing protective glue comprises the following steps:

[0067] Zirconium oxide is added to a 70wt% ethanol aqueous solution, stirred and mixed evenly, and then zinc oxide and hydroxypropyl methylcellulose are added and mixed evenly to obtain the product; the mass ratio of zirconium oxide, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:2.5:0.3:0.2.

[0068] Comparative Example 3

[0069] A production process of microcrystalline colored rock slabs comprises the following steps, calculated in parts by weight:

[0070] S1. Cooling the pressed green body from 85° C. to 52° C. and applying a base glaze, the base glaze comprising 30 parts of potassium feldspar, 12 parts of wollastonite, 8 parts of dolomite, 22 parts of quartz sand, 10 parts of kaolin, 15 parts of zirconium silicate, 1 part of carboxymethyl cellulose, 3 parts of calcined alumina, and 2 parts of zinc oxide;

[0071] S2. Inkjet print a pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, including 25 parts of zircon sand, 35 parts of quartz sand, 20 parts of potassium feldspar, 15 parts of calcite, 4 parts of dolomite, 1 part of carboxymethyl cellulose and 0.2 parts of titanium dioxide, remove excess dry particles and dry at 165°C, spray fixative protective glue and apply transparent microcrystalline dry particles, including 50 parts of quartz sand, 8 parts of borax, 15 parts of potassium feldspar, 20 parts of calcite, 3 parts of soda ash, 3 parts of kaolin, 0.8 parts of polyvinyl alcohol and 0.3 parts of zinc oxide, spray fixative protective glue and dry at 135°C;

[0072] S3. After firing at 1250℃ and polishing, you can get the microcrystalline colored crystal rock plate.

[0073] The preparation method of the fixing protective glue comprises the following steps:

[0074] X1. Add water to 3-aminopropyltriethoxysilane for hydrolysis, then add acid-activated zirconium oxide, the mass ratio of 3-aminopropyltriethoxysilane to water and acid-activated zirconium oxide being 1:0.25:0.8. After stirring for 1 hour, heat to 45° C. and stir for 1 hour. After centrifugation, wash and dry to obtain modified zirconium oxide;

[0075] X2. Add modified zirconium oxide to 70 wt% ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose, and mix evenly; the mass ratio of modified zirconium oxide, ethanol aqueous solution, zinc oxide, and hydroxypropyl methylcellulose is 1:2.5:0.3:0.2.

[0076] Test Example 1

[0077] The microcrystalline colored crystal rock panels prepared in the examples and comparative examples were tested for wear resistance, thermal shock resistance, chemical corrosion resistance, anti-slip properties, and radioactivity;

[0078] The inspection is based on GB / T 3810.7-2016 "Test methods for ceramic tiles - Part 7: Determination of surface abrasion resistance of glazed tiles"; GB / T 3810.9-2016 "Test methods for ceramic tiles - Part 9: Determination of thermal shock resistance"; GB / T 3810.13-2016 "Test methods for ceramic tiles - Part 13: Determination of chemical resistance"; GB / T 3810.14-2016 "Test methods for ceramic tiles - Part 14: Determination of pollution resistance"; GB / T 37798-2019 "Evaluation of the anti-slip grade of ceramic tiles"; and GB 6566-2010 "Limits of radionuclides in building materials".

[0079] Table 1

[0080]

[0081] It can be seen from Table 1 that compared with Control Example 1, the wear resistance and antifouling properties of the rock plate prepared in the embodiment are significantly better. This may be because the wear resistance of the surface is greatly improved by forming a rigid layer in the outermost layer in the embodiment. Zirconium oxide is a rigid particle with a high filling density and a dense coating. Zirconium oxide and tetraisopropyl titanate are hydrolyzed and cross-linked to form a covalent bond, which further improves the hardness. After high-temperature ceramicization, a dense protective layer is formed on the surface of the rock plate, which improves the wear resistance. Compared with Control Example 2, Example 1 uses Ti-O-Zr covalent bonding. Compared with physical blending, the bond energy of covalent bonding is higher and the surface is denser. In Control Example 3, 3-aminopropyltriethoxysilane is used to bond zirconium oxide, but the bond energy of Si-O-Zr is lower than that of Ti-O-Zr, so the overall performance is not as good as Example 1.

[0082] Compared with Example 1, Example 2 adds dodecyldimethylamine betaine, whose carboxylate can bind to zirconium oxide through coordination, and the quaternary ammonium groups are arranged in a directional manner to form a hydration layer, which repels dirt, thus improving antifouling and corrosion resistance. On this basis, Example 3 introduces an amino-terminated hyperbranched polymer, which can bind to modified zirconium oxide through various effects. The multiple long chains of the hyperbranched polymer form an interpenetrating structure, thereby enhancing the crosslinking strength. As a result, the surface layer is more dense, and thus the wear resistance is optimal.

[0083] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A production process of microcrystalline colored rock board, characterized in that: The steps include: S1. Cool the pressed green body from 80-90℃ to 50-55℃ and apply bottom glaze. S2. Inkjet print the pattern layer on the base glaze layer, print digital glue after positioning, apply colored crystal dry particles, remove excess dry particles and dry at 160-170℃, spray fixed protective glue and apply transparent microcrystalline dry particles, spray fixed protective glue and dry at 130-140℃; S3, after firing at 1200~1300℃ and polishing, the microcrystalline colored crystal rock plate is obtained; The preparation method of the fixing protective glue comprises the following steps: X1. Add tetraisopropyl titanate to anhydrous ethanol under an inert atmosphere, add acetylacetone and stir evenly, then add water dropwise for hydrolysis, then add acid-activated zirconium oxide, stir for 1-2 hours, then heat and stir for 1-2 hours, centrifuge, wash, and dry to obtain modified zirconium oxide; X2. Add modified zirconium oxide to ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose, and mix evenly.

2. The production process of the microcrystalline colored rock plate according to claim 1, characterized in that: The base glaze is composed of the following raw materials in parts by weight: 25-35 parts of potassium feldspar, 10-15 parts of wollastonite, 5-10 parts of dolomite, 20-25 parts of quartz sand, 8-12 parts of kaolin, 12-18 parts of zirconium silicate, 0.8-1.2 parts of carboxymethyl cellulose, 2-4 parts of calcined alumina and 1-3 parts of zinc oxide.

3. The production process of the microcrystalline colored rock board according to claim 1, characterized in that: The colored crystal dry particles are composed of the following raw materials in parts by weight: 20-30 parts of zircon sand, 30-40 parts of quartz sand, 15-25 parts of potassium feldspar, 10-20 parts of calcite, 2-6 parts of dolomite, 0.5-1.5 parts of carboxymethyl cellulose and 0.1-0.3 parts of titanium dioxide.

4. The production process of the microcrystalline colored rock plate according to claim 1, characterized in that: The microcrystalline dry particles are composed of the following raw materials in parts by weight: 40-60 parts of quartz sand, 6-10 parts of borax, 10-20 parts of potassium feldspar, 15-25 parts of calcite, 2-4 parts of soda ash, 2-4 parts of kaolin, 0.5-1 part of polyvinyl alcohol and 0.2-0.4 part of zinc oxide.

5. The production process of microcrystalline colored rock board according to claim 1, characterized in that: The mass ratio of the tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, and acid-activated zirconium oxide is 1:2-3:0.1-0.2:0.2-0.3:0.6-1.

6. The production process of microcrystalline colored rock board according to claim 1, characterized in that: The temperature range of the heating is 40-50°C.

7. The production process of microcrystalline colored rock board according to claim 1, characterized in that: The mass ratio of the modified zirconium oxide, the ethanol aqueous solution, the zinc oxide, and the hydroxypropyl methylcellulose is 1:2-3:0.2-0.4:0.1-0.

3.

8. The production process of microcrystalline colored rock board according to claim 1, characterized in that: The preparation method of the fixing protective glue comprises the following steps: X1. Tetraisopropyl titanate is added to anhydrous ethanol under an inert atmosphere, followed by the addition of acetylacetone, followed by dropwise addition of water for hydrolysis, followed by the addition of acid-activated zirconium oxide, and the mixture is stirred for 1-2 hours. Dodecyldimethylamine betaine is then added, and the mixture is heated to 40-50° C. and stirred for 1-2 hours. The mass ratio of tetraisopropyl titanate to anhydrous ethanol, acetylacetone, water, acid-activated zirconium oxide, and dodecyldimethylamine betaine is 1:2-3:0.1-0.2:0.2-0.3:0.6-1:1-1.

5. The mixture is centrifuged, washed, and dried to obtain modified zirconium oxide. X2. Add modified zirconium oxide to ethanol aqueous solution, stir and mix evenly, then add zinc oxide and hydroxypropyl methylcellulose. The mass ratio of modified zirconium oxide, ethanol aqueous solution, zinc oxide and hydroxypropyl methylcellulose is 1:2~3:0.2~0.4:0.1~0.

3. Mix evenly.

9. A microcrystalline colored rock board, characterized in that: Produced by the production process according to any one of claims 1 to 8.

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