CN114507086A - Preparation process of ceramic tile with medium and low gloss and ceramic tile - Google Patents
Preparation process of ceramic tile with medium and low gloss and ceramic tile Download PDFInfo
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- CN114507086A CN114507086A CN202210195446.9A CN202210195446A CN114507086A CN 114507086 A CN114507086 A CN 114507086A CN 202210195446 A CN202210195446 A CN 202210195446A CN 114507086 A CN114507086 A CN 114507086A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001681 protective effect Effects 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003377 acid catalyst Substances 0.000 claims abstract description 9
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 118
- 239000002346 layers by function Substances 0.000 claims description 53
- 230000003287 optical effect Effects 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 claims 3
- 239000010409 thin film Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 7
- 230000003746 surface roughness Effects 0.000 abstract description 6
- 238000005034 decoration Methods 0.000 abstract description 3
- 230000004313 glare Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 239000011449 brick Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5035—Silica
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to the technical field of ceramic tiles, in particular to a preparation process of a ceramic tile with medium and low gloss and a ceramic tile, which comprises the following steps: s1, mixing an organic solvent, tetraethyl silicate, methyl triethoxysilane, a surfactant, water and an acid catalyst in proportion, and stirring and reacting for 6-12 hours at 15-60 ℃ to obtain coating sol; s2, coating the coating sol on a protective glaze layer of the high-gloss ceramic tile, heating to the glass transition temperature of the transparent protective glaze layer, and annealing and shaping to obtain the ceramic tile with medium and low gloss. The anti-reflection film layer is additionally arranged on the surface of the protective glaze layer of the ceramic tile, so that the reflected light of the transparent protective glaze layer is reduced, the light transmittance is increased, the reflection glare of the transparent protective glaze layer is reduced, the transparency of the ceramic tile is increased, the pattern, texture definition and texture of the ceramic tile are improved, the smooth texture and surface roughness of the surface of the ceramic tile are not influenced, and the higher decoration requirement is met.
Description
Technical Field
The invention relates to the technical field of ceramic tiles, in particular to a preparation process of a ceramic tile with medium and low gloss and the ceramic tile.
Background
High gloss ceramic tiles such as full-glazed tiles are popular with consumers because of the texture and natural texture of natural marbles. However, compared with the natural luster of natural marble, the surface of the high-luster ceramic tile adopts a transparent full-protection glaze layer as a protection layer of middle patterns and patterns, however, the transparent protection glaze layer has obvious mismatch with the refractive index of air, the surface of the protection glaze is smooth and flat, and the roughness is low, so that the surface of the ceramic tile presents obvious specular reflection light, the light transmittance of the protection glaze layer is reduced to a certain extent by the specular reflection light, the definition of the patterns and the textures under the protection glaze is influenced, and the specular reflection light is stray light and easily causes light pollution, thereby disturbing the appreciation of human eyes on the patterns and the textures of the ceramic tile product.
In the prior art, the roughness of a protective glaze layer is increased, so that the original mirror reflection is converted into diffuse reflection, and the mirror polishing reflectivity of the glazed surface of the ceramic tile is reduced. For example, in patent No. 202011056439.8, sandstone dry particles are added into ceramic tile glaze, so that the roughness of the surface glaze layer is increased, diffuse reflection is realized, and the glossiness is within 5 degrees; alternatively, in patent No. 202011618990.7, ceramic tiles are maintained at low gloss by incorporating low gloss anti-slip particles in the surface glaze layer: 2-5 degrees. However, in the above scheme, the specular reflection is converted into the diffuse reflection by increasing the roughness, and although the glossiness of the surface of the glaze layer can be reduced, the total reflectivity of the surface of the glaze layer is not reduced, and even the total reflectivity can be increased, so that the light transmittance of the protective glaze layer is further reduced, and the visibility of human eyes for observing the color glaze layer and the pattern layer is further reduced.
Disclosure of Invention
The invention mainly aims to provide a preparation process of a ceramic tile with medium and low gloss and the ceramic tile, aiming at reducing the mirror reflection glare of a transparent protective glaze in the existing ceramic tile, thereby improving the light transmittance of the transparent protective glaze in the existing ceramic tile and obtaining the ceramic tile with more comfortable vision and clearer patterns and textures.
In order to realize the purpose, the invention provides a preparation process of a ceramic tile with medium and low gloss, which comprises the following steps: s1, synthesizing a coating sol: mixing organic solvent, tetraethyl silicate, methyl triethoxysilane, surfactant, water and acid catalyst according to the weight ratio of (30-60): 1: (0.1-1): (0.003-0.3): (2-6): (0.002-0.004), stirring and reacting for 6-12 hours under the heating condition of 15-60 ℃ to obtain coating sol;
s2, applying the coating sol on the transparent protective glaze layer of the high-gloss ceramic tile after cleaning and drying, and heating until the transparent protective glaze layer is at the glass transition temperature for annealing and shaping to obtain the ceramic tile with medium and low gloss.
Generally, clear water is adopted to clean and dry the surface of the ceramic tile, and then the subsequent coating operation is carried out, and the clean ceramic tile can be directly coated with the coating sol. When the ceramic tile is not coated with the coating sol, the ceramic tile is a high-gloss ceramic tile (such as a full-glazed ceramic tile), specifically more than 80 degrees, after the ceramic tile is coated with the coating sol and annealed and shaped, the glossiness of the ceramic tile can be reduced to 10-70 degrees, the ceramic tile is defined as low-gloss at 10-40 degrees and medium-gloss at 40-70 degrees, namely the ceramic tile is converted from the high-gloss ceramic tile into the ceramic tile with medium and low gloss.
The ceramic tile with medium and low gloss in the scheme has the advantages that the anti-reflection film layer is formed on the transparent protection glaze layer in a nano film coating mode to reduce the light reflectivity of the transparent protection glaze layer, so that the light transmittance of the transparent protection glaze layer is improved, the roughness of the surface of the transparent protection glaze layer is not increased, and the surface of the ceramic tile is still smooth. The preparation method comprises the steps of firstly preparing coating sol, coating the coating sol on a transparent protective glaze layer of a ceramic tile, annealing and curing the coating sol to form an optical functional layer on the surface of the transparent protective glaze, carrying out fusion reaction on the coating sol and the transparent protective glaze at the interface of the coating sol and the transparent protective glaze to form a compact mechanical functional layer when the annealing temperature is at the glass transition temperature of the transparent protective glaze, and combining the optical functional layer and the mechanical functional layer to form a low-high refractive index double-layer structure antireflection film layer. In addition, the porous aperture in the optical function layer is 2-30 nanometers, and the surface roughness of the film layer is 0.1-10 nanometers, so that the visible light haze of the surface of the film layer (the surface of the ceramic tile) is small, the transparency is high, and the definition of the pattern and the texture of the ceramic tile can be improved.
The main reactants of the coating sol are an organic solvent (specifically, absolute ethyl alcohol, isopropanol and the like), tetraethyl silicate, methyl triethoxysilane, a surfactant, water and an acid catalyst, and in the aspect of synthesis of the coating sol, the acid catalyst and the specific surfactant are selected, so that the formed antireflection film layer has a smaller pore diameter, the surface roughness of the antireflection film layer is lower, the haze can be almost considered, and the appearance is better. In addition, by using organic and inorganic silicon sources, better flexibility can be obtained, so that the antireflection film has better film-substrate bonding force and mechanical wear resistance. The preparation method comprises the steps of preparing a double-layer structure antireflection film layer with a porous optical functional layer and a compact mechanical functional layer by adopting a high-temperature annealing process near the glass transition temperature of a protective glaze, carrying out solvent evaporation induced self-assembly film forming mechanism on a coating sol by a dipping-lifting method after a ceramic tile is pulled up in a solution and in the solvent volatilization process, forming a chemical sol-gel wet film on a transparent protective glaze layer of the ceramic tile by regulating and controlling coating process parameters, and carrying out high-temperature annealing to the glass transition temperature of the transparent protective glaze to form the double-layer structure antireflection film consisting of the optical functional layer and the mechanical functional layer. Besides the dipping-pulling method, the coating layer can be coated by a roll coating method, and the coating sol is uniformly coated on the surface of the transparent protective glaze layer by a roll coating machine and then is annealed at high temperature.
Preferably, the surfactant is one of cetyl trimethyl ammonium bromide, a non-ionic block copolymer such as polyether F127 having an average molecular weight of 8000-13000, or a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123.
The surfactant in the scheme can play the effects of dispersion, penetration, solubilization, pore forming and the like, can improve the crystalline structure of the coating layer by utilizing the directional arrangement and the adsorption effect of the surfactant, prevents the coating layer from having surface defects such as pinholes and the like, and decomposes the surfactant to form mesopores with the pore diameter of 2-30 nanometers on the coating layer during high-temperature annealing, thereby forming the optical functional layer with lower refractive index.
Preferably, the acid catalyst is at least one of hydrochloric acid or acetic acid. Acid catalyst such as hydrochloric acid or acetic acid can make the film plating be acid catalysis condition, the hydrolysis speed of the precursor is faster than the polycondensation speed, the film plating sol forms polymer-form Si-O-Si three-dimensional chain network structure oligomer, the formed film plating layer is more compact, continuous and flat, and the mechanical strength is better.
Preferably, in step S2, the temperature is raised to 600-800 ℃ to make the transparent protective glaze layer at the glass transition temperature for annealing and shaping, wherein the annealing time is 10-120 min. At the annealing temperature, a porous optical functional layer can be formed after removal, a compact mechanical functional layer fused by coating sol and transparent protective glaze can also be formed, and meanwhile, a better optical anti-reflection effect and mechanical wear resistance are both considered.
In addition, the invention also provides a ceramic tile which is prepared by any one of the preparation processes of the ceramic tile with medium and low gloss, and the ceramic tile comprises an anti-reflection film layer, a transparent protective glaze layer and a ceramic tile body layer which are arranged from top to bottom in sequence. In actual production, a pattern texture layer and a ground coat layer can be arranged between the transparent protective glaze layer and the ceramic brick body layer, the ground coat layer is positioned above the ceramic brick body layer, and the pattern texture layer is positioned above the ground coat layer.
The antireflection film comprises an optical functional layer (the upper end of the layer is contacted with air) and a mechanical functional layer (the lower end of the layer is contacted with the transparent protective glaze layer) which are arranged in sequence from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 2-30 nanometers, the thickness of the film layer is 80-140 nanometers, the refractive index is 1.20-1.40, and the roughness is 0.1-10 nanometers. The optical function layer can ensure that the ceramic tile keeps relatively proper glossiness and light transmittance, the interference color of the coating layer is not obvious, the appearance color is neutral, and the decorative effect is good when the ceramic tile is directly observed by human eyes.
The mechanical functional layer is a compact and continuous film, the thickness of the film layer is 10-60 nanometers, the refractive index is 1.40-1.60, the refractive index is slightly larger than that of the optical functional layer, and the mechanical functional layer and the optical functional layer form a low-high refractive index double-layer film system antireflection film, so that the transparency of the transparent protective glaze and the color neutrality of the antireflection film can be further improved.
The preparation process of the ceramic tile with medium and low gloss and the ceramic tile have the following beneficial effects: the anti-reflection film layer is additionally arranged on the surface of the ceramic layer, so that the reflected light of the ceramic tile transparent protective glaze is reduced, the light transmittance is increased, the smooth texture and the surface roughness of the surface of the ceramic tile are not influenced, and the ceramic tile has the characteristics of smooth surface, medium gloss and low gloss. The antireflection film layer consists of an optical functional layer with low refractive index and a mechanical functional layer with high refractive index, has good optical antireflection and color neutral optical effects and wear-resistant mechanical properties, meets higher decoration requirements, improves clearer and more comfortable observation and appreciation of patterns and textures in the ceramic tile by human eyes, and avoids the problems of overhigh surface reflection light and overhigh surface roughness of low/matte ceramic tiles and overhigh surface reflection haze of high-gloss ceramic tiles in the prior art.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
A preparation process of a ceramic tile with medium and low gloss comprises the following steps:
s1, synthesizing a coating sol: mixing organic solvent, tetraethyl silicate, methyl triethoxysilane, surfactant, water and acid catalyst according to the weight ratio of (30-60): 1: (0.1-1): (0.003-0.3): (2-6): (0.002-0.004), stirring and reacting for 6-12 hours under the heating condition of 15-60 ℃ to obtain coating sol;
the surfactant is one of cetyl trimethyl ammonium bromide and nonionic block copolymer such as polyether F127 or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123.
S2, applying the coating sol on the cleaned and dried high-gloss ceramic tile transparent protective glaze layer, heating to 600-800 ℃ to enable the transparent protective glaze layer to be at the glass transition temperature for annealing and shaping, wherein the annealing time is 10-120min, and obtaining the ceramic tile with medium and low gloss.
The ceramic tile prepared by the preparation process comprises an anti-reflection film layer, a transparent protective glaze layer and a ceramic tile body layer which are sequentially arranged from top to bottom.
The antireflection film comprises an optical functional layer and a mechanical functional layer which are sequentially arranged from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 2-30 nanometers, the thickness of the film layer is 80-140 nanometers, the refractive index is 1.20-1.40, and the roughness is 0.1-10 nanometers.
The mechanical functional layer is a compact continuous film, the thickness of the film layer is 10-60 nanometers, the refractive index is 1.40-1.60, the refractive index is slightly larger than that of the optical functional layer, and the mechanical functional layer and the optical functional layer form a double-layer film system antireflection film with a low upper refractive index and a high lower refractive index.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
A preparation process of a low-gloss ceramic tile comprises the following steps:
s1, synthesizing a coating sol: anhydrous ethanol, tetraethyl silicate, methyltriethoxysilane, polyether F127 (average molecular weight 8000), water and hydrochloric acid were mixed in a ratio of 56: 1: 0.5: 0.008: 4: 0.003 of the molar ratio, and stirring and reacting for 6 hours under the heating condition of 60 ℃ to obtain coating sol;
s2, coating the film coating sol on the cleaned and dried ceramic tile transparent protective glaze layer by adopting a roll coating method, heating to 650 ℃ to enable the transparent protective glaze layer to be at the glass transition temperature, and annealing and shaping for 30min to obtain the low-gloss ceramic tile.
The ceramic tile prepared by the preparation process comprises an anti-reflection film layer, a transparent protective glaze layer, a pattern texture layer, a ground glaze layer and a ceramic tile body layer which are sequentially arranged from top to bottom. The antireflection film comprises an optical functional layer and a mechanical functional layer which are sequentially arranged from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 10 nanometers, the thickness of the film layer is 90 nanometers, the refractive index is 1.28, and the roughness is 3 nanometers.
The mechanical functional layer is a compact continuous film, the thickness of the film layer is 20 nanometers, and the refractive index is 1.43.
Example 2
A preparation process of a medium-gloss ceramic tile comprises the following steps:
s1, synthesizing a coating sol: mixing isopropanol, tetraethyl silicate, methyl triethoxysilane, hexadecyl trimethyl ammonium bromide, water and acetic acid according to a ratio of 50: 1: 0.1: 0.2: 4: 0.003 of the molar ratio, and stirring and reacting for 10 hours under the heating condition of 40 ℃ to obtain coating sol;
s2, applying the coating sol on the cleaned and dried high-gloss ceramic tile protective glaze layer by adopting a dipping-pulling method, heating to 700 ℃ to enable the transparent glaze polishing layer to be at the glass transition temperature, and annealing and shaping for 90min to obtain the medium-gloss ceramic tile.
The ceramic tile prepared by the preparation process comprises an anti-reflection film layer, a transparent protective glaze layer, a pattern texture layer, a ground glaze layer and a ceramic tile body layer which are sequentially arranged from top to bottom; the antireflection film comprises an optical functional layer and a mechanical functional layer which are sequentially arranged from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 2 nanometers, the thickness of the film layer is 100 nanometers, the refractive index is 1.30, and the roughness is 5 nanometers.
The mechanical functional layer is a compact continuous film, the thickness of the film layer is 45 nanometers, and the refractive index is 1.52.
Example 3
A preparation process of a medium-gloss ceramic tile comprises the following steps:
s1, synthesizing a coating sol: anhydrous ethanol, tetraethyl silicate, methyl triethoxysilane, a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, water and hydrochloric acid are mixed according to the weight ratio of 35: 1: 0.7: 0.03: 5: 0.004, stirring and reacting for 12 hours at the temperature of 20 ℃ to obtain coating sol;
s2, coating the coating sol on the transparent protective glaze layer by adopting a roller coating method, heating to 800 ℃ to enable the transparent polishing layer to be at the glass transition temperature for annealing and shaping, wherein the annealing time is 120min, and obtaining the ceramic tile with the middle gloss and the smooth surface.
The ceramic tile prepared by the preparation process comprises an anti-reflection film layer, a transparent protective glaze layer, a pattern texture layer, a ground glaze layer and a ceramic tile body layer which are sequentially arranged from top to bottom; the antireflection film comprises an optical functional layer and a mechanical functional layer which are sequentially arranged from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 26 nanometers, the thickness of the film layer is 70 nanometers, the refractive index is 1.4, and the roughness is 8 nanometers.
The mechanical functional layer is a compact continuous film, the thickness of the film layer is 60 nanometers, and the refractive index is 1.6.
Example 4
A preparation process of a low-gloss ceramic tile comprises the following steps:
s1, synthesizing a coating sol: anhydrous ethanol, tetraethyl silicate, methyltriethoxysilane, polyether F127 (average molecular weight 13000), water and hydrochloric acid were mixed in the following ratio of 56: 1: 1: 0.007: 4: 0.003 of the molar ratio, and stirring and reacting for 10 hours under the heating condition of 45 ℃ to obtain coating sol;
s2, coating the film coating sol on the transparent protective glaze layer of the washed and dried high-gloss ceramic tile by adopting a dipping-pulling method, heating to 720 ℃ to enable the transparent protective glaze layer to be at the glass transition temperature, and carrying out annealing and shaping for 60min to obtain the low-gloss ceramic tile.
The ceramic tile prepared by the preparation process comprises an anti-reflection film layer, a transparent protective glaze layer, a pattern texture layer, a ground glaze layer and a ceramic tile body layer which are sequentially arranged from top to bottom; the antireflection film comprises an optical functional layer and a mechanical functional layer which are sequentially arranged from top to bottom.
The optical function layer is a porous film layer, the aperture of the porous film is 15 nanometers, the thickness of the film layer is 100 nanometers, the refractive index is 1.35, and the roughness is 2 nanometers.
The mechanical functional layer is a compact continuous film, the thickness of the film layer is 40 nanometers, and the refractive index is 1.50.
Comparative example 1
The comparative example was conducted under the same conditions as in example 4 except that: the annealing temperature in this comparative example was 540 ℃. The glass transition temperature of the transparent protective glaze layer is not reached, and a mechanical functional layer is not formed, so that the glossiness of the ceramic tile is increased, and the wear resistance is reduced.
Comparative example 2
The comparative example was conducted under the same conditions as in example 4 except that: the annealing time is 5min, the annealing time in the comparative example is too short, the thickness of the formed mechanical functional layer is 5 nm, and the thickness does not meet the requirement of the mechanical functional layer, so that the glossiness of the ceramic tile is greatly improved, and the wear resistance is reduced.
Comparative example 3
The comparative example was conducted under the same conditions as in example 4 except that: in the comparative example, the molar ratio of the surfactant polyether F127 is only 0.001, and the addition amount of the surfactant polyether F127 is too low, so that the refractive index of the formed optical functional layer is 1.50, and the refractive index is too high, so that the glossiness of the ceramic tile is greatly improved, and the decorative effect is reduced.
Comparative example 4
The comparative example was conducted under the same conditions as in example 4 except that: in the comparative example, the thickness of the optical functional layer is 60nm, and the thickness of the optical functional layer is too low, so that the glossiness of the ceramic tile is greatly improved, and meanwhile, the decorative effect is reduced.
Comparative example 5
The comparative example was conducted under the same conditions as in example 4 except that: in the comparative example, the thickness of the optical functional layer is 150nm, and the thickness of the optical functional layer is too large, so that the glossiness of the ceramic tile is greatly improved, and meanwhile, the decorative effect is reduced.
It is known that both too thick and too thin optical functional layers can deteriorate the antireflection and reflection reducing effects.
Comparative example 6
The comparative example was conducted under the same conditions as in example 4 except that: in the comparative example, the addition molar ratio of the surfactant polyether F127 is 0.5, the content of the surfactant in the formula is too high, the refractive index of the optical functional layer is 1.15, namely, the refractive index of the optical functional layer is too low, so that the roughness and the glossiness are increased to different degrees, and the decorative effect and the wear resistance are reduced to some extent.
Comparative example 7
The comparative example was conducted under the same conditions as in example 4 except that: in the formula of the comparative example, polypropylene ethylene spheres (with the average particle size of 80 nanometers) are adopted to replace a surfactant polyether F127, the average pore size of an optical functional layer is 80 nanometers, the roughness and the glossiness are increased in different degrees, and the decorative effect and the wear resistance are reduced.
The examples 1 to 4 and the comparative examples 1 to 7 were subjected to the performance test, and the test results are shown in the following table:
table 1 table of performance test results
The decorative effect detection method comprises the following steps: the ceramic tile before being coated with the film is directly observed by human eyes, the observation results are divided into that no obvious difference is seen and that obvious difference is seen, the number of detection personnel is 20, if no obvious difference is seen above 18 bits in 20 observation personnel, the ceramic tile is marked as 'excellent', if no obvious difference is seen between 14 bits and 17 bits, the ceramic tile is marked as 'good', if no obvious difference is seen between 9 bits and 13 bits, the ceramic tile is marked as 'normal', and if no obvious difference is seen below 8 bits, the ceramic tile is marked as 'poor'.
According to the detection result, the surface roughness of the ceramic tile with medium and low gloss is small, the surface of the ceramic tile is smooth, the gloss can be kept within the range of 10-70 degrees, and meanwhile, the ceramic tile has excellent decoration effect and wear resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the content of the present specification or other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A preparation process of a ceramic tile with medium and low gloss is characterized by comprising the following steps:
s1, synthesizing a coating sol: mixing organic solvent, tetraethyl silicate, methyl triethoxysilane, surfactant, water and acid catalyst according to the weight ratio of (30-60): 1: (0.1-1): (0.003-0.3): (2-6): (0.002-0.004), stirring and reacting for 6-12 hours at 15-60 ℃ to obtain coating sol;
s2, applying the coating sol on the transparent protective glaze layer of the high-gloss ceramic tile, heating to the glass transition temperature of the transparent protective glaze layer, and annealing and shaping to obtain the ceramic tile with medium and low gloss.
2. The process for making a medium and low gloss ceramic tile according to claim 1, wherein said surfactant is one of cetyltrimethylammonium bromide or a non-ionic block copolymer.
3. The process for making a medium and low gloss ceramic tile according to claim 1, wherein said acid catalyst is at least one of hydrochloric acid or acetic acid.
4. The process for preparing medium and low gloss ceramic tiles according to claim 1, wherein in step S2, the temperature is raised to 600-800 ℃ to make the transparent protective glaze layer at the glass transition temperature for annealing and shaping, the annealing time is 10-120 min.
5. A ceramic tile, which is prepared by the process for preparing the ceramic tile with medium and low gloss as claimed in any one of claims 1-4, and comprises an anti-reflection film layer, a transparent protective glaze layer and a ceramic tile body layer which are arranged in sequence from top to bottom.
6. The ceramic tile of claim 5, wherein the antireflection film comprises an optical functional layer and a mechanical functional layer arranged from top to bottom.
7. The ceramic tile of claim 6, wherein the optically functional layer is a porous film having a pore size of 2-20 nm, a thickness of 80-140 nm, a refractive index of 1.20-1.40, and a roughness of 0.1-10 nm.
8. The ceramic tile according to claim 6, characterized in that the mechanical functional layer is a dense thin film with a thickness of 10-60 nm and a refractive index of 1.40-1.60.
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