WO2020177248A1 - 一种喷墨干粒装饰陶瓷砖及其制造方法 - Google Patents

一种喷墨干粒装饰陶瓷砖及其制造方法 Download PDF

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Publication number
WO2020177248A1
WO2020177248A1 PCT/CN2019/092696 CN2019092696W WO2020177248A1 WO 2020177248 A1 WO2020177248 A1 WO 2020177248A1 CN 2019092696 W CN2019092696 W CN 2019092696W WO 2020177248 A1 WO2020177248 A1 WO 2020177248A1
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Prior art keywords
dry
glaze
dry particle
parts
decoration
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PCT/CN2019/092696
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English (en)
French (fr)
Inventor
古战文
邓江文
刘学斌
沈荣伟
谭亮
王爱芳
Original Assignee
东莞市唯美陶瓷工业园有限公司
江西和美陶瓷有限公司
东莞市唯美装饰材料有限公司
重庆唯美陶瓷有限公司
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Application filed by 东莞市唯美陶瓷工业园有限公司, 江西和美陶瓷有限公司, 东莞市唯美装饰材料有限公司, 重庆唯美陶瓷有限公司 filed Critical 东莞市唯美陶瓷工业园有限公司
Priority to EP19918023.3A priority Critical patent/EP3901116B1/en
Publication of WO2020177248A1 publication Critical patent/WO2020177248A1/zh
Priority to US17/376,239 priority patent/US12030823B2/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C04B41/86—Glazes; Cold glazes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • 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
    • C04B41/0072—Heat treatment
    • 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
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
    • C04B41/4543—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension by spraying, e.g. by atomising
    • 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
    • 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
    • C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
    • C04B41/5307—Removal of physically bonded water, e.g. drying of hardened concrete
    • 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

Definitions

  • the invention relates to the technical field of ceramic tiles, in particular to an inkjet dry particle decorative ceramic tile and a manufacturing method thereof.
  • the current ceramic inkjet technology uses a combination of glue and dry particles to apply dry particles after inkjet. Glue is applied to the part where the dry particles need to be applied, and then the dry particles are applied to the surface of the tile. The dry particles that are not sticky by the glue are removed, and the dry particles that adhere to the glue are left. After firing, a ceramic tile with rich surface effects is produced.
  • the inkjet pattern decoration and sizing are integrated, and the glue is applied after the inkjet pattern.
  • the pattern is likely to be blurred;
  • the kiln When sucking away the dry particles that are not glued, the kiln is currently used to suck away the dry particles.
  • the fan inside the kiln rotates to form a negative pressure to suck away the dry particles that are not glued.
  • these dry particles are easy to stick to the wall and roof of the kiln.
  • the kiln When the kiln is suitable for the production of other types of layered products, it will cause defects such as burial, caverns, and pinholes on the right glazed surface of the product, and it takes manpower and material resources to remove Kiln wall and roof and dry grain;
  • the purpose of the present invention is to provide a method for manufacturing inkjet dry particle decorative ceramic tiles, which has simple operation steps, convenient control, high production efficiency, and low production cost.
  • Dry ink is used for spraying, which can be sprayed at the designated position on the surface of the body, so that the sprayed texture can accurately correspond to the pattern decoration texture, and the ceramic tile product can be made clear, distinct, and glaze gloss Low, good anti-skid effect, obvious dry grain, strong three-dimensional effect, rich color, stable physical and chemical properties, wide temperature adaptation range, and suitable for industrialized mass production.
  • Another object of the present invention is to provide an inkjet dry particle decorative ceramic tile, the dry particle decorative ceramic tile has clear patterns, distinct layers, obvious dry particle feeling, strong three-dimensional effect, and realizes the concave and convex mold surface on the flat body. Effect, low glaze gloss, good anti-skid effect, rich colors, stable physical and chemical properties, and suitable for industrialized mass production.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 40-60°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the present invention adopts the above steps to prepare dry particle decorative ceramic tiles.
  • the operation steps are simple and the control is convenient. It can reduce the process of glue spraying, spreading dry particles, absorbing dry particles and the layout of equipment in the production line, simplifying the process flow and improving production efficiency. , Reduce production difficulty and production cost, and can be suitable for industrialized mass production; and by spraying with dry ink, it can be sprayed on the designated position on the surface of the blank, so that the sprayed texture can accurately correspond to the pattern decoration texture. It can make the produced ceramic tile products have clear patterns, distinct layers, low glaze gloss, good anti-slip effect, obvious dry grain, strong three-dimensional effect, rich colors, stable physical and chemical properties, and a wide range of temperature adaptation.
  • the line texture decoration of the blank is performed by a robot digital cloth method, wherein the line texture of the blank and the texture of the subsequent pattern decoration may be consistent.
  • step A of the present invention by first decorating the green body with the base glaze, it can play the role of base and whitening the green body, so that the pattern lines are clearer during the subsequent inkjet treatment, and a stable green glaze bonding layer is formed with the green body , So that the spread of dry grains will form a clear sense of sand after firing, and the three-dimensional sense is strong.
  • the pattern decoration can improve the pattern decoration effect of the ceramic tile, so that the ceramic tile pattern is clear and layered, and the pattern texture of the pattern decoration can be consistent with the line texture of the green body; preferably, a wire mesh, Pattern decoration is carried out by means of rubber roller, inkjet printing, etc., and it is further preferred to use inkjet printing decoration. Install ink on the inkjet printing decoration equipment.
  • the color of the ink can be blue, red brown, black brown, orange, and spectrum.
  • the integrated ink volume of inkjet printing is less than 240PL, if the integrated ink volume of ink is 240PL
  • the product has a darker pattern and is prone to blurring of the pattern.
  • ink with a larger amount of ink is likely to cause separation of water and oil during subsequent spraying of protective glaze, which easily causes glaze avoidance and affects product quality.
  • the temperature of the blank is controlled at 40-60°C. At this time, the glaze of the blank does not have obvious water vapor volatilization, then the pattern decoration is carried out. If the glaze of the blank has obvious water vapor volatilization, then The phenomenon of sticking net, dripping ink, and pulling thread will occur during pattern decoration, which reduces the quality of the product.
  • the pattern-decorated body is dried for the first time, so that the ink can be fully dried and formed, and the subsequent spread of dry particles can prevent the undried and formed ink from causing fuzzy and chaotic pattern ink, so that The pattern is blurred, which reduces the clarity of the product's pattern.
  • the first drying adopts hot air drying or infrared wave drying, wherein the hot air drying can adopt preheating of a firing kiln or environmentally friendly natural gas as a heat source for drying, and the temperature is controlled to be 120-150°C.
  • the kiln used The length of the furnace is preferably 15-20 meters; the infrared wave drying method uses environmentally friendly natural gas, and the length of the equipment for infrared wave drying is preferably 8-15 meters.
  • the distance between the drying device and the pattern decoration device is more than 3 meters, so that the pattern ink fully adheres to the glaze bonding layer. If the distance between the two is less than 3 meters, the drying is performed too quickly, so that the ink is Its surface tension is self-clustered, which reduces the adhesion of the ink on the glaze surface, makes the pattern easy to be scraped off, and affects the quality of the product.
  • step D the dry particle ink is sprayed on the surface of the green body after the first drying, and the dry particles are spread on the surface of the green body by means of ink, which can make the dry particles evenly distributed on the surface of the green body and enhance the
  • the adhesion of the decorative surface of the pattern reduces the process of spraying glue and absorbing dry particles during the production process, and avoids that some dry particles adhered to the glue are blown off or absorbed during the kiln firing process, causing the dry particles to adhere to the kiln Wall or kiln roof, there are phenomena such as falling dirt, karst caves, pinholes, etc.; and can be spray-printed at the designated position on the surface of the green body, so that the spray-printed texture of the dry particles can accurately correspond to the decorative texture of the pattern, and the resulting ceramic Brick products have clear patterns, distinct layers, low glaze gloss, good anti-skid effect, obvious dry grain, strong three-dimensional effect, rich colors, and stable physical and chemical properties.
  • the second drying process can be performed to initially heat up and heat the body printed with the dry particle ink, so as to avoid the body printed with the dry particle ink in the subsequent firing process Cracking bricks and exploding billets are caused by rapid firing, which improves the quality stability of billets.
  • the second drying adopts hot-air drying or infrared wave drying, wherein the hot-air drying can use preheating of a firing kiln or environmentally friendly natural gas as a heat source for drying, and the temperature is controlled to be 120-150°C.
  • the kiln used The length of the furnace is preferably 15-20 meters; the infrared wave drying method uses environmentally friendly natural gas, and the length of the equipment for infrared wave drying is preferably 8-15 meters.
  • the chemical composition of the primer is:
  • the present invention uses the above-mentioned raw materials as the base glaze, and strictly controls the amount of each raw material, can make the prepared base glaze have better viscosity, hardness, mechanical strength and corrosion resistance, and reduce the glaze during the firing process.
  • the expansion coefficient makes the base glaze fully adhere and melt with the green body to form a stable green glaze bonding layer.
  • 18-23 parts of Al 2 O 3 is the intermediate oxide of the base glaze network.
  • it can usually capture free oxygen to form four coordinations to enter the silicon-oxygen network, strengthen the glass network structure, and improve the base glaze Hardness, mechanical strength and chemical resistance, reduce the expansion coefficient of the base glaze, and improve the vitrification ability, but too much Al 2 O 3 in the base glaze will significantly increase the refractory degree of the glaze and the glaze melt Viscosity, reduce the bonding stability of the glaze bonding layer;
  • 1.28-1.35 parts of CaO is a divalent network outer body oxide, which can enter and exit free oxygen at high temperatures, destroy the network structure, make the structure compact, increase the viscosity, and reduce the melting of the base glaze The viscosity of the body helps the melting of the base glaze, accelerates the solidification of the melt, reduces the expansion coefficient of the glaze, improves the surface hardness, chemical stability and mechanical strength of the glaze, and can promote a good combination with the body.
  • Li 2 O has a better fluxing effect.
  • Substituting lithium for sodium reduces the thermal expansion coefficient of the base glaze and improves the gloss, chemical stability and elasticity of the glaze;
  • 0.90 -1.0 part of ZnO can play a good fluxing effect in a large range, and can increase the gloss of the glaze, increase the whiteness of the glaze, reduce the expansion coefficient, increase the refractive index, promote opacification, and reduce the burning of the base glaze Shrinkage during the forming process, and reduce defects such as bald glaze and blistering due to shrinkage of the base glaze;
  • ZrO 2 can improve the whiteness and abrasion resistance of the glaze, and can increase the crack resistance and hardness of the glaze;
  • 4.80-4.90 parts of BaO can significantly improve the flux and refractive index of the base glaze, and increase the gloss of the glaze.
  • the temperature of the first drying is 120-150°C; in the step D, the inkjet volume of the dry particle ink is 2-3 kg/m 2 ; in the step D, the second The secondary drying temperature is 120-150°C.
  • the present invention can fully melt and combine the base glaze and the blank, improve the stability of the formed skin-glaze combination, avoid deglazing, blistering, etc., and make the spreading dry grain firing After the preparation, an obvious sense of sand is formed, and the three-dimensional effect is strong.
  • the volume expansion coefficient of the body after the base glaze decoration is 220-250/°C, and the whiteness is 0-75°.
  • the ink can be fully dried and formed, and the subsequent spreading of dry particles can avoid the phenomenon of fuzzy and chaotic pattern ink on the undried forming ink, making the pattern blurred. If the drying temperature is too low, the drying will be insufficient, which will easily cause the ink and the subsequent wetting agent to dissolve and penetrate each other, reducing the clarity of the pattern; if the drying temperature is too high, it will easily cause Drying too fast causes the pattern ink to form agglomerates due to its surface tension, which reduces the adhesion of the ink on the glaze surface, makes the pattern easy to be scraped off, and affects the quality of the product.
  • the dry particle ink By strictly controlling the inkjet volume of the dry particle ink, the dry particle ink can be evenly sprayed on the decorative surface of the body pattern, so that the printed texture and the pattern decorative texture accurately correspond, and the resulting ceramic tile product pattern can be clear and clear.
  • the level is clear; if the inkjet volume is too large, it is easy to cause the pattern and the spray texture of the dry particles to be blurred, which reduces the pattern definition of the product; if the inkjet volume is too small, the distribution of the dry particles is smaller, which reduces the blank
  • the dry grain feel and three-dimensional effect of the body reduce the three-dimensional effect of ceramic tiles.
  • the body printed with dry particle ink can be initially heated and heated to avoid the rapid firing of the body printed with dry particle ink in the subsequent firing process.
  • the phenomenon of cracked brick and exploded billet improves the quality stability of the billet. If the drying temperature is too high, it is easy to cause the dry ink to dry too fast, and cause cracking and cracking due to rapid firing; if the drying temperature is too low, the dry ink cannot be preheated and heated up. , It is easy to make the dry particle ink in the subsequent firing process easy to cause cracks and cracks due to rapid firing, which reduces the quality stability of ceramic tiles.
  • the protective glaze is sprayed by high-pressure spraying, the high-pressure spraying pressure of the protective glaze is 10-20 Bar, and the spraying amount of the protective glaze is 70-100 g/m 2 ; in the step F, firing The temperature of the system is 1180-1220°C, and the time is 60-80min.
  • the invention uses a high-pressure spray gun to spray protective glaze on the surface of the green body after spreading the dry particles, which can effectively protect the dry particles, improve the adhesion of the dry particles on the surface of the green body, and avoid the dry particles from being blown away or sucked away. Adhere to the kiln wall or kiln roof to avoid dirt, caves, pinholes, etc.
  • 4-6 high-pressure spray guns are used to spray the protective glaze to ensure the comprehensiveness and uniformity of spraying; further preferably, the spraying pressure of the high-pressure spray gun is 10-20 Bar, and the nozzle diameter of the high-pressure spray gun is 0.28-0.32 mm, the nozzle spray angle of the high-pressure spray gun is 90-120°.
  • the height between the nozzle of the high-pressure spray gun and the brick surface is at least 70cm to ensure the uniformity of spraying and avoid the high pressure to wash away the adhering dry particles. If the height of the nozzle and the brick surface is too small, the pressure sprayed by the nozzle is easy to rush Walking or blowing away the adhered dry particles will affect the three-dimensional feeling and quality of the product.
  • the crystal density of the protective glaze on the surface of the green body can be increased, the strength of the ceramic tile surface can be improved, scratches are not easily generated, and the dry particles can be melted and bonded to the green body. Improve the bonding stability of the green body and the dry particles, improve the quality of the product, and prevent the phenomenon of deglazing.
  • the dry particle ink includes the following raw materials by weight:
  • dry particle ink is prepared by using the above-mentioned kinds of raw materials.
  • the dry particles can be evenly distributed on the surface of the blank through the ink jet method, and the adhesion is high, and it is not easy to fall or fall off; among them, the dispersant improves the dry particles in the ink
  • the viscosity modifier increases the degree of binding between the dry particles and other raw materials in the ink system, so that the dry particles are evenly distributed on the surface of the body as the ink is sprayed; and the surface activity
  • the agent improves the adhesion of the dry particle ink on the surface of the blank, so that it stably adheres to the surface of the body, thereby improving the adhesion of the dry particle; while the solvent improves the dispersibility and solubility of the raw material, so that it spreads evenly on the body surface.
  • the dry particles can be selected according to the requirements of the ceramic tiles, high dry particles, medium dry particles or low temperature dry particles can be selected according to the temperature resistance performance, and transparent dry particles, red brown dry particles, and white goose dry particles can be selected according to the color effect. , Black dry particles, bright dry particles, etc., according to the actual needs of the hand feeling effect, the dry particles at different temperatures are matched, and different types of dry particles are selected for deployment according to the color of the product pattern.
  • each part of the dispersant includes 3-8 parts of polyethylene glycol, 10-12 parts of polyacrylamide and 2-5 parts of polyacrylate; each part of the viscosity modifier includes 20-30 parts of acrylic resin, 5-10 parts of polyethylene glycol methyl ether and 5-10 parts of ethanol; the surfactant is sodium lauryl sulfate, octylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, dodecyl trimethyl bromide At least one of ammonium hydroxide and ethoxylated fatty acid sorbitan ester.
  • the present invention can more effectively improve the dispersibility of the dry particles in the ink system, and ensure that the dry particles do not agglomerate before spraying.
  • polyethylene glycol has good water solubility and better compatibility with other raw materials, which can significantly Improve the dispersibility and solubility of the raw materials in the ink system;
  • the polyacrylamide and polyethylene glycol used in combination can prevent the granular dry particles from agglomerating, maintain the stability of the dispersion system, and prevent the dry particles from mixing After dispersion, layering occurs due to the effect of interfacial tension, which reduces the interfacial tension between liquid-liquid and solid-liquid in the ink system raw materials, and improves the dispersibility of the system;
  • the polyacrylate used can significantly disperse the dry particles evenly
  • the present invention maintains the viscosity of the dry particle ink at 500-800 cps by using the above-mentioned kinds of raw materials as the viscosity modifier, which can effectively adjust the fluidity of the dry particle ink, so that the dry particle ink can be evenly sprayed on the surface of the body. , It has excellent bonding with the green body and improves the adhesion of the dry particle layer.
  • the present invention can effectively improve the emulsification, solubilization, dispersibility, wettability and other properties of the dry particle ink system by using anionic and non-ionic surfactants, so that the raw materials of the dry particle ink can be fully dispersed , Emulsify, and adhere to the surface of the green body stably and uniformly to improve the adhesion of the dry particle layer; among them, sodium lauryl sulfate, octylphenol polyoxyethylene ether, and fatty acid polyoxyethylene ester are better.
  • the performance of emulsification, solubilization, wetting, dispersion, etc., and low irritation, easy to degrade; the ethoxylated fatty acid sorbitan ester can significantly improve the hydrophilicity and binding properties of the ink, and promote the stability of the dry ink Adhere to the surface of the green body to improve the adhesion of the dry particle layer on the green body.
  • each part of the auxiliary material includes 0.5-1.5 parts of pH adjuster, 1-2 parts of drier and 0.5-1.0 parts of preservative;
  • the pH adjuster is at least one of trimethylamine, triethanolamine and ammonia
  • the drier is a mixture composed of ethanol and isopropanol in a weight ratio of 1:3-4;
  • the preservative is 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane
  • each of the solvents is ethylene glycol butyl ether acetate, two A mixture of propylene glycol dimethyl ether and propylene glycol methyl ether in a weight ratio of 3-4:1:1.5-2.5.
  • the present invention can accurately adjust the pH value of the dry particle ink to present a weak alkaline system, promote the dispersibility and mutual solubility of various materials, and promote the uniform dispersion and attachment of the dry particle ink on the surface of the blank.
  • the solubility is high and the solubility is good.
  • the dispersibility of the dry particles is improved to make them uniformly dispersed on the surface of the body. , And good volatility.
  • the second drying process after spraying the dry ink, it can promote the volatilization and drying of the solvent of the ink, and can initially heat the dry particles and the body to make part of the solvent evaporate.
  • the firing and bonding are stabilized to avoid the presence of air bubbles in the dry particle layer caused by incomplete volatilization of some solvents, resulting in low adhesion, easy shedding, and low hardness of the dry particle layer.
  • the present invention can improve the anti-corrosion properties of the dry particle ink, and can improve the antibacterial and anti-mildew performance of the dry particle ink, and avoid the corrosion by mold or the environmental factors such as oxygen, heat, light, and chemical erosion. It will cause damage or damage, and then cause discoloration, perforation, peeling, loss of adhesion and other appearance and mechanical properties of the dry particle layer; among them, 2,2'-dihydroxy-5,5'-dichlorodi Phenylmethane and 2-hydroxybiphenyl can be effective by inhibiting microbial cell walls and intracellular enzymes.
  • the present invention can improve the solubility and mixing and dispersibility of the raw materials by using the above-mentioned kinds of raw materials as solvents, and improve the stability of the dry particle ink system, so that the viscosity and surface tension of the system are not easily changed by temperature changes.
  • the dry particles are uniformly dispersed on the surface of the green body, and have high volatility, and are easy to volatilize after drying and firing, thereby forming a dry particle layer of the green body with stable adhesion.
  • the protective glaze is a matt transparent protective glaze
  • the matt transparent protective glaze includes the following raw materials in parts by weight:
  • the present invention uses the above-mentioned raw materials as protective glaze and strictly controls the amount of each raw material to ensure that the dry particles are not blown off or sucked off during the kiln firing process, protect the dry particles, and improve the dry particles on the surface of the green body.
  • the adhesiveness of the dry particles prevents the dry particles from adhering to the wall or roof of the kiln due to the absorption of dry particles, thereby preventing the product from falling dirty, karst caves, pinholes, etc.; and the protective glaze is matte and transparent, which will not affect the performance of the body
  • the pattern effect after pattern decoration has high definition, and can improve the wear resistance of the ceramic tile surface, reduce its gloss, and have a matte frosting effect; preferably, the processing fineness of the protective glaze is controlled to a 325 mesh screen The remainder is 0.3-0.5%, the specific gravity is 1.30 ⁇ 0.01, and the gloss of the product formed after spraying protective glaze and firing is 5-8.
  • the chemical composition of the frit is:
  • the invention can reduce the glaze expansion coefficient of the protective glaze during the firing process by using the above-mentioned raw materials as the frit, and can discharge carbon dioxide in advance during the firing process, so as not to affect the flatness of the protective glaze and improve the ceramic tile Three-dimensional effect.
  • a dry particle decorative ceramic tile prepared by the method for manufacturing inkjet dry particle decorative ceramic tiles as described above, and the dry particle decorative ceramic tiles include The body layer, the underglaze layer, the pattern layer, the dry particle ink layer and the protective glaze layer, the underglaze layer has a thickness of 0.05-0.2mm, the pattern layer has a thickness of 0.05-0.1mm, and the dry particle layer
  • the thickness of the protective glaze layer is 0.5-1 mm, and the thickness of the protective glaze layer is 0.02-0.03 mm.
  • the dry particle decorative ceramic tiles of the present invention are made by the above steps (bottom glaze decoration-pattern decoration-first drying-spraying dry ink-second drying-spraying protective glaze-firing). Print at a designated location, so that the printed texture can accurately correspond to the decorative texture of the pattern.
  • the dry-grain decorative ceramic tiles produced have clear patterns, distinct layers, obvious dry-grain feeling and strong three-dimensional feeling, and achieve unevenness on the flat body Mold surface effect, low glaze gloss, good anti-slip effect, rich color, stable physical and chemical properties, and suitable for industrialized mass production.
  • the method for manufacturing dry particle decorative ceramic tiles of the present invention has simple operation steps and convenient control, can reduce the production line of glue spraying, spreading dry particles, absorbing dry particles and other processes and the layout of equipment, simplifying the process flow, improving production efficiency, and reducing
  • the production difficulty and production cost are suitable for industrialized mass production; by spraying with dry ink, it can be sprayed on the designated position on the surface of the blank, so that the sprayed texture can accurately correspond to the pattern decoration texture, and the dry particle size can be improved.
  • the uniformity of distribution and adhesion on the surface of the green body can make the produced ceramic tile products have clear patterns, distinct layers, low glaze gloss, good anti-slip effect, obvious dry grain, strong three-dimensional impression, rich color, and physical and chemical properties Stable, wide temperature adaptation range.
  • the dry particle decorative ceramic tile of the present invention has clear patterns, distinct layers, obvious dry particle feeling, strong three-dimensional effect, realizes the effect of concave and convex mold surface on the flat body, low glaze gloss, good anti-skid effect, rich color, and physicalization It has stable performance and can be applied to industrialized mass production.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 40°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 120°C; in the step D, the inkjet volume of the dry particle ink is 2kg/m 2 ; in the step D, the temperature of the second drying is 120°C.
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 10 Bar
  • the spraying amount of the protective glaze is 70 g/m 2
  • the firing temperature is 1180°C
  • the time is 80min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 3 parts of polyethylene glycol, 10 parts of polyacrylamide and 2 parts of polyacrylate; each part of the said viscosity modifier includes 20 parts of acrylic resin, 5 parts of polyethylene glycol methyl ether and 5 parts Ethanol;
  • the surfactant is sodium lauryl sulfate.
  • Each part of the auxiliary material includes 0.5 part of pH adjuster, 1 part of drier and 0.5 part of preservative; said pH adjuster is trimethylamine; said drier is made of ethanol and isopropanol in a weight ratio of 1: 3 composition; the preservative is sodium o-phenylphenol; each of the solvents is ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether and propylene glycol methyl ether in a weight ratio of 3:1:1.5 mixture.
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm
  • the thickness of the protective glaze layer It It is 0.02-0.03mm.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 45°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 130°C; in the step D, the inkjet volume of the dry particle ink is 2.2 kg/m 2 ; in the step D, the temperature of the second drying is 128 °C.
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 12 Bar
  • the spraying amount of the protective glaze is 80 g/m 2
  • the firing temperature is 1190°C
  • the time is 65min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 4 parts of polyethylene glycol, 10.5 parts of polyacrylamide and 3 parts of polyacrylate; each part of the said viscosity modifier includes 22 parts of acrylic resin, 6 parts of polyethylene glycol methyl ether and 6 parts Ethanol;
  • the surfactant is octylphenol polyoxyethylene ether.
  • Each part of the auxiliary material includes 0.8 parts of pH regulator, 1.2 parts of drier and 0.6 parts of preservative;
  • the pH regulator is trimethylamine;
  • the drier is made of ethanol and isopropanol in a weight ratio of 1: 3.2
  • the preservative is chloroacetamide;
  • each of the solvents is a mixture of ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether and propylene glycol methyl ether in a weight ratio of 3.2:1:1.8 .
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm
  • the thickness of the protective glaze layer It It is 0.02-0.03mm.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 50°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 135°C; in the step D, the inkjet volume of the dry particle ink is 2.5kg/m 2 ; in the step D, the temperature of the second drying is 135 °C.
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 15 Bar
  • the spraying amount of the protective glaze is 85 g/m 2
  • the firing temperature is 1200°C
  • the time is 70min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 5 parts of polyethylene glycol, 11 parts of polyacrylamide and 3.5 parts of polyacrylate; each part of the said viscosity modifier includes 25 parts of acrylic resin, 8 parts of polyethylene glycol methyl ether and 8 parts Ethanol;
  • the surfactant is fatty acid polyoxyethylene ester.
  • Each part of the auxiliary material includes 1.0 part of pH adjuster, 1.5 parts of drier and 0.8 part of preservative; said pH adjuster is triethanolamine; said drier is made of ethanol and isopropanol in a weight ratio of 1: 3.5
  • the composition of the mixture; the preservative is 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane; each of the solvents is ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether And propylene glycol methyl ether at a weight ratio of 3.5:1:2.0.
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm
  • the thickness of the protective glaze layer It It is 0.02-0.03mm.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 55°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 140°C; in the step D, the inkjet volume of the dry particle ink is 2.8 kg/m 2 ; in the step D, the temperature of the second drying is 132 °C.
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 18 Bar
  • the spraying amount of the protective glaze is 90 g/m 2
  • the firing temperature is 1210°C
  • the time is 65min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 7 parts of polyethylene glycol, 11.5 parts of polyacrylamide and 4 parts of polyacrylate; each part of the said viscosity modifier includes 28 parts of acrylic resin, 9 parts of polyethylene glycol methyl ether and 9 parts of Ethanol;
  • the surfactant is dodecyl trimethylammonium bromide.
  • Each part of the auxiliary material includes 1.3 parts of pH regulator, 1.8 parts of drier and 0.8 parts of preservative;
  • the pH regulator is triethanolamine;
  • the drier is made of ethanol and isopropanol in a weight ratio of 1: 3.8 composition;
  • the preservative is 2-hydroxybiphenyl;
  • each of the solvents is ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether and propylene glycol methyl ether in a weight ratio of 3.8:1:2.3 mixture.
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm
  • the thickness of the protective glaze layer It It is 0.02-0.03mm.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 60°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • Spray protective glaze spray protective glaze on the surface of the body after the second drying in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 150°C; in the step D, the inkjet volume of the dry particle ink is 3kg/m 2 ; in the step D, the temperature of the second drying is 150°C .
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 20 Bar
  • the spraying amount of the protective glaze is 100 g/m 2
  • the firing temperature is 1220°C
  • the time is 60min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersing agent includes 8 parts of polyethylene glycol, 12 parts of polyacrylamide and 5 parts of polyacrylate; each part of the viscosity modifier includes 30 parts of acrylic resin, 10 parts of polyethylene glycol methyl ether and 10 parts Ethanol;
  • the surfactant is ethoxylated fatty acid sorbitan ester.
  • Each part of the auxiliary material includes 1.5 parts of pH adjuster, 2 parts of drier and 1.0 part of preservative; the pH adjuster is ammonia; the drier is made of ethanol and isopropanol in a weight ratio of 1:4
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm
  • the thickness of the protective glaze layer It It is 0.02-0.03mm.
  • a method for manufacturing dry grain decorative ceramic tiles including the following steps:
  • Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 50°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B First drying: drying the body after the pattern decoration in step B;
  • Spray glue spray glue on the surface of the body after the first drying in step C;
  • step D Dry particle decoration: Sprinkle dry particles on the surface of the body after spraying glue in step D, perform dry particle decoration, and then perform a second drying;
  • Firing firing the green body after the second drying in step E to obtain dry-grain decorative ceramic tiles.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the first drying temperature is 135°C; in the step F, the firing temperature is 1200°C, and the time is 70 min.
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 50°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying for the first time: Dry the body after pattern decoration in step B for the first time;
  • Dry particle decoration spray dry particle ink on the surface of the body after the first drying in step C, perform dry particle decoration, and then perform the second drying;
  • step E Firing: firing the green body after the second drying in step D to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 135°C; in the step D, the inkjet volume of the dry particle ink is 2.5kg/m 2 ; in the step D, the temperature of the second drying is 135 °C.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 5 parts of polyethylene glycol, 11 parts of polyacrylamide and 3.5 parts of polyacrylate; each part of the said viscosity modifier includes 25 parts of acrylic resin, 8 parts of polyethylene glycol methyl ether and 8 parts Ethanol;
  • the surfactant is fatty acid polyoxyethylene ester.
  • Each part of the auxiliary material includes 1.0 part of pH adjuster, 1.5 parts of drier and 0.8 part of preservative; said pH adjuster is triethanolamine; said drier is made of ethanol and isopropanol in a weight ratio of 1: 3.5
  • the composition of the mixture; the preservative is 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane; each of the solvents is ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether And propylene glycol methyl ether at a weight ratio of 3.5:1:2.0.
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer and a dry particle ink sequentially arranged from bottom to top
  • the thickness of the underglaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.5-1mm.
  • Comparative Example 3 On the basis of Example 3, dry particles are dried only once before decoration, and dry particles are not dried after decoration
  • a method for manufacturing inkjet dry particle decorative ceramic tiles including the following steps:
  • A. Bottom glaze decoration decorate the bottom glaze on the surface of the body
  • Pattern decoration control the temperature of the body after the bottom glaze decoration in step A at 50°C, and then perform pattern decoration on the bottom glaze surface of the body;
  • step B Drying: drying the body after pattern decoration in step B;
  • Dry particle decoration spray dry particle ink on the surface of the dried body in step C for dry particle decoration;
  • Spray protective glaze spray protective glaze on the surface of the green body after the dry particle decoration in step D;
  • Firing firing the green body after spraying the protective glaze in step E to prepare dry grain decorative ceramic tiles with three-dimensional effects.
  • the green body is decorated with line texture by the digital cloth method of the manipulator.
  • the chemical composition of the primer is:
  • the temperature of the first drying is 135° C.; in the step D, the ink jet volume of the dry particle ink is 2.5 kg/m 2 .
  • the high-pressure spraying method is used for spraying the protective glaze
  • the high-pressure spraying pressure of the protective glaze is 15 Bar
  • the spraying amount of the protective glaze is 85 g/m 2
  • the firing temperature is 1200°C
  • the time is 70min.
  • the dry particle ink includes the following raw materials by weight:
  • Each part of the dispersant includes 5 parts of polyethylene glycol, 11 parts of polyacrylamide and 3.5 parts of polyacrylate; each part of the said viscosity modifier includes 25 parts of acrylic resin, 8 parts of polyethylene glycol methyl ether and 8 parts Ethanol;
  • the surfactant is fatty acid polyoxyethylene ester.
  • Each part of the auxiliary material includes 1.0 part of pH adjuster, 1.5 parts of drier and 0.8 part of preservative; said pH adjuster is triethanolamine; said drier is made of ethanol and isopropanol in a weight ratio of 1: 3.5
  • the composition of the mixture; the preservative is 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane; each of the solvents is ethylene glycol butyl ether acetate, dipropylene glycol dimethyl ether And propylene glycol methyl ether at a weight ratio of 3.5:1:2.0.
  • the protective glaze is a matte transparent protective glaze
  • the matte transparent protective glaze includes the following raw materials by weight:
  • the chemical composition of the frit is:
  • a dry particle decorative ceramic tile prepared by the above-mentioned inkjet dry particle decorative ceramic tile manufacturing method.
  • the dry particle decorative ceramic tile includes a body layer, a base glaze layer, a pattern layer, and a dry particle ink arranged in sequence from bottom to top
  • the thickness of the base glaze layer is 0.05-0.2mm
  • the thickness of the pattern layer is 0.05-0.1mm
  • the thickness of the dry particle layer is 0.2-0.5mm
  • the thickness of the protective glaze layer The thickness is 0.02-0.03mm.
  • Comparative Example 4 Commercially available conventional protective glaze used for protective glaze
  • step E a commercially available conventional protective glaze is used as the protective glaze.
  • Example 1 >7 level 4 8° Level 0
  • Example 2 >7 Level 5 7° Level 0
  • Example 3 >7 Level 5 5° Level 0
  • Example 4 >7 level 4 6° Level 0
  • Example 5 >7 level 4 8° Level 0 Comparative example 1
  • 6.0 level 2 11° level 2 Comparative example 2 6.0 Level 3 12° Level 1 Comparative example 3 5.0 level 2 8° Level 1 Comparative example 4 6.0 Level 3 10° Level 1
  • the wear resistance grade is tested using the GB/T 3810.7-2016 test method standard to observe the degree of surface wear traces of the sample after grinding at a specific grinding speed, and it is divided into 0-5 grades.
  • the specific grades are as follows :
  • the adhesion grade of the dry particle layer is tested according to the GB/T9286-98 cross-cut test method standard, and the dry particle layer shedding of the test sample is observed, and it is divided into 0-5 grades.
  • the specific grades are as follows:
  • the ceramic tile product made by the present invention has clear patterns, distinct layers, low glaze gloss, good anti-slip effect, obvious dry grain feeling, strong three-dimensional effect, rich color, high hardness, and high dry grain adhesion. , Stable physical and chemical properties.
  • Comparative Example 1 the common dry particle spreading process on the market was used to spread the dry particles directly after coating the glue on the blank, instead of the dry particle ink used in the present invention to prepare the dry particle layer.
  • the ceramic tiles have lower surface wear resistance, with a wear resistance grade of 2, the adhesion of dry particles is lower, and the adhesion of the dry particle layer is grade 2.
  • the gloss is slightly higher (11°), the slip resistance and dry grain feel are lower, and the hardness is slightly lower (level 6); it shows that the present invention can spray on the surface of the ceramic tile by using dry ink to spray.
  • the ink is fully dried and formed to prevent the subsequent spread of dry particles from causing blurry and chaotic pattern ink to the undried ink, and to improve the accuracy and adhesion of the dry particle ink on the surface of the pattern decoration layer.
  • the second drying process is carried out after the ink particles, which can initially heat up and heat the body printed with dry particle ink, avoiding the rapid firing of the body printed with dry particle ink in the subsequent firing process
  • the phenomenon of cracking and exploding bricks improves the adhesion and hardness of the dry grain layer, so that the ceramic brick body and the dry grains form a stable brick-grain-glaze bonding layer, which has obvious sand feeling and strong three-dimensional feeling ,
  • the pattern is clear, the color is rich, the hardness is high, the adhesion of the dry particle layer is high, it is not easy to fall off, the surface wear resistance is high, the gloss is low, and the anti-slip effect is good.
  • Example 2 compared with Example 3, the protective glaze is not sprayed at the end of the process, and the ceramic tiles produced have lower surface wear resistance, with a wear resistance grade of level 3 and lower dry particle adhesion (Level 1), high gloss (12°), low slip resistance and dry grain feel, and slightly lower hardness (6.0); it shows that the present invention sprays protective glaze on the surface of the green body after spreading dry particles , And strictly control the spraying pressure and spraying amount of the protective glaze, which can effectively protect the dry particles, improve the adhesion of the dry particles on the surface of the green body, and prevent the dry particles from being blown away or sucked away and causing the dry particles to adhere to the kiln wall Or the roof of the kiln, so as to prevent the product from falling dirt, karst caves, pinholes, etc., so that the prepared ceramic tile body and the dry particles form a stable green-glue-grain-glaze bonding layer, which has obvious sand grain and strong three-dimensional feeling.
  • the pattern is clear, the color
  • Comparative Example 3 compared with Example 3, in the process, only one drying was performed before the dry ink was sprayed, and the second drying was not performed after the dry ink was sprayed.
  • the surface of the ceramic tiles produced had low wear resistance and abrasion resistance.
  • the performance level is 2, the adhesion of the dry particles is low (level 1), the gloss is high (8°), the slip resistance and dry particle feel are low, and the hardness is slightly lower (5.0); indicating the present invention
  • the phenomenon of cracking bricks and frying blanks caused by rapid firing improves the adhesion and hardness of the dry particle layer, so that the ceramic tile body and the dry particles form a stable blank-grain-glaze bonding layer, with a sandy feeling Obvious, strong three-dimensional effect, clear pattern, rich color, high hardness, high adhesion of the dry particle layer, not easy to fall off, high surface abrasion resistance, low gloss, and good anti-slip effect.
  • the protective glaze used in the process adopts a commercially available conventional protective glaze instead of the protective glaze raw material formula of the present invention.
  • the ceramic tiles produced have lower surface wear resistance and wear resistance.
  • the performance level is 3, the adhesion of the dry particles is low (level 1), the gloss is high (10°), the slip resistance and dry particle feel are low, and the hardness is slightly lower (6.0);
  • the invented protective glaze can protect the dry particles, ensure that the dry particles are not blown off or sucked off during the kiln firing process, improve the adhesion of the dry particles on the surface of the green body, and avoid the dry particles from being sucked away and causing the dry particles to stick.

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Abstract

一种喷墨干粒装饰陶瓷砖及其制造方法，包括如下步骤：A、底釉装饰；B、图案装饰；C、第一次干燥；D、干粒装饰；E、喷涂保护釉；F、烧制。通过采用干粒墨水进行喷洒，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，提高干粒在坯体表面的分布均匀性和附着力，能使制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，物化性能稳定，温度适应范围广。

Description

一种喷墨干粒装饰陶瓷砖及其制造方法 技术领域
本发明涉及陶瓷砖技术领域，具体涉及一种喷墨干粒装饰陶瓷砖及其制造方法。
 背景技术
随着人们的生活水平日渐提高，在装饰、装修材料的选择上，对瓷砖的质量和美观的要求显著提高；同时随着社会的发展和科技的进步，陶瓷喷墨技术在陶瓷领域中的应用日益增加，使得市面上的陶瓷砖的表面效果越来越丰富。
而目前的陶瓷喷墨技术，是在喷墨后，采用胶水和干粒相结合的施加干粒方式，在需要施加干粒的部分涂上胶水，然后将干粒施加在瓷砖表面上，并将没有被胶水粘黏的干粒去除，剩下与胶水粘附的干粒，经烧成后制得表面效果丰富的陶瓷砖。
但目前的喷墨、施胶和施干粒等工艺中，仍存在较多的缺陷，使得陶瓷砖的表面立体效果不明显，生产效率低等问题：
（1）喷墨图案装饰和施胶为一体式，在喷墨图案后便进行施胶，当产品的颜色比较深、图案装饰需要喷墨墨量较大时，容易出现图案模糊不清；
（2）喷墨图案、施胶和干粒布料一体式，干粒布料下料时产生大量的粉尘，会影响喷墨设备的喷头正常工作，甚至会堵塞或损坏喷头，降低生产设备的使用寿命；
（3）吸走未被胶水粘黏的干粒时，目前有利用窑炉进行干粒的吸走，通过在窑炉内部的风机转动形成负压，吸走未被胶水粘黏的干粒，但这些干粒容易粘贴于窑墙和窑顶，当窑炉适用于其他类型层产品的生产时，会使得产品右釉面出现落葬、溶洞、针孔等缺陷，并需要花费人力物力去清除窑墙和窑顶和干粒；
（4）当粘上干粒后的坯体在窑炉里烧成时，胶水还没有完全挥发固化，釉和干粒还未开始熔融产生融体，坯面上的干粒被窑炉内的风机吹走或吸走，大大降低了产品釉面上的干粒量，甚至使得釉面上没有干粒，使得陶瓷砖成品的表面立体效果不明显，同时窑炉也会产生落脏现象，降低了陶瓷砖成品的质量。
 技术问题
为了克服现有技术中存在的缺点和不足，本发明的目的在于提供一种喷墨干粒装饰陶瓷砖的制造方法，该制造方法操作步骤简单，控制方便，生产效率高，生产成本低，通过采用干粒墨水进行喷洒，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，能使制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，物化性能稳定，温度适应范围广，可适用于工业化大规模生产。
本发明的另一目的在于提供一种喷墨干粒装饰陶瓷砖，该干粒装饰陶瓷砖图案清晰、层次分明，干粒感明显，立体感强，在平面坯体上实现了凹凸模面的效果，釉面光泽度低，防滑效果佳，色彩丰富，物化性能稳定，可适用于工业化大规模生产。
 技术解决方案
本发明的目的通过下述技术方案实现：一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在40-60℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
本发明通过采用上述步骤制备干粒装饰陶瓷砖，操作步骤简单，控制方便，能减少生产线的喷胶水、铺撒干粒、吸干粒等工序及其设备的布局，简化工艺流程，提高生产效率，降低生产难度和生产成本，可适用于工业化大规模生产；且通过采用干粒墨水进行喷洒，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，能使制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，物化性能稳定，温度适应范围广。
优选的，在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰，其中，坯体的线条纹理与后续的图案装饰的纹理可以为一致的。
本发明步骤A通过先对坯体进行底釉装饰，能对坯体起到打底增白的作用，使得后续进行喷墨处理时图案纹路更为清晰，与坯体形成稳定的坯釉结合层，使得铺撒干粒烧制后形成明显的沙粒感，立体感强。
步骤B进行图案装饰，能提高陶瓷砖的图案装饰效果，使制得的陶瓷砖图案清晰、层次分明，且图案装饰的图案纹理可以与坯体的线条纹理相一致；优选的，采用丝网、胶辊、喷墨打印等方式进行图案装饰，进一步优选的，采用喷墨打印装饰的，在喷墨打印装饰设备上安装墨水，墨水的颜色可以为蓝色、红棕、黑棕、橘黄、谱黄、柠檬黄、大红、深金黄、黑色、亮光、白色等，根据实际的装饰图案进行喷墨打印；另外，优选的，喷墨打印的墨水综合墨量小于240PL，若墨水综合墨量在240PL以上时，产品图案较深，容易出现图案模糊不清的现象，同时墨量较大的墨水容易在后续喷涂保护釉时产生水油分离的现象，容易产生避釉的现象，影响产品的质量。而在图案装饰时，坯体的温度控制在40-60℃，此时坯体的釉面没有明显的水蒸汽挥发，则进行图案装饰，若坯体的釉面有明显的水蒸汽挥发，则会在图案装饰时出现粘网、滴墨、拉线等现象，降低了产品的质量。
其后，步骤C先对图案装饰后的坯体进行第一次干燥，能使油墨充分干燥成型，避免后续铺撒的干粒对未干燥成型的油墨造成模糊、混乱的图案墨水的现象，使得图案模糊不清，降低了产品的图案清晰度。优选的，所述第一次干燥采用热风干燥或红外线波光干燥方式，其中的热风干燥可采用烧成窑的预热或环保天然气作为热源进行干燥，并控制温度为120-150℃，使用的窑炉长度优选为15-20米；而红外线波光干燥方式则采用环保天然气，进行红外线波光干燥的设备长度优选为8-15米。优选的，上述干燥设备与图案装饰设备之间的距离在3米以上，使得图案墨水充分附着于坯釉结合层，若两者之间的距离小于3米，则过快进行干燥，使得油墨由于其表面张力而自成团，降低了油墨在釉面上的附着力，使得图案易于涂刮掉落，影响产品的质量。
步骤D中，在第一次干燥后的坯体面采用干粒墨水进行喷洒，通过油墨的方式将干粒铺撒于坯体表面，能使干粒在坯体表面分布均匀，增强了在坯体图案装饰面的附着力，减少生产过程中喷涂胶水、吸干粒等工序，避免部分粘附有胶水的干粒在窑炉烧制过程中被吹掉或吸掉，造成干粒粘附于窑墙或窑顶，出现落脏、溶洞、针孔等现象；并能在坯体表面的指定位置进行喷印，使干粒的喷印纹理可与图案装饰纹理精准对应，能使制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，物化性能稳定。
而在喷印干粒墨水后，再进行第二次干燥处理，能对喷印有干粒墨水的坯体进行初步升温加热，避免喷印有干粒墨水的坯体在后续的烧制过程中因快速烧制而产生裂砖、炸坯的现象，提高了坯体的质量稳定性。优选的，所述第二次干燥采用热风干燥或红外线波光干燥方式，其中的热风干燥可采用烧成窑的预热或环保天然气作为热源进行干燥，并控制温度为120-150℃，使用的窑炉长度优选为15-20米；而红外线波光干燥方式则采用环保天然气，进行红外线波光干燥的设备长度优选为8-15米。
优选的，所述步骤A中，所述底釉的化学组份为：
SiO 2   65-67% Al 2O 3   17-23% Fe 2O 3   0.10-0.15% CaO 1.28-1.35%
MgO 0.6-0.7% K 2O 2.0-2.8% Na 2O 3.18-3.25% TiO 2   0.08-0.12%
ZrO 2   0-2.17% BaO 4.80-4.90% ZnO 0.90-1.0%。  
本发明通过采用上述原料作为底釉，并严格控制各原料的用量，能使制得的底釉具有较佳的粘度、硬度、机械强度和耐腐蚀性，并降低底釉在烧成过程中的膨胀系数，使得底釉与坯体充分附着、熔融，形成稳定的坯釉结合层。
其中，18-23份的Al 2O 3为底釉网络中间体氧化物，在釉熔融过程中，通常能夺取游离氧形成四配位而进入硅氧网络，加强玻璃网络结构，提高底釉的硬度、机械强度和耐化学侵蚀能力，降低底釉的膨胀系数，提高玻璃化能力，但Al 2O 3在底釉中的含量过多则会明显增大釉的难熔程度和釉熔体的粘度，降低坯釉结合层的结合稳定性；1.28-1.35份的CaO是二价网络外体氧化物，能在高温下入出游离氧，破坏网络结构，使结构紧密、黏度增加，降低底釉熔体的粘度，有助于底釉的熔融，加速熔体的固化，降低釉的膨胀系数，提高釉面硬度、化学稳定性和机械强度，并能促进与坯体的良好结合，若CaO的用量过多，则会提高底釉的耐火度，在烧成底釉过程中析出微小晶粒，降低底釉失透；0.6-0.7份的MgO是二价网络外体氧化物，高温下提供游离氧，增加底釉的流动性，使其易于涂覆于坯体上，增加与坯体的结合性，并能增大助熔范围，降低釉的膨胀系数，促进坯釉结合层的形成，减弱底釉的发裂倾向，改善缩釉现象，提高釉面的白度；K 2O、Na 2O和Li 2O均为底釉网络外体氧化物，在釉熔融过程中，都具有极强的“断网”作用，能显著降低釉在熔融温度和粘度，Li 2O的助熔作用较佳，用锂置换钠则降低底釉的热膨胀系数，提高釉的光泽度、化学稳定性和弹性；0.90-1.0份的ZnO能在较大范围内起到良好的助熔作用，并可增加釉的光泽，提高釉面白度，降低膨胀系数，提高折射率，促进乳浊，并能减少底釉在烧成过程中的收缩，并减少因底釉收缩而出现的秃釉、起泡等缺陷；ZrO 2能提高釉面白度和耐磨性，而且能增大抗釉面龟裂性和釉面硬度；4.80-4.90份的BaO能显著提高底釉的助熔性和折射率，增加釉面光泽。
优选的，所述步骤C中，第一次干燥的温度为120-150℃；所述步骤D中，干粒墨水的喷墨量为2-3kg/m 2；所述步骤D中，第二次干燥的温度为120-150℃。
本发明通过对坯体进行底釉装饰，能使底釉与坯体充分熔融、结合，提高形成的皮釉结合体的稳定性，避免出现脱釉、起泡等现象，使得铺撒干粒烧制后形成明显的沙粒感，立体感强，优选的，底釉装饰后的坯体体积膨胀系数为220-250/℃，白度为0-75°。
而通过严格控制图案装饰后坯体的第一次干燥温度，能使油墨充分干燥成型，避免后续铺撒的干粒对未干燥成型的油墨造成模糊、混乱的图案墨水的现象，使得图案模糊不清，降低了产品的图案清晰度；若干燥温度过低，则干燥不充分，容易使得油墨与后续的润湿剂相互溶渗透，降低了图案的清晰度；若干燥温度过高，则容易使得干燥过快，使得图案油墨由于其表面张力而自成团，降低了油墨在釉面上的附着力，使得图案易于涂刮掉落，影响产品的质量。
而通过严格控制干粒墨水的喷墨量，能将干粒墨水均匀地喷涂于坯体图案装饰表面，使得喷印的纹理与图案装饰纹理精准对应，能使制得的陶瓷砖产品图案清晰、层次分明；若喷墨量过大，容易造成图案和干粒的喷涂纹理模糊不清，降低了产品的图案清晰度；若喷墨量过小，则干粒的分布量较小，降低了坯体的干粒手感和立体感，降低了陶瓷砖的图案立体感。
而通过严格控制第二次干燥的温度，能对喷印有干粒墨水的坯体进行初步升温加热，避免喷印有干粒墨水的坯体在后续的烧制过程中因快速烧制而产生裂砖、炸坯的现象，提高了坯体的质量稳定性。若干燥温度过高，则容易使得干粒墨水干燥过快，并因快速烧制而产生裂砖、炸坯的现象；若干燥温度过低，则未能对干粒墨水进行初步预热和升温，容易使得干粒墨水在后续的烧制过程中容易因快速烧制而产生裂砖、炸坯的现象，降低了陶瓷砖的质量稳定性。
优选的，所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为10-20Bar，保护釉的喷釉量为70-100g/m 2；所述步骤F中，烧制的温度为1180-1220℃，时间为60-80min。
本发明通过采用高压喷枪在铺撒干粒后的坯体面喷涂保护釉，能对干粒进行有效保护，提高干粒在坯体面的粘附性，避免干粒被吹走或吸走造成干粒粘附于窑墙或窑顶，进而避免产品出现落脏、溶洞、针孔等现象。并严格控制喷涂的压强和保护釉的喷釉量，保证喷涂的均匀性，避免因高压冲走粘附的干粒，避免因釉量过多而降低了坯体表面的立体感；若压强过大，则容易因喷涂压强过大而冲走坯体表面的干粒；若压强过小，则容易导致保护釉的喷出雾度过小，降低了喷涂的均匀性；若喷釉量过低，则降低了对干粒和坯体的保护程度；若喷釉量过高，则容易因釉量过多而降低了坯体表面的立体感。
优选的，采用4-6支高压喷枪进行保护釉的喷涂，确保喷涂的全面性和均匀性；进一步优选的，所述高压喷枪的喷涂压强为10-20Bar，高压喷枪的喷嘴直径为0.28-0.32mm，高压喷枪的喷嘴喷雾角度为90-120°。优选的，高压喷枪的喷嘴与砖面的高度至少70cm，保证喷涂的均匀性，并避免高压冲走粘附的干粒，若喷嘴与砖面的高度过小，则喷嘴喷出的压力容易冲走或吹走已粘附好的干粒，影响产品的立体沙粒感和质量。
而通过严格控制最后的烧制温度和时间，能使坯体表面的保护釉结晶密度大，提高陶瓷砖面的强度，不易产生刮痕，并能使干粒熔融并粘合于坯体上，提高坯体与干粒的粘结稳定性，提高产品的质量，不易出现脱釉等现象。
优选的，所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          30-40份
分散剂        5-10份
粘度调节剂    0.05-0.15份
表面活性剂    0.2-0.3份
辅料          2-5份
溶剂          60-80份。
本发明通过采用上述种类的原料制备干粒墨水，能干粒通过墨水的喷墨方式均匀分布于坯体的表面，且附着力高，不易掉落或脱落；其中，分散剂提高了干粒在墨水中的分散性，并提高各原料的分散度；粘度调节剂则提高干粒与其他原料在墨水体系中的结合度，使得干粒随着墨水的喷洒而均匀分布于坯体表面；而表面活性剂则提高干粒墨水在坯体表面的附着力，使其稳定附着于坯体表面，进而提高干粒的附着性能；而溶剂则提高原料的分散性和溶解性，使其均匀铺展于坯体表面。优选的，所述干粒可根据瓷砖的需求选择，按照耐温性能可选高干粒、中干粒或低温干粒，按照色彩效果可选透明干粒、红棕干粒、白鹅干粒、黑色干粒、亮光干粒等，根据实际需求的手感效果进行不同温度的干粒搭配，同时根据产品图案色调选择不同干粒种类进行调配。
优选的，每份所述分散剂包括3-8份聚乙二醇、10-12份聚丙烯酰胺和2-5份聚丙烯酸酯；每份所述粘度调节剂包括20-30份丙烯酸树脂、5-10份聚乙二醇甲醚和5-10份乙醇；所述表面活性剂为十二烷基硫酸钠、辛基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、十二烷基三甲溴化铵和乙氧基化脂肪酸缩水山梨醇酯中的至少一种。
本发明通过采用上述种类的原料复配作为分散剂，与采用单一种类分散剂相比，能更有效地提高干粒在墨水体系中的分散性，保证干粒微粒在喷洒之前不发生团聚，并促使在喷洒干粒墨水时干粒均匀分布于坯体表面，进一步提高干粒在坯体表面的附着力；其中，聚乙二醇水溶性佳，与其他原料的相容性较佳，能显著提高墨水体系中的原料分散性和溶解性；而采用的聚丙烯酰胺与聚乙二醇复配使用，能阻止颗粒状的干粒凝聚，保持分散体系的稳定性，并避免干粒颗粒在搅拌分散后由于界面张力的作用而分层，降低墨水体系原料中液-液和固-液间的界面张力，提高体系分散性；而采用的聚丙烯酸酯能显著将干粒分散均匀，避免纳米粉体的干粒由于较大的比表面积和高表面能而产生自团聚现象，起到高效分散的作用。
而本发明通过采用上述种类的原料复配作为粘度调节剂，使干粒墨水的粘度保持在500-800cps，能有效调节干粒墨水的流动性，使得干粒墨水能均匀地喷洒于坯体表面，与坯体之间具有优良的结合性，提高干粒层的附着力。
而本发明通过采用阴离子型和非离子型的表面活性剂复配，能有效提高干粒墨水体系的乳化性、增溶性、分散性、润湿性等性能，使得干粒墨水各原料能充分分散、乳化，并稳定地、均匀地附着于坯体表面，提高干粒层的附着力；其中，采用的十二烷基硫酸钠、辛基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯具有较佳的乳化、增溶、润湿、分散等性能，且刺激性低、易降解；采用的乙氧基化脂肪酸缩水山梨醇酯能显著提高墨水的亲水性和结合性，促使干粒墨水稳定地附着于坯体表面，提高干粒层在坯体上的附着力。
优选的，每份所述辅料包括0.5-1.5份pH调节剂、1-2份催干剂和0.5-1.0份防腐剂；所述pH调节剂为三甲氨、三乙醇胺和氨水中的至少一种；所述催干剂是由乙醇和异丙醇以重量比为1:3-4组成的混合物；所述防腐剂为2,2'-二羟基-5,5'-二氯二苯基甲烷、氯乙酰胺、邻苯基苯酚钠、2-羟基联苯和N-(2-羟基丙基)氨基甲醇中的至少一种；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3-4:1:1.5-2.5组成的混合物。
本发明通过采用上述种类的pH调节剂，能精准地调控干粒墨水的pH值呈弱碱性体系，促进各物料的分散性和互溶性，并促使干粒油墨均匀分散附着于坯体表面。而通过采用乙醇和异丙醇复配作为催干剂，溶解度高，促溶性好，在提高干粒墨水体系的物料互溶性前提下，提高干粒的分散性，使其均匀分散于坯体表面，且挥发性好，在喷洒干粒墨水后的第二次干燥工序中，能促进墨水的溶剂挥发和干燥，并能对干粒和坯体进行初步升温加热，使得部分溶剂挥发的干粒墨水在后续的烧制过程稳定地烧制结合，避免存在部分溶剂挥发不完全而导致干粒层中存在气泡导致干粒层附着力低，容易脱落，硬度低。
而本发明通过采用上述的防腐剂，能提高干粒墨水的防腐蚀性，并能提高干粒墨水的抗菌防霉性能，避免受到霉菌侵蚀或受氧、热、光、化学侵蚀物等环境因素而造成破坏或损伤，进而造成干粒层的变色、穿孔、剥落、失去附着力等外观性能和力学性能受损；其中，采用的2,2'-二羟基-5,5'-二氯二苯基甲烷和2-羟基联苯能通过抑制微生物细胞壁及细胞内的酶而致效。
而本发明通过采用上述种类的原料作为溶剂，能提高各原料的溶解性和混合分散性，并提高干粒油墨体系的稳定性，使体系的粘度、表面张力等不易受温度的变化而变化，使得干粒颗粒均匀分散于坯体表面，且挥发性高，经干燥和烧制后容易挥发，进而形成附着稳定的坯体干粒层。
优选的，所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5-6份
碳酸钡           6-8份
钾长石           15-20份
熔块             35-45份
煅烧氧化铝       5-10份
烧滑石           10-14份
白云石           1-5份
高岭土           6-8份
超细石英粉       1-3份。
本发明通过采用上述原料为保护釉，并严格控制各原料的用量，能保证干粒在窑炉烧制过程中不被吹掉或吸掉，对干粒进行保护，提高干粒在坯体表面的粘附性，避免干粒吸走造成干粒粘附于窑墙或窑顶，进而避免产品出现落脏、溶洞、针孔等现象；且保护釉呈哑光透明，不会影响坯体经图案装饰后的图案效果，清晰度高，并能提高陶瓷砖表面的耐磨性，降低其光泽度，具有哑光磨砂的效果；优选的，所述保护釉的加工细度控制为325目筛余0.3-0.5%，比重为1.30±0.01，经喷涂保护釉及烧制后成型的产品光泽度为5-8。
优选的，所述熔块的化学组份为：
SiO 2 45.25-46.25% Al 2O 3 19-21% Fe 2O 3  0.05-0.10% CaO 2.35-2.65%
MgO 0.75-1.15% K 2O 1.8-2.0% Na 2O 4.5-4.8% TiO 2  0.2-0.3%
B 2O 3  0.04-0.08% BaO 15.0-15.4% ZnO 6.0-6.5% SrO 3.4-3.8%。
本发明通过采用上述原料为熔块，能降低保护釉在烧制过程中的釉料膨胀系数，并可在烧制过程把二氧化碳等提前排出，从而不影响保护釉面平整度，提高陶瓷砖的立体效果。
本发明的另一目的通过下述技术方案实现：一种如上所述喷墨干粒装饰陶瓷砖的制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
本发明的干粒装饰陶瓷砖由上述步骤（底釉装饰-图案装饰-第一次干燥-喷涂干粒墨水-第二次干燥-喷涂保护釉-烧制）制得，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，制得的干粒装饰陶瓷砖图案清晰、层次分明，干粒感明显，立体感强，在平面坯体上实现了凹凸模面的效果，釉面光泽度低，防滑效果佳，色彩丰富，物化性能稳定，可适用于工业化大规模生产。
 有益效果
本发明制造干粒装饰陶瓷砖的方法，操作步骤简单，控制方便，能减少生产线的喷胶水、铺撒干粒、吸干粒等工序及其设备的布局，简化工艺流程，提高生产效率，降低生产难度和生产成本，可适用于工业化大规模生产；通过采用干粒墨水进行喷洒，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，提高干粒在坯体表面的分布均匀性和附着力，能使制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，物化性能稳定，温度适应范围广。
本发明的干粒装饰陶瓷砖图案清晰、层次分明，干粒感明显，立体感强，在平面坯体上实现了凹凸模面的效果，釉面光泽度低，防滑效果佳，色彩丰富，物化性能稳定，可适用于工业化大规模生产。
 本发明的最佳实施方式
为了便于本领域技术人员的理解，下面结合实施例对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。
实施例1
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在40℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2   65% Al 2O 3   18.5% Fe 2O 3   0.15% CaO 1.35%
MgO 0.7% K 2O 2.8% Na 2O 3.35% TiO 2   0.08%
ZrO 2   2.17% BaO 4.90% ZnO 1.0%。  
所述步骤C中第一次干燥的温度为120℃；所述步骤D中，干粒墨水的喷墨量为2kg/m 2；所述步骤D中，第二次干燥的温度为120℃。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为10Bar，保护釉的喷釉量为70g/m 2；所述步骤F中，烧制的温度为1180℃，时间为80min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          30份
分散剂        5份
粘度调节剂    0.05份
表面活性剂    0.2份
辅料          2份
溶剂          60份。
每份所述分散剂包括3份聚乙二醇、10份聚丙烯酰胺和2份聚丙烯酸酯；每份所述粘度调节剂包括20份丙烯酸树脂、5份聚乙二醇甲醚和5份乙醇；所述表面活性剂为十二烷基硫酸钠。
每份所述辅料包括0.5份pH调节剂、1份催干剂和0.5份防腐剂；所述pH调节剂为三甲氨；所述催干剂是由乙醇和异丙醇以重量比为1:3组成的混合物；所述防腐剂为邻苯基苯酚钠；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3:1:1.5组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5份
碳酸钡           6份
钾长石           15份
熔块             35份
煅烧氧化铝       5份
烧滑石           10份
白云石           1份
高岭土           6份
超细石英粉       1份。
所述熔块的化学组份为：
SiO 2   45.25% Al 2O 3   19% Fe 2O 3   0.10% CaO 2.45%
MgO 0.75% K 2O 2.0% Na 2O 4.8% TiO 2   0.26%
B 2O 3   0.04% BaO 15.4% ZnO 6.5% SrO 3.8%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
实施例2
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在45℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2  66% Al 2O 3   19% Fe 2O 3   0.13% CaO 1.33%
MgO 0.68% K 2O 2.6% Na 2O 3.23% TiO 2   0.11%
ZrO 2   1.06% BaO 4.88% ZnO 0.98%。  
所述步骤C中，第一次干燥的温度为130℃；所述步骤D中，干粒墨水的喷墨量为2.2kg/m 2；所述步骤D中，第二次干燥的温度为128℃。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为12Bar，保护釉的喷釉量为80g/m 2；所述步骤F中，烧制的温度为1190℃，时间为65min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          32份
分散剂        6份
粘度调节剂    0.08份
表面活性剂    0.23份
辅料          3份
溶剂          65份。
每份所述分散剂包括4份聚乙二醇、10.5份聚丙烯酰胺和3份聚丙烯酸酯；每份所述粘度调节剂包括22份丙烯酸树脂、6份聚乙二醇甲醚和6份乙醇；所述表面活性剂为辛基酚聚氧乙烯醚。
每份所述辅料包括0.8份pH调节剂、1.2份催干剂和0.6份防腐剂；所述pH调节剂为三甲氨；所述催干剂是由乙醇和异丙醇以重量比为1:3.2组成的混合物；所述防腐剂为氯乙酰胺；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3.2:1:1.8组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5.2份
碳酸钡           6.5份
钾长石           16份
熔块             38份
煅烧氧化铝       6份
烧滑石           11份
白云石           2份
高岭土           6.5份
超细石英粉       1.5份。
所述熔块的化学组份为：
SiO 2  45.5%  Al 2O 3   19% Fe 2O 3   0.09% CaO 2.60%
MgO 1.01% K 2O 1.90% Na 2O 4.6% TiO 2  0.25%
B 2O 3  0.05% BaO 15.1% ZnO 6.2% SrO 3.7%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
实施例3
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在50℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2  65%  Al 2O 3   20% Fe 2O 3   0.12% CaO 1.31%
MgO 0.64% K 2O 2.4% Na 2O 3.21% TiO 2  0.10%
ZrO 2   1.5% BaO 4.82% ZnO 0.90%。  
所述步骤C中，第一次干燥的温度为135℃；所述步骤D中，干粒墨水的喷墨量为2.5kg/m 2；所述步骤D中，第二次干燥的温度为135℃。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为15Bar，保护釉的喷釉量为85g/m 2；所述步骤F中，烧制的温度为1200℃，时间为70min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          35份
分散剂        8份
粘度调节剂    0.10份
表面活性剂    0.25份
辅料          3.5份
溶剂          70份。
每份所述分散剂包括5份聚乙二醇、11份聚丙烯酰胺和3.5份聚丙烯酸酯；每份所述粘度调节剂包括25份丙烯酸树脂、8份聚乙二醇甲醚和8份乙醇；所述表面活性剂为脂肪酸聚氧乙烯酯。
每份所述辅料包括1.0份pH调节剂、1.5份催干剂和0.8份防腐剂；所述pH调节剂为三乙醇胺；所述催干剂是由乙醇和异丙醇以重量比为1:3.5组成的混合物；所述防腐剂为2,2'-二羟基-5,5'-二氯二苯基甲烷；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3.5:1:2.0组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5.5份
碳酸钡           7份
钾长石           18份
熔块             40份
煅烧氧化铝       8份
烧滑石           12份
白云石           3份
高岭土           7份
超细石英粉       2份。
所述熔块的化学组份为：
SiO 2 45.75%   Al 2O 3  19.05% Fe 2O 3  0.08% CaO 2.51%
MgO 0.95% K 2O 1.91% Na 2O 4.67% TiO 2  0.25%
B 2O 3  0.06% BaO 15.19% ZnO 6.18% SrO 3.40%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
实施例4
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在55℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2   66% Al 2O 3   20% Fe 2O 3   0.11% CaO 1.30%
MgO 0.61% K 2O 2.2% Na 2O 3.19% TiO 2   0.09%
ZrO 2   0.8% BaO 4.80% ZnO 0.90%。  
所述步骤C中，第一次干燥的温度为140℃；所述步骤D中，干粒墨水的喷墨量为2.8kg/m 2；所述步骤D中，第二次干燥的温度为132℃。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为18Bar，保护釉的喷釉量为90g/m 2；所述步骤F中，烧制的温度为1210℃，时间为65min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          38份
分散剂        9份
粘度调节剂    0.13份
表面活性剂    0.28份
辅料          4份
溶剂          75份。
每份所述分散剂包括7份聚乙二醇、11.5份聚丙烯酰胺和4份聚丙烯酸酯；每份所述粘度调节剂包括28份丙烯酸树脂、9份聚乙二醇甲醚和9份乙醇；所述表面活性剂为十二烷基三甲溴化铵。
每份所述辅料包括1.3份pH调节剂、1.8份催干剂和0.8份防腐剂；所述pH调节剂为三乙醇胺；所述催干剂是由乙醇和异丙醇以重量比为1:3.8组成的混合物；所述防腐剂为2-羟基联苯；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3.8:1:2.3组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5.8份
碳酸钡           7.5份
钾长石           19份
熔块             43份
煅烧氧化铝       9份
烧滑石           13份
白云石           4份
高岭土           7.5份
超细石英粉       2.5份。
所述熔块的化学组份为：
SiO 2   46.0% Al 2O 3   19.5% Fe 2O 3   0.06% CaO 2.35%
MgO 0.77% K 2O 1.85% Na 2O 4.6% TiO 2   0.22%
B 2O 3   0.05% BaO 15.0% ZnO 6.1% SrO 3.5%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
实施例5
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在60℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2   68% Al 2O 3   19% Fe 2O 3   0.10% CaO 1.28%
MgO 0.6% K 2O 2.0% Na 2O 3.18% TiO 2   0.08%
BaO 4.83% ZnO 0.93%。    
所述步骤C中，第一次干燥的温度为150℃；所述步骤D中，干粒墨水的喷墨量为3kg/m 2；所述步骤D中，第二次干燥的温度为150℃。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为20Bar，保护釉的喷釉量为100g/m 2；所述步骤F中，烧制的温度为1220℃，时间为60min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          40份
分散剂        10份
粘度调节剂    0.15份
表面活性剂    0.3份
辅料          5份
溶剂          80份。
每份所述分散剂包括8份聚乙二醇、12份聚丙烯酰胺和5份聚丙烯酸酯；每份所述粘度调节剂包括30份丙烯酸树脂、10份聚乙二醇甲醚和10份乙醇；所述表面活性剂为乙氧基化脂肪酸缩水山梨醇酯。
每份所述辅料包括1.5份pH调节剂、2份催干剂和1.0份防腐剂；所述pH调节剂为氨水；所述催干剂是由乙醇和异丙醇以重量比为1:4组成的混合物；所述防腐剂为N-(2-羟基丙基)氨基甲醇；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为4:1:2.5组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       6份
碳酸钡           8份
钾长石           20份
熔块             45份
煅烧氧化铝       10份
烧滑石           14份
白云石           5份
高岭土           8份
超细石英粉       3份。
所述熔块的化学组份为：
SiO 2   46.5% Al 2O 3   19.41% Fe 2O 3   0.05% CaO 2.35%
MgO 0.75% K 2O 1.8% Na 2O 4.5% TiO 2   0.2%
B 2O 3   0.04% BaO 15.0% ZnO 6.0% SrO 3.4%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
对比例1（采用常见的涂布胶水-铺撒干粒工艺）
一种干粒装饰陶瓷砖制造方法，包括如下步骤：
    A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在50℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行干燥；
D、喷涂胶水：在步骤C第一次干燥后的坯体表面喷印胶水；
E、干粒装饰：在步骤D喷涂胶水后的坯体表面铺撒干粒，进行干粒装饰，然后进行第二次干燥；
F、烧制：将步骤E经第二次干燥后的坯体进行烧制，制得干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2   65% Al 2O 3   20% Fe 2O 3   0.12% CaO 1.31%
MgO 0.64% K 2O 2.4% Na 2O 3.21% TiO 2   0.10%
ZrO 2   1.5% BaO 4.82% ZnO 0.90%。  
所述步骤C中，第一次干燥的温度为135℃；所述步骤F中，烧制的温度为1200℃，时间为70min。
对比例2（实施例3的基础上不采用保护釉）
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在50℃，然后在坯体的底釉面进行图案装饰；
C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
E、烧制：将步骤D经第二次干燥后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2   65% Al 2O 3   20% Fe 2O 3   0.12% CaO 1.31%
MgO 0.64% K 2O 2.4% Na 2O 3.21% TiO 2   0.10%
ZrO 2   1.5% BaO 4.82% ZnO 0.90%。  
所述步骤C中，第一次干燥的温度为135℃；所述步骤D中，干粒墨水的喷墨量为2.5kg/m 2；所述步骤D中，第二次干燥的温度为135℃。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          35份
分散剂        8份
粘度调节剂    0.10份
表面活性剂    0.25份
辅料          3.5份
溶剂          70份。
每份所述分散剂包括5份聚乙二醇、11份聚丙烯酰胺和3.5份聚丙烯酸酯；每份所述粘度调节剂包括25份丙烯酸树脂、8份聚乙二醇甲醚和8份乙醇；所述表面活性剂为脂肪酸聚氧乙烯酯。
每份所述辅料包括1.0份pH调节剂、1.5份催干剂和0.8份防腐剂；所述pH调节剂为三乙醇胺；所述催干剂是由乙醇和异丙醇以重量比为1:3.5组成的混合物；所述防腐剂为2,2'-二羟基-5,5'-二氯二苯基甲烷；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3.5:1:2.0组成的混合物。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层和干粒墨水层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm。
对比例3（实施例3的基础上，干粒装饰前只进行一次干燥，干粒装饰后不进行干燥）
一种喷墨干粒装饰陶瓷砖的制造方法，包括如下步骤：
A、底釉装饰：在坯体的表面进行底釉装饰；
B、图案装饰：将步骤A底釉装饰后的坯体温度控制在50℃，然后在坯体的底釉面进行图案装饰；
C、干燥：将步骤B进行图案装饰后的坯体进行干燥；
D、干粒装饰：在步骤C干燥后的坯体表面喷洒干粒墨水，进行干粒装饰；
E、喷涂保护釉：在步骤D干粒装饰后的坯体表面喷涂保护釉；
F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
在所述步骤A之前，采用机械手数码布料方式对坯体进行线条纹理装饰。
所述步骤A中，所述底釉的化学组份为：
SiO 2  65% Al 2O 3  20% Fe 2O 3  0.12% CaO 1.31%
MgO 0.64% K 2O 2.4% Na 2O 3.21% TiO 2  0.10%
ZrO 2  1.5% BaO 4.82% ZnO 0.90%。  
所述步骤C中，第一次干燥的温度为135℃；所述步骤D中，干粒墨水的喷墨量为2.5kg/m 2。
所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为15Bar，保护釉的喷釉量为85g/m 2；所述步骤F中，烧制的温度为1200℃，时间为70min。
所述步骤D中，所述干粒墨水包括如下重量份的原料：
干粒          35份
分散剂        8份
粘度调节剂    0.10份
表面活性剂    0.25份
辅料          3.5份
溶剂          70份。
每份所述分散剂包括5份聚乙二醇、11份聚丙烯酰胺和3.5份聚丙烯酸酯；每份所述粘度调节剂包括25份丙烯酸树脂、8份聚乙二醇甲醚和8份乙醇；所述表面活性剂为脂肪酸聚氧乙烯酯。
每份所述辅料包括1.0份pH调节剂、1.5份催干剂和0.8份防腐剂；所述pH调节剂为三乙醇胺；所述催干剂是由乙醇和异丙醇以重量比为1:3.5组成的混合物；所述防腐剂为2,2'-二羟基-5,5'-二氯二苯基甲烷；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3.5:1:2.0组成的混合物。
所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
煅烧氧化锌       5.5份
碳酸钡           7份
钾长石           18份
熔块             40份
煅烧氧化铝       8份
烧滑石           12份
白云石           3份
高岭土           7份
超细石英粉       2份。
所述熔块的化学组份为：
SiO 2 45.75% Al 2O 3 19.05% Fe 2O 3 0.08% CaO 2.51%
MgO 0.95% K 2O 1.91% Na 2O 4.67% TiO 2 0.25%
B 2O 3 0.06% BaO 15.19% ZnO 6.18% SrO 3.40%。
一种如上所述喷墨干粒装饰陶瓷砖制造方法制得的干粒装饰陶瓷砖，该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.2-0.5mm，所述保护釉层的厚度为0.02-0.03mm。
对比例4（保护釉采用的市售的常规保护釉）
本对比例与上述实施例3的区别在于：
所述步骤E中，所述保护釉采用的市售的常规保护釉。
将上述实施例1-5和对比例1-4制得的干粒装饰陶瓷砖进行硬度、耐磨性、光泽度和层间附着力等性能性能测试，测试结果如下所示：
  莫氏硬度 耐磨性等级 光泽度 干粒层的附着力等级
实施例1 ＞7 4级 8° 0级
实施例2 ＞7 5级 7° 0级
实施例3 ＞7 5级 5° 0级
实施例4 ＞7 4级 6° 0级
实施例5 ＞7 4级 8° 0级
对比例1 6.0 2级 11° 2级
对比例2 6.0 3级 12° 1级
对比例3 5.0 2级 8° 1级
对比例4 6.0 3级 10° 1级
其中，耐磨性等级采用GB/T 3810.7-2016试验方法标准进行测试，观察样品在特定研磨转数下研磨后的表面磨损痕迹的程度，并分为0-5级，具体级别分级如下所示：
级别 可见磨损的研磨转数
0 100
1 150
2 600
3 750，1500
4 2100，6000，12000
5 ＞12000
所述干粒层的附着力等级采用GB/T9286-98划格试验方法标准进行测试，观察测试试样的干粒层脱落情况，并分为0-5级，具体级别分级如下所示：
级别 情况说明
0 边缘完全平滑，没有脱落现象
1 在划格切口交叉处和/或切口边缘有脱落，但交叉切割面积影响明显不大于5%
2 在划格切口交叉处和/或沿切口边缘有脱落，受影响的交叉切割面积明显大于5%，但明显不大于15%
3 切割边缘部分或全部以大碎片脱落，和/或在各自不同部位上部分或全部剥落，受影响的交叉切割面积明显大于15%，但明显不大于35%
4 沿切口边缘有大碎片脱落，和/或在一些方格部分或全部出现脱落，受影响的交叉切割面积明显大于35%，但明显不大于65%
5 剥落程度超过4级
由上述测试数据可知，本发明制得的陶瓷砖产品图案清晰、层次分明，釉面光泽度低，防滑效果佳，干粒感明显，立体感强，色彩丰富，硬度高，干粒附着力高，物化性能稳定。
对比例1中，采用市面上常见的铺撒干粒工艺，在坯体上涂布胶水后直接铺撒干粒，而并非本发明采用的干粒墨水制备干粒层，对比例1制得的陶瓷砖与本发明各实施例制得的陶瓷砖相比，表面耐磨性较低，耐磨性等级为2级，干粒的附着力较低，干粒层的附着力等级为2级，而光泽度稍偏高（为11°），防滑性和干粒感较低，硬度稍低（等级为6级）；说明本发明通过采用干粒墨水在陶瓷砖的坯体表面喷洒，能在坯体表面的指定位置进行喷印，使喷印的纹理可与图案装饰纹理精准对应，提高干粒在坯体表面的分布均匀性和附着力，并在图案装饰后进行第一次干燥，使油墨充分干燥成型，避免后续铺撒的干粒对未干燥成型的油墨造成模糊、混乱的图案墨水的现象，提高干粒油墨的在图案装饰层表面的精准性和附着力，且在喷印干粒墨水后再进行第二次干燥处理，能对喷印有干粒墨水的坯体进行初步升温加热，避免喷印有干粒墨水的坯体在后续的烧制过程中因快速烧制而产生裂砖、炸坯的现象，提高了干粒层的附着力和硬度等性能，使制得的陶瓷砖坯体与干粒形成稳定的坯-粒-釉结合层，沙粒感明显，立体感强，图案清晰，色彩丰富，硬度高，干粒层的附着力高，不易脱落，表面耐磨性高，光泽度低，防滑效果佳。
对比例2中，与实施例3相比，在工艺的最后不进行保护釉的喷涂，制得的陶瓷砖表面耐磨性较低，耐磨性等级为3级，干粒的附着力较低（等级为1级），光泽度偏高（为12°），防滑性和干粒感较低，硬度稍低（为6.0）；说明本发明通过在铺撒干粒后的坯体面喷涂保护釉，并严格控制保护釉的喷涂压强和喷釉量，能对干粒进行有效保护，提高干粒在坯体面的粘附性，避免干粒被吹走或吸走造成干粒粘附于窑墙或窑顶，进而避免产品出现落脏、溶洞、针孔等现象，使制得的陶瓷砖坯体与干粒形成稳定的坯-胶-粒-釉结合层，沙粒感明显，立体感强，图案清晰，色彩丰富，硬度高，干粒层的附着力高，不易脱落，表面耐磨性高，光泽度低，防滑效果佳。
对比例3，与实施例3相比，在工艺中仅喷洒干粒墨水前进行一次干燥，喷洒干粒墨水后没有进行第二次干燥，制得的陶瓷砖表面耐磨性较低，耐磨性等级为2级，干粒的附着力较低（等级为1级），光泽度偏高（为8°），防滑性和干粒感较低，硬度稍低（为5.0）；说明本发明通过在喷印干粒墨水后再进行第二次干燥处理，能对喷印有干粒墨水的坯体进行初步升温加热，避免喷印有干粒墨水的坯体在后续的烧制过程中因快速烧制而产生裂砖、炸坯的现象，提高了干粒层的附着力和硬度等性能，使制得的陶瓷砖坯体与干粒形成稳定的坯-粒-釉结合层，沙粒感明显，立体感强，图案清晰，色彩丰富，硬度高，干粒层的附着力高，不易脱落，表面耐磨性高，光泽度低，防滑效果佳。
对比例3，与实施例3相比，工艺中采用的保护釉是采用市售的常规保护釉，而不是本发明的保护釉原料配方，制得的陶瓷砖表面耐磨性较低，耐磨性等级为3级，干粒的附着力较低（等级为1级），光泽度偏高（为10°），防滑性和干粒感较低，硬度稍低（为6.0）；说明喷涂本发明的保护釉，能对干粒进行保护，保证干粒在窑炉烧制过程中不被吹掉或吸掉，提高干粒在坯体面的粘附性，避免干粒吸走造成干粒粘附于窑墙或窑顶，进而避免产品出现落脏、溶洞、针孔等现象，同时能提高陶瓷砖表面的耐磨性，降低其光泽度，具有哑光磨砂的效果，使制得的陶瓷砖坯体与干粒形成稳定的坯-胶-粒-釉结合层，沙粒感明显，立体感强，图案清晰，色彩丰富，硬度高，干粒层的附着力高，不易脱落，表面耐磨性高，光泽度低，防滑效果佳。
 工业实用性
以上所描述的仅为本发明的较佳实施例，上述具体实施例不是对本发明的限制。在本发明的技术思想范畴内，可以出现各种变形及修改，凡本领域的普通技术人员根据以上描述所做的润饰、修改或等同替换，均属于本发明所保护的范围。

Claims (10)

  1. 一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：包括如下步骤：
    A、底釉装饰：在坯体的表面进行底釉装饰；
    B、图案装饰：将步骤A底釉装饰后的坯体温度控制在40-60℃，然后在坯体的底釉面进行图案装饰；
    C、第一次干燥：将步骤B进行图案装饰后的坯体进行第一次干燥；
    D、干粒装饰：在步骤C第一次干燥后的坯体表面喷洒干粒墨水，进行干粒装饰，然后进行第二次干燥；
    E、喷涂保护釉：在步骤D第二次干燥后的坯体表面喷涂保护釉；
    F、烧制：将步骤E喷涂保护釉后的坯体进行烧制，制得具有立体效果的干粒装饰陶瓷砖。
  2. 根据权利要求1所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述步骤A中，所述底釉的化学组份为：
    SiO 2  65-67% Al 2O 3  17-23% Fe 2O 3  0.10-0.15% CaO 1.28-1.35% MgO 0.6-0.7% K 2O 2.0-2.8% Na 2O 3.18-3.25% TiO 2 0.08-0.12% ZrO 2 0-2.17% BaO 4.80-4.90% ZnO 0.90-1.0%  
    。
  3. 根据权利要求1所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述步骤C中，第一次干燥的温度为120-150℃；所述步骤D中，干粒墨水的喷墨量为2-3kg/m 2；所述步骤D中，第二次干燥的温度为120-150℃。
  4. 根据权利要求1所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述步骤D中，所述干粒墨水包括如下重量份的原料：
    干粒          30-40份
    分散剂        5-10份
    粘度调节剂    0.05-0.15份
    表面活性剂    0.2-0.3份
    辅料          2-5份
    溶剂          60-80份。
  5. 根据权利要求4所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：每份所述分散剂包括3-8份聚乙二醇、10-12份聚丙烯酰胺和2-5份聚丙烯酸酯；每份所述粘度调节剂包括20-30份丙烯酸树脂、5-10份聚乙二醇甲醚和5-10份乙醇；所述表面活性剂为十二烷基硫酸钠、辛基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、十二烷基三甲溴化铵和乙氧基化脂肪酸缩水山梨醇酯中的至少一种。
  6. 根据权利要求4所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：每份所述辅料包括0.5-1.5份pH调节剂、1-2份催干剂和0.5-1.0份防腐剂；所述pH调节剂为三甲氨、三乙醇胺和氨水中的至少一种；所述催干剂是由乙醇和异丙醇以重量比为1:3-4组成的混合物；所述防腐剂为2,2'-二羟基-5,5'-二氯二苯基甲烷、氯乙酰胺、邻苯基苯酚钠、2-羟基联苯和N-(2-羟基丙基)氨基甲醇中的至少一种；每份所述溶剂为乙二醇丁醚乙酸酯、二丙二醇二甲醚和丙二醇甲醚以重量比为3-4:1:1.5-2.5组成的混合物。
  7. 根据权利要求1所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述步骤E中，所述保护釉为哑光透明保护釉，所述哑光透明保护釉包括如下重量份的原料：
    煅烧氧化锌       5-6份
    碳酸钡           6-8份
    钾长石           15-20份
    熔块             35-45份
    煅烧氧化铝       5-10份
    烧滑石           10-14份
    白云石           1-5份
    高岭土           6-8份
    超细石英粉       1-3份。
  8. 根据权利要求7所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述熔块的化学组份为：
    SiO 2 45.25-46.25% Al 2O 3 19-21% Fe 2O 3 0.05-0.10% CaO 2.35-2.65% MgO 0.75-1.15% K 2O 1.8-2.0% Na 2O 4.5-4.8% TiO 2 0.2-0.3% B 2O 3  0.04-0.08% BaO 15.0-15.4% ZnO 6.0-6.5% SrO 3.4-3.8%
    。
  9. 根据权利要求1所述的一种喷墨干粒装饰陶瓷砖的制造方法，其特征在于：所述步骤E中，喷涂保护釉的采用高压喷涂方式，保护釉的高压喷涂压强为10-20Bar，保护釉的喷釉量为70-100g/m 2；所述步骤F中，烧制的温度为1180-1220℃，时间为60-80min。
  10. 一种如权利要求1-9任一项所述喷墨干粒装饰陶瓷砖的制造方法制得的干粒装饰陶瓷砖，其特征在于：该干粒装饰陶瓷砖包括由下至上依次设置的坯体层、底釉层、图案层、干粒墨水层和保护釉层，所述底釉层的厚度为0.05-0.2mm，所述图案层的厚度为0.05-0.1mm，所述干粒层的厚度为0.5-1mm，所述保护釉层的厚度为0.02-0.03mm。
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