WO2016176872A1 - 陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用 - Google Patents

陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用 Download PDF

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WO2016176872A1
WO2016176872A1 PCT/CN2015/079170 CN2015079170W WO2016176872A1 WO 2016176872 A1 WO2016176872 A1 WO 2016176872A1 CN 2015079170 W CN2015079170 W CN 2015079170W WO 2016176872 A1 WO2016176872 A1 WO 2016176872A1
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Prior art keywords
parts
inkjet ink
large red
solvent
red
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PCT/CN2015/079170
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English (en)
French (fr)
Inventor
梁桐灿
汪永清
余国明
欧家瑞
Original Assignee
广东宏陶陶瓷有限公司
景德镇陶瓷大学
广东宏宇新型材料有限公司
广东宏海陶瓷实业发展有限公司
广东宏威陶瓷实业有限公司
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Application filed by 广东宏陶陶瓷有限公司, 景德镇陶瓷大学, 广东宏宇新型材料有限公司, 广东宏海陶瓷实业发展有限公司, 广东宏威陶瓷实业有限公司 filed Critical 广东宏陶陶瓷有限公司
Priority to US15/572,481 priority Critical patent/US10669216B2/en
Priority to EP15891124.8A priority patent/EP3284732B1/en
Priority to BR112017022595-6A priority patent/BR112017022595B1/pt
Publication of WO2016176872A1 publication Critical patent/WO2016176872A1/zh

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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
    • C04B41/86—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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
    • 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
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C03C8/12—Frit compositions, i.e. in a powdered or comminuted form containing lead containing titanium or zirconium
    • 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
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • 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
    • C04B41/50—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
    • C04B41/5022—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 vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.

Definitions

  • the invention relates to a high temperature large red inkjet ink for ceramic decoration, a preparation method and application thereof.
  • Inkjet printing technology has been used in the ceramic industry for more than ten years. Because inkjet printing uses a non-contact printing method, it is a kind of ink that is sprayed through the nozzle to the surface of various media to be printed. There is no excessive requirement for the surface shape of the printing medium.
  • the design information of the design is input into the computer system of the inkjet printing machine, and the printing can be performed. Do not have to be plated like the traditional printing technology, so the inkjet printing
  • the technical operation is simple, the development cycle is short, the labor intensity of the employees is low, and the production can be carried out according to the quantity, and the personalized customization needs can be fully realized. However, its requirements for ink are harsh.
  • the particle size of the ink is almost all nanometer.
  • the type of ink is still relatively small, like the high temperature, the red ink is blank, and the big red is One of the most important ternary colors, the lack of large red, the decorative effect of ceramic products is not bright enough, not colorful enough, which is the biggest problem in the world of ceramic inkjet printing technology.
  • the object of the present invention is to overcome the above disadvantages and to provide a high temperature large red inkjet for ceramic decoration.
  • Ink and preparation method and application thereof on the basis of not making major changes to the existing inkjet ink production process and inkjet printing equipment and inkjet printing process, focusing on the basic glaze powder composition of high temperature and large red inkjet ink, The composition of the base glaze powder frit, the formulation of the solvent, the grinding method of the base glaze powder and the large red material, the optimization of the particle size, the formulation and processing method of the ink, etc., so as to adjust and optimize the high temperature red inkjet ink The performance meets the requirements of the inkjet printing machine, and the ceramic tile printed with high temperature and large red inkjet ink is sprayed with high temperature and large red inkjet ink after being fired at high temperature (1080 ° C ⁇ 1230 ° C).
  • the color of the decorative surface of the ceramic tile is bright red, the color is dazzling, the red is pure, and the color of the inkjet ink printing with other colors is bright, colorful and wide.
  • the technology has strong universality and is easy to promote in the industry.
  • the invention relates to a high temperature large red inkjet ink for ceramic decoration, which is prepared according to the following parts by weight:
  • the base glaze powder is prepared by the following parts by weight:
  • the frit is formulated with the following weight percent components:
  • the large red material is superfinely ground with cadmium, selenium and red coated pigments
  • Solvent It is prepared in the following parts by weight:
  • the solubility parameter of the weakly polar to medium polar organic solvent is 14-23 (J/cm 3 ) 1/2 , and the commonly used weakly to medium polar organic solvents in the ceramic field can be selected.
  • a further step is that the weakly polar to medium polar organic solvents are tetrahydrofuran, cyclohexanone, castor oil, ethylene glycol butyl ether, diethylene glycol butyl ether, dichloroethane, kerosene, n-pentanol. And one or more mixtures of isoamyl alcohols.
  • the dispersing agent is an oil-soluble small molecular weight organic substance, which is a mixture of one or more of BYKJET-9131, BYKJET-9132, BYKJET-9133, Solsperse 20000, Solsperse 17000 and Solsperse 8000;
  • the stabilizer is an oil-soluble large molecular weight organic substance, which is a mixture of one or more of epoxy resin, polyvinyl butyral, DISPERBYK-109, DISPERBYK-115, DISPERBYK-174 and DISPERBYK-180.
  • the invention also relates to a method for preparing a high temperature large red inkjet ink for ceramic decoration, comprising the following steps:
  • the base glaze powder is formulated in the following parts by weight:
  • the frit is formulated with the following weight percent components:
  • the solvent is formulated in the following parts by weight:
  • the solubility parameter of the weakly polar to medium polar organic solvent is 14-23 (J/cm 3 ) 1/2 , and the commonly used weakly to medium polar organic solvents in the ceramic field can be selected.
  • a further step is that the weakly polar to medium polar organic solvents are tetrahydrofuran, cyclohexanone, castor oil, ethylene glycol butyl ether, diethylene glycol butyl ether, dichloroethane, kerosene, n-pentanol. And one or more mixtures of isoamyl alcohols.
  • the dispersant is an oil-soluble small molecular weight organic substance, which is BYKJET-9131, BYKJET-9132, BYKJET-9133, Solsperse 20000, Solsperse 17000, and One or more of the Solsperse 8000 classes;
  • the stabilizer is an oil-soluble large molecular weight organic substance, which is a mixture of one or more of epoxy resin, polyvinyl butyral, DISPERBYK-109, DISPERBYK-115, DISPERBYK-174 and DISPERBYK-180.
  • the cadmium selenium red coated color material is ground to a particle size of ⁇ 5 ⁇ m by an ultrafine sand mill, a planetary mill or other ultrafine grinder, wherein d 50 ⁇ 0.7 ⁇ m, and d 90 ⁇ 2.5 ⁇ m, a large red material is obtained;
  • High temperature large red inkjet inks are formulated in the following parts by weight:
  • step B Weigh the solvent prepared in step B according to the above parts by weight, put it into a stainless steel or plastic bucket with a stirring device or an ultrasonic device or both, and then weigh the base glaze prepared in step A. Powder, while stirring (ultrasonic), slowly add the base glaze powder to the solvent until the base glaze powder is evenly mixed with the solvent, and then slowly stir the remaining large red material into the mixture until it is stirred. Uniform, and finally ball milled to the inkjet printing machine with ultra-fine sand mill, planetary grinder or other ultra-fine grinder, and placed in a plastic bucket to store high-temperature red inkjet ink.
  • the invention also relates to a high-temperature large red inkjet printing ceramic tile, and the high-temperature large red inkjet ink prepared by the preparation method of the above-mentioned ceramic decoration high-temperature large red inkjet ink and other color spray according to the design requirement of the pattern design.
  • Ink ink is sequentially loaded into the ink tank of the inkjet printing machine, and inkjet printing is performed on the normal-bottomed, glazed ceramic slab, and then enters the roller kiln for firing, and the firing temperature ranges from 1080 ° C to 1230. °C, after edging, grading and other processes, the finished product.
  • the particle size is optimized, the ink composition and processing method are adjusted and optimized, so that the performance of the high temperature and large red inkjet ink reaches the requirements of the ink jet printer, and the high temperature and large red inkjet ink is printed.
  • the ceramic tile is fired at high temperature (1080°C ⁇ 1230°C)
  • the color of the ceramic tile surface printed with high temperature and large red inkjet ink is bright red, colorful and dazzling, and other colors.
  • the inkjet ink printing overlay presents a colorful color with bright colors, colorful colors and a wide color gamut. Since the high-temperature large red inkjet ink for ceramic decoration of the present invention has a fineness in order to meet the use requirements of the head, the particle size d 50 ⁇ 0.5 ⁇ m and d 90 ⁇ 1 ⁇ m. It is well known that the finer the fineness of the colorant, the more difficult it is to color, so the inkjet ink has not been so many types so far, and the high-color ink that is pure in color at high temperatures (above 1000 ° C) has been inkjet printing technology in ceramics.
  • the inventors separately separate the base glaze powder and the cadmium selenium red-coated color material during the processing, and in the fineness control, the basic glaze powder is as fine as possible; path In the system 0.5 ⁇ m or less, wherein 50 ⁇ 0.25 ⁇ m d, d 90 ⁇ 0.4 ⁇ m, such an aspect can make fine fineness based glaze powder melting starting temperature becomes lower, on the other hand can ensure the performance of the ink Under the premise (the current performance requirements of the ink is d 50 ⁇ 0.5 ⁇ m, d 90 ⁇ 1 ⁇ m), the fineness of the large red material can be slightly thicker to favor the large red color.
  • the base glaze powder is mixed with the solvent evenly during the slow stirring process, and then the large red color material is added while slowly stirring, so that Let the base glaze powder form a colloidal suspension with the solvent.
  • the colloidal suspension will slowly wet the large red material and the large red material particles.
  • a gel-like protective film is formed around the surface to ensure that the color material and the base glaze powder are not separated by fineness, and the phase separation phenomenon is ensured, thereby ensuring the use performance of the ink, and the protective film is also heated at a high temperature. It can protect the cadmium and selenium red mass from oxidation and vulcanization.
  • the hair color is bright and pure, because the method of adding titanium white powder and cerium oxide in the base glaze powder is not added to the basic frit, because the titanium dioxide and cerium oxide react with other oxides when the frit is added.
  • the new compound will reduce the protection of the cadmium-selenium red mass. Since the fineness of the base glaze powder is very fine and the initial melting temperature is low, the inventors discovered through observation of a high temperature microscope during the test that the base glaze powder of the present invention starts to melt at 650 ° C, at this time, titanium dioxide and cerium oxide.
  • these melts are wrapped around the chromic cadmium selenide crystal chromophore, thus protecting the cadmium selenide crystal chromophore. Since the proper amount of cerium oxide, cerium oxide and cerium oxide is added to the base glaze powder of the present invention, lanthanum, cerium and lanthanum are all lanthanoid elements, and all of them are members of rare earth elements, and all of them can form stable complex ions and organic chelating agents.
  • the trivalent cation of the compound, the mixed rare earth element can be used as a decolorizing agent, a desulfurizing agent and an oxidizing agent for the glass body at a high temperature, and it is the special properties of these rare earth elements at a high temperature that can ensure the chromophore of the cadmium selenide crystal at a high temperature. It will not be vulcanized and oxidized, thus ensuring the high red color of the high-temperature red ink is pure and vivid.
  • the main component of the inkjet printing machine, the nozzle is a high-precision electronic component. The performance requirements of the ink are very high.
  • ink properties such as viscosity, fluidity, surface tension, electrical conductivity, air bubbles, etc.
  • ink properties such as viscosity, fluidity, surface tension, electrical conductivity, air bubbles, etc.
  • it will cause blockage and even burn out the nozzle, thus affecting the normal use of the inkjet printer.
  • due to the large red color effect it is very sensitive to the atmosphere of the kiln during the firing process, and slightly mutated.
  • the desired effect cannot be achieved, so the solvent in the inkjet ink needs to ensure good stability of the ink and its viscosity, fluidity, surface tension, electrical conductivity, bubbles, etc. are not easily changed during use, and the solvent in the ink is at a high temperature.
  • the residue during volatilization can not affect the color development of large red.
  • the composition of common solvents is mostly composed of oily organic matter and high molecular polymer, and at the same time Preservatives and suspending agents are added to some solvents. These organic substances are used in high temperature.
  • the generated gas has a great influence on the atmosphere of the kiln, which has a great influence on the high-temperature color-increasing effect of the large red, and the preservative, suspending agent and high-molecular polymer added in the common solvent are calcined at a high temperature of 600 ° C or higher.
  • the residual residue content is relatively high.
  • the optimization of the processing method can ensure that the ink is not trapped in the ink, does not generate electric charge and destroys the molecular chain of the colloidal suspension; at the same time, it can ensure that the base glaze powder and the color material are uniformly dispersed and not easy to agglomerate, thereby ensuring the performance of the ink. .
  • the high temperature and large red inkjet ink has stable performance, can adapt to all ceramic inkjet printing models and various types of nozzles on the market, and can also be used together with inkjet inks of other colors currently on the market to make ceramics.
  • the color of the surface decoration of the product is more vivid and the color range is wider.
  • FIG. 1 is a flow chart of a production process for preparing a high temperature large red inkjet ink for ceramic decoration of the present invention, a preparation method thereof, and an application thereof:
  • the corresponding proportion of raw materials are selected: quartz, potassium sodium feldspar, talc, calcium carbonate, potassium carbonate, zinc oxide, barium carbonate, zirconium powder, red lead dan, cerium oxide and cerium oxide. All the raw materials have a particle size of less than 150 mesh, are mixed in a mixer for 30 minutes, and are melted in a frit furnace. The melting temperature is 1500 ° C to 1520 ° C, and the water is quenched into frit pellets to obtain a frit.
  • the frit, kaolin, titanium dioxide, cerium oxide, carboxymethyl cellulose, sodium tripolyphosphate and water are added together into the ball mill to form a sieve with a fineness of 325 mesh. 0.2% to 0.4% of the glaze slurry, sieved by iron removal, dried and powdered, and then ground with a superfine sand mill, planetary ball mill or other ultrafine grinder to a particle size of ⁇ 0.5 ⁇ m , wherein d 50 ⁇ 0.25 ⁇ m, d 90 ⁇ 0.4 ⁇ m, that is, a base glaze powder is obtained.
  • Frit Kaolin Titanium dioxide Ceria Carboxymethyl cellulose sodium tripolyphosphate water 1# 86 2 6 6 0.02 0.2 37 2# 88 3 4 5 0.03 0.4 38.5 3# 90 2 4 4 0.04 0.3 40 4# 86 4 5 5 0.03 0.4 38.5
  • the dispersant and the stabilizer are respectively dissolved in a weakly polar to medium-polar organic solvent and stirred uniformly to obtain a solvent.
  • the solubility parameter of the weakly polar to medium polar organic solvent is 14-23 (J/cm 3 ) 1/2 , which is tetrahydrofuran, cyclohexanone, castor oil, ethylene glycol butyl ether, diethylene glycol butyl ether. Mixing one or more of dichloroethane, kerosene, n-pentanol, and isoamyl alcohol.
  • weakly to medium polarity organic solvents various commonly used weakly to medium polarity organic solvents in the field of ceramics having a solubility parameter of 14-23 (J/cm 3 ) 1/2 can also be used.
  • the dispersing agent is an oil-soluble small molecular weight organic substance, which is a mixture of one or more of BYKJET-9131, BYKJET-9132, BYKJET-9133, Solsperse 20000, Solsperse 17000 and Solsperse 8000;
  • the stabilizer is an oil-soluble large molecular weight organic substance, which is a mixture of one or more of epoxy resin, polyvinyl butyral, DISPERBYK-109, DISPERBYK-115, DISPERBYK-174 and DISPERBYK-180.
  • the cadmium selenium red coated color material is ground to a particle size of ⁇ 5 ⁇ m by an ultrafine sand mill, a planetary ball mill or other ultrafine grinder, wherein d 50 ⁇ 0.7 ⁇ m, d 90 ⁇ 2.5 ⁇ m, that is, a large red material is obtained.
  • step A prepare the obtained base glaze powder, and slowly add the base glaze powder to the solvent while stirring (ultrasonic) until the base glaze powder is uniformly mixed with the solvent, and then slowly mix the remaining large red material into the mixture while stirring. In the liquid, until the mixing is uniform, and finally ball milled to the inkjet printing machine with the ultra-fine sand mill, planetary grinder or other ultra-fine grinder to meet the requirements of the use parameters, and placed in a plastic bucket to store high temperature. Red inkjet ink.
  • the high-temperature large red inkjet ink prepared in the above steps and the inkjet ink of other colors are sequentially loaded into the ink cartridge of the inkjet printing machine, in the normal-bottomed, glazed ceramic.
  • the brick is subjected to inkjet printing, and then enters the roller kiln for firing.
  • the firing temperature ranges from 1080 ° C to 1230 ° C, and is finished into a finished product by grinding, grading and the like.
  • the color of the product is stable, and the hair color of each part of the kiln is consistent without color difference.
  • the printed area is bright and pure red, and the color is bright and dazzling, moist and bright, and the sun is shining, and the printing is measured by a color measuring instrument.
  • the color L*, a*, b* value, glaze color redness a* value is 57.28, showing a typical red color.
  • the color hair color is bright and pure, the color is rich, the color gamut is wide, and the decorative effect and artistic beauty are strong.
  • the main indicators of the tested products are shown in Table 5 below.

Abstract

一种陶瓷装饰用高温大红色喷墨墨水的制备方法及其应用，在不对现有的喷墨墨水的生产工艺及喷墨印花生产工艺做出重大改变的基础上，重点对高温大红色喷墨喷水的基础釉粉的配方组成、基础釉粉熔块的组成、溶剂的配方组成、基础釉粉及大红色料的研磨方法及粒径的优选，从而使高温大红色喷墨墨水的性能达到喷墨印花机的使用要求，并使喷印了高温大红色喷墨墨水的陶瓷砖在经高温烧制后，表面装饰的颜色呈现鲜艳纯正的大红色、釉面润泽光亮、灿若朝阳，与其它颜色的喷墨墨水印花叠加处的颜色鲜艳、色彩丰富、色域宽广，突破了陶瓷装饰用喷墨墨水高温大红色发色不纯、甚至发不了色的世界性难题，同时该技术具备较强的普适性，易于在行业内推广。

Description

陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用 技术领域：
本发明涉及一种陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用。
背景技术：
喷墨印花技术在陶瓷行业中的应用已有十多年历史了，由于喷墨印花采用的是非接触式的印花方式，它是一种将墨水通过喷头喷射到各种待印介质表面，因此对待印介质的表面形状没有过多的要求，印花时是将设计的图稿信息输入喷墨印花机的电脑系统中，即可进行印花，不要像传统的印花技术要先经过制版，因此喷墨印花技术操作简单、开发周期短、员工劳动强度低，可按量生产，完全可实现个性化的定制需求。但其对墨水的要求比较苛刻，由于喷头的孔径小，墨水的粒径几乎要全部达到纳米级。众所周知，从发色角度来说，色料的粒径越小，其发色越困难，因此到目前为止，墨水的种类还比较少，像高温大红色墨水更是一片空白，而大红色又是最重要的三元色之一，缺少大红色，陶瓷产品的装饰效果就显得不够鲜艳、不够绚丽多彩，这也是目前世界陶瓷喷墨印花技术上最大的难题。
发明内容：
本发明的目的在于克服上述缺点，提供一种陶瓷装饰用高温大红色喷墨 墨水和制备方法及其应用，在不对现有喷墨墨水的生产工艺及喷墨印花设备和喷墨印花工艺做出重大改变的基础上，重点对高温大红色喷墨墨水的基础釉粉组成、基础釉粉熔块的组成、溶剂的配方组成、基础釉粉及大红色料的研磨方法及粒径的优选、墨水的配方组成及加工方法等进行调整与优化，从而使高温大红色喷墨墨水的性能达到喷墨印花机的使用要求，并使喷印了高温大红色喷墨墨水的陶瓷砖在经高温烧制后(1080℃～1230℃)，单一喷印了高温大红色喷墨墨水的陶瓷砖表面装饰的颜色呈鲜艳的大红色，色彩鲜艳夺目、大红色纯正，与其它颜色喷墨墨水印花叠加处的颜色鲜艳、绚丽多彩、色域宽广。同时该技术具备较强的普适性，易于在行业内推广。
为解决上述问题，本发明通过以下技术方案实现；
本发明的一种陶瓷装饰用高温大红色喷墨墨水，其按以下重量份组分配制：
基础釉粉15～25份，大红色料15～25份，溶剂50～70份；
其中的基础釉粉：按以下重量份组分配制：
熔块86～90份，高岭土2～4份，钛白粉4～6份，氧化铈4～6份，外加羧甲基纤维素0.02～0.04份，三聚磷酸钠0.2～0.4份，水37～40份；
其中熔块按以下重量百分比组分配制：
SiO258.5～60.5％，Al2O36.5～8.5％，CaO 8.5～10.5％，MgO 0.2～0.4％，K2O 3.5～5.5％，Na2O 0.6～0.8％，ZnO 2.5～4.5％，SrO 0.6～0.8％，ZrO22.5～4.5％，PbO 0.8～1.2％，Gd2O30.6～0.8％，La2O33～5％，所有的组分之和为100％；
其中的大红色料为镉硒红包裹色料超细研磨而成；
其中的溶剂：按以下重量份组分配制：
弱极性～中等极性有机溶剂100份，分散剂0.4～2.4份，稳定剂1～3.4份；
其中弱极性～中等极性有机溶剂的溶度参数为14-23(J/cm3)1/2，可以选用本陶瓷领域内的常用的弱极性～中等极性有机溶剂。
更近一步的是方案是：弱极性～中等极性有机溶剂为四氢呋喃、环己酮、蓖麻油、乙二醇丁醚、二乙二醇丁醚、二氯乙烷、煤油、正戊醇以及异戊醇类的一种或多种混合。
其中分散剂为油溶性的小分子量有机物，为BYKJET-9131、BYKJET-9132、BYKJET-9133、Solsperse 20000、Solsperse 17000以及Solsperse 8000类中的一种或多种混合；
其中稳定剂为油溶性的大分子量有机物，为环氧树脂、聚乙烯醇缩丁醛、DISPERBYK-109、DISPERBYK-115、DISPERBYK-174以及DISPERBYK-180类中的一种或多种混合。
本发明还涉及一种陶瓷装饰用高温大红色喷墨墨水的制备方法，其包括以下步骤：
A、基础釉粉的制备：
基础釉粉按以下重量份组分配制：
熔块86～90份，高岭土2～4份，钛白粉4～6份，氧化铈4～6份，外加羧甲基纤维素0.02～0.04份，三聚磷酸钠0.2～0.4份，水37～40份一起入球磨机磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经除铁过筛、烘干打粉，然后再用超细砂磨机、行星式研磨机或其它超细研磨机将此粉料磨细至粒径为≤0.5μm，其中d50≤0.25μm，d90≤0.40μm，即得 到基础釉粉；
其中熔块按以下重量百分比组分配制：
SiO258.5～60.5％，Al2O36.5～8.5％，CaO 8.5～10.5％，MgO 0.2～0.4％，K2O 3.5～5.5％，Na2O 0.6～0.8％，ZnO 2.5～4.5％，SrO 0.6～0.8％，ZrO22.5～4.5％，PbO 0.8～1.2％，Gd2O30.6～0.8％，La2O33～5％，所有的组分之和为100％；
将含上述组分的粒度均小于150目的石英、钾钠长石、滑石、碳酸钙、碳酸钾、氧化锌、碳酸锶、锆英粉、红丹粉、氧化钆以及氧化镧，按照上述组分范围配料、混合机混合、熔块池窑熔制，熔制的温度范围1500℃～1520℃，然后水淬成熔块颗粒，烘干即得熔块；
B、溶剂的制备：
溶剂按以下重量份组分配制：
弱极性～中等极性有机溶剂100份，分散剂0.4～2.4份，稳定剂1～3.4份；
按照上述重量份组分分别将分散剂和稳定剂溶解于弱极性～中等极性有机溶剂中搅拌均匀即得溶剂；
其中弱极性～中等极性有机溶剂的溶度参数为14-23(J/cm3)1/2，可以选用本陶瓷领域内的常用的弱极性～中等极性有机溶剂。
更近一步的是方案是：弱极性～中等极性有机溶剂为四氢呋喃、环己酮、蓖麻油、乙二醇丁醚、二乙二醇丁醚、二氯乙烷、煤油、正戊醇以及异戊醇类的一种或多种混合。
其中分散剂为油溶性的小分子量有机物，为BYKJET-9131、BYKJET-9132、BYKJET-9133、Solsperse 20000、Solsperse 17000以及 Solsperse 8000类中的一种或多种混合；
其中稳定剂为油溶性的大分子量有机物，为环氧树脂、聚乙烯醇缩丁醛、DISPERBYK-109、DISPERBYK-115、DISPERBYK-174以及DISPERBYK-180类中的一种或多种混合。
C、大红色料的制备：
将镉硒红包裹色料用超细砂磨机、行星式研磨机或其它超细研磨机磨细至粒径≤5μm，其中d50≤0.7μm，d90≤2.5μm即得到大红色料；
D、高温大红色喷墨墨水的制备：
高温大红色喷墨墨水按以下重量份组分配制：
基础釉粉15～25份，大红色料15～25份，溶剂50～70份；
按上述重量份组分先称取步骤B中制备得到的溶剂，放入有搅拌装置或超声装置或两者兼而有之的不锈钢或塑料桶中，然后称取步骤A中制备得到的基础釉粉，一边搅拌(超声)一边慢慢将基础釉粉加入溶剂中，直到基础釉粉与溶剂混合均匀后，再一边搅拌一边慢慢将剩下的大红色料放入此混合液中，直到搅拌均匀，最后用超细砂磨机、行星式研磨机或其它超细研磨机球磨至喷墨印花机所需的使用参数要求，经过筛放入塑料桶中储存即得高温大红色喷墨墨水。
本发明还涉及一种高温大红色喷墨印花陶瓷砖，根据图案设计需要，将上述的陶瓷装饰用高温大红色喷墨墨水的制备方法中制备得到的高温大红色喷墨墨水与其它颜色的喷墨墨水按顺序装入喷墨印花机的墨水盒中，在正常施了底、面釉的陶瓷砖坯上进行喷墨印花，然后进入辊道窑进行烧成，烧成温度范围为1080℃～1230℃，经过磨边、分级等工序，即制成成品。
本发明的陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用，通过优化基础釉粉的组成、基础釉粉熔块的组成、溶剂的配方组成、基础釉粉及大红色料的研磨方法及粒径的优选、墨水的配方组成及加工方法等进行调整与优化，从而使高温大红色喷墨墨水的性能达到喷墨印花机的使用要求，并使喷印了高温大红色喷墨墨水的陶瓷砖在经高温烧制后(1080℃～1230℃)，单一喷印了高温大红色喷墨墨水的陶瓷砖表面装饰的颜色呈现鲜艳的大红色，色彩鲜艳夺目、大红色纯正，与其它颜色喷墨墨水印花叠加处呈现多彩的颜色，且颜色鲜艳、绚丽多彩、色域宽广。由于本发明的陶瓷装饰用的高温大红色喷墨墨水为了达到喷头的使用要求，其细度很细，其粒度d50≤0.5μm，d90≤1μm。众所周知，色料细度越细，其发色越困难，因此喷墨墨水至今为止种类不多，而在高温下(高于1000℃)时发色纯正的大红色墨水自从喷墨印花技术在陶瓷行业应用以来至今仍是一片空白，为了突破这个行业内的世界性难题，本申请的发明人通过数万次的试验，通过优化基础釉粉的组成、基础釉粉熔块的组成，首先在基础釉粉熔块中添加了适量对大红色发色有促进作用的CaO、PbO、SrO、ZrO2等氧化物。众所周知，在众多能使陶瓷制品获得大红色装饰效果的色剂中，唯独以硫硒化镉为发色剂的色料能产生色泽最鲜艳、发色最纯正的装饰效果，但由于硫硒化镉热稳定性差，在空气加热时，超过500℃即开始分解，高于800℃时会完全分解氧化而变黑，甚至完全失红颜色，因此现在市场上的镉硒红色料为了稳定发色均是以ZrSO4细小晶体包裹硫硒化镉晶体发色团，但即便如此，这种包裹型的镉硒红色料呈色也不稳定，在烧制中对窑室的气氛十分敏感，易氧化或受SO2影响而变黑，同时ZrSO4的包裹型结构在外力作用下易造成破坏，以及ZrSO4 细小晶体在超过1000℃高温时又极易与硫硒化镉晶体发色团分离，从而失去保护硫硒化镉晶体发色团的作用，因此本发明人在加工过程中将基础釉粉与镉硒红包裹色料单独分开研磨，在细度控制方面，基础釉粉尽量细；其粒径控制在0.5μm以下，其中d50≤0.25μm，d90≤0.4μm，一方面这样细的细度可以使基础釉粉的始融温度变得更低，另一方面又可以在保证墨水使用性能的前提下(墨水目前使用性能要求是d50≤0.5μm，d90≤1μm)使大红色料的细度可以稍粗一点，以有利大红色的发色。因为色料的细度越细其发色效果越差；在墨水加工时先将基础釉粉在慢慢搅拌过程中与溶剂混合均匀，然后一边慢慢搅拌一边加入大红色色料，这样可以先让基础釉粉与溶剂形成一种胶状的悬浮液，当在慢慢搅拌过程中加入大红色料时，这些胶状的悬浮液就会慢慢润湿大红色料，并在大红色料颗粒周围形成一个胶状的保护膜，一方面保证了色料与基础釉粉不会因细度的不同，而产生分相现象，保证了墨水的使用性能，同时这层保护膜在高温煅烧时还可以保护镉硒红色料团不被氧化、硫化。从而使发色鲜艳纯正，因为基础釉粉中的钛白粉、氧化铈的加入方法不是添加在基础熔块中，因为熔块配料时加入，则钛白粉、氧化铈会与其它氧化物反应并生成新的化合物，会降低对镉硒红色料团的保护作用。由于基础釉粉的细度很细，始融温度低，本发明人在试验过程中通过可视化高温显微镜观测发现本发明中的基础釉粉在650℃时就开始熔融，此时钛白粉、氧化铈与基础熔块粉共同作用形成一种低温像搪瓷釉一样的融体，这些融体包裹在硫硒化镉晶体发色团周围，从而对硫硒化镉晶体发色团起到保护作用。由于本发明的基础釉粉中添加了适量的氧化镧、氧化铈、氧化钆，镧、铈、钆都是镧系元素，它们都是稀土元素的成员，都能形成稳定的络离子和 有机螯合物的三价阳离子，混合稀土元素在高温中可用作玻璃体的脱色剂、脱硫剂和氧化剂，正是这些稀土元素在高温中的特殊性能，可以确保硫硒化镉晶体发色团在高温中不会被硫化、氧化，从而保证了高温大红色墨水的大红色发色纯正、鲜艳夺目。众所周知，喷墨印花机的核心部件——喷头，是一种高精密的电子元件，对墨水的性能要求非常高，在生产过程中墨水性能如粘度、流动性、表面张力、电导率、气泡等一旦发生细小的变化就会造成堵塞，甚至烧坏喷头，从而影响喷墨印花机的正常使用；同时由于大红色的发色效果在烧制过程中对窑室的气氛十分敏感，稍有变异便不能达到预期效果，因此喷墨墨水中的溶剂需要保证墨水具有良好稳定性及在使用过程中其粘度、流动性、表面张力、电导率、气泡等不容易产生变化，同时墨水中的溶剂在高温挥发时的残留物还不能对大红色的发色产生影响，因此高温大红喷墨墨水的溶剂配方组成也较为关键，普通溶剂的构成大都是采用油性的有机物及高分子聚合物构成，同时为了保证储存，有些溶剂里还添加了防腐剂及悬浮剂，这些有机物在高温中挥发产生的气体对窑炉的气氛影响特别大，从而对大红色的高温发色效果产生很大的影响，同时普通溶剂里添加的防腐剂、悬浮剂及高分子聚合物在600℃或以上高温煅烧下，其残留的残渣物含量比较高，由于硫硒化镉热稳定性差，在空气中加热时，超过500℃即开始分解，高于800℃时会完全分解而变黑，甚至完全失去红颜色，因此这些残渣物严重影响了硫硒化镉晶体的发色，本发明人通过数百次试验，根据市场上各种溶剂对大红色高温发色产生的不同影响，并借助先进的分析仪器设备，对高温大红色喷墨墨水的溶剂的配方组成进行优化，使溶剂在保证良好的喷墨印刷机使用要求的同时在400℃煅烧下能够完全挥发，并不留残渣物， 从而确保大红色印花釉的发色效果。加工方法的优化，可以保证墨水中不会夹带有气泡，不会产生电荷及破坏胶体悬浮液的分子链；同时还可以保证基础釉粉及色料分散均匀不易结团，从而保障了墨水的性能。
本发明提供的陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用有如下优点：
1、由于优化了基础釉粉的组成、基础釉粉的熔块化学组成、溶剂的配方组成、基础釉粉及大红色料的研磨方法及粒径的优选、墨水的加工方法及配方组成等，从而使高温大红色喷墨墨水通过喷墨印花方式喷印在陶瓷砖产品表面，在高温(1080℃～1230℃)煅烧下大红色发色纯正、鲜艳夺目，从而突破了陶瓷装饰用喷墨墨水缺少高温大红色的世界性难题，从而使喷墨印花技术在陶瓷装饰领域的应用提供了更广阔的前景。
2、该高温大红色喷墨墨水性能稳定，可适应目前市场上所有的陶瓷喷墨印花机型及各种型号的喷头，还可以与目前市场上的其它颜色的喷墨墨水一起使用，使陶瓷产品表面装饰的颜色更加鲜艳，色彩范围更为宽广。
3、喷印该陶瓷装饰用高温大红色喷墨墨水的陶瓷砖产品，其产品质量不会受到任何影响，装饰色彩更为宽广、接近自然、图案设计更便捷，主要技术指标：磨擦系数、耐酸碱性、表面质量、铅镉溶出量、放射性均达到GB/T4100-2006及HJ/T297-2006标准要求。
4、采用现有的喷墨墨水及喷墨印花的生产工艺，使大红色发色对窑炉烧成气氛的敏感度大大降低，易于实现产业化规模。
附图说明：
图1是制备本发明的陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用的生产工艺流程图：
具体实施方式：
下面结合实施例对本发明作进一步详细说明。
实例1、
本发明的陶瓷装饰用高温大红色喷墨墨水和制备方法及其应用，首先制备基础釉粉：
制备熔块：
按表1的化学组成成分选取相应比例的原料：石英、钾钠长石、滑石、碳酸钙、碳酸钾、氧化锌、碳酸锶、锆英粉、红铅丹、氧化钆以及氧化镧，进行配料，所有的原料粒度均小于150目，在混料机中混合30分钟，在熔块炉内熔制，熔制温度1500℃～1520℃，水淬成熔块颗粒烘干即得熔块。
表1、熔块的化学组成成分表(重量百分比，％)
  SiO2 Al2O3 CaO MgO K2O Na2O ZnO SrO ZrO2 PbO Gd2O3 La2O3
1# 60.5 6.5 10.5 0.2 5.5 0.6 4.5 0.6 4.5 0.8 0.8 5
2# 58.5 8.5 10.5 0.4 4.5 0.8 4.5 0.8 4.5 1.2 0.8 5
3# 59.5 7.5 10.5 0.3 5.5 0.7 4.2 0.7 4.5 1 0.6 5
4# 60.5 8.5 9.5 0.4 5.5 0.8 4.5 0.8 3.5 1.2 0.8 4
5# 60.5 8.5 8.5 0.3 4.8 0.8 4.5 0.8 4.4 1.2 0.7 5
6# 60.5 8.5 10.5 0.4 5.5 0.8 3.5 0.8 4.5 1.2 0.8 3
7# 60.3 8.4 10.4 0.4 3.5 0.8 4.5 0.8 4.3 1.1 0.7 4.8
8# 60.5 8.5 10.5 0.4 5.4 0.7 4 0.7 2.5 1.1 0.8 4.9
9# 60.4 8.4 10.4 0.3 5.5 0.7 2.5 0.8 4.4 1.1 0.7 4.8
制备基础釉粉：
按表2基础釉粉配方组成称取熔块、高岭土、钛白粉、氧化铈、羧甲基 纤维素、三聚磷酸钠与水一起入球磨机磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经除铁过筛、烘干打粉，然后再用超细砂磨机、行星式球磨机或其它超细研磨机将此粉料磨细至粒径为≤0.5μm，其中d50≤0.25μm，d90≤0.4μm，即得到基础釉粉。
表2、基础釉粉配方组成成分表(重量份)
  熔块 高岭土 钛白粉 氧化铈 羧甲基纤维素 三聚磷酸钠 水
1# 86 2 6 6 0.02 0.2 37
2# 88 3 4 5 0.03 0.4 38.5
3# 90 2 4 4 0.04 0.3 40
4# 86 4 5 5 0.03 0.4 38.5
制备溶剂：
按表3溶剂配方组成分别将分散剂和稳定剂溶解于弱极性～中等极性有机溶剂中搅拌均匀即得溶剂。
表3、溶剂配方组成成分表(重量份)
  弱极性～中等极性有机溶剂 分散剂 稳定剂
1# 100 0.4 3.4
2# 100 1.4 1.6
3# 100 2.4 1.0
4# 100 0.8 2.8
5# 100 1.9 2.2
其中弱极性～中等极性有机溶剂的溶度参数为14-23(J/cm3)1/2，为四氢呋喃、环己酮、蓖麻油、乙二醇丁醚、二乙二醇丁醚、二氯乙烷、煤油、正戊醇以及异戊醇类的一种或多种混合。弱极性到中等极性有机溶剂也可以选用溶度参数为14-23(J/cm3)1/2的本陶瓷领域内的各种常用的弱极性～中等极性有 机溶剂。
其中分散剂为油溶性的小分子量有机物，为BYKJET-9131、BYKJET-9132、BYKJET-9133、Solsperse 20000、Solsperse 17000以及Solsperse 8000类中的一种或多种混合；
其中稳定剂为油溶性的大分子量有机物，为环氧树脂、聚乙烯醇缩丁醛、DISPERBYK-109、DISPERBYK-115、DISPERBYK-174以及DISPERBYK-180类中的一种或多种混合。
制备大红色料：
将镉硒红包裹色料用超细砂磨机、行星式球磨机或其它超细研磨机磨细至粒径≤5μm，其中d50≤0.7μm，d90≤2.5μm，即得到大红色料。
制备高温大红色喷墨墨水：
按表4高温大红色喷墨墨水的配方组成称取上述步骤中制备得到的溶剂，放入有搅拌装置或超声装置或两者兼而有之的不锈钢或塑料桶中，然后称取步骤A中制备得到的基础釉粉，一边搅拌(超声)一边慢慢将基础釉粉加入溶剂中，直到基础釉粉与溶剂混合均匀后，再一边搅拌一边慢慢将剩下的大红色料放入此混合液中，直到搅拌均匀，最后用超细砂磨机、行星式研磨机或其它超细研磨机球磨至喷墨印花机所需的使用参数要求，经过筛放入塑料桶中储存即得高温大红色喷墨墨水。
表4、高温大红色喷墨墨水配方组成成分表(重量份)
  基础釉粉 大红色料 溶剂
1# 15 20 65
2# 20 25 55
3# 25 15 60
4# 25 25 50
5# 15 15 70
制备高温大红色喷墨印花陶瓷砖：
最后根据图案设计的需要，将上述步骤中制备得到的高温大红色喷墨墨水与其它颜色的喷墨墨水按顺序装入喷墨印花机的墨水盒中，在正常施了底、面釉的陶瓷砖坯上进行喷墨印花，然后进入辊道窑进行烧成，烧成温度范围为1080℃～1230℃，经过磨边、分级等工序，即制成成品。且产品颜色稳定，窑炉各部位的发色一致无色差。观察产品表面，在单一喷印了上述高温大红色喷墨墨水的陶瓷砖产品，其印花处呈现鲜艳纯正的大红色，且色彩鲜艳夺目、润泽光亮、灿若朝阳，通过测色仪测其印花处颜色L*，a*，b*值、釉面颜色红度a*值为57.28，呈现典型的大红颜色。在与其它颜色喷墨墨水叠加处，颜色发色鲜艳纯正、色彩丰富、色域宽广，装饰效果及艺术美感强。经检测产品主要指标如下表5。
表5、产品质量检验结果
Figure PCTCN2015079170-appb-000001
Figure PCTCN2015079170-appb-000002
综上所述，仅为本发明的较佳实例而已，并非对本发明作任何形式上的限制；凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，利用以所揭示的技术内容而做出的些许变更、修饰与演变的等同变化，均视为本发明的等效实例；同时，凡根据本发明的实质技术对以上实施例所作出的任何等同变化的变更、修饰与演变，均仍属于本发明的技术方案的保护范围之内。

Claims (5)

  1. 一种陶瓷装饰用高温大红色喷墨墨水，其特征在于：
    高温大红色喷墨墨水：按以下重量份组分配制：
    基础釉粉15～25份，大红色料15～25份，溶剂50～70份；
    其中的基础釉粉：按以下重量份组分配制：
    熔块86～90份，高岭土2～4份，钛白粉4～6份，氧化铈4～6份，外加羧甲基纤维素0.02～0.04份，三聚磷酸钠0.2～0.4份，水37～40份；
    其中熔块按以下重量百分比组分配制：
    SiO258.5～60.5％，Al2O36.5～8.5％，CaO 8.5～10.5％，MgO 0.2～0.4％，
    K2O 3.5～5.5％，Na2O 0.6～0.8％，ZnO 2.5～4.5％，SrO 0.6～0.8％，
    ZrO22.5～4.5％，PbO 0.8～1.2％，Gd2O30.6～0.8％，La2O33～5％，所有的组分之和为100％；
    其中的大红色料为镉硒红包裹色料超细研磨而成；
    其中的溶剂：按以下重量份组分配制：
    弱极性～中等极性有机溶剂100份，分散剂0.4～2.4份，稳定剂1～3.4份；
    其中弱极性～中等极性有机溶剂的溶度参数为14-23(J/cm3)1/2；
    其中分散剂为油溶性的小分子量有机物，为BYKJET-9131、BYKJET-9132、BYKJET-9133、Solsperse 20000、Solsperse 17000以及Solsperse8000类中的一种或多种混合；
    其中稳定剂为油溶性的大分子量有机物，为环氧树脂、聚乙烯醇缩丁醛、DISPERBYK-109、DISPERBYK-115、DISPERBYK-174以及DISPERBYK-180 类中的一种或多种混合。
  2. 根据权利要求1所述的陶瓷装饰用高温大红色喷墨墨水，其特征在于：
    弱极性～中等极性有机溶剂为四氢呋喃、环己酮、蓖麻油、乙二醇丁醚、二乙二醇丁醚、二氯乙烷、煤油、正戊醇以及异戊醇类的一种或多种混合。
  3. 一种陶瓷装饰用高温大红色喷墨墨水的制备方法，其特征在于：
    其包括以下步骤：
    A、基础釉粉的制备：
    基础釉粉按以下重量份组分配制：
    熔块86～90份，高岭土2～4份，钛白粉4～6份，氧化铈4～6份，外加羧甲基纤维素0.02～0.04份，三聚磷酸钠0.2～0.4份，水37～40份一起入球磨机磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经除铁过筛、烘干打粉，然后再用超细砂磨机、行星式研磨机或其它超细研磨机将此粉料磨细至粒径为≤0.5μm，其中d50≤0.25μm，d90≤0.40μm，即得到基础釉粉；
    其中熔块按以下重量百分比组分配制：
    SiO2 58.5～60.5％，Al2O3 6.5～8.5％，CaO 8.5～10.5％，MgO 0.2～0.4％，K2O 3.5～5.5％，Na2O 0.6～0.8％，ZnO 2.5～4.5％，SrO 0.6～0.8％，ZrO2 2.5～4.5％，PbO 0.8～1.2％，Gd2O3 0.6～0.8％，La2O3 3～5％，所有的组分之和为100％；
    将含上述组分的粒度均小于150目的石英、钾钠长石、滑石、碳酸钙、碳酸钾、氧化锌、碳酸锶、锆英粉、红丹粉、氧化钆以及氧化镧，按照上述组分范围配料、混合机混合、熔块池窑熔制，熔制的温度范围1500℃～1520℃， 然后水淬成熔块颗粒，烘干即得熔块；
    B、溶剂的制备：
    溶剂按以下重量份组分配制：
    弱极性～中等极性有机溶剂100份，分散剂0.4～2.4份，稳定剂1～3.4份；
    按照上述重量份组分分别将分散剂和稳定剂溶解于弱极性～中等极性有机溶剂中搅拌均匀即得溶剂；
    其中弱极性～中等极性有机溶剂的溶度参数为14-23(J/cm3)1/2；
    其中分散剂为油溶性的小分子量有机物，为BYKJET-9131、BYKJET-9132、BYKJET-9133、Solsperse 20000、Solsperse 17000以及Solsperse8000类中的一种或多种混合；
    其中稳定剂为油溶性的大分子量有机物，为环氧树脂、聚乙烯醇缩丁醛、DISPERBYK-109、DISPERBYK-115、DISPERBYK-174以及DISPERBYK-180类中的一种或多种混合；
    C、大红色料的制备：
    将镉硒红包裹色料用超细砂磨机、行星式研磨机或其它超细研磨机磨细至粒径≤5μm，其中d50≤0.7μm，d90≤2.5μm即得到大红色料；
    D、高温大红色喷墨墨水的制备：
    高温大红色喷墨墨水按以下重量份组分配制：
    基础釉粉15～25份，大红色料15～25份，溶剂50～70份；
    按上述重量份组分先称取步骤B中制备得到的溶剂，放入有搅拌装置或超声装置或两者兼而有之的不锈钢或塑料桶中，然后称取步骤A中制备得到的基础釉粉，一边搅拌一边慢慢将基础釉粉加入溶剂中，直到基础釉粉与溶 剂混合均匀后，再一边搅拌一边慢慢将剩下的大红色料放入此混合液中，直到搅拌均匀，最后用超细砂磨机、行星式研磨机或其它超细研磨机球磨至喷墨印花机所需的使用参数要求，经过筛放入塑料桶中储存即得高温大红色喷墨墨水。
  4. 根据权利要求3所述的陶瓷装饰用高温大红色喷墨墨水的制备方法，其特征在于：
    弱极性～中等极性有机溶剂为四氢呋喃、环己酮、蓖麻油、乙二醇丁醚、二乙二醇丁醚、二氯乙烷、煤油、正戊醇以及异戊醇类的一种或多种混合。
  5. 一种高温大红色喷墨印花陶瓷砖，其特征在于：
    根据图案设计需要，将权利要求2中的方法制备得到的高温大红色喷墨墨水与其它颜色的喷墨墨水按顺序装入喷墨印花机的墨水盒中，在正常施了底、面釉的陶瓷砖坯上进行喷墨印花，然后进入辊道窑进行烧成，烧成温度范围为1080℃～1230℃，经过磨边、分级等工序，即制成成品。
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