CN107778991B - Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof - Google Patents
Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof Download PDFInfo
- Publication number
- CN107778991B CN107778991B CN201711064663.XA CN201711064663A CN107778991B CN 107778991 B CN107778991 B CN 107778991B CN 201711064663 A CN201711064663 A CN 201711064663A CN 107778991 B CN107778991 B CN 107778991B
- Authority
- CN
- China
- Prior art keywords
- ink
- ceramic ink
- powder
- zirconium
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 8
- 235000011046 triammonium citrate Nutrition 0.000 claims description 8
- 239000001393 triammonium citrate Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 8
- 229940007718 zinc hydroxide Drugs 0.000 claims description 8
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229920003081 Povidone K 30 Polymers 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 15
- 239000011787 zinc oxide Substances 0.000 abstract description 15
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 14
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 47
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 13
- 239000012463 white pigment Substances 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010020 roller printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
-
- 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
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to zirconium-free water-based ceramic ink for super-white ink-jet printing and a preparation method thereof. The invention adopts two inorganic white pigments, namely zinc oxide and hydroxyapatite nano powder to mix, and because the two powders have different particle characteristics, the interaction between the particles is weakened, thereby avoiding particle aggregation, the ceramic ink has uniform particle size under the action of a dispersing agent, the average particle size is less than 290nm, the ink has no demixing and sedimentation after standing for 8 days, the stability is good, the Hunter whiteness average value after being decorated on a glaze surface is more than 92, and the requirement of the ink for ceramic ink-jet printing is met.
Description
Technical Field
The invention relates to zirconium-free super-white ceramic ink and a preparation method thereof, which are mainly used for ceramic ink-jet printing and belong to the field of ceramic ink.
Background
The ceramic ink-jet printing technology is a non-contact printing technology without printing plate, and can directly image electronic images on the surface of ceramic, and through intelligent color matching, the patterns are well-arranged, and small-batch and multi-color tests or production can be completed in a short time. Compared with screen printing and roller printing, the ink-jet printing technology has the advantages of high efficiency, convenience, energy conservation and environmental protection, and is a ceramic decoration technology with high application value. Ceramic ink is the core of ceramic ink-jet printing technology, and there are more than 14 ceramic inks that have been successfully developed, including blue, brown, yellow, pink, etc. For example, the Chinese invention patent "a red ceramic ink for inkjet printing and a method for using the same" (CN 103045003A) discloses a red ceramic ink for inkjet printing, which is composed of a soluble metal complex and an organic solvent. The Chinese invention patent yellow ceramic ink for ink-jet printing (CN 103342917B) discloses yellow ceramic ink for ink-jet printing, which consists of inorganic pigment powder, a surfactant, a solvent and a dispersant. The Chinese invention patent (CN 106009897A) discloses a preparation method of blue ceramic ink for ink-jet printing.
At present, most researches on white ceramic ink are zirconium-containing and titanium-containing oily ink which takes organic matters as additives, and whiteness and stability are difficult to guarantee. For example, the Chinese invention patent "oil-based white ink for ink-jet recording" (CN 101027370B) discloses an oil-based white ink prepared by using titanium oxide as a ceramic coloring material and adding a resin, an organic solvent and a nonionic surfactant. The Chinese invention patent (CN 103224725B) discloses an oily white ink compounded by a plurality of oxides such as silicon oxide, aluminum oxide and the like. The oily ink has the problems of toxicity of organic solvents and the like, and the water-soluble organic solvent is the development direction of the ceramic ink in the future. The Chinese invention patent (CN 103804993B) discloses an aqueous white ink for preparing a zirconium oxide and silicon oxide mixed pigment by a sol-gel method. Zirconium oxide has the advantages of high whiteness, good stability and the like as a white material for ink-jet printing, but zirconium is easy to coexist with hafnium, hafnium has certain radioactivity, and the preparation cost of zirconium oxide is high, so that the development of white water-based ceramic ink with less zirconium or no zirconium has the significance of energy conservation and environmental protection.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides the ceramic ink for the ultra-white zirconium-free water-based ink-jet printing, which has high whiteness and good ink rheology and is suitable for ceramic ink-jet printing, and the preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the water-based ceramic ink is prepared by mixing and ball-milling nano zinc oxide powder and nano hydroxyapatite powder, adding a solvent and a dispersant, ball-milling and ultrasonically dispersing.
According to the scheme, the average grain size of the nano zinc oxide powder is 21.9-61.8 nm, and the nano zinc oxide powder is prepared by the following method: adding triammonium citrate powder into a zinc acetate solution with the concentration of 0.1-0.3 mol/L, uniformly stirring to obtain a transparent solution, adding absolute ethyl alcohol to obtain a zinc hydroxide suspension, adjusting the pH value of the zinc hydroxide suspension to 8-10 by using an ammonia water solution, heating the zinc hydroxide suspension at 60-80 ℃ for 2-4 h to obtain sol, drying the sol, and calcining to obtain nano zinc oxide powder.
According to the scheme, the mass ratio of the zinc acetate to the triammonium citrate in the transparent solution is 50-60: 40 to 50.
According to the scheme, the drying temperature is 80-100 ℃, the drying time is 5-10 hours, the calcining temperature is 500-700 ℃, and the calcining time is 8-12 hours.
According to the scheme, the average grain size of the nano hydroxyapatite powder is 21.9-61.8 nm, and the nano hydroxyapatite powder is prepared by the following method: mixing Ca (NO)3)2Solution and (NH)4)2HPO4And mixing the solutions to obtain a mixed solution, adjusting the pH value of the mixed solution to 8-10 by using an ammonia water solution, heating the mixed solution at 60-80 ℃ for 2-4 h to obtain gel, drying the gel, and calcining to obtain nano hydroxyapatite powder.
According to the scheme, the Ca (NO)3)2Solution and (NH)4)2HPO4The volume concentration of the solution is 40-60%.
According to the scheme, the drying temperature is 80-100 ℃, the drying time is 5-10 hours, the calcining temperature is 600-700 ℃, and the calcining time is 8-12 hours.
The invention also provides a preparation method of the zirconium-free water-based ceramic ink for super white ink-jet printing, which comprises the following steps: mixing nano zinc oxide powder and nano hydroxyapatite powder according to a mass ratio of 10-90: 10-90, mixing, performing ball milling for 3-6 hours to obtain composite powder, adding a solvent and a dispersing agent into the obtained composite powder, performing ball milling and mixing for 2-4 hours to obtain a suspension, and performing ultrasonic dispersion on the suspension uniformly to obtain the white ceramic ink.
Preferably, the solvent is ethanol, and the dispersant is one or a mixture of any two or more of polyethylene glycol, sodium dodecyl benzene sulfonate, povidone K30 and glycerol in any proportion.
Preferably, the mass percentages of the composite powder, the solvent and the dispersant in the suspension are as follows: 30-40% of composite powder, 50-60% of solvent and 5-10% of dispersing agent.
Preferably, the ultrasonic dispersion time is 30-60 min.
The invention adopts a sol-gel method to prepare nano zinc oxide and nano hydroxyapatite powder with uniform size and high purity, and then adds a solvent, a suspension, a dispersant and the like to prepare the zirconium-free and heavy metal-free water-based ceramic ink for super-white ink-jet printing. The hydroxyapatite can effectively inhibit the zinc oxide from growing in the calcining process, and the mixing of the two nano-powders can play the roles of reflecting and scattering light to the maximum extent, so that the whiteness of the hydroxyapatite is equivalent to that of a white material containing zirconium. Meanwhile, the additive is selected and added to play a good role in resisting precipitation, promoting suspension and keeping whiteness, for example, STTP can eliminate electrostatic attraction among powder particles, increase repulsive force, break micelle agglomeration, release wrapped free water, reduce viscosity of glaze slip and increase rheological property, and finally the ceramic ink for ultrawhite zirconium-free water-based inkjet printing, which is suitable for ceramic inkjet printing, is obtained.
The invention has the beneficial effects that:
1. according to the invention, two inorganic nano zinc oxide and hydroxyapatite powder are mixed, and because the two powder particles have different characteristics, hydroxyl exists in the hydroxyapatite and is easy to react with an organic additive to form surface coating, so that the interaction among the particles is weakened, and the attractive force among the hydroxyapatite particles is further weakened by taking ethanol as a solvent, so that the particle aggregation is avoided, therefore, under the action of a dispersing agent, the ceramic ink has uniform particle size, the average particle size is less than 290nm, after standing for 8 days, the ink has no layering and sedimentation, the stability is good, the Hunter whiteness average value after being decorated on a glaze surface is greater than 92, and the requirement of the ink for ceramic ink-jet printing is met.
2. The preparation process of the ultra-white zirconium-free ceramic ink is simple, wherein the calcination temperature of the composite white pigment is only 600-700 ℃, and the zirconia pigment is prepared by burning at the high temperature of 1500 ℃ in the prior art. Therefore, the cost of the white ceramic ink is only 1/3-1/2 of zirconium-containing ink.
Drawings
FIG. 1 is an XRD spectrum of a composite white pigment of zinc oxide and hydroxyapatite prepared in example 1 of the present invention;
FIG. 2 is a graph showing a particle size distribution of the ceramic ink prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
The preparation method of the zirconium-free ultra-white water-based ceramic ink for ink-jet printing comprises the following specific steps:
1) preparation of composite white pigment
Preparation of nano zinc oxide powder
Adding triammonium citrate powder into a zinc acetate solution with the concentration of 0.1mol/L, magnetically stirring and mixing for 30min to obtain a transparent solution, adding absolute ethyl alcohol to obtain a zinc hydroxide suspension, adding 5 volume percent of ammonia water to adjust the pH value to 8, carrying out water bath at 80 ℃ for 2h to obtain sol, drying at 80 ℃ for 8h in an electric heating constant temperature drying oven, and calcining at 500 ℃ for 12h in a resistance furnace to obtain nano zinc oxide powder.
The mass fraction of zinc acetate in the transparent solution is 60%, and the mass fraction of triammonium citrate is 40%.
Preparation of nano hydroxyapatite powder
Mixing Ca (NO)3)2And (NH)4)2HPO4Mixing the solution for 30min to obtain a mixed solution, adjusting the pH to 8 with 5% ammonia water by volume percentage, carrying out water bath at 60 ℃ for 2h to obtain gel, drying at 80 ℃ for 5h in an electrothermal constant-temperature drying oven, and calcining at 600 ℃ for 9h in a resistance furnace to obtain nano hydroxyapatite powder.
Ca (NO) in the above mixed solution3)2Solution and (NH)4)2HPO4The volume percentages of the solutions were all 50%.
Preparation of composite powder of nano zinc oxide and hydroxyapatite
Mixing the nano zinc oxide and the nano hydroxyapatite powder obtained in the first step and the second step by mass percent: 70% of zinc oxide and 30% of hydroxyapatite are mixed and ball milled for 3 hours to obtain the composite white pigment.
2) Preparation of white ceramic ink
And (4) adding a solvent and a dispersing agent into the composite powder obtained in the third step to obtain a mixture, performing ball milling and mixing for 2 hours to obtain a suspension, and performing ultrasonic treatment in an ultrasonic cleaner for 30min to obtain the white ceramic ink.
The solvent is ethanol, and the dispersant is 1:1 mixture of polyethylene glycol and glycerol. Wherein the amount of the composite powder accounts for 40 percent of the total mass of the mixture, the addition amount of the solvent accounts for 55 percent of the total mass of the mixture, and the addition amount of the dispersant accounts for 5 percent of the total mass of the mixture.
As shown in fig. 1, which is an XRD spectrum of the composite white pigment of zinc oxide and hydroxyapatite prepared in this example, it can be seen that the crystals of zinc oxide and hydroxyapatite are relatively intact. Fig. 2 is a particle size distribution diagram of the ceramic ink prepared in this example, and it can be seen that the particle sizes of the powders in the ceramic ink are uniform and normally distributed.
Tests prove that the average grain size of the nano zinc oxide and hydroxyapatite composite powder is 33nm, the average grain size of the prepared white ceramic ink is 290nm, and the Hunter whiteness after being decorated on a glaze surface is 93, so that the ink meets the requirements of ink for ceramic ink-jet printing.
Example 2
The preparation method of the zirconium-free ultra-white water-based ceramic ink for ink-jet printing comprises the following specific steps:
1) preparation of composite white pigment
Preparation of nano zinc oxide powder
Adding triammonium citrate powder into a zinc acetate solution with the concentration of 0.3mol/L, magnetically stirring and mixing for 50min to obtain a transparent solution, adding absolute ethyl alcohol to obtain a zinc hydroxide suspension, adding 6 volume percent ammonia water to adjust the pH value to 10, carrying out water bath at 60 ℃ for 4h to obtain sol, drying at 100 ℃ for 5h in an electric heating constant-temperature drying oven, and calcining at 700 ℃ for 8h in a resistance furnace to obtain nano zinc oxide powder.
The mass fraction of zinc acetate in the transparent solution is 40%, and the mass fraction of triammonium citrate is 60%.
Preparation of nano hydroxyapatite powder
Mixing Ca (NO)3)2And (NH)4)2HPO4Mixing the solution for 30min to obtain a mixed solution, adjusting the pH to 9 with 5% ammonia water by volume percentage, carrying out water bath at 70 ℃ for 3h to obtain gel, drying at 100 ℃ for 5h in an electrothermal constant-temperature drying oven, and calcining at 500 ℃ for 12h in a resistance furnace to obtain nano hydroxyapatite powder.
Ca (NO) in the above mixed solution3)2The volume percentage of the solution is 60%, (NH)4)2HPO4The volume percentage of the solution was 40%.
Preparation of composite powder of nano zinc oxide and hydroxyapatite
Mixing the nano zinc oxide and the nano hydroxyapatite powder obtained in the first step and the second step by mass percent: 50% of zinc oxide and 50% of hydroxyapatite are mixed and ball-milled for 4 hours to obtain the composite white pigment.
2) Preparation of white ceramic ink
And (4) adding a solvent and a dispersing agent into the composite powder obtained in the third step to obtain a mixture, performing ball milling and mixing for 3 hours to obtain a suspension, and performing ultrasonic treatment in an ultrasonic cleaner for 50min to obtain the white ceramic ink.
The solvent is ethanol, and the dispersant is a mixture of polyethylene glycol, sodium dodecyl benzene sulfonate and povidone K30, which respectively account for 30%, 30% and 40%. Wherein the amount of the composite powder accounts for 30 percent of the total mass of the mixture, the addition amount of the solvent accounts for 60 percent of the total mass of the mixture, and the addition amount of the dispersant accounts for 10 percent of the total mass of the mixture.
Tests prove that the average grain size of the nano zinc oxide and hydroxyapatite composite powder is 42nm, the average grain size of the prepared white ceramic ink is 275nm, and the Hunter whiteness after being decorated on a glaze surface is 92, so that the ink meets the requirements of ink for ceramic ink-jet printing.
Claims (9)
1. The zirconium-free ultra-white water-based ceramic ink for ink-jet printing is characterized in that: the water-based ceramic ink is prepared by mixing and ball-milling nano zinc oxide powder and nano hydroxyapatite powder, adding a solvent and a dispersant, ball-milling and ultrasonically dispersing;
the preparation method comprises the following steps: mixing nano zinc oxide powder and nano hydroxyapatite powder according to a mass ratio of 10-90: 10-90, mixing, performing ball milling for 3-6 hours to obtain composite powder, adding a solvent and a dispersing agent into the obtained composite powder, performing ball milling and mixing for 2-4 hours to obtain a suspension, and performing ultrasonic dispersion on the suspension uniformly to obtain white ceramic ink;
the solvent is ethanol; the dispersing agent is one or a mixture of more than two of polyethylene glycol, sodium dodecyl benzene sulfonate, povidone K30 and glycerol in any proportion.
2. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 1, wherein: the average grain size of the nano zinc oxide powder is 21.9-61.8 nm, and the nano zinc oxide powder is prepared by the following method: adding triammonium citrate powder into a zinc acetate solution with the concentration of 0.1-0.3 mol/L, uniformly stirring to obtain a transparent solution, adding absolute ethyl alcohol to obtain a zinc hydroxide suspension, adjusting the pH value of the zinc hydroxide suspension to 8-10 by using an ammonia water solution, heating the zinc hydroxide suspension at 60-80 ℃ for 2-4 h to obtain sol, drying the sol, and calcining to obtain nano zinc oxide powder.
3. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 2, characterized in that: the mass ratio of the zinc acetate to the triammonium citrate in the transparent solution is 50-60: 40 to 50.
4. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 2, characterized in that: the drying temperature is 80-100 ℃, the drying time is 5-10 h, the calcining temperature is 500-700 ℃, and the calcining time is 8-12 h.
5. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 1, wherein: the average grain size of the nano hydroxyapatite powder is 21.9-61.8 nm, and the nano hydroxyapatite powder is prepared by the following method: mixing Ca (NO)3)2Solution and (NH)4)2HPO4And mixing the solutions to obtain a mixed solution, adjusting the pH value of the mixed solution to 8-10 by using an ammonia water solution, heating the mixed solution at 60-80 ℃ for 2-4 h to obtain gel, drying the gel, and calcining to obtain nano hydroxyapatite powder.
6. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 5, wherein: the Ca (NO)3)2Solution and (NH)4)2HPO4The volume concentration of the solution is 40-60%.
7. The aqueous ceramic ink for zirconium-free ultra-white inkjet printing according to claim 5, wherein: the drying temperature is 80-100 ℃, the drying time is 5-10 h, the calcining temperature is 600-700 ℃, and the calcining time is 8-12 h.
8. A method for preparing the zirconium-free water-based ceramic ink for ultra-white ink-jet printing according to any one of claims 1 to 7, which is characterized by comprising the following steps: mixing nano zinc oxide powder and nano hydroxyapatite powder according to a mass ratio of 10-90: 10-90, mixing, performing ball milling for 3-6 hours to obtain composite powder, adding a solvent and a dispersing agent into the obtained composite powder, performing ball milling and mixing for 2-4 hours to obtain a suspension, and performing ultrasonic dispersion on the suspension uniformly to obtain the white ceramic ink.
9. The preparation method according to claim 8, wherein the mass percentages of the composite powder, the solvent and the dispersant in the suspension are as follows: 30-40% of composite powder, 50-60% of solvent and 5-10% of dispersing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711064663.XA CN107778991B (en) | 2017-11-02 | 2017-11-02 | Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711064663.XA CN107778991B (en) | 2017-11-02 | 2017-11-02 | Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107778991A CN107778991A (en) | 2018-03-09 |
| CN107778991B true CN107778991B (en) | 2021-05-04 |
Family
ID=61431455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711064663.XA Expired - Fee Related CN107778991B (en) | 2017-11-02 | 2017-11-02 | Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778991B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641479B (en) * | 2018-04-13 | 2021-09-07 | 山东国瓷康立泰新材料科技有限公司 | Ultra-white ceramic ink for ink-jet printing and preparation method thereof |
| CN109535846A (en) * | 2018-12-21 | 2019-03-29 | 湖北工业大学 | A kind of preparation method based on hydroxide radical phosphorite nanocrystalline fluorescence invisible ink |
| CN109749516A (en) * | 2018-12-29 | 2019-05-14 | 武汉理工大学 | A kind of inkjet printing photochromic ceramic ink and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224725A (en) * | 2013-04-08 | 2013-07-31 | 佛山市道氏科技有限公司 | White glaze printing ink for ceramic ink-jet printing and preparation method thereof |
| CN103804993A (en) * | 2013-11-27 | 2014-05-21 | 佛山市明朝科技开发有限公司 | Extra-white aqueous ceramic ink-jet ink and preparation method thereof |
| KR20150057718A (en) * | 2013-11-20 | 2015-05-28 | 주식회사 엘지생활건강 | Solid coating preparation for tooth whitening |
| CN107266977A (en) * | 2017-06-07 | 2017-10-20 | 佛山市帆思科材料技术有限公司 | Antibacterial functional ink and preparation method and application thereof |
-
2017
- 2017-11-02 CN CN201711064663.XA patent/CN107778991B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224725A (en) * | 2013-04-08 | 2013-07-31 | 佛山市道氏科技有限公司 | White glaze printing ink for ceramic ink-jet printing and preparation method thereof |
| KR20150057718A (en) * | 2013-11-20 | 2015-05-28 | 주식회사 엘지생활건강 | Solid coating preparation for tooth whitening |
| CN103804993A (en) * | 2013-11-27 | 2014-05-21 | 佛山市明朝科技开发有限公司 | Extra-white aqueous ceramic ink-jet ink and preparation method thereof |
| CN107266977A (en) * | 2017-06-07 | 2017-10-20 | 佛山市帆思科材料技术有限公司 | Antibacterial functional ink and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107778991A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107778991B (en) | Zirconium-free ultra-white water-based ceramic ink for ink-jet printing and preparation method thereof | |
| EP0659843B1 (en) | Non-brilliant pigment | |
| JPH06145556A (en) | Pigment containing carbon black | |
| CN103804993B (en) | A kind of extra white aqueous ceramic jetted ink and preparation method thereof | |
| AU2013312024B2 (en) | Gold pigment | |
| CN100455630C (en) | Method for preparing nanometer cobalt blue dye | |
| CN108864752B (en) | Water-dispersible pigment red 57:1 modified pigment and preparation method thereof | |
| CN109504179B (en) | Matte effect printing ink for ceramic glaze and preparation method thereof | |
| CN103525184B (en) | Environmental-protection stamp-pad ink and preparation method thereof | |
| JPH07268240A (en) | Carbon containing pigment | |
| EP3728485A1 (en) | Effect pigments | |
| JP2000505039A (en) | Use of β-type rare earth metal sulfide as a color pigment and method for producing the same | |
| CN111320901A (en) | Solid watercolor containing amino silanization inorganic powder and preparation method thereof | |
| CN113479895B (en) | Method for preparing superfine zirconium silicate and zirconium silicate-based coating pigment by one-step precipitation method | |
| CN112457717B (en) | Water-based ceramic ink for ink-jet printing and preparation method and application thereof | |
| CN109679411B (en) | Preparation method of titanium dioxide pigment-coated aqueous dispersion | |
| CN103881421B (en) | Nanometer surface modifier and preparation method and using method thereof | |
| CN103013185A (en) | Inorganic yellow pigment and preparation method thereof | |
| CN106009786B (en) | A kind of doping type high infrared reflection rare earth sesquifide γ Ce2S3Coat nacreous mica pigment and preparation method thereof | |
| CN109608906B (en) | Superfine aluminum oxide coated bismuth molybdate yellow pigment and preparation method thereof | |
| CN109504203B (en) | Color-light water-based functional coating suitable for indoor entertainment and preparation method and application thereof | |
| CN112358744B (en) | Preparation method of submicron-grade superfine wrapped cadmium sulfoselenide pigment | |
| DE102009059102A1 (en) | Process for the preparation of encapsulated metal colloids as inorganic color pigments | |
| CN101565555A (en) | Rare earth complex red pigment with excellent pigment performance and application thereof | |
| CN106752374B (en) | Ceramic ink with good stability and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210504 |