CN112898825B - Submicron-grade large red zirconium silicate coated pigment and preparation method thereof - Google Patents
Submicron-grade large red zirconium silicate coated pigment and preparation method thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
Abstract
The invention relates to the field of inorganic pigments, in particular to a submicron bright red cadmium sulfoselenide coated zirconium silicate pigment and a preparation method thereof. The obtained coated pigment has good dispersibility, narrow particle size distribution range (the particle size is mainly distributed in 0.15-0.75 micrometer, and the average particle size is 0.35-0.50 micrometer), is mainly composed of approximately spherical or ellipsoidal particles, presents bright red color, and has L value, a value and b value of 54-58, 42-46 and 20-28 respectively when the pigment performance is expressed by CIEL a b system. The invention can prepare the completely wrapped submicron zirconium silicate wrapped cadmium sulfoselenide bright red pigment by controlling the synthesis process step by step and only adopting single microemulsion, thereby not only reducing the using amount of oil and alcohol substances, but also greatly reducing the using amount of zirconium silicate wrappage and improving the color performance, and being beneficial to reducing the production cost of the wrapped pigment and reducing the environmental protection pressure of the production process.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of inorganic pigments, in particular to a large red zirconium silicate coated pigment suitable for ink-jet printing and laser 3D printing.
[ background ] A method for producing a semiconductor device
Ink jet printing technology has been developed as one of the main ceramic decoration technologies, and the development of new ceramic laser printing technology represents a new trend of ceramic decoration technology development. Red is one of the three primary colors of ceramic printing decoration, and the lack of bright red ceramic ink greatly affects the ceramic ink-jet printing decoration effect for a long time. Cadmium sulfoselenide (CdSe) x S 1-x ) The pigment is the only inorganic pigment which is known at present and can present bright red, but the pigment is a non-oxide material and is easy to be oxidized and decomposed in an air environment above 500 ℃ to lose red, so the pigment cannot be directly applied to ceramic decoration. By using zirconium silicate (ZrSiO) having excellent high temperature resistance and chemical stability 4 ) The cadmium sulfoselenide is coated and modified, the stable temperature of the cadmium sulfoselenide in most ceramic glaze materials can be increased to more than 1300 ℃ while the color generation of the pigment is not influenced, and therefore, the zirconium silicate coated cadmium sulfoselenide pigment is widely applied to traditional ceramic glaze decoration. Pigments for ceramic ink-jet printing inks generally require a maximum particle size of less than 1 micron (average particle size of several hundred nanometers) to improve ink stability and satisfy the limitation of printer head pore size and improve print pattern accuracy. For ceramic laser printing, it is required to control the particle size of pigment particles with a large density to several hundred nanometers, and to improve powder flowability, it is also required to have a high shape of pigment particles.
In the current industrial production, the zirconium silicate coated cadmium sulfoselenide pigment is generally prepared by a liquid-phase coprecipitation method, and is calcined at high temperature to obtain the pigment with compact zirconium silicate inclusion, the particle size distribution of the coated pigment particles is wide, the shape of the coated pigment particles is irregular, the particle size of most particles reaches 15-30 microns, and the actual coating rate is very low and is only 8% -10%. When the coating pigment is prepared by the process, after high-temperature calcination, most of cadmium sulfoselenide which is not effectively coated needs to be removed by soaking with a large amount of strong acid, and the coating pigment can be applied to ceramic decoration, so that the production efficiency is low and the environmental protection pressure is high. The more disadvantageous is that the common encapsulated red pigment needs to be crushed, ground and refined for a long time in order to meet the requirement of ink preparation on particle size, but most zirconium silicate inclusion bodies are damaged in the crushing process, and the exposed cadmium sulfoselenide is decomposed at high temperature so that the pigment can only show light pink and even completely loses red. Therefore, the coating rate of the zirconium silicate coated cadmium sulfoselenide pigment with the core-shell structure is improved, and the integral granularity of the coated pigment is effectively reduced, so that the key technical problem of preparing the scarlet ink for ceramic decoration is always solved.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a submicron bright red zirconium silicate coated cadmium sulfoselenide pigment and a preparation method thereof. The obtained coated pigment has good dispersibility, narrow particle size distribution range (the particle size is mainly distributed in the range of 0.15-0.75 micrometer, the average particle size is 0.35-0.50 micrometer), is mainly composed of approximately spherical or ellipsoidal particles, is bright red, and has L value, a value and b value of 54-58, 42-46 and 20-28 respectively when the pigment performance is expressed by CIEL a b system.
The invention discloses a submicron zirconium silicate coated cadmium sulfoselenide bright red pigment, which is characterized in that: the chemical composition is as follows: cdSe x S 1-x @ZrSiO 4 (x＝0.22～0.32)，ZrSiO 4 With CdSe x S 1-x The molar ratio of (A) is 4-6; when CIEL a b system is adopted to represent the performance of the pigment, the L value, a value and b value are respectively 54-57, 42-46 and 20-28;
the submicron zirconium silicate-coated cadmium sulfoselenide bright red pigment is obtained by adopting a single micro-emulsion method and controlling the synthesis process step by step, and comprises the following specific steps:
(1) Mixing sodium sulfide (Na) 2 S), selenium (Se) powder, sodium hydroxide (NaOH), sodium Dodecyl Benzene Sulfonate (SDBS) and Cetyl Trimethyl Ammonium Bromide (CTAB) are dissolved in hot deionized water to obtain a mixed solution A, wherein Se is x S 1-x The concentration is 0.5-2 mol/L, and the mass percentage content of SDBS and CTAB is 0.3-0.8%; will react with Se x S 1-x Equimolar amounts of cadmium salts (e.g. CdCl) 2 、Cd(NO 3 ) 2 Or CdSO 4 Etc.) dissolved in deionized water to obtain Cd 2+ The concentration of the solution B is 0.5 to 2 mol/L;
(2) Stirring and mixing n-octane, n-octanol and fatty alcohol-polyoxyethylene ether according to the mass ratio of 100 to 20-25;
(3) Dropwise adding the solution B into the microemulsion obtained in the step (2), continuously stirring, fully mixing and reacting for 1-2 h, and generating CdSe compositely coated by SDBS and CTAB in the microemulsion x S 1-x Precipitate particles;
(4) Dissolving Tetraethoxysilane (TEOS) in mixed solution of ethanol and water to obtain solution C with TEOS concentration of 1-2 mol/L, and dissolving ZrOCl 2 Or Zr (NO) 3 ) 4 ·5H 2 Dissolving zirconium salt such as O and lithium fluoride (LiF) in deionized water to obtain Zr 4+ The solution D with the concentration of 2-3 mol/L, the Si/Zr molar ratio in the solution C and the solution D is 1.1-1.2, and the addition amount of the lithium fluoride is ZrSiO theoretically available 4 4-6% of the mass;
(5) Adding the solution C into the microemulsion obtained in the step (3), fully stirring for 2-3 h to ensure that the tetraethoxysilane is fully hydrolyzed and deposited in a composite surfactant micelle structure in CdSe x S 1-x The surface of the particle forms a tightly adsorbed porous structure SiO 2 Adding the solution D into the precursor, and continuously stirring for 3-4 h to ensure that Zr-OH is adsorbed and deposited on the porous SiO 2 Adding ethanol solution of polyoxyethylene polyoxypropylene ether block copolymer into the precursor structureDemulsifying, and finally obtaining a pigment-coated precursor precipitate through centrifugal separation;
(6) And (4) washing the precipitate obtained in the step (5) by using deionized water and industrial ethanol once respectively, drying for 6 hours at the temperature of 80-100 ℃, then rapidly heating to 500 ℃ at the speed of 20-25 ℃/min, keeping the temperature for 1 hour, heating to 850-1000 ℃ at the speed of 5 ℃/min, and calcining for 1 hour to obtain the zirconium silicate coated cadmium sulfoselenide pigment.
Compared with the prior art, the invention has the following advantages:
1. the invention can prepare the completely wrapped submicron zirconium silicate wrapped cadmium sulfoselenide bright red pigment by only adopting single microemulsion through controlling the synthesis process step by step, not only can reduce the dosage of oil and alcohol substances, but also can greatly reduce the dosage of zirconium silicate wrapped matter (ZrSiO) 4 /CdSe x S 1-x The molar ratio is reduced from 10-20.
2. The present invention is in CdSe x S 1-x In the synthesis process, anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) and cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) are simultaneously introduced, and the synthesized CdSe can be obtained by the composite action of the two surfactants x S 1-x The micelle is taken as a template, a silicon oxide precursor (Si-OH) obtained after hydrolysis can be closely adsorbed and deposited on the micelle to form a porous network structure, a zirconium oxide precursor (Zr-OH) obtained after hydrolysis in the subsequent process is further adsorbed and deposited in the porous network structure, and thus, the surface of the particle is subjected to CdSe by the method that the micelle is taken as a template x S 1-x The surface of the particle forms a tightly adsorbed wrapper precursor, and Zr and Si elements are uniformly distributed, which is helpful to promote ZrSiO in the high-temperature calcination process 4 And (4) synthesizing.
3. The ethanol solution of the polyoxyethylene polyoxypropylene ether segmented copolymer is adopted to replace common acetone for demulsification, so that the dispersibility of the coating pigment precursor precipitate and the coating pigment obtained by calcination after demulsification can be improved, and the cost can be reduced.
4. In the technical scheme of the invention, in the heating and calcining process of the coating pigment precursor, a rapid heating system (20-25 ℃/min) is adopted at the temperature below 500 ℃, so that organic matters in the coating precursor can be rapidly burnt out, and the coating generates structural collapse and rapid shrinkage, thereby being beneficial to reducing CdSe in the heating process x S 1-x In contact with air, zrSiO 4 The density of the wrapping layer is improved synthetically.
5. The zirconium silicate coated cadmium sulfoselenide pigment provided by the invention is bright red, has good dispersibility and narrow particle size distribution range (the particle size of the particles is mainly distributed between 0.15 and 75 micrometers, and the average particle size is between 0.35 and 0.50 micrometer), mainly comprises approximately spherical or ellipsoidal particles, and can simultaneously meet the technical requirements of ceramic ink-jet printing and laser printing.
[ description of the drawings ]
The following detailed description of embodiments of the invention is provided in conjunction with the appended drawings, in which:
FIG. 1 is a TEM photograph of a zirconium silicate-coated cadmium sulfoselenide pigment (synthesized by keeping the temperature at 900 ℃ for 1 hour);
FIG. 2 is an XRD spectrum of a zirconium silicate coated cadmium sulfoselenide pigment (synthesized by heat preservation at 900 ℃ for 1 hour);
[ detailed description ] embodiments
The first embodiment is as follows:
preparation of ZrSiO 4 Encapsulation of CdSe x S 1-x Pigment wherein x =0.3, zrSiO 4 /CdSe x S 1-x The molar ratio is 5. First Na 2 Dissolving S, se powder, naOH, SDBS and CTAB in hot water to obtain solution A, wherein Se is x S 1-x The concentration is 1mol/L, the mass percentage content of SDBS and CTAB is 0.6%, and the pH of the solution is adjusted to be =13 by NaOH; will react with Se x S 1-x Equimolar amount of Cd (NO) 3 ) 2 Dissolving the Cd in deionized water to obtain Cd 2+ The concentration of the solution B is 2 mol/L. Stirring and mixing n-octane, n-octanol and fatty alcohol-polyoxyethylene ether according to the mass ratio of 100. Then dropwise adding the solution B into the microemulsion, and continuously stirring for 2 hours to ensure that the CdSe x S 1-x After the synthesis reaction process is fully carried out, 1mol/L ethyl orthosilicate (TEOS) alcohol aqueous solution is dripped, the mixture is continuously stirred for 2 hours, and then 2mol/L ZrOCl is dripped 2 And LiF (Si/Zr molar ratio is controlled to be 1.1, lithium fluoride content is ZrSiO) 4 4 percent of the mass), continuously stirring for 4 hours, adding an ethanol solution of 10 percent polyoxyethylene polyoxypropylene ether segmented copolymer for demulsification, and finally obtaining the pigment-coated precursor precipitate through centrifugal separation.
Washing the precipitate with deionized water and industrial alcohol, drying at 100 deg.c for 6 hr, heating to 500 deg.c at 25 deg.c/min for 1 hr, heating to 900 deg.c at 5 deg.c/min, and calcining for 1 hr to obtain the zirconium silicate coated cadmium sulfoselenide pigment. The particle size distribution is mainly distributed between 0.2 and 0.6 micron, the average particle size is 0.4 micron, the values of L, a and b are respectively 56, 46 and 25, the red pigment presents bright red, and the red value a of the existing ink-jet printing coating red pigment is only 20 to 30 generally. FIG. 1 is a TEM photograph of a coated pigment obtained according to the present invention; FIG. 2 is an XRD pattern of the coated pigment, showing that the obtained coated pigment mainly consists of zirconium silicate crystal phase and CdSexS1-x crystal phase, and compared with the existing coated pigment, cdSe x S 1-x The diffraction peak intensity of the crystal phase is obviously improved because the content of the inclusion is greatly reduced by adopting the technology of the invention.
Example two:
ZrSiO was prepared by the same method as in example one 4 Encapsulation of CdSe x S 1-x Pigment wherein x =0.22, zrSiO 4 /CdSe x S 1-x The mol ratio is 6 4 6% of the mass, and the other preparation methods and procedures are the same as in example one. The obtained coated pigment has a particle size distribution of 0.3-0.75 μm, an average particle size of 0.5 μm, L, a, b values of 57, 42 and 28, respectively, and is vivid red.
The above description is only a preferred embodiment of the present invention, and it should be noted that a person skilled in the art can make various changes, modifications, substitutions and alterations to the embodiments without departing from the technical principles of the present invention, and such changes, modifications, substitutions and alterations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A submicron zirconium silicate coated cadmium sulfoselenide bright red pigment is characterized in that: the chemical composition is as follows: cdSe x S 1-x @ZrSiO 4 ，x=0.22～0.32，ZrSiO 4 With CdSe x S 1-x The molar ratio of (A) is 4-6; when the pigment performance is expressed by a CIEL a b system, the L value, a value and b value are respectively 54-57, 42-46 and 20-28;
the submicron zirconium silicate coated cadmium sulfoselenide bright red pigment is obtained by adopting a single microemulsion method and controlling the synthesis process step by step, and comprises the following specific steps:
(1) Mixing sodium sulfide (Na) 2 S), selenium (Se) powder, sodium hydroxide (NaOH), sodium Dodecyl Benzene Sulfonate (SDBS) and Cetyl Trimethyl Ammonium Bromide (CTAB) are dissolved in hot deionized water to obtain a mixed solution A, wherein Se is x S 1-x The concentration is 0.5-2 mol/L, and the mass percentage content of SDBS and CTAB is 0.3-0.8%; will react with Se x S 1-x An equimolar amount of a cadmium salt selected from CdCl 2 、Cd(NO 3 ) 2 Or CdSO 4 Dissolving in deionized water to obtain Cd 2+ The concentration of the solution B is 0.5 to 2 mol/L;
(2) Stirring and mixing n-octane, n-octanol and fatty alcohol-polyoxyethylene ether according to the mass ratio of 100 to 20-25;
(3) Dropwise adding the solution B into the microemulsion obtained in the step (2), continuously stirring, fully mixing and reacting for 1-2 h, and generating CdSe compositely coated by SDBS and CTAB in the microemulsion x S 1-x Precipitate particles;
(4) Dissolving Tetraethoxysilane (TEOS) in ethanol/water mixed solution to obtain solution C with TEOS concentration of 1-2 mol/L, and dissolving ZrOCl 2 Or Zr (NO) 3 ) 4 ·5H 2 Dissolving O zirconium salt and lithium fluoride (LiF) in deionized water to obtain Zr 4+ The solution D with the concentration of 2-3 mol/L, the Si/Zr molar ratio in the solution C and the solution D is 1.1-1.2, and the adding amount of the lithium fluoride is ZrSiO theoretically obtained 4 4-6% of the mass;
(5) Adding the solution C into the microemulsion obtained in the step (3), fully stirring for 2-3 h to fully hydrolyze ethyl orthosilicate and deposit the ethyl orthosilicate in a composite surfactant micelle structure in CdSe x S 1-x The surface of the particle forms a tightly adsorbed porous structure SiO 2 Adding the solution D into the precursor, and continuously stirring for 3-4 h to ensure that Zr-OH is adsorbed and deposited on the porous SiO 2 Adding an ethanol solution of a polyoxyethylene polyoxypropylene ether segmented copolymer into the precursor structure for demulsification, and finally obtaining a pigment-coated precursor precipitate through centrifugal separation;
(6) And (4) washing the precipitate obtained in the step (5) by using deionized water and industrial ethanol once respectively, drying for 6 hours at the temperature of 80-100 ℃, then rapidly heating to 500 ℃ at the speed of 20-25 ℃/min, keeping the temperature for 1 hour, heating to 850-1000 ℃ at the speed of 5 ℃/min, and calcining for 1 hour to obtain the zirconium silicate coated cadmium sulfoselenide pigment.
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| CN101786902B (en) * | 2010-03-04 | 2013-03-20 | 陕西科技大学 | Preparation method for zirconium silicate wrapped cadmium sulfide selenide scarlet pigment |
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| CN108276805B (en) * | 2018-01-31 | 2020-02-14 | 江西金环颜料有限公司 | Zirconium silicate coated cadmium sulfoselenide pigment for ceramic ink-jet printing or ceramic dry mixing and preparation method thereof |
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