CN103666112A - Colored glaze mixed type noctilucent ink for ceramic ink-jet printing and preparation method thereof - Google Patents
Colored glaze mixed type noctilucent ink for ceramic ink-jet printing and preparation method thereof Download PDFInfo
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Abstract
The invention provides a colored glaze mixed type noctilucent ink for ceramic ink-jet printing and a preparation method thereof, and belongs to the ceramic brick decoration technology. The colored glaze mixed type noctilucent ink for ceramic ink-jet printing includes the components by the mass percentage: 28%-35% of a coloring material; 10%-15% of a glaze powder; 2%-5% of a long afterglow luminescent material; 1%-5% of magnesium carbonate; 45%-55% of diglycol; 1-3% of a dispersant; 0.5%-2% of a binding agent; and 0.5%-2% of a surface active agent. An ink-jet printing layer formed after ink-jet printing on a ceramic brick blank by using the ink can be directly fired, and the formed printing layer has a noctilucent effect, can be applied for use in instruction and marking, is more safe, can replace staircase indicator lights, can save energy, and also can present more abundant display effect.
Description
Technical field
The present invention relates to a kind of ceramic tile decoration technique, be specially a kind of ceramic ink jet printing ink, more specifically, relate to color glaze mixed type noctilucence ink and preparation method thereof for a kind of ceramic ink jet printing.
Background technology
Inkjet technology is a kind of contactless digital printed technology of succeeding in developing late 1970s.It by ink by the nozzle ejection on printhead to various dielectric surfaces, realized monochromatic or colored word or the image printing of noncontact, high-speed, low noise.At the beginning of 21 century, U.S. Ferro Corp develops the oil-based ink that is adapted at carrying out on pottery spray ink Printing, at the corresponding number of patent application of China, is 00818261.2.With this, started the widespread use of inkjet technology at architectural pottery production field.As a kind of brand-new ceramic decoration theory, ceramic decoration can make full use of abundant computer data by colour print technology, digital technique is incorporated in traditional architectural pottery product, make ceramic decoration closely follow era step, embody fashion characteristic, meet the requirement of people's personalization, ceramic decoration technology is pushed to a new stage.
Inkjet technology is compared tool with the traditional decoration means of ceramic tile production and is had the following advantages: (1) energy-saving and emission-reduction, product broken away from batch production, need film-making, screen cloth, mechanical etc. in the middle of operation, shorten and change the line of production the cycle, significantly enhance productivity, also reduced the loss of changing the line of production in process; (2) print procedure is completely by computer control, in production process, can carry out complicated pattern decorative, and the precision of pattern and repeatable raising, can greatly improve mechanization degree and the production efficiency of decoration process, also can complete the even customization of single products of short run; (3) contactless, can on male and fomale(M&F), print, the decoration of some special-shaped products is become easily, greatly enrich decorative effect.
But ink-jet printed technique belongs to a kind of surface decoration technique, at ceramic tile surface, by printing of inkjet printer, form predetermined pattern, main component in current disclosed ink set is tinting material/colorant and solvent, and makes tinting material/colorant additive such as homodisperse dispersion agent in solvent.How not wear-resisting the printed layer that spray ink Printing forms is, even after high temperature sintering, in the printed layer of ceramic tile surface, is easier to wearing and tearing yet, therefore needs to execute layer of transparent more and protect glaze to protect printed layer.This make the production cost of ink-jet printed series ceramic wall floor tile and the production cycle all very high.
Long after glow luminous material is commonly called as luminescent powder, has unsaturated energy level in its electronic structure, under illumination condition, absorbs photon energy, make electronics generation energy level transition, and in darker environment, the energy of electron absorption can discharge, and produces fluorescent effect.At present, long after glow luminous material mostly is and adds in glaze in the application of ceramic, makes luminous glaze.Luminous glaze can be used as referential index effect, the indicating bit of staircase for example, and the indicating bit of room switch etc., and can allow goods present abundant effect.But for current ceramic ink jet printing, with ink, be not suitable for adding long after glow luminous material and make noctilucence ink, and the luminous glaze transparency of using long after glow luminous material to make is lower, be also not suitable as the protective layer of ink-jet printed layer.
Summary of the invention
The object of the invention is to propose color glaze mixed type noctilucence ink and preparation method thereof for a kind of ceramic ink jet printing, while using ceramic ink jet printing provided by the invention to produce ceramic wall and floor bricks product with color glaze mixed type noctilucence ink, ink-jet printed rear direct high temperature burns till, without executing again after transparency protected glaze high temperature again after ink-jet printed, burn till, glaze composition in ink is meeting melting when burning till, color development component in ink is dispersed in wherein uniformly, and then make ink-jet printed layer wear-resisting especially, by adding long after glow luminous material, when burning till, long after glow luminous material is melted in glaze and forms sosoloid, acquisition has the ink-jet printed layer of luminous effect.
For reaching this object, the present invention by the following technical solutions: color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing, comprising various components be by mass percentage: colorant: 28%～35%; Powdered frit: 10%～15%; Long after glow luminous material: 2%～5%; Magnesiumcarbonate: 1%～5%; Glycol ether: 45%～55%; Dispersion agent: 1～3%; Bonding agent: 0.5%～2%; Tensio-active agent: 0.5%～2%.
Preferably, at above-mentioned spray ink Printing, with in color glaze mixed type noctilucence ink, described long after glow luminous material is following aluminate base long persistence luminescent material: SrAl
2o
4: Eu, Dy; CaAl
2o
4: Eu, Nd; Sr
4al
14o
25: Eu, one or more combinations in Dy.
Preferably, at above-mentioned spray ink Printing, with in color glaze mixed type noctilucence ink, described long after glow luminous material is following silicate-base long after glow luminous material: Sr
2mgSi
2o
7: Eu, Dy; Ca
2mgSi
2o
7: Eu, Dy; MgSiO
3: Mn, Eu, one or more combinations in Dy.
Preferably, at above-mentioned spray ink Printing, with in color glaze mixed type noctilucence ink, described long after glow luminous material is following phosphate long afterglow luminous material: Ca
3(PO
4)
2: Eu, Gd; Sr
3(PO
4)
2: Eu, Gd; Ba
3(PO
4)
2: Eu, one or more combinations in Gd.
In order to make ink go for high temperature, burning till, preferably, is that praseodymium yellow, reddish brown, orange, cobalt blue, spinel are one or more combinations in black pigment at above-mentioned a kind of ceramic ink jet printing with the colorant described in color glaze mixed type noctilucence.
In order to make after sintering, the printed layer of using ink provided by the invention to form has good texture, preferably, at above-mentioned a kind of ceramic ink jet printing, by the chemical composition mass percent of the powdered frit described in color glaze mixed type noctilucence, be: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 8%～12%; Magnesium oxide 4%～5%; Potassium oxide: 1%～3%; Sodium oxide: 3%～5%; Barium oxide: 2%～4%; Zinc oxide: 1%～2%; Zirconium white: 1%～2%; Loss on ignition :≤1%; Water :≤0.5%.
Above-mentioned a kind of ceramic ink jet printing is weakly alkaline with color glaze mixed type noctilucence ink; Its PH is minimum to the corrodibility of shower nozzle between 7～8 time.
When above-mentioned a kind of ceramic ink jet printing is with in color glaze mixed type noctilucence ink during solid content >=50%, there is particularly preferred color development effect.
The present invention also provides the preparation method of a kind of above-mentioned a kind of ceramic ink jet printing with color glaze mixed type noctilucence ink: it comprises the steps:
The siccative of step 1) colorant, long after glow luminous material, powdered frit mixes; By colorant: long after glow luminous material: the mass ratio of powdered frit is that 28～35:2～5:10～15 take, and then pours in quick mixer and mixes.
Step 2) comminution by gas stream; The colorant, long after glow luminous material, the powdered frit compound that adopt high speed jet mill to mix step 1) are beaten powder, obtain the ultrafine powder that particle diameter reaches 10 μ m～50 μ m.
Step 3) batching and one-level ball milling; Be in mass ratio: 40～55:1～5:45～60 take step 2) ultrafine powder, magnesiumcarbonate, the glycol ether that obtain, then pour into and take aluminum oxide ball milling in the ball mill of ball lining and ball, Ball-milling Time 12～24 hours, obtains the mixed slurry that particle diameter is 1～10 μ m.
Step 4) batching and secondary ball milling; The ratio that is in mass ratio 86～120:1～3:0.5～2:0.5～2 takes mixed slurry, dispersion agent, bonding agent, the tensio-active agent that step 3) obtains, pouring double-planet formula high speed ball mill into grinds, milling time 4～10 hours, obtains ink work in-process.
Step 5) constant-temperature vacuum filters; The ink work in-process that step 4) is obtained, in the constant temperature a mixing bowl of 80～100 ℃, then vacuumize, vibration at high speed, use aperture≤10 μ m strainer filtering, obtain ink finished product.
Preferably, in preparation method at above-mentioned a kind of ceramic ink jet printing with color glaze mixed type noctilucence, the colorant described in step 1) tails over≤0.05% for reach 325 order standard analysiss through 700～850 ℃ of temperature lower calcinations, granularities, the powdery praseodymium yellow of moisture content≤0.5%, reddish brown, orange, cobalt blue, spinel are one or more combinations in black pigment.
Preferably, in preparation method at above-mentioned a kind of ceramic ink jet printing with color glaze mixed type noctilucence, glaze described in step 1) is silicon-dioxide 45～50 for selecting chemical composition mass ratio: aluminum oxide 18～22: ferric oxide 0～0.2: titanium dioxide 0～0.3: calcium oxide 8～12: magnesium oxide 4～5: potassium oxide 1～3: sodium oxide 3～5: barium oxide 2～4: zinc oxide 1～2: the raw material of zirconium white 1～2 is through 700～850 ℃ of calcinings, calcination time 1～3 hour, obtains the grog of loss on ignition≤1%, moisture content≤0.5%.
For fear of introducing impurity, obtain good grinding effect, to stablize ink quality, in the preparation method at a kind of ceramic ink jet printing with color glaze mixed type noctilucence, the ball mill performance requriements using in step 3) is as follows: ball adopts isostatic pressing process, diameter 10～35mm; The Chemical Composition mass percent of ball lining, ball is: aluminium sesquioxide >=95%, silicon-dioxide 2%～5%, ferric oxide≤0.1%, volume density >=3.7 gram/cc of ball lining, ball, ball milling cycle abrasion≤0.1 ‰ of ball lining, ball, Mohs' hardness >=9.5.
For fear of introducing impurity, obtain good grinding effect, to stablize ink quality, in the preparation method at a kind of ceramic ink jet printing with color glaze mixed type noctilucence, in the double-planet formula high speed ball mill using in step 4), the material of ball grinder and ball is zirconium white.
Compared with the existing technology scheme provided by the invention has following advantage:
1, ink complete processing is simple, practical, after ink jet unit spray ink Printing, need in printed layer, not impose one deck ink protection glaze again.By kiln, burn till, after color glaze mixed type ink sintering, self can form one deck wear-resisting printed layer closely, this has simplified the production technique that spray ink Printing is decorated greatly, and reduces production costs, enhances productivity.
2, use the ink-jet printed layer that this kind of ink forms after spray ink Printing on ceramic adobe to there is luminous effect, go for the use of indication, mark, safer, also can substitute stair pilot lamp, can save energy, and can also present the more bandwagon effect of horn of plenty.
3, in color glaze mixed type ink set, introduce magnesiumcarbonate; play outside the suspension stability, anti-caking effect effect that strengthens ink; because it is alkalescence; in the course of processing, react with closing in acid colorant generation soda acid in ink, and make ink be weakly alkaline; the acid ink of making compared with prior art is compared; be more conducive to the protection (the expensive printing head of acid meeting corrosion) of ink jet unit printhead, extend the work-ing life of shower nozzle, cost-saving.
4, color glaze mixed type ink solids content is high, and granularity is less, and color development effect is better than existing ink.
5, the solvent that color glaze mixed type ink adopts is glycol ether (boiling point is 245 ℃), does not have the problem of solvent evaporates, safer to the mankind and environment.
Embodiment
Below by embodiment, further illustrate technical scheme of the present invention.
Embodiment 1-10
The ceramic ink jet printing that embodiment 1-10 provides uses the component formula of color glaze mixed type noctilucence as following table 1.
Table 1
The colorant of selecting in embodiment 1 is praseodymium yellow, and long after glow luminous material is chosen as aluminate base long persistence luminescent material SrAl
2o
4: Eu, Dy(green fluorescence), prepared ink colour generation is yellow, environment by bright turn dark after, phosphor persistence time>=4 hour.The chemical composition mass percent of powdered frit is in this embodiment: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 8%～12%; Magnesium oxide 4%～5%; Potassium oxide: 1%～3%; Sodium oxide: 3%～5%; Barium oxide: 2%～4%; Zinc oxide: 1%～2%; Zirconium white: 1%～2%; Loss on ignition :≤1%; Water :≤0.5%.By above chemical composition mass percent, those skilled in the art calculate formula consumption by the chemical analysis results of Sai Geershi and the conventional mineral of Production of Ceramics or frit class raw material, therefore only provided the chemical composition requirement of powdered frit here, for the raw material in the different places of production or the frit of different chemical component, those skilled in the art's selection of can arranging in pairs or groups flexibly.Here a given concrete powdered frit batching is filled a prescription: albite 35%, and potassium felspar sand 7%, aluminum oxide 6%, Wingdale 10, kaolin 10, burns talcum 10%, barium carbonate 5%, wollastonite 7%, clear frit 5%, zirconium silicate 5%.But need explanation, above formula does not form any limitation of the invention.
The ink preparation technology of the present embodiment 1 is as follows:
The present invention also provides the preparation method of a kind of above-mentioned a kind of ceramic ink jet printing with color glaze mixed type noctilucence: it comprises the steps:
Step 1) colorant, long after glow luminous material SrAl
2o
4: Eu, Dy(green fluorescence) and the siccative of powdered frit mix; Press colorant: long after glow luminous material SrAl
2o
4: Eu, Dy(green fluorescence): the mass ratio of powdered frit is that 28:2:15 takes, and then pours in quick mixer and mixes.
Step 2) comminution by gas stream; The colorant, long after glow luminous material, the powdered frit compound that adopt high speed jet mill to mix step 1) are beaten powder, obtain the ultrafine powder that particle diameter reaches 10 μ m～50 μ m.
The principle of work of comminution by gas stream is once described: micronizer mill and cyclonic separator, fly-ash separator, induced draft fan form a whole set of crushing system here.After pressurized air is dried after filtration, by laval nozzle high-velocity jet, enter crushing chamber, at the joint place of multiply high pressure draft, material is repeatedly collided, is rubbed, is sheared and pulverized, material after pulverizing moves to graded region with upstream under blower fan draft effect, under the powerful centrifugal action producing at the stage turbine of high speed rotating, make thickness feed separation, the fine particle that meets granularity requirements enters cyclonic separator by grading wheel and fly-ash separator is collected, and coarse particles drops to disintegrating area to be continued to pulverize.Above Jet Mill is known equipment, can buy and obtain in market.
Step 3) batching and one-level ball milling; Be in mass ratio: 45:1:47 takes step 2) ultrafine powder, magnesiumcarbonate, the glycol ether that obtain, then pour into and take aluminum oxide ball milling in the ball mill of ball lining and ball, Ball-milling Time 12～24 hours, obtaining particle diameter is the mixed slurry of 1 μ m～10 μ m.
For fear of introducing impurity, obtain good grinding effect, to stablize ink quality, in the present embodiment, the ball mill performance requriements using in step 3) is as follows: ball adopts isostatic pressing process, diameter 10～35mm; The Chemical Composition mass percent of ball lining, ball is: aluminium sesquioxide >=95%, silicon-dioxide 2%～5%, ferric oxide≤0.1%, volume density >=3.7 gram/cc of ball lining, ball, ball milling cycle abrasion≤0.1 ‰ of ball lining, ball, Mohs' hardness >=9.5.
Step 4) batching and secondary ball milling; For the ratio of 93:3:2:2 takes mixed slurry, dispersion agent, bonding agent, the tensio-active agent that step 3) obtains, pour double-planet formula high speed ball mill into and grind in mass ratio, milling time 4～10 hours, obtains ink work in-process.
Dispersion agent is mainly some water-soluble and oil soluble high score subclass, phenylformic acid and derivative, polyacrylic acid and multipolymers thereof etc.
Bonding agent is to ensure that ceramic body or the colorant printed have certain intensity, is convenient to production operation, stablizes the mobility of ink, and resin can play the dual function of bonding agent and dispersion agent conventionally.Resin is divided into the synthetic resins of natural resin and aggretion type, bonding agent in formula adopt aggretion type resin as: a kind of in polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Tensio-active agent be control ink factory surface tension in applicable scope.As carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof.
The principle of work of double-planet formula ball mill is: two major planets axles in (rotation) are installed on the traffic cycle of (revolution), do single planetary running.Two mini-roundabouts are installed again simultaneously on two major planets axles and four ball grinder protecting seats (putting ball grinder uses) are installed on (revolution) two mini-roundabouts in (rotation), do the running of double-planet formula.Ball grinder is the in the situation that of this running up, and the mill ball in ball grinder has formed very large high-frequency percussion power, straight line impact force, friction, material is carried out to quick fine grinding material under the effect of mass force, mixes and dispersed sample.It is known equipment, can be by buying and obtain on the market.
For fear of introducing impurity, obtain good grinding effect, to stablize ink quality, in the present embodiment 1, in the double-planet formula high speed ball mill using in step 4), the material of ball grinder and ball is zirconium white.
Step 5) constant-temperature vacuum filters; The ink work in-process that step 4) is obtained, in the constant temperature a mixing bowl of 80～100 ℃, then vacuumize, vibration at high speed, use aperture≤10 μ m strainer filtering, obtain ink finished product.
Certainly, for easy to use, in the present embodiment 1, the packing of bottling again after the ink after step 5) constant-temperature vacuum filters is cooled to room temperature, can be delivered on ceramic ink jet printing production line and use.
Embodiment 2
Formula is referring to each constituent mass ratio given in table 1.In the present embodiment, the colorant using for cobalt blue and spinel be that black pigment makes for 1:2 mixes in mass ratio, the ink color that both ratios can be allocated the in actual use as required consumption of arranging in pairs or groups, and also can add other pigment where necessary, such as: praseodymium yellow, reddish brown, orange etc.Long after glow luminous material is chosen as aluminate base long persistence luminescent material " CaAl
2o
4: Eu, Nd " (blue-fluorescence) and " Sr
4al
14o
25: Eu, Dy " (blue-fluorescence) make for 1:3 mixes in mass ratio.
In the present embodiment, preparation method is substantially the same manner as Example 1, and difference is that the raw material of the colorant using in the present embodiment carries out re-using after calcination process in advance.Be specially: by cobalt blue and spinel be black pigment at 700～850 ℃ of temperature lower calcinations, and reach that granularity reaches that 325 order standard analysiss tail over≤0.05%, could be as the raw material of colorant after moisture content≤0.5%.
So the ink color development of preparation is more stable compared with the technique of embodiment 1.Because the raw material of preparing colorant is after calcining, foreign matter content is wherein less, and also homogeneous more of mineral composition.
Use ink-jet printed layer that this ink spray ink Printing forms by bright turning after dark, can present blue-fluorescence, phosphor persistence time >=2 hour at environment.
Embodiment 3
In the present embodiment, colorant be reddish brown and orange by quality, be that 1:3 mixes and makes, and colorant raw material also passes through as the calcination processing of embodiment 2.Long after glow luminous material is chosen as silicate-base long after glow luminous material " Sr
2mgSi
2o
7: Eu, Dy " (blue-fluorescence).
In the present embodiment, the raw material of preparing powdered frit also needs to calcine rear use.Be specially the raw material of preparing powdered frit is calcined in high temperature silicon carbon bar furnace, 700～850 ℃ of calcining temperatures, calcination time 1～3 hour.So just can obtain the grog of loss on ignition≤1%, moisture content≤0.5%.Use the grog after calcining can stablize ink performance as glaze powder raw material, this is because the raw mineral materials of not calcining wherein has more organism, loss on ignition is higher, use the raw material that loss on ignition is higher can make the printed layer of ink formation may have more needle pore defect after burning till as glaze powder raw material, cause printed layer crude, affect visual appearance.
The preparation technology of embodiment 4 and embodiment 5 is substantially the same manner as Example 3, and difference is that the raw material of prepared colorant is respectively reddish brown and orange, and the long after glow luminous material using is respectively " Ca
2mgSi
2o
7: Eu, Dy " (green fluorescence) and " MgSiO
3: Mn, Eu, Dy " (red fluorescence).
The ink-jet printed layer that the prepared ink spray ink Printing of embodiment 4 forms can present blue-fluorescence, phosphor persistence time >=2 hour at environment by bright turning after dark.
The ink-jet printed layer that the prepared ink spray ink Printing of embodiment 5 forms can present blue-fluorescence at environment by bright turning after dark, and the phosphor persistence time is only about 1 hour.
Embodiment 6 is substantially the same manner as Example 1, and institute's difference is, selected long after glow luminous material is phosphate long afterglow luminous material Ca
3(PO
4)
2: Eu(green fluorescence), this kind of luminescent material is longer time of persistence, and more stable.
Embodiment 7 is substantially the same manner as Example 2, and institute's difference is, selected long after glow luminous material is phosphate long afterglow luminous material " Sr
3(PO
4)
2: Eu " and " Gd; Ba
3(PO
4)
2: Eu, Gd " according to mass ratio, be to use after 1:1 mixes.
Embodiment 8 is substantially the same manner as Example 3, and institute's difference is the selection of long after glow luminous material, and long after glow luminous material is chosen as aluminate base long persistence luminescent material " SrAl in the present embodiment
2o
4: Eu, Dy ", " CaAl
2o
4: Eu, Nd ", " Sr
4al
14o
25: Eu, Dy " according to mass ratio, be that 1:1:1 mixes use.Also can have corresponding effect, but printed layer texture is poor.
Embodiment 9 and embodiment 10 and embodiment and embodiment 4 and embodiment 5 are basic identical, and institute's difference is the selection in long after glow luminous material.In embodiment 9, be chosen as silicate-base long after glow luminous material " Sr
2mgSi
2o
7: Eu, Dy ", " Ca
2mgSi
2o
7: Eu, Dy ", " MgSiO
3: Mn, Eu, Dy " three is in mass ratio that 1:1:1 mixes and uses; Embodiment 10 is phosphate long afterglow luminous material " Ca
3(PO
4)
2: Eu, Gd ", " Sr
3(PO
4)
2: Eu, Gd ", " Ba
3(PO
4)
2: Eu, Gd " for mixing, uses 1:2:1 in mass ratio.
Need in addition explanation, long after glow luminous material is not limited to above-mentioned aluminate-base, phosphate base, silicate-base, and other long after glow luminous material is also applicable, for example: Cd
2ge
7o
16: Mn; MgSnO
4: Mn; Zn
3ga
2ge
2o
10: Cr etc.; And the ratio of the multiple long after glow luminous material providing in above embodiment is also exemplary, those skilled in the art can select the kind of long after glow luminous material, multiple blend proportion according to actual needs, nor are limited to the mixing of identical alkali.
The pH value of measuring embodiment 1-10 ink, between 7～8, is weakly alkaline; And insolubles particle diameter≤10 μ m in ink, so surface does not have large corner angle, there is good stability and rheological, can not wear and tear, stop up and corrode shower nozzle, extend the work-ing life of shower nozzle, cost-saving.
Know-why of the present invention has below been described in conjunction with specific embodiments.These are described is in order to explain principle of the present invention, and can not be interpreted as by any way limiting the scope of the invention.Explanation based on herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, within these modes all will fall into protection scope of the present invention.
Claims (11)
1. a color glaze mixed type noctilucence ink for ceramic ink jet printing, comprising various components be by mass percentage: colorant: 28%～35%; Powdered frit: 10%～15%; Long after glow luminous material: 2%～5%; Magnesiumcarbonate: 1%～5%; Glycol ether: 45%～55%; Dispersion agent: 1～3%; Bonding agent: 0.5%～2%; Tensio-active agent: 0.5%～2%.
2. color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing as claimed in claim 1, is characterized in that, described long after glow luminous material is: SrAl
2o
4: Eu, Dy; CaAl
2o
4: Eu, Nd; Sr
4al
14o
25: Eu, Dy; Sr
2mgSi
2o
7: Eu, Dy; Ca
2mgSi
2o
7: Eu, Dy; MgSiO
3: Mn, Eu, Dy; Ca
3(PO
4)
2: Eu, Gd; Sr
3(PO
4)
2: Eu, Gd; Ba
3(PO
4)
2: Eu, one or more combinations in Gd.
3. color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing as described in any one in claim 1～2, is characterized in that, described colorant is that praseodymium yellow, reddish brown, orange, cobalt blue, spinel are one or more combinations in black pigment.
4. color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing as claimed in claim 3, is characterized in that, the chemical composition mass percent of described powdered frit is: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 8%～12%; Magnesium oxide 4%～5%; Potassium oxide: 1%～3%; Sodium oxide: 3%～5%; Barium oxide: 2%～4%; Zinc oxide: 1%～2%; Zirconium white: 1%～2%; Loss on ignition :≤1%; Water :≤0.5%.
5. color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing as claimed in claim 4, is characterized in that, the pH value of described ink is between 7～8.
6. color glaze mixed type noctilucence ink for a kind of ceramic ink jet printing as claimed in claim 4, is characterized in that solid content >=50% in described ink.
7. the preparation method of color glaze mixed type noctilucence ink for an a kind of ceramic ink jet printing as claimed in claim 1: it comprises the steps:
The siccative of step 1) colorant, long after glow luminous material, powdered frit mixes; By colorant: long after glow luminous material: the mass ratio of powdered frit is that 28～35:2～5:10～15 take, and then pours in quick mixer and mixes;
Step 2) comminution by gas stream; The colorant, long after glow luminous material, the powdered frit compound that adopt high speed jet mill to mix step 1) are beaten powder, obtain the ultrafine powder that particle diameter reaches 10 μ m～50 μ m;
Step 3) batching and one-level ball milling; Be in mass ratio: 40～55:1～5:45～60 take step 2) ultrafine powder, magnesiumcarbonate, the glycol ether that obtain, then pour into and take aluminum oxide ball milling in the ball mill of ball lining and ball, Ball-milling Time 12～24 hours, obtains the mixed slurry that particle diameter is 1～10 μ m;
Step 4) batching and secondary ball milling; The ratio that is in mass ratio 86～120:1～3:0.5～2:0.5～2 takes mixed slurry, dispersion agent, bonding agent, the tensio-active agent that step 3) obtains, pouring double-planet formula high speed ball mill into grinds, milling time 4～10 hours, obtains ink work in-process;
Step 5) constant-temperature vacuum filters; The ink work in-process that step 4) is obtained, in the constant temperature a mixing bowl of 80～100 ℃, then vacuumize, vibration at high speed, use aperture≤10 μ m strainer filtering, obtain ink finished product.
8. the preparation method of color glaze mixed type noctilucence ink for a ceramic ink jet printing as claimed in claim 7, it is characterized in that, in order to reach through 700～850 ℃ of temperature lower calcinations, granularities, 325 order standard analysiss tail over≤0.05% to the colorant described in step 1), the powdery praseodymium yellow of moisture content≤0.5%, reddish brown, orange, cobalt blue, spinel are one or more combinations in black pigment.
9. the preparation method of color glaze mixed type noctilucence ink for ceramic ink jet printing as claimed in claim 7 or 8, it is characterized in that, glaze described in step 1) is silicon-dioxide 45～50 for selecting chemical composition mass ratio: aluminum oxide 18～22: ferric oxide 0～0.2: titanium dioxide 0～0.3: calcium oxide 8～12: magnesium oxide 4～5: potassium oxide 1～3: sodium oxide 3～5: barium oxide 2～4: zinc oxide 1～2: the raw material of zirconium white 1～2 is through 700～850 ℃ of calcinings, calcination time 1～3 hour, obtains the grog of loss on ignition≤1%, moisture content≤0.5%.
10. a preparation method for color glaze mixed type noctilucence ink for ceramic ink jet printing as claimed in claim 7, is characterized in that, the ball mill performance requriements using in step 3) is as follows: ball adopts isostatic pressing process, diameter 10mm～35mm; The Chemical Composition mass percent of ball lining, ball is: aluminium sesquioxide >=95%, silicon-dioxide 2%～5%, ferric oxide≤0.1%, volume density >=3.7 gram/cc of ball lining, ball, ball milling cycle abrasion≤0.1 ‰ of ball lining, ball, Mohs' hardness >=9.5.
11. 1 kinds of ceramic ink jet printings as claimed in claim 7 preparation method of color glaze mixed type noctilucence ink, is characterized in that, in the double-planet formula high speed ball mill using in step 4), the material of ball grinder and ball is zirconium white.
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| CN104402531A (en) * | 2014-10-29 | 2015-03-11 | 万利(中国)有限公司 | 3D glaze material and preparation method thereof |
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| CN111620564A (en) * | 2020-05-06 | 2020-09-04 | 佛山科学技术学院 | Luminous glaze with humidity adjusting function |
| CN111620564B (en) * | 2020-05-06 | 2022-03-25 | 佛山科学技术学院 | Luminous glaze with humidity adjusting function |
| CN111777332A (en) * | 2020-06-15 | 2020-10-16 | 黄冈市蕲春县新天地瓷业有限公司 | Noctilucent glaze, noctilucent ceramic and preparation method thereof |
| CN113480177A (en) * | 2021-07-26 | 2021-10-08 | 广东道氏技术股份有限公司 | Ceramic digital ink with matte carving effect and application thereof |
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