CN103666112B - Ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof - Google Patents
Ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof, belong to technology of ceramic tile decoration.Ceramic ink jet printing color glaze mixed type noctilucence ink provided by the invention, comprising component 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%.Can directly burn till after the ink-jet printed layer using this kind of ink to be formed after spray ink Printing on ceramic adobe, and the printed layer formed has luminous effect, go for the use of instruction, mark, safer, also stair pilot lamp can be substituted, can save energy, and the bandwagon effect of more horn of plenty can also be presented.
Description
Technical field
The present invention relates to a kind of technology of ceramic tile decoration, be specially a kind of ceramic ink jet printing ink, more specifically, relate to a kind of ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof.
Background technology
Inkjet technology is a kind of contactless digital printing technologies succeeded in developing late 1970s.It by ink by the nozzle ejection on printhead on various dielectric surface, achieve noncontact, high speed, the monochrome of low noise or the word of colour or image printing.At the beginning of 21 century, Ferro Corporation develops the oil-based ink being adapted at pottery carrying out spray ink Printing, is 00818261.2 at the corresponding number of patent application of China.The widespread use of inkjet technology at architectural pottery production field is started with this.As a kind of brand-new ceramic decoration theory, ceramic decoration colour print technology can make full use of abundant computer data, digital technique is incorporated in traditional architectural pottery product, ceramic decoration is made to closely follow era step, embody stylistic features, meet the requirement of people's personalization, ceramic decoration technology is pushed to a new stage.
Inkjet technology tool compared with the traditional decoration means of ceramic tile production has the following advantages: (1) energy-saving and emission-reduction, product has been broken away from batch production needs film-making, screen cloth, the intermediate step such as mechanical, shorten and change the line of production the cycle, significantly enhance productivity, also reduce the loss in the process of changing the line of production; (2) print procedure is completely by computer control, complicated pattern decorative can be carried out in production process, and the precision of pattern improves with repeatable, greatly can improve mechanization degree and the production efficiency of decoration process, also can complete the short run even customization of single products; (3) contactless, can print on male and fomale(M&F), make the decoration of some special-shaped products become easy, extreme enrichment decorative effect.
But ink-jet printed technique belongs to a kind of surface decoration technique, namely predetermined pattern is formed at ceramic tile surface by printing of inkjet printer, main component at present in disclosed ink set is tinting material/colorant and solvent, and makes tinting material/colorant additive such as homodisperse dispersion agent in a solvent.The printed layer that spray ink Printing is formed is how not wear-resisting, even after high temperature sintering, is easier to wearing and tearing in the printed layer of ceramic tile surface yet, and therefore need executes layer of transparent protection glaze to protect printed layer more.This make the production cost of ink-jet printed series ceramic Wall or 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, and under illumination condition, absorb photons 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 as referential index effect, the indicating bit of such as staircase, the indicating bit etc. of room switch, and goods can be allowed to present abundant effect.But current ceramic ink jet printing ink is not suitable for adding long after glow luminous material and makes noctilucence ink, and the luminous glaze transparency using long after glow luminous material to make is lower, is also not suitable as the protective layer of ink-jet printed layer.
Summary of the invention
The object of the invention is to propose a kind of ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof, when using ceramic ink jet printing color glaze mixed type noctilucence ink provided by the invention to produce ceramic wall and floor bricks product, ink-jet printed rear direct high temperature burns till, without the need to after executing transparency protected glaze again after ink-jet printed again high temperature burn till, Glaze Composition in ink is meeting melting when burning till, chromophoe constituent 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, obtain the ink-jet printed layer with luminous effect.
For reaching this object, the present invention by the following technical solutions: a kind of ceramic ink jet printing color glaze mixed type noctilucence ink, 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, in above-mentioned spray ink Printing 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: one or more combinations in Eu, Dy.
Preferably, in above-mentioned spray ink Printing 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: one or more combinations in Mn, Eu, Dy.
Preferably, in above-mentioned spray ink Printing 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: one or more combinations in Eu, Gd.
Going for high temperature to make ink to burn till, preferably, is one or more combinations in praseodymium yellow, reddish brown, orange, cobalt blue, spinel system black pigment at the colorant described in above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence.
After making sintering, the printed layer using ink provided by the invention to be formed has good texture, preferably, the chemical composition mass percent of the powdered frit described in above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence 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%.
Above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence ink is weakly alkaline; It is minimum to the corrodibility of shower nozzle when its PH is between 7 ~ 8.
When in above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence ink during solid content >=50%, there is particularly preferred hair color effect.
The present invention also provides a kind of preparation method of above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence ink: it comprises the steps:
The siccative mixing of step 1) colorant, long after glow luminous material, powdered frit; 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 adopting high speed jet mill to mix step 1), long after glow luminous material, powdered frit compound carry out beating powder, obtain the ultrafine powder that particle diameter reaches 10 μm ~ 50 μm.
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 aluminum oxide be ball lining and ball ball mill in ball milling, Ball-milling Time 12 ~ 24 hours, obtains the mixed slurry that particle diameter is 1 ~ 10 μm.
Step 4) batching and secondary ball milling; Be mixed slurry, dispersion agent, bonding agent, the tensio-active agent that the ratio of 86 ~ 120:1 ~ 3:0.5 ~ 2:0.5 ~ 2 takes step 3) and obtains in mass ratio, pour double planetary high speed ball mill into grind, milling time 4 ~ 10 hours, obtains ink work in-process.
Step 5) constant-temperature vacuum filters; Ink work in-process step 4) obtained, in the constant temperature a mixing bowl of 80 ~ 100 DEG C, then carry out vacuumizing, vibration at high speed, use aperture≤10 μm strainer filtering, obtain ink.
Preferably, in the preparation method of above-mentioned a kind of ceramic ink jet printing color glaze mixed type noctilucence, the colorant described in step 1) be reach that 325 order standard analysiss tail over≤0.05% through 700 ~ 850 DEG C of temperature lower calcinations, granularity, the powdery praseodymium yellow of moisture content≤0.5%, one or more combinations in reddish brown, orange, cobalt blue, spinel system black pigment.
Preferably, in the preparation method of above-mentioned a kind of ceramic ink jet printing 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 DEG C of calcinings, calcination time 1 ~ 3 hour, obtains the grog of loss on ignition≤1%, moisture content≤0.5%.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in a kind of preparation method of ceramic ink jet printing color glaze mixed type noctilucence, the ball mill performance requriements used 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.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in a kind of preparation method of ceramic ink jet printing color glaze mixed type noctilucence, in the double planetary high speed ball mill used 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, does not need in printed layer, impose one deck ink protection glaze again.Burnt till by kiln, after color glaze mixed type ink sintering, self can form one deck printed layer wear-resisting closely, which greatly simplifies the production technique of spray ink Printing decoration, and reduce production cost, enhance productivity.
2, the ink-jet printed layer using this kind of ink to be formed after spray ink Printing on ceramic adobe has luminous effect, go for the use of instruction, mark, safer, also can substitute stair pilot lamp, can save energy, and the bandwagon effect of more horn of plenty can also be presented.
3, magnesiumcarbonate is introduced in color glaze mixed type ink set; play outside the suspension stability of enhancing ink, anti-caking effect effect; because it is in alkalescence; in the course of processing, react with closing in the acid colorants generation soda acid in ink, and make ink be weakly alkaline; the acid ink made compared with prior art is compared; be more conducive to the protection (acidity can corrode expensive printing head) 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 hair color effect is better than existing ink.
5, color glaze mixed type ink adopt solvent be glycol ether (boiling point is 245 DEG C), there is not the problem of solvent evaporates, to the mankind and environment safer.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1-10
The component formula of the ceramic ink jet printing color glaze mixed type noctilucence that embodiment 1-10 provides is as following table 1.
Table 1
The colorant selected 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, after environment is dark by bright turn, fluorescence duration 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, the chemical analysis results that those skilled in the art commonly use mineral or frit class raw material by Sai Geershi and Production of Ceramics calculates formula consumption, therefore the chemical composition requirement of powdered frit is only gived here, for the raw material of Different sources or the frit of different chemical component, those skilled in the art can arrange in pairs or groups selection flexibly.Here a given concrete powdered frit batch formula: albite 35%, 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 to illustrate, 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 a kind of preparation method of above-mentioned a kind of ceramic ink jet printing 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 powdered frit siccative mixing; By 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 adopting high speed jet mill to mix step 1), long after glow luminous material, powdered frit compound carry out beating powder, obtain the ultrafine powder that particle diameter reaches 10 μm ~ 50 μm.
Here the principle of work of illustratively comminution by gas stream: micronizer mill and cyclonic separator, fly-ash separator, induced draft fan form a whole set of crushing system.Pressurized air is after filtration after drying, crushing chamber is entered by laval nozzle high-velocity jet, at the joint place material of multiply high pressure draft by impact several times, friction, shearing and pulverizing, material after pulverizing moves to graded region with upstream under blower fan draft effect, under the powerful centrifugal action that the stage turbine of high speed rotating produces, make thickness feed separation, the fine particle meeting granularity requirements enters cyclonic separator and fly-ash separator collection by grading wheel, and coarse particles drops to disintegrating area to be continued to pulverize.Above Jet Mill is known device, can buy 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 aluminum oxide be ball lining and ball ball mill in ball milling, Ball-milling Time 12 ~ 24 hours, obtains the mixed slurry that particle diameter is 1 μm ~ 10 μm.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in the present embodiment, the ball mill performance requriements used 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; In mass ratio 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 planetary high speed ball mill into and grind, milling time 4 ~ 10 hours, obtain ink work in-process.
Dispersion agent is some water-soluble and oil soluble high score subclass, phenylformic acid and derivative, polyacrylic acid and multipolymers thereof etc. mainly.
Bonding agent ensures that the ceramic body of printing or colorant have certain intensity, and be convenient to production operation, stablize the mobility of ink, usual resin can play the dual function of bonding agent and dispersion agent.Resin is divided into the synthetic resins of natural resin and aggretion type, bonding agent in formula adopt polymerization type resin as: a kind of in polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Tensio-active agent is that the surface tension of control ink factory is in the scope be applicable to.As carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof.
The principle of work of double planetary ball mill is: on the traffic cycle of one (revolution), be provided with two major planets axles in (rotation), does the running of single file planetary.Two mini-roundabouts are installed again simultaneously on two major planets axles and four ball grinder protecting seats (putting ball grinder to use) are installed on (revolution) two mini-roundabouts in (rotation), do double planetary running.Ball grinder is when this running up, and the mill ball in ball grinder defines very large high-frequency percussion power, straight line impact force, friction to material, carries out quick fine grinding to material under the effect of mass force, mixing and dispersed sample.It is known device, can by buying acquisition on the market.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in the present embodiment 1, in the double planetary high speed ball mill used in step 4), the material of ball grinder and ball is zirconium white.
Step 5) constant-temperature vacuum filters; Ink work in-process step 4) obtained, in the constant temperature a mixing bowl of 80 ~ 100 DEG C, then carry out vacuumizing, vibration at high speed, use aperture≤10 μm strainer filtering, obtain ink.
Certainly, in order to easy to use, in the present embodiment 1, carry out bottling packaging after the ink after step 5) constant-temperature vacuum filters is cooled to room temperature again, can be delivered on ceramic ink jet printing production line and use.
Embodiment 2
Fill a prescription see each constituent mass ratio given in table 1.In the present embodiment, the colorant used is for cobalt blue and spinel system black pigment are in mass ratio for 1:2 mixing is obtained, the ink color that both ratios can be allocated in actual use as required carries out collocation consumption, 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) in mass ratio for 1:3 mixing is obtained.
In the present embodiment, preparation method is substantially the same manner as Example 1, and difference is, re-uses after the raw material of the colorant used in the present embodiment carries out calcination process in advance.Be specially: by cobalt blue and spinel system black pigment at 700 ~ 850 DEG C of temperature lower calcinations, and reach that granularity reaches that 325 order standard analysiss tail over≤0.05%, could as the raw material of colorant after moisture content≤0.5%.
The ink color development of preparation like this is more stable compared with the technique of embodiment 1.Because prepare the raw material of colorant after calcining, foreign matter content is wherein less, and mineral composition is also more homogeneous.
The ink-jet printed layer using this ink jet to print formation can present blue-fluorescence, fluorescence duration time >=2 hour after environment is dark by bright turn.
Embodiment 3
In the present embodiment, colorant is that reddish brown and orange to be that 1:3 mixes by quality obtained, and Pigment Material also passes through the calcination processing as 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 preparing powdered frit also needs to carry out calcining rear use.Be specially and the raw material preparing powdered frit is calcined in high temperature silicon carbon bar furnace, calcining temperature 700 ~ 850 DEG C, 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 do not calcined wherein has more organism, loss on ignition is higher, the printed layer using the higher raw material of loss on ignition ink can be made to be formed as glaze powder raw material may have more needle pore defect after burning till, 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 used is respectively " Ca
2mgSi
2o
7: Eu, Dy " (green fluorescence) and " MgSiO
3: Mn, Eu, Dy " (red fluorescence).
Ink jet prepared by embodiment 4 prints the ink-jet printed layer formed can present blue-fluorescence, fluorescence duration time >=2 hour after environment is dark by bright turn.
Ink jet prepared by embodiment 5 prints the ink-jet printed layer formed can present blue-fluorescence after environment is dark by bright turn, and fluorescence duration time is only 1 hours.
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 for 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 1:1 mixing after use.
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 " be that 1:1:1 is used in combination according to mass ratio.Also can have corresponding effect, but printed layer texture is poor.
Embodiment 9 is substantially identical with embodiment 5 with embodiment 4 with embodiment with embodiment 10, and institute's difference is the selection in long after glow luminous material.Silicate-base long after glow luminous material " Sr is chosen as in embodiment 9
2mgSi
2o
7: Eu, Dy ", " Ca
2mgSi
2o
7: Eu, Dy ", " MgSiO
3: Mn, Eu, Dy " three is that 1:1:1 is used in combination in mass ratio; 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 " be that 1:2:1 is used in combination in mass ratio.
Need in addition to illustrate, 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 suitable for, such as: 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 provided 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.
Measure the pH value of embodiment 1-10 ink, between 7 ~ 8, in weakly alkaline; And insolubles particle diameter≤10 μm in ink, so surface does not have large corner angle, there is excellent stability and rheological, can not wear and tear, block and corrode shower nozzle, extend the work-ing life of shower nozzle, cost-saving.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.
Claims (7)
1. a ceramic ink jet printing color glaze mixed type noctilucence ink, 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%; Described colorant is one or more combinations in praseodymium yellow, reddish brown, orange, cobalt blue, spinel system black pigment; 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%.
2. a kind of ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 1, it 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: one or more combinations in Eu, Gd.
3. a kind of ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 1, it is characterized in that, the pH value of described ink is between 7 ~ 8.
4. a kind of ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 1, is characterized in that, solid content >=50% in described ink.
5. the preparation method of an a kind of ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 1: it comprises the steps:
The siccative mixing of step 1) colorant, long after glow luminous material, powdered frit; 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 adopting high speed jet mill to mix step 1), long after glow luminous material, powdered frit compound carry out beating powder, obtain the ultrafine powder that particle diameter reaches 10 μm ~ 50 μm;
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 aluminum oxide be ball lining and ball ball mill in ball milling, Ball-milling Time 12 ~ 24 hours, obtains the mixed slurry that particle diameter is 1 ~ 10 μm;
Step 4) batching and secondary ball milling; Be mixed slurry, dispersion agent, bonding agent, the tensio-active agent that the ratio of 86 ~ 120:1 ~ 3:0.5 ~ 2:0.5 ~ 2 takes step 3) and obtains in mass ratio, pour double planetary high speed ball mill into grind, milling time 4 ~ 10 hours, obtains ink work in-process;
Step 5) constant-temperature vacuum filters; Ink work in-process step 4) obtained, in the constant temperature a mixing bowl of 80 ~ 100 DEG C, then carry out vacuumizing, vibration at high speed, use aperture≤10 μm strainer filtering, obtain ink;
Colorant described in step 1) be reach that 325 order standard analysiss tail over≤0.05% through 700 ~ 850 DEG C of temperature lower calcinations, granularity, the powdery praseodymium yellow of moisture content≤0.5%, one or more combinations in reddish brown, orange, cobalt blue, spinel system black pigment;
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 DEG C of calcinings, calcination time 1 ~ 3 hour, obtains the grog of loss on ignition≤1%, moisture content≤0.5%.
6. a preparation method for ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 5, it is characterized in that, the ball mill performance requriements used 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.
7. a preparation method for ceramic ink jet printing color glaze mixed type noctilucence ink as claimed in claim 5, it is characterized in that, in the double planetary high speed ball mill used in step 4), the material of ball grinder and ball is zirconium white.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310638849.7A CN103666112B (en) | 2013-12-02 | 2013-12-02 | Ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof |
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| CN201310638849.7A CN103666112B (en) | 2013-12-02 | 2013-12-02 | Ceramic ink jet printing color glaze mixed type noctilucence ink and preparation method thereof |
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| CN104402531B (en) * | 2014-10-29 | 2016-04-13 | 万利(中国)有限公司 | A kind of 3D glaze and preparation method thereof |
| CN105887510A (en) * | 2016-05-18 | 2016-08-24 | 太仓市好心情印务有限公司 | Long-acting luminous non-woven fabric bag |
| CN105925064A (en) * | 2016-06-01 | 2016-09-07 | 佛山市高明区海帝陶瓷原料有限公司 | Wall brick ceramic ink with noctilucent effect and preparation method thereof |
| CN107473592A (en) * | 2017-08-18 | 2017-12-15 | 佛山市石湾裕龙陶瓷有限公司 | A kind of ceramic ink jet printing furnace transmutation glaze and preparation method thereof |
| CN108976911A (en) * | 2018-07-09 | 2018-12-11 | 山东汇龙色釉新材料科技有限公司 | It is a kind of to burn ceramic marking ink and its preparation process three times |
| CN109626975A (en) * | 2019-02-27 | 2019-04-16 | 佛山石湾鹰牌陶瓷有限公司 | A kind of firing process of the big plate of ceramics |
| 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 |
| EP4059733A1 (en) | 2021-03-18 | 2022-09-21 | Gerresheimer Glas GmbH | Counterfeit-proof marking of individual primary packaging means using digital printing of ceramic inks with spectral markers |
| 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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Effective date of registration: 20170419 Address after: 528031 Chancheng, Foshan District, Jiangwan, No. three, No., layer 8, layer two Co-patentee after: Guangdong Dongpeng Holdings Co., Ltd. Patentee after: Foshan Dongpeng Ceramic Co., Ltd. Co-patentee after: Fengcheng Dongpeng Ceramic Co., Ltd. Address before: Chancheng District of Jiangwan city of Foshan province Guangdong three road 528031 No. 8 two Foshan city Eastroc Ceramics Co. Ltd Co-patentee before: Guangdong Dongpeng Holdings Co., Ltd. Patentee before: Foshan Dongpeng Ceramic Co., Ltd. Co-patentee before: Fengcheng Dongpeng Ceramic Co., Ltd. Co-patentee before: Guangdong Dongpeng Ceramic Co., Ltd. |