CN103602144A - Ceramic ink-jet printing colored glaze mixed type antibacterial ink and preparation method thereof - Google Patents
Ceramic ink-jet printing colored glaze mixed type antibacterial ink and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ceramic ink-jet printing colored glaze mixed type antibacterial ink and a preparation method thereof, and belongs to the ceramic brick decoration technology. The ceramic ink-jet printing colored glaze mixed type antibacterial ink provided by the invention comprises the components by the mass percentage: 28%-35% of a coloring material, 11.5%-17% of a calcium-based glaze powder, 0.5%-3% of an antibacterial agent containing silver ions, 1%-5% of magnesium carbonate, 45%-55% of diethylene glycol, 1-3% of a dispersant, 0.5%-2% of a bonding agent, and 0.5%-2% of a surface active agent. An ink-jet printing layer formed after ink-jet printing of the ink on a ceramic brick blank has good antibacterial effect after sintering, and moreover, the printing layer is resistant to wear and lasting in antibacterial effect, and is especially suitable for bottom surface decoration of public space having urgent antibacterial requirements.
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 antibacterial ink of color glaze mixed type and preparation method thereof for a kind of ceramic ink jet printing.
Background technology
Bacterium, mould has very large harm as pathogenic bacteria to the mankind and animals and plants, and the health that affects people is threat to life even, has brought great financial loss.Therefore the research of anti-biotic material and goods thereof causes people's concern day by day, and the demand of antimicrobial prod will form huge market.It is high that ceramic tile has intensity, long service life, and the feature such as decorative effect is abundant is the most conventional material of construction of people always, is also one of maximum material of the daily contact of people.Therefore, if can make ceramic tile product there is antibacterial, beyond doubt for HUMAN HEALTH increases a guarantee.
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.It is 00818261.2 that 21 century Chu， U.S. Ferro Corp develops the corresponding number of patent application of oil-based ink ， China that is adapted at carrying out on pottery spray ink Printing.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.
Application publication number is: the Chinese invention patent of CN103382328A discloses a kind of ceramic ink jet printing with ink and had the ceramic tile of antibacterial.In above patent documentation, be by add antiseptic-germicide in ink, soluble inorganic salt and the calcium phosphate of antiseptic-germicide one or more antibacterial ions in containing silver, copper, zine ion form, in antiseptic-germicide, the shared mass fraction of calcium phosphate is 8%～20%, and all the other are the soluble inorganic salt that contains one or more antibacterial ions in silver, copper, zine ion.The ceramic tile of using this kind of ink to produce has good antibacterial effect, but the antibiotic layer fastness to rubbing that adobe forms at ceramic brick surface after ink-jet is burnt till is inadequate, is easy to wearing and tearing and loses antibacterial effect in use procedure.
Summary of the invention
The object of the invention is to propose antibacterial ink of color glaze mixed type 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 the antibacterial ink of color glaze mixed type, 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, calcium base glaze meal component in ink is meeting melting when burning till, antiseptic-germicide and the colorant parcel of silver ions will be contained in ink, silver ions in ink-jet printed layer can play good antibacterial effect, colorant presents the pattern of ink-jet printed formation, calcium base powdered frit can make formed ink-jet printed layer wear-resisting especially, guarantee the effectively lasting of antibacterial effect.
For reaching this object, the present invention by the following technical solutions: the antibacterial ink of color glaze mixed type for a kind of ceramic ink jet printing, comprising various components be by mass percentage: colorant: 28%～35%; Calcium base powdered frit: 11.5%～17%; The antiseptic-germicide that contains silver ions: 0.5%～3%; Magnesiumcarbonate: 1%～5%; Glycol ether: 45%～55%; Dispersion agent: 1～3%; Bonding agent: 0.5%～2%; Tensio-active agent: 0.5%～2%.
In order to obtain good antibacterial effect, and the high temperature of applicable ceramic wall and floor bricks goods burns till, preferably, at above-mentioned ceramic ink jet printing, use in the antibacterial ink of color glaze mixed type, the calcium phosphate that to contain the mass fraction that accounts in the described antiseptic-germicide that contains silver ions be 8%～20%, all the other components are silver-colored soluble inorganic salt.
In order to make ink go for high temperature, burn till, preferably, at above-mentioned a kind of ceramic ink jet printing, with in the antibacterial ink of color glaze mixed type, described colorant is that praseodymium yellow, reddish brown, orange, cobalt blue, spinel are one or more combinations in black pigment.
For the printed layer of using ink provided by the invention to form after sintering has good texture and wear resistance, preferably, at above-mentioned a kind of ceramic ink jet printing, by the chemical composition mass percent of the calcium base powdered frit described in the antibacterial ink of color glaze mixed type, be: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 10%～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 the antibacterial ink of color glaze mixed type; Its pH value 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 the antibacterial ink of color glaze mixed type 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 the antibacterial ink of color glaze mixed type: it comprises the steps:
The siccative of step 1) colorant, the antiseptic-germicide that contains silver ions, calcium base powdered frit mixes; By colorant: the antiseptic-germicide that contains silver ions: the mass ratio of calcium base powdered frit is that 28～35:0.5～3:11.5～17 take, and then pours in quick mixer and mixes.
Step 2) comminution by gas stream; The colorant, the antiseptic-germicide that contains silver ions and the calcium base 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 the antibacterial ink of color glaze mixed type, 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 the antibacterial ink of color glaze mixed type, calcium base powdered frit 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 10～12: 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 the antibacterial ink of color glaze mixed type, 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 the antibacterial ink of color glaze mixed type, 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, this kind of ink has good antibacterial effect, and wear-resisting especially after the ink-jet printed layer burning forming at ceramic brick surface spray ink Printing, and antibacterial effect is lasting.
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 1-5
The ceramic ink jet printing that embodiment 1-5 provides uses the component formula of the antibacterial ink of color glaze mixed type as following table 1.
Table 1
The colorant of selecting in embodiment 1 is praseodymium yellow, and the antiseptic-germicide that contains silver ions is the mixture of Silver Nitrate and calcium phosphate, and wherein the mass fraction of calcium phosphate is 8%, and all the other are Silver Nitrate.The chemical composition mass percent of calcium base powdered frit is in this embodiment: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 10%～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 calcium base 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 the antibacterial ink of color glaze mixed type: it comprises the steps:
The siccative of step 1) colorant, the antiseptic-germicide that contains silver ions and calcium base powdered frit mixes; By colorant: the antiseptic-germicide that contains silver ions: the mass ratio of calcium base powdered frit is that 28:2:15 takes, and then pours in quick mixer and mixes.
Step 2) comminution by gas stream; The colorant, the antiseptic-germicide that contains silver ions and the calcium base 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.
For the antibacterial effect of tested inks, use above ink spray ink Printing on ceramic adobe to form after ink-jet printed layer, enter 1100～1230 ℃, tunnel furnace and burn till, obtain having the ceramic tile of antibacterial effect.
Adopt inhibition zone method to check qualitatively the antibacterial effect of ink, the bacterial classification of employing is streptococcus aureus and intestinal bacteria, and substratum is nutrient agar medium, and culture temperature is 37 ℃, and incubation time is 24h, and the bacteria suspension concentration of making is 2.0 * 10
6/ ml～2.0 * 10
7/ ml.Formed antibacterial circle diameter is 18mm～22mm.Sterilization rate test result is: 6 hours sterilization rates are that 94%, 24 hour sterilization rate is that 99%, 48 hour sterilization rate is 99%.
In addition, for testing above ink, form the wear resistance of printed layer and the antibacterial effect after long-term practical wearing and tearing, above product is simulated to use wear testing, wear testing to select Mohs' hardness be 3～4 abrasive material, in printed layer, rub and imitate paving for 1000 times and use the effect after 2 years.After friction, to sample cleaning, drying, whether fuzzyly then observe ink-jet printed layer pattern, and test according to the method described above antibacterial effect.Visual inspection, ink-jet printed layer is without noticeable wear, and pattern is still clear, and just glossiness slightly declines before.Antibacterial effect test result is as follows: inhibition zone size is 16～21mm; Sterilization rate test result is: 6 hours sterilization rates are that 92%, 24 hour sterilization rate is that 99%, 48 hour sterilization rate is 99%.
For explanation advantage of the present invention, employing application publication number is: the ceramic tile that the disclosed a kind of ceramic ink jet printing of Chinese invention patent of CN103382328A is prepared with ink, through above wear testing, the basic wearing and tearing of ink-jet printed layer, antibacterial effect is also lost substantially, therefore it is not suitable for being used in the public space bottom surface decoration that wear rate is higher, and the ground of these public spaces is also urgent to antibacterial demand exactly.
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.The antiseptic-germicide that contains silver ions is the mixture of Silver Nitrate and calcium phosphate, and wherein the mass fraction of calcium phosphate is 12%, and all the other are Silver Nitrate.
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.
Adopt inhibition zone method to check qualitatively the antibacterial effect of ink, the bacterial classification of employing is streptococcus aureus and intestinal bacteria, and substratum is nutrient agar medium, and culture temperature is 37 ℃, and incubation time is 24h, and the bacteria suspension concentration of making is 2.0 * 10
6/ ml～2.0 * 10
7/ ml.Formed antibacterial circle diameter is 20mm～22mm.Sterilization rate test result is: 6 hours sterilization rates are that 95%, 24 hour sterilization rate is that 99%, 48 hour sterilization rate is 99%.
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.The antiseptic-germicide that contains silver ions is the mixture of Silver Nitrate and calcium phosphate, and wherein the mass fraction of calcium phosphate is 15%, and all the other are Silver Nitrate.
In the present embodiment, the raw material of preparing calcium base powdered frit also needs to calcine rear use.Be specially the raw material of preparing calcium base 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 calcium base 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; The antiseptic-germicide that contains silver ions is the mixture of Silver Nitrate and calcium phosphate, and wherein the mass fraction of calcium phosphate is 20%, and all the other are Silver Nitrate.
The pH value of measuring embodiment 1-5 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 antibacterial ink for ceramic ink jet printing, comprising various components be by mass percentage: colorant: 28%～35%; Calcium base powdered frit: 11.5%～17%; The antiseptic-germicide that contains silver ions: 0.5%～3%; Magnesiumcarbonate: 1%～5%; Glycol ether: 45%～55%; Dispersion agent: 1～3%; Bonding agent: 0.5%～2%; Tensio-active agent: 0.5%～2%.
2. the antibacterial ink of color glaze mixed type for a kind of ceramic ink jet printing as claimed in claim 1, is characterized in that, described in contain silver ions antiseptic-germicide in contain the calcium phosphate that the mass fraction that accounts for is 8%～20%, all the other components are silver-colored soluble inorganic salt.
3. the antibacterial ink of color glaze mixed type for a kind of ceramic ink jet printing as claimed in claim 1 or 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. a kind of ceramic ink jet printing antibacterial ink of color glaze mixed type as claimed in claim 3, is characterized in that, the chemical composition mass percent of described calcium base powdered frit is: silicon-dioxide: 45%～50%; Aluminum oxide 18%～22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 10%～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. a kind of ceramic ink jet printing antibacterial ink of color glaze mixed type as claimed in claim 4, is characterized in that, the pH value of described ink is between 7～8.
6. a kind of ceramic ink jet printing antibacterial ink of color glaze mixed type as claimed in claim 4, is characterized in that solid content >=50% in described ink.
7. the preparation method of the antibacterial ink of color glaze mixed type for an a kind of ceramic ink jet printing as claimed in claim 1: it comprises the steps:
The siccative of step 1) colorant, the antiseptic-germicide that contains silver ions, calcium base powdered frit mixes; By colorant: the antiseptic-germicide that contains silver ions: the mass ratio of calcium base powdered frit is that 28～35:0.5～3:11.5～17 take, and then pours in quick mixer and mixes;
Step 2) comminution by gas stream; The colorant, the antiseptic-germicide that contains silver ions and the calcium base 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 the antibacterial ink of color glaze mixed type 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 antibacterial ink for ceramic ink jet printing as claimed in claim 7 or 8, it is characterized in that, calcium base powdered frit 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 10～12: 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, obtain loss on ignition≤1%, the grog of moisture content≤0.5%.
10. a preparation method for the antibacterial ink of color glaze mixed type 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 the antibacterial ink of color glaze mixed type, 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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| CN201310638468.9A CN103602144B (en) | 2013-12-02 | 2013-12-02 | Ceramic ink-jet printing colored glaze mixed type antibacterial ink and preparation method thereof |
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| CN105819898A (en) * | 2016-03-15 | 2016-08-03 | 山东镭泽智能科技有限公司 | Cobalt blue pigment for laser ink and preparation method thereof |
| CN105968958A (en) * | 2016-06-01 | 2016-09-28 | 佛山市高明区海帝陶瓷原料有限公司 | Anti-fouling antibacterial wall brick ceramic ink and preparing method thereof |
| CN105968959A (en) * | 2016-06-01 | 2016-09-28 | 佛山市高明区海帝陶瓷原料有限公司 | Wall brick ceramic ink with antibacterial effect and preparation method thereof |
| CN106009927A (en) * | 2016-06-01 | 2016-10-12 | 佛山市高明区海帝陶瓷原料有限公司 | Wall brick ceramic ink for improving color gamut range, and preparation method thereof |
| CN106009929A (en) * | 2016-06-01 | 2016-10-12 | 佛山市高明区海帝陶瓷原料有限公司 | Antistatic antibacterial wall brick ceramic ink and preparation method thereof |
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| CN101351344A (en) * | 2005-12-29 | 2009-01-21 | 通用电气公司 | Ink composition for making glass and ceramic surfaces |
| CN103382328A (en) * | 2013-07-19 | 2013-11-06 | 广东东鹏陶瓷股份有限公司 | Antibacterial ink for ceramic ink-jet printing and ceramic tile with antibacterial function |
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| CN101351344A (en) * | 2005-12-29 | 2009-01-21 | 通用电气公司 | Ink composition for making glass and ceramic surfaces |
| CN103382328A (en) * | 2013-07-19 | 2013-11-06 | 广东东鹏陶瓷股份有限公司 | Antibacterial ink for ceramic ink-jet printing and ceramic tile with antibacterial function |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105819898A (en) * | 2016-03-15 | 2016-08-03 | 山东镭泽智能科技有限公司 | Cobalt blue pigment for laser ink and preparation method thereof |
| CN105819898B (en) * | 2016-03-15 | 2018-05-08 | 山东镭泽智能科技有限公司 | Laser ink zaffre and preparation method thereof |
| CN105968958A (en) * | 2016-06-01 | 2016-09-28 | 佛山市高明区海帝陶瓷原料有限公司 | Anti-fouling antibacterial wall brick ceramic ink and preparing method thereof |
| CN105968959A (en) * | 2016-06-01 | 2016-09-28 | 佛山市高明区海帝陶瓷原料有限公司 | Wall brick ceramic ink with antibacterial effect and preparation method thereof |
| CN106009927A (en) * | 2016-06-01 | 2016-10-12 | 佛山市高明区海帝陶瓷原料有限公司 | Wall brick ceramic ink for improving color gamut range, and preparation method thereof |
| CN106009929A (en) * | 2016-06-01 | 2016-10-12 | 佛山市高明区海帝陶瓷原料有限公司 | Antistatic antibacterial wall brick ceramic ink and preparation method thereof |
| CN106348792A (en) * | 2016-08-26 | 2017-01-25 | 高名胜 | Manufacturing method of antibacterial ceramic tiles |
| CN106348792B (en) * | 2016-08-26 | 2019-06-14 | 淄博新博陶瓷科技有限公司 | A kind of manufacturing method of antibiotic ceramic tile |
| CN111732339A (en) * | 2020-07-23 | 2020-10-02 | 广东特地陶瓷有限公司 | Antibacterial digital glaze for ink-jet printing, preparation method and functional ceramic |
| CN117859768A (en) * | 2024-03-11 | 2024-04-12 | 佛山市东鹏陶瓷有限公司 | Composite antiviral agent and preparation method thereof, protective glaze, ceramic tile and preparation method 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. |