CN106009929A - Antistatic antibacterial wall brick ceramic ink and preparation method thereof - Google Patents
Antistatic antibacterial wall brick ceramic ink and preparation method thereof Download PDFInfo
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- CN106009929A CN106009929A CN201610377231.3A CN201610377231A CN106009929A CN 106009929 A CN106009929 A CN 106009929A CN 201610377231 A CN201610377231 A CN 201610377231A CN 106009929 A CN106009929 A CN 106009929A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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Abstract
The invention discloses an antistatic antibacterial wall brick ceramic ink and a preparation method thereof. The wall brick ceramic ink comprises the following components by mass: 35-45% of a pigment, 3-8% of a dispersant, 40-50% of a solvent, 2-5% of a surface additive, 0.1-0.5% of a leveling agent, 0.3-0.8% of a defoaming agent, 0.5-1% of a binding agent, 0.08-0.1% of an anti-settling agent, 4-8% of a composite antistatic agent and 1-2% of a composite antibacterial agent. The ceramic ink not only has antibacterial function but also has antistatic function.
Description
Technical field
The present invention relates to technology of ceramic tile decoration field, anti-electrostatic antibiotic wall brick ceramic ink having particularly related to a kind of ceramic ink jet printing and preparation method thereof.
Background technology
In daily life, in the winter being especially dried in the north, indoor have " electric " everywhere, and touching door handle can be electrically shocked, and touching water pipe can be electrically shocked, and going home to hold a baby in one's arms also can be electrically shocked, and even unblanks to touch keyhole, also can be electrically shocked.Research finds, these shock phenomenon bring the biggest harm, the physiological equilibrium of impact person human body can to the body & mind of people, cause all illness subtlely, accelerate human senescence.
Antibacterial, mycete has the biggest harm as pathogen to the mankind and animals and plants, affects the health even threat to life of people, brings great economic loss.Therefore the research of anti-biotic material and goods thereof causes the concern of people day by day, and the demand of antibacterial product will constitute huge market.
Wall brick, no matter household interior decoration, or for commercial production or public place, after meeting outward appearance practicality, how to make it possess more function concerned in terms of health of people guarantee, be also that industry researcher is kept up with the trend of the times and life wind vane and the thinking made.Anti-static ceramic tile is extensively applied by every profession and trade at present, but according to using wire gauze or copper strips construction more complicated in the past, cost is high, and of long duration oxidizable, it is difficult to ensure that the stability of volume resistance；Also having and use anti-electrostatic antibiotic wall brick ceramic ink to obtain the wall brick with anti-static effect, but stability is more weak, abrasion resistance is inadequate, easily weares and teares and lose anti-static effect during use.At present, there is the ceramic ink of more anti-electrostatic antibiotic function, but in prior art, its antibacterial stability of wall brick being coated with antibacterial ink is more weak, and both effect is more difficult takes into account, and abrasion resistance is inadequate, is easy to abrasion and loses antibacterial and anti-static effect during use.
Summary of the invention
The technical problem to be solved there is provided a kind of not only to have been possessed antibacterial functions but also had possessed the ceramic ink of anti-electrostatic antibiotic of electrostatic-proof function.Present invention also offers the preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink.
The technical problem to be solved is achieved by the following technical programs:
A kind of anti-electrostatic antibiotic wall brick ceramic ink, including various components be by mass percentage: colorant 35 ~ 45%, dispersant 3 ~ 8%, solvent 40 ~ 50%, surface additive 2 ~ 5%, levelling agent 0.1～0.5%, defoamer 0.3～0.8%, bonding agent 0.5 ~ 1%, anti-settling agent 0.08～0.1%, compounded antistatic agent 4 ~ 8% and complex antimicrobials 1 ~ 2%；Described compounded antistatic agent by the first antistatic composite powder and second antistatic part by weight (1 ~ 2): (1 ~ 2) mixing forms, wherein said first antistatic composite powder is mixed by weight 13:1 with Graphene by the first conductor oxidate, and described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 15 ~ 25%, tin ash 40 ~ 60% and copper oxide 25 ~ 40%；Described second antistatic composite powder is mixed by weight 8:1 by the second conductor oxidate and multi-walled carbon nano-tubes, and described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 15 ~ 30%, oxidation receive 60 ~ 80 and diboron trioxide 5 ~ 10%；Described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=(1 ~ 3): 1, described inorganic antiseptic: organic antibacterial agent=2:1.
In the present invention, described first oxide is made up of following raw material by weight percentage: zinc oxide 20%, tin ash 50% and copper oxide 30%；Described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 20%, oxidation receive 70 and diboron trioxide 10%.
In the present invention, described colorant be praseodymium yellow, cobalt blue, reddish brown, orange, chrome tin pink, cobalt black at least one.Described inorganic antiseptic is the soluble inorganic salt of one or more compositions in silver, zinc, copper ion.Described organic antibacterial agent is parabens.
In the present invention, described dispersant is any one of water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid and derivant thereof.The trade name that dispersant can list includes BYK161, BYK163, BYK164, BYK168, EFKA4310, EFKA 4400, EFKA4401, Nuosperse FX9086, Solsperse 24000, Tego710, Tego671, but is not limited to this.
In the present invention, described surface additive is amino or amido and salt thereof.Surface additive is at least one in NP-4, Span-80, AEO-3 and SRE-48000.Described bonding agent generally uses polymerizing resin, and such as the one in polyethylene, polypropylene, polrvinyl chloride and polystyrene resin, polymerizing resin plays combination and scattered dual function.
In the present invention, at least one during described solvent is de-aromatic hydrocarbon solvent, environmental protection hydrocarbon solvent, alcohols, cycloalkane solvent.
In the present invention, levelling agent is polyether modified siloxane, and the trade name that levelling agent can list includes BYK306, BYK333, Levaslip 8629, but is not limited to this.Defoamer is the polymer-type defoamer without organosilicon, and the trade name that defoamer can list includes BYK051, BYK052, but is not limited to this.Anti-settling agent is at least one in polyamide wax, oxidic polyethylene, and the trade name that anti-settling agent can list includes Disparlon NS-5501, Disparlon 6650, but is not limited to this.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 30 ~ 60min, then add Graphene mix and blend dispersion 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 30 ~ 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of complex antimicrobials: inorganic-organic composite antibiotic agent, Graphene are mixed in proportion stirring 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(4) being placed in UV light region by toner, ultraviolet source irradiance controls at 200 ~ 300W/m2Scope, irradiation 30 ~ 60min；First powder for antistatic and the second powder for antistatic are respectively put in microwave oven, under 700 ~ 1000W microwave power, microwave treatment 1 ~ 10min；
(5) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 30 ~ 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 8 ~ 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.
In the present invention, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
There is advantages that
Ceramic ink surface obtained by the present invention does not has big corner angle, has excellent stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective；The product that the product that the present invention provides is antistatic, antibacterial two functions are compatible, after tested, product reaches country's anti-static ceramic tile standard GB26539-2011 requirement, the requirement of " antibacterial ceramic products anti-microbial property " JC/T897-2002.Achieve on identical product, have antistatic, antibacterial two performances concurrently, improve its stability simultaneously, extend anti-electrostatic antibiotic effect, both economized on resources, reduce product cost, expand again range of application, and construction and installation are convenient.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1
A kind of antistatic wall brick ceramic ink, including various components be by mass percentage: praseodymium yellow 42%, EFKA4310 3%, diethylene glycol 45%, NP-4 2.5%, BYK306 0.3%, BYK051 0.6%, Disparlon 6,650 0.1%, polyethylene 0.5% and compounded antistatic agent 6%；Described compounded antistatic agent is made up of by weight 1:2 mixing the first antistatic composite powder and second antistatic part, wherein said first antistatic composite powder is mixed by weight 13:1 with Graphene by the first conductor oxidate, and described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 15%, tin ash 60% and copper oxide 25%；Described second antistatic composite powder is mixed by weight 8:1 by the second conductor oxidate and multi-walled carbon nano-tubes, and described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 30%, oxidation receive 65% and diboron trioxide 5%.
The preparation method of a kind of antistatic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) being placed in UV light region by toner, ultraviolet source irradiance controls at 300W/m2Scope, irradiation 40min；First powder for antistatic and the second powder for antistatic are respectively put in microwave oven, under 700W microwave power, microwave treatment 5min；
(4) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
Obtained ceramic ink surface does not has big corner angle, has excellent stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance level Four, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.2 × 107Ω；Surface gloss is higher, decorative effect is preferable, meets GB/T4100-2006 national standard, is a kind of excellent static-electricity proof tile.
Embodiment 2
Based on embodiment 1, difference is: described toner is reddish brown；Described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 20%, tin ash 50% and copper oxide 30%；Described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 20%, oxidation receive 70% and diboron trioxide 10%.
Obtained ceramic ink surface does not has big corner angle, has excellent stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance level Four, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 3.2 × 106Ω；Surface gloss is higher, decorative effect is preferable, meets GB/T4100-2006 national standard, is a kind of excellent static-electricity proof tile.
Embodiment 3
Based on embodiment 1, difference is: described toner is cobalt blue and reddish brown mixture；Described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 25%, tin ash 40% and copper oxide 35%；Described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 15%, oxidation receive 80% and diboron trioxide 5%.
Obtained ceramic ink surface does not has big corner angle, has excellent stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance level Four, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 4.8 × 107Ω；Surface gloss is higher, decorative effect is preferable, meets GB/T4100-2006 national standard, is a kind of excellent static-electricity proof tile.
Comparative example 1
Based on embodiment 1, difference is: described first antistatic composite powder and the second antistatic composite powder are not added with Graphene and multi-walled carbon nano-tubes respectively.
The preparation method of a kind of antistatic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
Obtained ceramic ink surface does not has big corner angle, has good stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance three grades, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.8 × 108Ω。
Comparative example 2
Based on embodiment 1, difference is: described first antistatic composite powder adds Graphene.
The preparation method of a kind of antistatic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
Obtained ceramic ink surface does not has big corner angle, has stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance three grades, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 6.4 × 109Ω。
Comparative example 3
Based on embodiment 1, difference is: described second antistatic composite powder adds multi-walled carbon nano-tubes.
The preparation method of a kind of antistatic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
Obtained ceramic ink surface does not has big corner angle, has stability and rheological characteristic, will not wear and tear, blocks and corrode shower nozzle, extends the service life of shower nozzle, cost-effective.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance three grades, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 3.6 × 109Ω。
Comparative example 4
Based on embodiment 1, difference is: do not dose described compounded antistatic agent, i.e. a kind of antistatic wall brick ceramic ink, including various components be by mass percentage: praseodymium yellow 45%, EFKA4310 4%, diethylene glycol 45%, NP-4 4.5%, BYK306 0.3%, BYK051 0.6%, Disparlon 6,650 0.1%, polyethylene 0.5%.
The preparation method of a kind of antistatic wall brick ceramic ink, comprises the following steps: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
Obtained ceramic ink surface does not has big corner angle, has stability and rheological characteristic, weares and teares, blocks and corrode shower nozzle sometimes, limits the service life of shower nozzle.In the present embodiment, select the technique disclosed in application publication number CN103113133A, preparation adobe, the ceramic ink then selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then klining is entered, preparation Ceramic Tiles, test shows, abrasion resistance two grades, product after sintering according to GB26539 2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.2 × 1014Ω；Surface gloss is general, decorative effect is general.
Embodiment 4
A kind of anti-electrostatic antibiotic wall brick ceramic ink, including various components be by mass percentage: praseodymium yellow 40%, EFKA4310 3%, diethylene glycol 45%, NP-4 2.5%, BYK306 0.3%, BYK051 0.6%, Disparlon 6,650 0.1%, polyethylene 0.5%, compounded antistatic agent 6% and complex antimicrobials 2%；Described compounded antistatic agent is made up of by weight 1:2 mixing the first antistatic composite powder and second antistatic part, wherein said first antistatic composite powder is mixed by weight 13:1 with Graphene by the first conductor oxidate, and described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 15%, tin ash 60% and copper oxide 25%；Described second antistatic composite powder is mixed by weight 8:1 by the second conductor oxidate and multi-walled carbon nano-tubes, and described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 30%, oxidation receive 65% and diboron trioxide 5%；Described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=1:1, described inorganic antiseptic: organic antibacterial agent=2:1；Described inorganic antiseptic is the soluble inorganic salt of silver ion, based on inorganic antiseptic gross weight, is added with the calcium phosphate of 5%；Described organic antibacterial agent is parabens.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of complex antimicrobials: inorganic-organic composite antibiotic agent, Graphene are mixed in proportion stirring 50min, use grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(4) being placed in UV light region by toner, ultraviolet source irradiance controls at 300W/m2Scope, irradiation 40min；First powder for antistatic, the second powder for antistatic and complex antimicrobials are respectively put in microwave oven, under 700W microwave power, microwave treatment 5min；
(5) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, abrasion resistance level Four, and the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.5 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 98.6% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 98.2%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect, sheet resistance 9.2 × 10 according to the method described above7Ω, colibacillary bacteriostasis rate is 98.0%, and the bacteriostasis rate to staphylococcus aureus is 97.9%.
Embodiment 5
Based on embodiment 4, difference is: described toner is reddish brown；Described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=2:1, described inorganic antiseptic: organic antibacterial agent=2:1；Described inorganic antiseptic is silver ion and the soluble inorganic salt of copper ion combination, based on inorganic antiseptic gross weight, is added with the calcium phosphate of 5%；Described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 20%, tin ash 50% and copper oxide 30%；Described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 20%, oxidation receive 70% and diboron trioxide 10%.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, abrasion resistance level Four, and the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 3.5 × 106Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 99.4% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 99.6%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 8.5 × 106Ω, colibacillary bacteriostasis rate is 99.0%, and the bacteriostasis rate to staphylococcus aureus is 99.2%.
Embodiment 6
Based on embodiment 4, difference is: described toner is cobalt blue and reddish brown mixture；Described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=3:1, described inorganic antiseptic: organic antibacterial agent=2:1；Described inorganic antiseptic is the soluble inorganic salt of silver ion, based on inorganic antiseptic gross weight, is added with the calcium phosphate of 5%；Described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 25%, tin ash 40% and copper oxide 35%；Described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 15%, oxidation receive 80% and diboron trioxide 5%.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, abrasion resistance level Four, and the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.0 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 97.4% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 98.2%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 8.1 × 107Ω, colibacillary bacteriostasis rate is 96.8%, and the bacteriostasis rate to staphylococcus aureus is 97.8%.
Comparative example 5
Based on embodiment 4, difference is: described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=1:3.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of complex antimicrobials: inorganic-organic composite antibiotic agent, Graphene are mixed in proportion stirring 50min, use grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(5) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.5 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 92.7% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 93.2%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 9.2 × 107Ω, colibacillary bacteriostasis rate is 91.2%, and the bacteriostasis rate to staphylococcus aureus is 92.3%.
Comparative example 6
Based on embodiment 4, difference is: described complex antimicrobials is inorganic antiseptic, and described inorganic antiseptic is the soluble inorganic salt of silver ion, based on inorganic antiseptic gross weight, is added with the calcium phosphate of 5%.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.5 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 85.2% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 86.8%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 9.2 × 107Ω, colibacillary bacteriostasis rate is 84.0%, and the bacteriostasis rate to staphylococcus aureus is 85.4%.
Comparative example 7
Based on embodiment 4, difference is: described complex antimicrobials is organic antibacterial agent.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.5 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 86.4% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 87.6%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 9.1 × 107Ω, colibacillary bacteriostasis rate is 84.7%, and the bacteriostasis rate to staphylococcus aureus is 85.3%.
Comparative example 8
Based on embodiment 4, difference is: described complex antimicrobials is inorganic-organic composite antibiotic agent, described inorganic antiseptic: organic antibacterial agent=2:1；Described inorganic antiseptic is the soluble inorganic salt of silver ion, based on inorganic antiseptic gross weight, is added with the calcium phosphate of 5%.
The preparation method of a kind of anti-electrostatic antibiotic wall brick ceramic ink, comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 60min, then add Graphene mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.Wherein, the grinding bead of described grinder is the zirconium oxide bead of diameter 0.5 ~ 2nm, controls temperature of charge≤40 DEG C in process of lapping.
In the present embodiment, select the technique disclosed in application publication number CN103113133A, prepare adobe, then the ceramic ink selecting the present embodiment to be provided in adobe carries out ink-jet printed, forms printed layer, then enters klining, preparation Ceramic Tiles, surface gloss is high, good decorating effect.Test shows, the product after sintering according to GB26539-2011 " anti-static ceramic tile " standard detection the present embodiment, sheet resistance is 5.5 × 107Ω；According to JC/T897-2002 " antibacterial ceramic products anti-microbial property " standard detection, being 88.4% to colibacillary bacteriostasis rate, the bacteriostasis rate to staphylococcus aureus is 89.6%.Being simulated using wear testing by above product, the abrasive material that wear testing selects Mohs' hardness to be 3～4, in printed layer, the effect after paving uses 2 years is imitated in friction for 1000 times.After friction, sample clean is dried, then observe whether ink-jet printed layer pattern obscures, and test anti-electrostatic antibiotic effect according to the method described above, sheet resistance is 9.3 × 107Ω, colibacillary bacteriostasis rate is 86.2%, and the bacteriostasis rate to staphylococcus aureus is 87.1%.
Embodiment described above only have expressed embodiments of the present invention; it describes more concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme using the form of equivalent or equivalent transformation to be obtained, all should fall within the scope and spirit of the invention.
Claims (10)
1. an anti-electrostatic antibiotic wall brick ceramic ink, including various components be by mass percentage: colorant 35 ~ 45%, dispersant 3 ~ 8%, solvent 40 ~ 50%, surface additive 2 ~ 5%, levelling agent 0.1～0.5%, defoamer 0.3～0.8%, bonding agent 0.5 ~ 1%, anti-settling agent 0.08～0.1%, compounded antistatic agent 4 ~ 8% and complex antimicrobials 1 ~ 2%；Described compounded antistatic agent by the first antistatic composite powder and second antistatic part by weight (1 ~ 2): (1 ~ 2) mixing forms, wherein said first antistatic composite powder is mixed by weight 13:1 with Graphene by the first conductor oxidate, and described first conductor oxidate is made up of following raw material by weight percentage: zinc oxide 15 ~ 25%, tin ash 40 ~ 60% and copper oxide 25 ~ 40%；Described second antistatic composite powder is mixed by weight 8:1 by the second conductor oxidate and multi-walled carbon nano-tubes, and described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 15 ~ 30%, oxidation receive 60 ~ 80 and diboron trioxide 5 ~ 10%；Described complex antimicrobials is the mixture of inorganic-organic composite antibiotic agent and Graphene, and weight ratio is: inorganic-organic composite antibiotic agent: Graphene=(1 ~ 3): 1, described inorganic antiseptic: organic antibacterial agent=2:1.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described first oxide is made up of following raw material by weight percentage: zinc oxide 20%, tin ash 50% and copper oxide 30%.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described second conductor oxidate is made up of following raw material by weight percentage: calcium oxide 20%, oxidation receive 70 and diboron trioxide 10%.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described inorganic antiseptic is the soluble inorganic salt of one or more compositions in silver, zinc, copper ion.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described organic antibacterial agent is parabens.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described dispersant is any one of water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid and derivant thereof.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described colorant be praseodymium yellow, cobalt blue, reddish brown, orange, chrome tin pink, cobalt black at least one.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described surface additive is amino or amido and salt thereof.
Anti-electrostatic antibiotic wall brick ceramic ink the most according to claim 1, it is characterised in that described solvent is at least one in de-aromatic hydrocarbon solvent, environmental protection hydrocarbon solvent, alcohols, cycloalkane solvent.
10. a preparation method for anti-electrostatic antibiotic wall brick ceramic ink, it comprises the following steps:
The preparation of (1) first antistatic composite powder: zinc oxide, tin ash, copper oxide are mixed in proportion dispersed with stirring 30 ~ 60min, then add Graphene mix and blend dispersion 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
The preparation of (2) second antistatic composite powders: by calcium oxide, oxidation receives and diboron trioxide is mixed in proportion dispersed with stirring 30 ~ 60min, then adds multi-walled carbon nano-tubes mix and blend dispersion 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(3) preparation of complex antimicrobials: inorganic-organic composite antibiotic agent, Graphene are mixed in proportion stirring 40 ~ 60min, uses grinder to grind 10h so that it is particle diameter distribution≤3 μm；
(4) being placed in UV light region by toner, ultraviolet source irradiance controls at 200 ~ 300W/m2Scope, irradiation 30 ~ 60min；First powder for antistatic, the second powder for antistatic and complex antimicrobials are respectively put in microwave oven, under 700 ~ 1000W microwave power, microwave treatment 1 ~ 10min；
(5) preparation of ceramic ink: proportionally weighed by each component in formula, then carries out disperseing 30 ~ 60min with homogenizer；Scattered mixed liquor is loaded in grinder, grind 8 ~ 12h, obtain the ink semi-finished product of particle diameter distribution≤1 μm；The agitator tank of semi-finished product ink is filled malleation, uses the strainer filtering of aperture≤1 μm, obtain finished product ink.
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