CN106280708A

CN106280708A - A kind of ceramic ink jet anion ceramic ink and preparation method thereof that can sink

Info

Publication number: CN106280708A
Application number: CN201610748808.7A
Authority: CN
Inventors: 徐常山; 于庆九; 邱杰华
Original assignee: FOSHAN CITY GAOMING DISTRICT HAIDI CERAMIC MATERIALS Co Ltd
Current assignee: FOSHAN CITY GAOMING DISTRICT HAIDI CERAMIC MATERIALS Co Ltd
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2017-01-04

Abstract

The invention discloses a kind of ceramic ink jet anion ceramic ink and preparation method thereof that can sink, this preparation method comprises the following steps: step A, the sagging glaze of preparation；Step B, weighing sagging glaze, dispersant, surface additive, defoamer, bonding agent in proportion, surplus is solvent, grinds to obtain ink semi-finished product；Step C, filter to obtain ink.Compare with the existing ceramic ink that sink, ceramic ink of the present invention and paint ink with the use of, can more fully image show the concavo-convex texture true to nature of ceramic tile, third dimension is strong, improve the decorative effect of ceramic tile further, create the pattern being a splendid legacy, also extensively can apply in the field such as ceramics and Antique Imitation Tiles；Simultaneously through reasonably collocation anion complex, conductive filler and antimicrobial composite material, three's synergism, ceramic ink is had, and excellent antibacterial is antifouling, purify air characteristics and electrostatic-proof function, has widened the range of application of the ceramic ink that can sink further.

Description

A kind of ceramic ink jet anion ceramic ink and preparation method thereof that can sink

Technical field

The present invention relates to ceramic technology field, particularly relate to a kind of ceramic ink jet negative ion ceramic ceramic ink that can sink Water and preparation method thereof.

Background technology

Antibacterial, mycete has the biggest harm as pathogen to the mankind and animals and plants, and the health affecting people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and goods thereof causes the concern of people, antibacterial product day by day Demand will constitute huge market.

For environmental conservation aspect, negative aeroion can eliminate foreign flavor indoors and various harmful gas.In interior decoration During leftovers leftovers in the art work that the uses benzene, formaldehyde, ketone, the irritative gas such as ammonia and the daily life that evaporate Acid smell, the harmful abnormal flavour such as medicated cigarette, with the material rich in anion, negative aeroion of its release can be effectively Eliminated, reach to purify the purpose of air, and golden staphylococci, escherichia coli, candidiasis and mycete etc. are had well press down Make and use.

Ceramic ink jet technology is as a kind of new contactless, no pressure, printing technology without forme, undoubtedly by current ceramic tile Fashion, personalization, development trend art up, small lot, multi-color, low-carbon environment-friendly have pushed a new height to.From Since within 2009, China introduces First ceramic ink jet machine, the development of ceramic ink jet printing technology is advanced by leaps and bounds, and obtains a large amount of Application.Through development in a few years, the market share of ceramic ink jet product is more and more higher, also the advantage of ceramic ink jet technology is sent out Wave incisively and vividly.

There is the use of the ceramic ink of sagging effect, it is possible to make Ceramic Tiles more fully image shows concavo-convex stricture of vagina Reason, skin texture true to nature, soft texture, break the ice-cold impression of ceramic tile, allow people experience from vision and sense of touch more marvellous Texture.With ceramic ink jet printing paint ink with the use of, be possible not only to improve further the decorative effect of ceramic tile, also Adapt to digital development trend.But rarely having at present and report the sunk ceramic ink about functional type, therefore technology needs Improve, need research and development functional type badly and can sink ceramic ink, such as the function such as antibacterial, antistatic, deodorizer, anion, expand further Its range of application wide.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of ceramic ink jet anion pottery that can sink Ink and preparation method thereof.

The technical problem to be solved is achieved by the following technical programs:

A kind of ceramic ink jet is with sinking the preparation method of anion ceramic ink, and it comprises the following steps:

Step A, preparation sink glaze: by 30 ~ 40% V2O5,40 ~ 50% Bi2O3,7 ~ 12% Ba2CO3,4 ~ 8% ZnO, 2 ~ 6% SiO2,1 ~ 3% Al2O3,1 ~ 3%(K2O+Na2O) mixing sand milling uniform；Add 0.5 ~ 5% antibiotic complex and sand milling is uniform；Again Adding 2 ~ 6% anion complex, sand milling uniformly prepares compound；Compound is dispensed in loading fire resistant sagger, carry out 800 ~ 1100 DEG C of high temperature meltings, obtain the slurry of molten state；By slurry water quenching cooling, and it is broken into graininess, obtains sagging glaze；

Step B, weigh 20 ~ 35% sink glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% combine Agent, 1 ~ 6% conductive filler, surplus is solvent, carries out disperseing 30 ~ 60min in adding homogenizer；By scattered mixed liquor Load in sand mill, sand milling 8 ~ 12h, obtain the ink semi-finished product that particle diameter is distributed between 200 ~ 500nm；

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 80～100 DEG C, then carry out evacuation, height Speed vibration, filtration, obtain ink.

A kind of ceramic ink jet anion ceramic ink that can sink, it contains the component of following percentage by weight: 20 ~ 35% Sink glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% bonding agent, 1 ~ 6% conductive filler, surplus For solvent；Wherein, described sagging glaze contains the component of following percentage by weight: 30 ~ 40% V2O5,45 ~ 50% Bi2O3,7 ~ 12% Ba2CO3,4 ~ 8% ZnO, 2 ~ 6% SiO2,1 ~ 3% Al2O3,1 ~ 3%(K2O+Na2O), 0.5 ~ 5% antibiotic complex and 2 ~ 6% negative Ion complex.

In the present invention, described conductive filler preparation method is as follows: by 30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin, 1 ~ 8% CNT, 2 ~ 6% aluminium powders, 5 ~ 10% white carbon blacks and 1 ~ 10% Graphene are sufficiently mixed, and add appropriate butyl acetate and put into ball Grinding machine disperses dispergation, after discharge, detects, adjust the slurry being configured to apply；By this slurry coating on substrate, it is dried Film forming；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped off this substrate, obtains conduction Holey carbon film.

In the present invention, described anion complex preparation method is as follows: by 5 ~ 10% coral fossil, 10 ~ 15% tourmaline, 20 ~ 35% opals, 1 ~ 5% serpentine, 5 ~ 10% Maifanitums, 1 ~ 5% rare ice stone, 1 ~ 5% hokutolite, 1 ~ 5% doctor Wang Shi, 5 ~ 10% shellfishes Shell, 10 ~ 15% kieselguhr, 1 ~ 3% iron sesquioxide, 2 ~ 5% aluminium sesquioxide, 3 ~ 8% zirconium oxides and 1 ~ 5% zirconium phosphate mix homogeneously, Add in grinding equipment and carry out superfine grinding, until particle diameter distribution is at 50 ~ 80nm, sieve, be dried, can be prepared by described negative Ion powder.Taking 5 ~ 10g anion powder to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 1 ~ 2h obtains the most even stable dividing Dissipate liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, Roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to having when CNT is near 8 DEG C Having hydrophilic, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has thin Aqueous being driven away by hydrone leaves behind anion powder and adsorbs in multiple net holes of carbon nanotube mesh film；After drying, will inhale This substrate is scraped off, it is thus achieved that anion powder/CNT with the carbon nanotube mesh film of anion powder.

In the present invention, described dispersant is water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid And any one of derivant.The trade name that dispersant can list include BYK161, BYK163, BYK164, BYK168, EFKA4310, EFKA 4400, EFKA4401, Nuosperse FX9086, Solsperse 24000, Tego710, Tego671, But it is not limited to this.

In the present invention, described surface additive is amino or amido and salt thereof.Surface additive is NP-4, Span-80, At least one in AEO-3 and SRE-48000.

In the present invention, described solvent is in de-aromatic hydrocarbon solvent, environmental protection hydrocarbon solvent, alcohols, cycloalkane solvent At least one.Described bonding agent generally uses polymerizing resin, such as polyethylene, polypropylene, polrvinyl chloride and polystyrene tree One in fat, polymerizing resin plays combination and scattered dual function.Described defoamer is the polymer without organosilicon Type defoamer, the trade name that defoamer can list includes BYK051, BYK052, but is not limited to this.

In the present invention, described antibiotic complex can prepare by the following method:

(1) weigh 0.3 ~ 1gC60 powder, measure the concentrated sulphuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and concentrated sulphuric acid Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, Graphene quantum dot (GQDs) suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, swash Photoirradiation power is 0.5 ~ 2W；Standby；

(2) ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise add Enter concentration be 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2 ~ 3: 1), ultrasonic agitation 10 ~ 20min；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solution, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying, obtains GQDs/Ag₂O；

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration be 0.005 ~ 0.05mol/L cerous nitrate aqueous solution, being added dropwise over concentration after 30 ~ 60min is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1 ~ 0.2:0.2 ~ 0.4；Continue ultrasonic Stirring, regulation mixed solution pH value is to 7.0；Limit ultrasonic agitation, it is the hydrazine hydrate of 50% that limit adds 4 ~ 8mL mass fraction, 30 ~ Reduction reaction 0.5 ~ 1h at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, reduction reaction at 85 DEG C are added After 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:1 ~ 3), regulation PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；It is centrifuged and cleans with acetone and deionized water successively Obtain precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in hydrogen Fluoric acid carries out ultrasonic 10 ~ 15min with ultrasonic power 100 ~ 150W, removes local, surface silicon dioxide, be centrifuged and be dried, it is thus achieved that Antibacterial powder；

(5), under nitrogen environment, it is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and the concentration that concentration is 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids mixes with volume ratio 2 ~ 4:2, is simultaneously introduced the antibacterial powder that step (4) prepares, after magnetic agitation 60 ~ 120min Adding aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise drip Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, Mill to obtain nano polyaniline/antibacterial powder complex；

(6) prepare TiO 2 sol by sol-gel process, in colloidal sol, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% Amine/antibacterial powder complex, mix homogeneously；Still aging 3～5d 60 DEG C～120 DEG C of rearmounted baking oven drying；After milling by gained again Calcine 1 ~ 2h at compound 400～550 DEG C, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(7) by the most mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial powder complex Close, add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detect, adjust the slurry being configured to apply Material；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, protect Temperature 1 ~ 2h；Film is scraped off this substrate, it is thus achieved that antibiotic complex.

It is preferred that increase by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in In aqueous solution, it is added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/ Ag-Zn-Ce/SiO₂Weight ratio be 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash for several times, is dried Obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

In the present invention, described antibiotic complex can also prepare by the following method:

(3) 1 ~ 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.05 ~ 0.5g/100mlZnO Quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filter, be washed with deionized for several times, Vacuum drying, obtains GQDs/Ag₂O/ZnO antibacterial powder；

(4), under nitrogen environment, it is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and the concentration that concentration is 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids mixes with volume ratio 2 ~ 4:2, is simultaneously introduced the antibacterial powder that step (4) prepares, after magnetic agitation 60 ~ 120min Adding aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise drip Ammonium persulfate., aniline It is 1:1 with Ammonium persulfate. mol ratio；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, Mill to obtain nano polyaniline/antibacterial powder complex；

(5) prepare TiO 2 sol by sol-gel process, in colloidal sol, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% Amine/antibacterial powder complex, mix homogeneously；Still aging 3～5d 60 DEG C～120 DEG C of rearmounted baking oven drying；After milling by gained again Calcine 1 ~ 2h at compound 400～550 DEG C, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(6) by the most mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial powder complex Close, add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detect, adjust the slurry being configured to apply Material；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, protect Temperature 1 ~ 2h；Film is scraped off this substrate, it is thus achieved that antibiotic complex.

It is preferred that increase by a step between step (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in In aqueous solution, it is added dropwise over GQDs/Ag₂In O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO For 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/ZnO/ Graphene Antibacterial powder.

There is advantages that this method loads in carbon nano net and fixes antibacterial, not only prevent it Reunite, significantly improve the stability of the antibacterial such as metal nanoparticle so that it is can more preferably be dispersed in ceramic ink jet ink, and tool There are more efficient antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antibacterial simultaneously, Have a more preferable antibacterial effect compared to single silver nano antibacterial agent, antibacterial persistently；Anion complex can be the most uninterrupted Anion releasing, under having light or no light condition all can uninterrupted anion releasing, effectively purify air, decomposing formaldehyde etc. has Machine gas, improves IAQ (indoor air quality), also has antibacterial effect, be of value to health.With the existing ceramic ink that sink Comparing, dispensing science of the present invention, rationally, quality stability is good, can preserve for a long time, has good inkjet printing in preparation Can, with ceramic ink jet printing paint ink with the use of, can more fully image show the concavo-convex texture true to nature of ceramic tile, Third dimension is strong, improves the decorative effect of ceramic tile further, creates the pattern being a splendid legacy, also can lead at ceramics and Antique Imitation Tiles etc. Territory is extensively applied；Simultaneously through reasonably collocation anion complex, conductive filler and antimicrobial composite material, three is collaborative to be made Have with so that ceramic ink that excellent antibacterial is antifouling, purify air characteristics and electrostatic-proof function, widened further and can sink The range of application of ceramic ink.

Detailed description of the invention

Technical scheme is further illustrated below by concrete preferred implementation.

Embodiment 1

A kind of ceramic ink jet anion ceramic ink and preparation method thereof that can sink, this preparation method comprises the following steps:

Step A, preparation sink glaze: by 40% V2O5,35% Bi2O3,7% Ba2CO3,5% ZnO, 2% SiO2,2% Al2O3, 2%(K2O+Na2O) mixing sand milling is uniform；Add 5% antibiotic complex and sand milling is uniform；Add 2% anion complex, sand milling Uniformly prepare compound；Compound is dispensed in loading fire resistant sagger, carry out 1000 DEG C of high temperature meltings, obtain the slurry of molten state Material；By slurry water quenching cooling, and it is broken into graininess, obtains sagging glaze；

Step B, weigh 20% and sink glaze, 8% Solsperse 24000,5% Span-80,0.3% BYK052,3% polystyrene Resin, 6% conductive filler and 57.7% environmental protection hydrocarbon solvent, carry out in adding homogenizer disperseing 60min；Scattered is mixed Close liquid and load in sand mill, sand milling 10h, obtain the ink semi-finished product that particle diameter is distributed between 200 ~ 500nm；

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 90 DEG C, then carry out evacuation, shake at a high speed Dynamic, filtration, obtains ink.

Wherein, described conductive filler preparation method is as follows: by 40% epoxy resin, 46% phenolic resin, 1% CNT, 2% Aluminium powder, 10% white carbon black and 1% Graphene are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, Detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then nitrogen filled protection it is placed on In atmosphere furnace, it is warmed up to 1000 DEG C, is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film.

Wherein, described anion complex preparation method is as follows: by 10% coral fossil, 10% tourmaline, 35% opal, 1% serpentine, 10% Maifanitum, 5% rare ice stone, 1% hokutolite, 5% doctor Wang Shi, 5% shell, 10% kieselguhr, 1% iron sesquioxide, 3% aluminium sesquioxide, 3% zirconium oxide and 1% zirconium phosphate mix homogeneously, add in grinding equipment and carry out superfine grinding, until granule is straight Footpath is distributed in 50 ~ 80nm, sieves, and is dried, can be prepared by described anion powder.Take 8g anion powder and be scattered in 120ml ultra-pure water In, water bath sonicator 2h obtains the most even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, will Dispersion liquid adds in the substrate of concave shape, meanwhile, rolls around roller, makes this homogeneous dispersion be scattered in this carbon nano-tube network In shape film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to the multiple of carbon nanotube mesh film Net hole；Being warming up to about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind anion powder and adsorb in carbon nanometer In multiple net holes of pipe reticular membrane；After drying, the carbon nanotube mesh film being adsorbed with anion powder is scraped off this substrate, it is thus achieved that negative Ion powder/CNT.

Wherein, described antibiotic complex prepares by the following method:

(1) weigh 0.6gC60 powder, measure the concentrated sulphuric acid that 100ml mass fraction is 98%, C60 powder and concentrated sulphuric acid are being burnt Mixing in Bei, beaker is placed in ice-water bath, stirs with the speed of 600rpm simultaneously, obtains mixed liquor；Weigh 1g potassium permanganate powder, Add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, react 4h；Quickly add Enter 120ml pure water, filter, then dialyse 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (GQDs) and hang Supernatant liquid；100rpm speed stirring GQDs suspension, simultaneously laser irradiation 40min, laser irradiation power is 1W；Standby；

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.1mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.05mol/L cerous nitrate Aqueous solution, being added dropwise over concentration after 30min is 0.005mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.1:0.4；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 10min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(7) 30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 2

Step A, preparation sink glaze: by 33% V2O5,40% Bi2O3,7% Ba2CO3,6% ZnO, 2% SiO2,3% Al2O3, 2%(K2O+Na2O) mixing sand milling is uniform；Add 3% antibiotic complex and sand milling is uniform；Add 4% anion complex, sand milling Uniformly prepare compound；Compound is dispensed in loading fire resistant sagger, carry out 1000 DEG C of high temperature meltings, obtain the slurry of molten state Material；By slurry water quenching cooling, and it is broken into graininess, obtains sagging glaze；

Step B, weigh 30% and sink glaze, 5% Solsperse 24000,3% Span-80,0.5% BYK052,2% polystyrene Resin, 3% conductive filler and 56.5% environmental protection hydrocarbon solvent, carry out in adding homogenizer disperseing 60min；Scattered is mixed Close liquid and load in sand mill, sand milling 10h, obtain the ink semi-finished product that particle diameter is distributed between 200 ~ 500nm；

Wherein, described conductive filler preparation method is as follows: by 35% epoxy resin, 42% phenolic resin, 5% CNT, 4% Aluminium powder, 8% white carbon black and 6% Graphene are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, Detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then nitrogen filled protection it is placed on In atmosphere furnace, it is warmed up to 1000 DEG C, is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film.

Wherein, described anion complex preparation method is as follows: by 8% coral fossil, 12% tourmaline, 25% opal, 3% Serpentine, 8% Maifanitum, 3% rare ice stone, 3% hokutolite, 3% doctor Wang Shi, 8% shell, 12% kieselguhr, 2% iron sesquioxide, 5% 3 Al 2 O, 6% zirconium oxide and 2% zirconium phosphate mix homogeneously, add in grinding equipment and carry out superfine grinding, until particle diameter divides Cloth, at 50 ~ 80nm, sieves, and is dried, can be prepared by described anion powder.Take 8g anion powder to be scattered in 120ml ultra-pure water, water Bathe ultrasonic 2h and obtain the most even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, by dispersion liquid Add in the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film In, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；Being warming up to about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind anion powder and adsorb at CNT In multiple net holes of reticular membrane；After drying, the carbon nanotube mesh film being adsorbed with anion powder is scraped off this substrate, it is thus achieved that bear from Sub-powder/CNT.

Wherein, described antibiotic complex prepares by the following method:

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.2mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.03mol/L cerous nitrate Aqueous solution, being added dropwise over concentration after 30min is 0.03mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.2:0.3；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic to be stirred Mixing, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide Number is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 12min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(7) 45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 3

Step A, preparation sink glaze: by 30% V2O5,43% Bi2O3,5.5% Ba2CO3,8% ZnO, 4% SiO2,2% Al2O3,1%(K2O+Na2O) mixing sand milling uniform；Add 0.5% antibiotic complex and sand milling is uniform；Add 6% anion multiple Compound, sand milling uniformly prepares compound；Compound is dispensed in loading fire resistant sagger, carry out 1000 DEG C of high temperature meltings, melted Melt the slurry of state；By slurry water quenching cooling, and it is broken into graininess, obtains sagging glaze；

Step B, weigh 35% and sink glaze, 3% Solsperse 24000,2% Span-80,0.8% BYK052,1% polystyrene Resin, 1% conductive filler and 57.2% environmental protection hydrocarbon solvent, carry out in adding homogenizer disperseing 60min；Scattered is mixed Close liquid and load in sand mill, sand milling 10h, obtain the ink semi-finished product that particle diameter is distributed between 200 ~ 500nm；

Wherein, described conductive filler preparation method is as follows: by 30% epoxy resin, 41% phenolic resin, 8% CNT, 6% Aluminium powder, 5% white carbon black and 10% Graphene are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, Detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then nitrogen filled protection it is placed on In atmosphere furnace, it is warmed up to 1000 DEG C, is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film.

Wherein, described anion complex preparation method is as follows: by 5% coral fossil, 15% tourmaline, 20% opal, 5% Serpentine, 5% Maifanitum, 1% rare ice stone, 5% hokutolite, 1% doctor Wang Shi, 10% shell, 15% kieselguhr, 3% iron sesquioxide, 2% Aluminium sesquioxide, 8% zirconium oxide and 5% zirconium phosphate mix homogeneously, add in grinding equipment and carry out superfine grinding, until particle diameter It is distributed in 50 ~ 80nm, sieves, be dried, can be prepared by described anion powder.Take 8g anion powder to be scattered in 120ml ultra-pure water, Water bath sonicator 2h obtains the most even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, will dispersion Liquid adds in the substrate of concave shape, meanwhile, rolls around roller, makes this homogeneous dispersion be scattered in this carbon nanotube mesh film In, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；Being warming up to about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind anion powder and adsorb at CNT In multiple net holes of reticular membrane；After drying, the carbon nanotube mesh film being adsorbed with anion powder is scraped off this substrate, it is thus achieved that bear from Sub-powder/CNT.

Wherein, antibiotic complex prepares by the following method:

(2) ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.5mol/L ammonium dihydrogen phosphate (ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1), ultrasonic agitation 20min；Being added dropwise over 1mol/L sodium hydroxide solution, regulation pH value, to 11, then stands, is centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag₂O；

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in 100ml aqueous solution；Being added dropwise over concentration is 0.005mol/L nitric acid Cerium aqueous solution, being added dropwise over concentration after 30min is 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag₂O aqueous solution, cerous nitrate water Solution and zinc nitrate aqueous solution volume ratio are 1:0.2:0.4；Continuing ultrasonic agitation, regulation mixed solution pH value is to 7.0；Limit is ultrasonic Stirring, it is the hydrazine hydrate of 50% that limit adds 6mL mass fraction, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass is added Mark is the hydrazine hydrate of 50%, at 85 DEG C after reduction reaction 36h；Filter, be washed with deionized for several times, vacuum drying, GQDs/Ag₂O/Ag-Zn-Ce；

(4) by 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Afterwards add volume ratio 4:1 water and Ammonia, is stirring evenly and then adding into tetraethyl orthosilicate (with GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2), regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；Will This is deposited at 90 DEG C and is dried 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put Under argon gas atmosphere, carry out 600 DEG C of heat treatment 1h, after being cooled to room temperature, be immersed in Fluohydric acid. and surpass with ultrasonic power 100W Sound 15min, removes local, surface silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

(5) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(6) prepare TiO 2 sol by sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial powder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To forge at gained complex 500 DEG C after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(7) 40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 4

Preparation method based on embodiment 2, difference is: increase following steps between step (4) and (5): take three-dimensional sea Continuous shape Graphene ultrasonic agitation is scattered in aqueous solution, is added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In aqueous solution, three-dimensional Spongy graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；The ultrasonic 90min of 50W, stands, deionized water Washing for several times, is dried to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

Three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml 98% concentrated sulphuric acid mix homogeneously, is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml and go Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with in 5ml 30% H2O2 with unnecessary KMnO4, The color of mixed solution is brown color, filtered while hot, and with deionized water cyclic washing to neutral, ultrasonic disperse obtains GO；Take 200ml mass fraction is in the discoid reaction utensil that the graphene oxide solution of 5mg/ml pours diameter 25cm, high 2cm into, adds Ascorbic acid (VC) 0.5g stirring makes it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, in reaction utensil Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, lyophilization, obtain flexibility three-dimensional sponge shape Graphene.

Embodiment 5

Preparation method based on embodiment 1, difference is: described antibiotic complex prepares by the following method:

(3) 1gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.5g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(6) 30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 6

Preparation method based on embodiment 2, difference is: described antibiotic complex prepares by the following method:

(3) 2gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.2g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Mycopowder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To calcine at gained complex 500 DEG C after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial powder complex；

(6) 45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 7

Preparation method based on embodiment 3, difference is: described antibiotic complex prepares by the following method:

(3) 3gGQDs/Ag is taken₂O ultrasonic agitation is scattered in aqueous solution；Being added dropwise over concentration is 0.05g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

(4) under nitrogen environment, by protonic acid solution that concentration is 0.2mol/L and detergent alkylate sulphur that concentration is 0.1mol/L Acid mixes with volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) prepares, and adds aniline, antibacterial powder after magnetic agitation 100min After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/antibacterial powder is multiple Compound；

(5) prepare TiO 2 sol by sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial powder complex, mix homogeneously；The drying of 90 DEG C of the rearmounted baking oven of still aging 4d；To forge at gained complex 500 DEG C after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial powder complex；

(6) 40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial powder complex are sufficiently mixed, add suitable The butyl acetate of amount puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This is starched Material is coated on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1.5h；Film is scraped From this substrate, it is thus achieved that antibiotic complex.

Embodiment 8

Preparation method based on embodiment 6, difference is: increase such as next step between step (3) and (4): take three-dimensional Spongy graphene ultrasonic agitation is scattered in aqueous solution, is added dropwise over GQDs/Ag₂In O/ZnO aqueous solution, three-dimensional sponge shape stone Ink alkene and GQDs/Ag₂The weight ratio of O/ZnO is 1:3；The ultrasonic 90min of 50W, stands, and deionized water wash for several times, is dried GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

Comparative example 1

Preparation method based on embodiment 1, difference is: described antibiotic complex is the titanium dioxide carrying metal antibacterial agent Titanium；It is not added with conductive filler；Described anion complex is anion powder, by 8% coral fossil, 12% tourmaline, 25% albumen Stone, 4% serpentine, 7% Maifanitum, 4% rare ice stone, 4% hokutolite, 3% doctor Wang Shi, 8% shell, 12% kieselguhr, 2% 3 oxidation two Ferrum, 3% aluminium sesquioxide, 5% zirconium oxide and 3% zirconium phosphate mix homogeneously, add in grinding equipment and carry out superfine grinding, until Grain diameter Distribution, at 50 ~ 80nm, is sieved, and is dried, can be prepared by described anion powder.

Comparative example 2

Preparation method based on embodiment 5, difference is: described antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；It is not added with anion complex；Described conductive filler is mixed by aluminium powder, white carbon black and Graphene.

The ceramic ink preparing embodiment 1 ~ 8 and comparative example 1,2 carries out performance test, test result display ink viscosity Being 15 ~ 35mPa s, surface tension between 200 ~ 400nm, has good in 25 ~ 40mN/m, even particle size distribution, mean diameter Good stability and Ink Jet Printing Performance.With ceramic ink jet printing paint ink with the use of, utilize ink jet printer directly at porcelain Spray printing on adobe body, after burning till, brick face has been createed the effect that lines is the most orderly, uneven, the solid being a splendid legacy Sense, feel is fine and smooth, more common wallpaper class ornament materials more texture and solid sense.

Embodiment 1 ~ 8 and comparative example 1,2 are carried out the performance tests such as antibacterial, test result such as following table:

Sterilization rate: take 10⁵The escherichia coli 0.1ml of individual/ml, is spread evenly across spraying and burns till the ceramic tile face of ceramic ink On, at indoor placement 2h, then bacterium solution sterilized water is eluted in culture medium, at 37 DEG C, cultivates 24h, then detection bacterium number, Calculate sterilization rate.

Heat stability is tested: is placed in electric furnace by the ceramic tile spraying and burning till ceramic ink, is raised to 200 DEG C from room temperature, Insulation 20min, puts into rapidly in 25 DEG C of water, takes out and dry after 10min, and glaze layer is without temperature shock crackle and tests its sterilization rate.

Wear testing: selecting Mohs' hardness is the abrasive material of 3～4, is rubbing by spraying and burn till on the ceramic tile of ceramic ink Wipe and imitate the effect after paving uses 2 years for 1000 times.

Antifouling test: selection chrome green is pollutant.

Sterilizing Evaluation for Uniformity: choose 100 regions on glaze modelled after an antique and carry out sterilizing test, the data recorded are carried out all Evenness analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When the uniformity is more than 97%, then be labeled as ▲；When uniformly Degree more than 90% and less than 97%, is then labeled as ☆；When the uniformity is less than 90%, then it is labeled as.

Anion burst size: use Japan to produce COM-3010PRO type ion detector test anion burst size, by this sample Product are positioned over 1m³Test box (length is 1m) in, record air-anion concentration in air (initial and 24h)；Adopt Test with Han Wang M1 type haze table, PM2.5 concentration (1h and 24h) in test box；(formaldehyde is dense to drip 0.1mg formaldehyde in test box Degree 0.1mg/m³), record concentration of formaldehyde after 24h.

Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained Art scheme, all should fall within the scope and spirit of the invention.

Claims

1. ceramic ink jet is with sinking the preparation method of anion ceramic ink, and it comprises the following steps:

The ceramic ink jet the most according to claim 1 preparation method of the anion ceramic ink that can sink, it is characterised in that The preparation method of described antibiotic complex is as follows:

(1) weigh 0.3 ~ 1gC60 powder, measure the concentrated sulphuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and concentrated sulphuric acid Mixing in beaker, beaker is placed in ice-water bath, stirs with the speed of 500 ~ 600rpm simultaneously, obtains mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, adds in above-mentioned mixed liquor slowly；Remove ice-water bath, change water-bath into, keep bath temperature 30 ~ 40 DEG C, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialyse 3 ~ 5 days with the bag filter that molecular cut off is 1000, GQDs suspension；100 ~ 150rpm speed stirring GQDs suspension, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 0.5~2W；Standby；

(2) ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise add Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, ultrasonic agitation 10 ~ 20min；It is added dropwise over 0.5 ~ 1mol/L hydroxide Sodium solution, regulation pH value, to 11, then stands, is centrifuged, and with deionized water and ethanol alternately washing three times, is vacuum dried, GQDs/Ag₂O；

(4) by 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitation is scattered in aqueous solution；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into, regulation pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, react 30 ~ 60min；Carry out It is centrifuged and cleans with acetone and deionized water successively and obtain precipitation；This is deposited at 80 ~ 90 DEG C and is dried 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of heat Process 1 ~ 2h, after being cooled to room temperature, be immersed in Fluohydric acid. and carry out ultrasonic 10 ~ 15min with ultrasonic power 100 ~ 150W, remove table Local, face silicon dioxide, is centrifuged and is dried, it is thus achieved that antibacterial powder；

The ceramic ink jet the most according to claim 2 preparation method of the anion ceramic ink that can sink, it is characterised in that Increase by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight Amount ratio is 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/Ag-Zn- Ce/SiO₂/ Graphene antibiosis powder.

4. ceramic ink jet is with sinking the preparation method of anion ceramic ink, and it comprises the following steps:

Step C, ink semi-finished product step B obtained, in the constant temperature a mixing bowl of 80～100 DEG C, then carry out evacuation, height Speed vibration, filtration, obtain ink；

Wherein, the preparation method of described antibiotic complex is as follows:

The ceramic ink jet the most according to claim 4 preparation method of the anion ceramic ink that can sink, it is characterised in that Increase by a step between step (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in aqueous solution, be added dropwise over GQDs/Ag₂In O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1 ~ 5；10 ~ 100W surpasses Sound 60 ~ 120min, stands, and deionized water wash for several times, is dried to obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

6., according to the preparation method of the anion ceramic ink that can sink of the ceramic ink jet described in claim 1 or 4, its feature exists In, described conductive filler preparation method is as follows: by 30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin, 1 ~ 8% CNT, 2 ~ 6% Aluminium powder, 5 ~ 10% white carbon blacks and 1 ~ 10% Graphene are sufficiently mixed, and add appropriate butyl acetate and put into dispersion dispergation in ball mill, row After material, detect, adjust the slurry being configured to apply；By this slurry coating on substrate, drying and forming-film；Then nitrogen charging it is placed on In special atmosphere oven, it is warmed up to 900 ~ 1000 DEG C, is incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous netted carbon film.

7., according to the preparation method of the anion ceramic ink that can sink of the ceramic ink jet described in claim 1 or 4, its feature exists In, described anion complex preparation method is as follows: by 5 ~ 10% coral fossil, 10 ~ 15% tourmaline, 20 ~ 35% opals, 1 ~ 5% serpentine, 5 ~ 10% Maifanitums, 1 ~ 5% rare ice stone, 1 ~ 5% hokutolite, 1 ~ 5% doctor Wang Shi, 5 ~ 10% shells, 10 ~ 15% kieselguhr, 1 ~ 3% iron sesquioxide, 2 ~ 5% aluminium sesquioxide, 3 ~ 8% zirconium oxides and 1 ~ 5% zirconium phosphate mix homogeneously, add in grinding equipment Row superfine grinding, until particle diameter distribution is at 50 ~ 80nm, sieves, and is dried, can be prepared by described anion powder；Take 5 ~ 10g to bear Ion powder is scattered in 100 ~ 200ml ultra-pure water, and water bath sonicator 1 ~ 2h obtains the most even stable dispersion liquid；To have carbon nanometer When the substrate of pipe reticular membrane is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this Homogeneous dispersion is scattered in this carbon nanotube mesh film, owing to there is hydrophilic when CNT is near 8 DEG C, and this dispersion liquid It is attracted to multiple net holes of carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and is caught up with by hydrone Walk to leave behind anion powder to adsorb in multiple net holes of carbon nanotube mesh film；After drying, the carbon of anion powder will be adsorbed with Nanotube reticular membrane scrapes off this substrate, it is thus achieved that anion powder/CNT.

8. the ceramic ink jet anion ceramic ink that can sink, it is characterised in that it contains the group of following percentage by weight Part: 20 ~ 35% sink glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% bonding agent, 1 ~ 6% conduction Filler, surplus is solvent；Wherein, described sagging glaze contains the component of following percentage by weight: 30 ~ 40% V2O5,45 ~ 50% Bi2O3,7 ~ 12% Ba2CO3,4 ~ 8% ZnO, 2 ~ 6% SiO2,1 ~ 3% Al2O3,1 ~ 3%(K2O+Na2O), 0.5 ~ 5% antibacterial multiple Compound and 2 ~ 6% anion complex.