CN106634204A

CN106634204A - Antibacterial ceramic ink with depression effects for ceramic inkjet and preparation method thereof

Info

Publication number: CN106634204A
Application number: CN201610748961.XA
Authority: CN
Inventors: 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: 2017-05-10

Abstract

The invention discloses antibacterial ceramic ink with depression effects for ceramic inkjet and a preparation method thereof. The preparation method comprises the following steps: a step A, preparation of glaze with depression effects; a step B, glaze with depression effects, a dispersant, a surface additive, an antifoaming agent, a binder, and the balance being a solvent are weighed according to a proportion, and an ink semi-finished product is grinded; a step C, an ink finished product is filtered. Compared with prior ceramic ink with depression effects, the ceramic and pigment ink are matched for usage, in order to fully and visually present accidented and vivid texture of the tiles with good stereo perception, further the decorative effects of the tiles are improved, patterns with extraordinary splendor are created, and the ink can be widely applied to ceramics and antique bricks and other fields. At the same time, a negative ion compound, a deodorant and an antibacterial composite material are reasonably matched, the three materials are synergetic, so that the ceramic ink has excellent antibacterial, antifouling and air purifying characteristics, further application ranges of the ceramic ink with depression effects are widened.

Description

A kind of ceramic ink jet use can sink anti-bacteria ceramic ink and preparation method thereof

Technical field

The present invention relates to ceramic technology field, a kind of more particularly to ceramic ink jet use can sink anti-bacteria ceramic ink And preparation method thereof.

Background technology

Bacterium, mould has very big harm to the mankind and animals and plants as pathogen, and the health for affecting people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and its product increasingly causes the concern of people, antibacterial product Demand will constitute huge market.

For environmental protection aspect, negative aeroion can eliminate foreign flavor indoors and various pernicious gases.Fit up indoors During leftovers leftovers in the irritative gas such as the art work that the uses benzene, formaldehyde, ketone, the ammonia that evaporate and daily life The harmful peculiar smell such as acid smell, cigarette, with the material rich in anion, the negative aeroion of its release can be effectively Eliminated, reached the purpose of purify air, and had suppression well to golden staphylococci, Escherichia coli, candida albicans and mould etc. Make and use.

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

The use of the ceramic ink with sagging effect, can make the more abundant image of Ceramic Tiles shows concavo-convex line Reason, skin texture true to nature, soft texture, break the ice-cold impression of ceramic tile, allow people to experience from vision and tactile more marvellous Texture.With using cooperatively for ceramic ink jet printing paint ink, the decorative effect of ceramic tile not only can be further improved, Adapt to digital development trend.But the sunk ceramic ink with regard to functional form is rarely reported at present, therefore technology needs Improve, needing research and development functional form badly can sink ceramic ink, such as antibacterial, antistatic, deodorant, anion function, further expand Wide its range of application.

The content of the invention

In order to solve above-mentioned the deficiencies in the prior art, the anti-bacteria ceramic ink the invention provides a kind of ceramic ink jet use can sink Water and preparation method thereof.

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

A kind of ceramic ink jet use can sink the preparation method of anti-bacteria ceramic ink, and it is comprised the following steps：

Step A, the sagging glaze of preparation：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 is uniform；Add 0.5 ~ 5% antibiotic complex and sand milling is uniform；Plus Enter 1 ~ 5% deodorant and sand milling is uniform；2 ~ 6% anion compounds are added, sand milling is uniformly obtained compound；Compound is dispensed In being fitted into fire resistant sagger, 800 ~ 1100 DEG C of high temperature meltings are carried out, obtain the slurry of molten state；By slurry water quenching cooling, and crush Into graininess, sagging glaze is obtained；

Step B, weigh 20 ~ 35% sink glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% combine Agent, balance of solvent, adding in homogenizer carries out 30 ~ 60min of dispersion；Scattered mixed liquor is fitted in sand mill, 8 ~ 12h of sand milling, obtains ink semi-finished product of the particle diameter distribution between 200 ~ 500nm；

Then step C, the ink semi-finished product for obtaining step B are vacuumized, high in 80～100 DEG C of constant temperature a mixing bowl Speed vibration, filtration, obtain ink.

A kind of ceramic ink jet use can sink anti-bacteria ceramic ink, and it contains the component of following percentage by weight：Under 20 ~ 35% Sunken glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% bonding agent, balance of solvent；Wherein, it is 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, 1 ~ 5% deodorant and 2 ~ 6% it is negative from Sub- compound.

In the present invention, the deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：5%ZrO₂, 10% TiO₂, 16%SiO₂, 4%V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, Carry out sand milling in the big flow circulation horizontal sand mill for putting into the exploitation of PUHLER companies, control particle diameter between 10 ~ 300nm, Obtain inorganic oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, inorganic oxide, 100 ~ 200W ultrasounds 100 is added ~ 300rpm stirs 1 ~ 2h, in allowing nano material well into diatom soil pores, the cleaning of multiple suction filtration, and dry deodorant；Wherein The diatomite is 1 with the weight ratio of inorganic oxide:1~8.

In the present invention, the anion compound preparation method is as follows：By 5 ~ 10% astroies, 10 ~ 15% tourmaline, 20 ~ 35% opals, 1 ~ 5% serpentine, 5 ~ 10% medical stones, 1 ~ 5% Strange ice stone, 1 ~ 5% hokutolite, 1 ~ 5% Doctor king stone, 5 ~ 10% shellfishes Shell, 10 ~ 15% diatomite, 1 ~ 3% di-iron trioxide, 2 ~ 5% alundum (Al2O3)s, 3 ~ 8% zirconium oxides and 1 ~ 5% basic zirconium phosphate are well mixed, Adding in grinding equipment carries out ultra-fine grinding, until particle diameter distribution is in 50 ~ 80nm, sieves, and is dried, you can be obtained described negative Ion powder.Take 5 ~ 10g negative ion powders to be scattered in 100 ~ 200ml ultra-pure waters, 1 ~ 2h of water bath sonicator obtains uniform stable point Dispersion liquid；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, Roller is rolled around, the homogeneous dispersion is scattered in the carbon nanotube mesh film, due to having when CNT is near 8 DEG C There is hydrophily, the dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；About 25 DEG C are warming up to, CNT has to be dredged It is aqueous and hydrone is driven away leave behind negative ion powder adsorb in multiple net holes of carbon nanotube mesh film；After drying, will inhale Carbon nanotube mesh film with negative ion powder scrapes off the substrate, obtains negative ion powder/CNT.

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

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

In the present invention, during the solvent is to take off aromatic hydrocarbon solvent, environmentally friendly hydrocarbon solvent, alcohols, cycloalkane solvent At least one.The bonding agent is usually used polymerizing resin, such as polyethylene, polypropylene, polyvinyl chloride and polystyrene tree One kind in fat, polymerizing resin is played and combined and scattered double action.The defoamer is the polymer without organosilicon Type defoamer, the trade name that defoamer can be included includes BYK051, BYK052, but not limited to this.

In the present invention, the antibiotic complex can be obtained by the following method：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mix in beaker, beaker is placed in ice-water bath, while stirring with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained Graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser 30 ~ 60min of irradiation, swashs Light irradiation power is 0.5 ~ 2W；It is standby；

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

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration for 0.005 ~ The 0.05mol/L cerous nitrate aqueous solution, it is 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions that concentration is added dropwise over after 30 ~ 60min, GQDs/Ag₂The O aqueous solution, the cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1~0.2:0.2~0.4；Continue ultrasound Stirring, adjusts mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 30 ~ 0.5 ~ 1h of reduction reaction at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50%, the reduction reaction at 85 DEG C are added After 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:1~3）, adjust PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Carry out being centrifuged and cleaned with acetone and deionized water successively Precipitated；2 ~ 4h is dried at this is deposited in into 80 ~ 90 DEG C, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂Being placed under argon gas atmosphere carries out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, after being cooled to room temperature, is immersed in hydrogen 10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, surface local silica is removed, is centrifuged and is dried, obtained Antibacterial powder；

（5）It is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and concentration that concentration is 0.05 ~ 0.5mol/L under nitrogen environment Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, while adding step（4）Obtained antibacterial powder, after 60 ~ 120min of magnetic agitation Aniline is added, antibacterial powder is 2 with aniline mass ratio:12~18；Persistently stir after 60 ~ 90min, ammonium persulfate, aniline is dropwise added dropwise It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried afterwards for several times, Mill to obtain nano polyaniline/antibacterial flour complexes；

（6）TiO 2 sol is prepared with sol-gel process, the nanometer polyphenyl for accounting for 0.01 ~ 1.0wt% of colloidal sol is added in colloidal sol Amine/antibacterial flour complexes, is well mixed；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；Gained is answered after milling 1 ~ 2h is calcined at 400～550 DEG C of compound, polyaniline is removed, poriferous titanium dioxide/antibacterial flour complexes are obtained；

（7）30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes are fully mixed Close, add appropriate butyl acetate to be put in ball mill and disperse dispergation, after discharge, detection, adjustment are configured to the slurry that can be applied Material；By this slurry coating on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 ~ 1000 DEG C are warmed up to, are protected 1 ~ 2h of temperature；Film is scraped off into the substrate, antibiotic complex is obtained.

It is preferred that in step（4）With（5）Between increase by a step：Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in In the aqueous solution, GQDs/Ag is added dropwise over₂O/Ag-Zn-Ce/SiO₂In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/ Ag-Zn-Ce/SiO₂Weight ratio be 1:1~5；10 ~ 100W, 60 ~ 120min of ultrasound, stand, and deionized water is washed for several times, are dried Obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

In the present invention, the antibiotic complex can also be obtained by the following method：

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.05 ~ 0.5g/100mlZnO The 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 powders；

（4）It is the ten of 0.05 ~ 0.5mol/L by protonic acid solution and concentration that concentration is 0.05 ~ 0.5mol/L under nitrogen environment Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, while adding step（4）Obtained antibacterial powder, after 60 ~ 120min of magnetic agitation Aniline is added, antibacterial powder is 2 with aniline mass ratio:12~18；Persistently stir after 60 ~ 90min, ammonium persulfate, aniline is dropwise added dropwise It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried afterwards for several times, Mill to obtain nano polyaniline/antibacterial flour complexes；

（5）TiO 2 sol is prepared with sol-gel process, the nanometer polyphenyl for accounting for 0.01 ~ 1.0wt% of colloidal sol is added in colloidal sol Amine/antibacterial flour complexes, is well mixed；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；Gained is answered after milling 1 ~ 2h is calcined at 400～550 DEG C of compound, polyaniline is removed, poriferous titanium dioxide/antibacterial flour complexes are obtained；

（6）30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes are fully mixed Close, add appropriate butyl acetate to be put in ball mill and disperse dispergation, after discharge, detection, adjustment are configured to the slurry that can be applied Material；By this slurry coating on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 ~ 1000 DEG C are warmed up to, are protected 1 ~ 2h of temperature；Film is scraped off into the substrate, antibiotic complex is obtained.

It is preferred that in step（3）With（4）Between increase by a step：Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in In the aqueous solution, GQDs/Ag is added dropwise over₂In the O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO For 1:1~5；10 ~ 100W, 60 ~ 120min of ultrasound, stand, and deionized water is washed for several times, dry GQDs/Ag₂O/ZnO/ Graphenes Antibacterial powder.

The present invention has the advantages that：This method is loaded and fixed antiseptic in carbon nano net, not only prevents it Reunite, significantly improve the stability of the antiseptics such as metal nanoparticle so as to can more preferably be dispersed in ceramic ink jet ink, and have There are more efficient antibacterial activity and silver ion not to overflow oxidation stain；The anti-microbial property of various antiseptics is compounded with simultaneously, There is more preferable antibacterial effect compared to single silver nano antibacterial agent, antibacterial is lasting；Anion compound can be efficiently uninterrupted Anion releasing, in the case where having light or no light condition can uninterrupted anion releasing, effective purify air, decomposing formaldehyde etc. has Machine gas, improves IAQ, and the also effect with antibacterial is beneficial to health；Inorganic oxide main component has More than 10 kinds of magnesium, aluminium, iron etc. trace element favourable to human body, because it is a kind of special polarity crystalline solid of structure, itself energy It is long-term to produce electron ion, and negative aeroion is forever discharged, reach the effect of deodorant purify air.With existing ceramic ink of sinking Water is compared, dispensing science of the present invention, and it is reasonable to prepare, and quality stability is good, can preserve for a long time, with good inkjet printing Can, used cooperatively with paint ink with ceramic ink jet printing, more fully image the concavo-convex texture true to nature of ceramic tile can be shown, Third dimension is strong, further improves the decorative effect of ceramic tile, creates the pattern being a splendid legacy, and can also lead in ceramics and Antique Imitation Tiles etc. Extensively apply in domain；Simultaneously through rational collocation anion compound, deodorant and antimicrobial composite material, three's synergy, So that ceramic ink has excellent antibacterial antifouling and purify air characteristic, the application model of the ceramic ink that can sink further has been widened Enclose.

Specific embodiment

Technical scheme is further illustrated below by specific preferred embodiment.

Embodiment 1

A kind of ceramic ink jet use can sink anti-bacteria ceramic ink and preparation method thereof, and the preparation method is comprised the following steps：

Step A, the sagging glaze of preparation：By 40% V2O5,35% Bi2O3,7% Ba2CO3,5% ZnO, 2% SiO2,2% Al2O3, 1%（K2O+Na2O）Mixing sand milling is uniform；Add 5% antibiotic complex and sand milling is uniform；Add 1% deodorant and sand milling is uniform；Again Add 2% anion compound, sand milling that compound is uniformly obtained；Compound is dispensed and is fitted in fire resistant sagger, carry out 1000 DEG C high Temperature is founded, and obtains the slurry of molten state；By slurry water quenching cooling, and graininess is broken into, obtains sagging glaze；

Step B, weigh 20% sink glaze, 8% Solsperse 24000,5% Span-80,0.3% BYK052,3% polystyrene Resin and 63.7% environmentally friendly hydrocarbon solvent, adding in homogenizer carries out dispersion 60min；Scattered mixed liquor is loaded into sand In grinding machine, sand milling 10h obtains ink semi-finished product of the particle diameter distribution between 200 ~ 500nm；

Then step C, the ink semi-finished product for obtaining step B are vacuumized, are shaken at a high speed in 90 DEG C of constant temperature a mixing bowl Dynamic, filtration, obtains ink.

Wherein, the anion compound preparation method is as follows：By 10% astroies, 10% tourmaline, 35% opal, 1% serpentine, 10% medical stone, 5% Strange ice stone, 1% hokutolite, 5% Doctor king stone, 5% shell, 10% diatomite, 1% di-iron trioxide, 3% alundum (Al2O3), 3% zirconium oxide and 1% basic zirconium phosphate are well mixed, and adding in grinding equipment carries out ultra-fine grinding, until particle is straight Footpath is distributed in 50 ~ 80nm, sieves, and is dried, you can the negative ion powder is obtained.Take 8g negative ion powders and be scattered in 120ml ultra-pure waters In, water bath sonicator 2h obtains uniform stable dispersion liquid；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, will Dispersion liquid is added in the substrate of concave shape, meanwhile, roller is rolled around, make the homogeneous dispersion be scattered in the carbon nano-tube network In shape film, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to the multiple of carbon nanotube mesh film Net hole；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives away hydrone and leaves behind negative ion powder and adsorb in carbon nanometer In multiple net holes of pipe reticular membrane；After drying, the carbon nanotube mesh film for being adsorbed with negative ion powder is scraped off into the substrate, born Ion powder/CNT.

Wherein, the deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：5%ZrO₂, 10%TiO₂, 16%SiO₂, 4%V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, put into Sand milling is carried out in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the aqueous solution of 120ml, adds inorganic oxide, 200W ultrasounds 200rpm stirring 2h to allow and receive During rice material is well into diatom soil pores, the cleaning of multiple suction filtration, dry deodorant；Wherein described diatomite and inorganic oxide The weight ratio of thing is 1:8.

Wherein, the antibiotic complex is obtained by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, while stirring with the speed of 600rpm, obtain mixed liquor；1g potassium permanganate powders are weighed, In slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It is quick to add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）It is outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, while laser irradiation 40min, laser irradiation power is 1W；It is standby；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；Being added dropwise over concentration is 0.1mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solutions, adjusts pH value to 11, then stands, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.05mol/L cerous nitrates The aqueous solution, is added dropwise over concentration for 0.005mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min₂The O aqueous solution, cerous nitrate are water-soluble Liquid is 1 with zinc nitrate aqueous solution volume ratio:0.1:0.4；Continue ultrasonic agitation, adjust mixed solution pH value to 7.0；Side ultrasound is stirred Mix, side adds the hydrazine hydrate that 6mL mass fractions are 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass point is added Number is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Carry out being centrifuged and being cleaned with acetone and deionized water successively being precipitated；Will This is dried 3h at being deposited in 90 DEG C, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W Sound 10min, removes surface local silica, is centrifuged and is dried, and obtains antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:18 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）TiO 2 sol is prepared with sol-gel process, is added in colloidal sol and is accounted for the nano polyaniline of colloidal sol 1.0wt%/anti- Bacterium powder compound, is well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（7）30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 2

Step A, the sagging glaze of preparation：By 33% V2O5,40% Bi2O3,7% Ba2CO3,5% ZnO, 2% SiO2,2% Al2O3, 1%（K2O+Na2O）Mixing sand milling is uniform；Add 3% antibiotic complex and sand milling is uniform；Add 3% deodorant and sand milling is uniform；Again Add 4% anion compound, sand milling that compound is uniformly obtained；Compound is dispensed and is fitted in fire resistant sagger, carry out 1000 DEG C high Temperature is founded, and obtains the slurry of molten state；By slurry water quenching cooling, and graininess is broken into, obtains sagging glaze；

Step B, weigh 30% sink glaze, 5% Solsperse 24000,3% Span-80,0.5% BYK052,2% polystyrene Resin and 59.5% environmentally friendly hydrocarbon solvent, adding in homogenizer carries out dispersion 60min；Scattered mixed liquor is loaded into sand In grinding machine, sand milling 10h obtains ink semi-finished product of the particle diameter distribution between 200 ~ 500nm；

Wherein, the anion compound preparation method is as follows：By 8% astroies, 12% tourmaline, 25% opal, 3% Serpentine, 8% medical stone, 3% Strange ice stone, 3% hokutolite, 3% Doctor king stone, 8% shell, 12% diatomite, 2% di-iron trioxide, 5% 3 Al 2 O, 6% zirconium oxide and 2% basic zirconium phosphate are well mixed, and adding in grinding equipment carries out ultra-fine grinding, until particle diameter point Cloth sieves in 50 ~ 80nm, is dried, you can the negative ion powder is obtained.Take 8g negative ion powders to be scattered in 120ml ultra-pure waters, water Bath ultrasound 2h obtains uniform stable dispersion liquid；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, by dispersion liquid In adding the substrate of concave shape, meanwhile, roller is rolled around, make the homogeneous dispersion be scattered in the carbon nanotube mesh film In, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives away hydrone and leaves behind negative ion powder and adsorb in CNT In multiple net holes of reticular membrane；After drying, the carbon nanotube mesh film for being adsorbed with negative ion powder is scraped off into the substrate, acquisition bear from Sub- powder/CNT.

Wherein, the preparation method of the deodorant is as follows：Mix the raw material of following percentage by weight：5%ZrO₂, 10%TiO₂, 16%SiO₂, 4%V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, put into Sand milling is carried out in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the aqueous solution of 120ml, adds inorganic oxide, 200W ultrasounds 200rpm stirring 2h to allow and receive During rice material is well into diatom soil pores, the cleaning of multiple suction filtration, dry deodorant；Wherein described diatomite and inorganic oxide The weight ratio of thing is 1:5.

Wherein, the antibiotic complex is obtained by the following method：

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；Being added dropwise over concentration is 0.2mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solutions, adjusts pH value to 11, then stands, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.03mol/L cerous nitrates The aqueous solution, is added dropwise over concentration for 0.03mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min₂The O aqueous solution, cerous nitrate are water-soluble Liquid is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.3；Continue ultrasonic agitation, adjust mixed solution pH value to 7.0；Side ultrasound is stirred Mix, side adds the hydrazine hydrate that 6mL mass fractions are 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass point is added Number is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Carry out being centrifuged and being cleaned with acetone and deionized water successively being precipitated；Will This is dried 3h at being deposited in 90 DEG C, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W Sound 12min, removes surface local silica, is centrifuged and is dried, and obtains antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:15 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）TiO 2 sol is prepared with sol-gel process, is added in colloidal sol and is accounted for the nano polyaniline of colloidal sol 0.5wt%/anti- Bacterium powder compound, is well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（7）45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 3

Step A, the sagging glaze of preparation：By 30% V2O5,43% Bi2O3,5.5% Ba2CO3,5% ZnO, 2% SiO2,2% Al2O3、1%（K2O+Na2O）Mixing sand milling is uniform；Add 0.5% antibiotic complex and sand milling is uniform；Add 5% deodorant and sand Mill is uniform；6% anion compound is added, sand milling is uniformly obtained compound；Compound is dispensed and is fitted in fire resistant sagger, entered 1000 DEG C of high temperature meltings of row, obtain the slurry of molten state；By slurry water quenching cooling, and graininess is broken into, obtains sagging glaze；

Step B, weigh 35% sink glaze, 3% Solsperse 24000,2% Span-80,0.8% BYK052,1% polystyrene Resin and 58.2% environmentally friendly hydrocarbon solvent, adding in homogenizer carries out dispersion 60min；Scattered mixed liquor is loaded into sand In grinding machine, sand milling 10h obtains ink semi-finished product of the particle diameter distribution between 200 ~ 500nm；

Wherein, the anion compound preparation method is as follows：By 5% astroies, 15% tourmaline, 20% opal, 5% Serpentine, 5% medical stone, 1% Strange ice stone, 5% hokutolite, 1% Doctor king stone, 10% shell, 15% diatomite, 3% di-iron trioxide, 2% Alundum (Al2O3), 8% zirconium oxide and 5% basic zirconium phosphate are well mixed, and adding in grinding equipment carries out ultra-fine grinding, until particle diameter 50 ~ 80nm is distributed in, is sieved, be dried, you can the negative ion powder is obtained.Take 8g negative ion powders to be scattered in 120ml ultra-pure waters, Water bath sonicator 2h obtains uniform stable dispersion liquid；When substrate with carbon nanotube mesh film is placed in into about 8 DEG C, will disperse Liquid is added in the substrate of concave shape, meanwhile, roller is rolled around, make the homogeneous dispersion be scattered in the carbon nanotube mesh film In, due to having hydrophily when CNT is near 8 DEG C, the dispersion liquid is attracted to multiple nets of carbon nanotube mesh film Hole；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives away hydrone and leaves behind negative ion powder and adsorb in CNT In multiple net holes of reticular membrane；After drying, the carbon nanotube mesh film for being adsorbed with negative ion powder is scraped off into the substrate, acquisition bear from Sub- powder/CNT.

Wherein, the preparation method of the deodorant is as follows：Mix the raw material of following percentage by weight：5%ZrO₂, 10%TiO₂, 16%SiO₂, 4%V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, put into Sand milling is carried out in the big flow circulation horizontal sand mill of PUHLER companies exploitation, control particle diameter obtains inorganic between 10 ~ 300nm Oxide；Diatomite is dispersed in the aqueous solution of 120ml, adds inorganic oxide, 200W ultrasounds 200rpm stirring 2h to allow and receive During rice material is well into diatom soil pores, the cleaning of multiple suction filtration, dry deodorant；Wherein described diatomite and inorganic oxide The weight ratio of thing is 1:1.

Wherein, antibiotic complex is obtained by the following method：

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；Being added dropwise over concentration is 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solutions, adjusts pH value to 11, then stands, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise over for 0.005mol/L nitric acid The cerium aqueous solution, is added dropwise over concentration for 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag after 30min₂The O aqueous solution, cerous nitrate water Solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.4；Continue ultrasonic agitation, adjust mixed solution pH value to 7.0；Side ultrasound Stirring, side adds the hydrazine hydrate that 6mL mass fractions are 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL mass is added Fraction is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out being centrifuged and being cleaned with acetone and deionized water successively being precipitated；Will This is dried 3h at being deposited in 90 DEG C, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Put 600 DEG C of heat treatment 1h are carried out under argon gas atmosphere, after being cooled to room temperature, is immersed in hydrofluoric acid and is surpassed with ultrasonic power 100W Sound 15min, removes surface local silica, is centrifuged and is dried, and obtains antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:12 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial flour complexes, are well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To forge at 500 DEG C of gained compound after milling 1h is burnt, polyaniline is removed, poriferous titanium dioxide/antibacterial flour complexes are obtained；

（7）40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 4

Based on the preparation method of embodiment 2, difference is：Step（4）With（5）Between increase following steps：Take three-dimensional sea Continuous shape Graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂It is three-dimensional in the aqueous solution Spongy graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；50W ultrasound 90min, stand, deionized water Washing for several times, dry GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

Three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO3 in ice-water bath with 250ml 98% concentrated sulfuric acid is well mixed, and is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml to go Ionized water, is warming up to 98 DEG C of reaction 20min；Add the dilution of 270ml water, and with the H2O2 of 5ml 30% and unnecessary KMnO4, The color of mixed solution is brown color, is filtered while hot, and deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；Take 200ml mass fractions pour diameter 25cm into for the graphene oxide solution of 5mg/ml, in the discoid reaction utensil of high 2cm, add Ascorbic acid (VC) 0.5g stirrings are sufficiently mixed it；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, freeze-drying obtains the three-dimensional sponge shape Graphene of flexibility.

Embodiment 5

Based on the preparation method of embodiment 1, difference is：The antibiotic complex is obtained by the following method：

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.5g/100mlZnO quantum dots The 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 powders；

（4）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:18 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）TiO 2 sol is prepared with sol-gel process, is added in colloidal sol and is accounted for the nano polyaniline of colloidal sol 1.0wt%/anti- Bacterium powder compound, is well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（6）30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 6

Based on the preparation method of embodiment 2, difference is：The antibiotic complex is obtained by the following method：

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.2g/100mlZnO quantum dots The 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 powders；

（4）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:15 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）TiO 2 sol is prepared with sol-gel process, is added in colloidal sol and is accounted for the nano polyaniline of colloidal sol 0.5wt%/anti- Bacterium powder compound, is well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（6）45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 7

Based on the preparation method of embodiment 3, difference is：The antibiotic complex is obtained by the following method：

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise over for 0.05g/100mlZnO quantum dots The 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 powders；

（4）Under nitrogen environment, by the detergent alkylate sulphur that protonic acid solution and concentration that concentration is 0.2mol/L are 0.1mol/L Acid is with volume ratio 3:2 mixing, while adding step（4）Obtained antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:12 persistently stir after 90min, and ammonium persulfate is dropwise added dropwise, and aniline is 1 with ammonium persulfate mol ratio:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial flour complexes, are well mixed；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To forge at 500 DEG C of gained compound after milling 1h is burnt, polyaniline is removed, poriferous titanium dioxide/antibacterial flour complexes are obtained；

（6）40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, are added suitable The butyl acetate of amount is put in ball mill and disperses dispergation, and after discharge, detection, adjustment are configured to the slurry that can be applied；This is starched Material is coated on substrate, drying and forming-film；Then in being placed on nitrogen filled protection atmosphere furnace, 900 DEG C are warmed up to, are incubated 1.5h；Film is scraped From the substrate, antibiotic complex is obtained.

Embodiment 8

Based on the preparation method of embodiment 6, difference is：Step（3）With（4）Between increase such as next step：Take three-dimensional Spongy graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag₂In the O/ZnO aqueous solution, three-dimensional sponge shape stone Black alkene and GQDs/Ag₂The weight ratio of O/ZnO is 1:3；50W ultrasound 90min, stand, and deionized water is washed for several times, dry GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

Comparative example 1

Based on the preparation method of embodiment 1, difference is：The antibiotic complex is the titanium dioxide for carrying metal antibacterial agent Titanium；It is not added with anion compound；The preparation method of the deodorant is as follows：Mix the raw material of following percentage by weight：5% ZrO₂, 10%TiO₂, 16%SiO₂, 4%V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, carry out sand milling in the big flow circulation horizontal sand mill for putting into the exploitation of PUHLER companies, control particle diameter 10 ~ Between 500nm, inorganic oxide, i.e. deodorant is obtained.

Comparative example 2

Based on the preparation method of embodiment 5, difference is：The antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；It is not added with deodorant；The anion compound preparation method is as follows：By 5% astroies, 15% tourmaline, 20% albumen Stone, 5% serpentine, 5% medical stone, 1% Strange ice stone, 5% hokutolite, 1% Doctor king stone, 10% shell, 15% diatomite, 3% 3 oxidation two Iron, 2% alundum (Al2O3), 8% zirconium oxide and 5% basic zirconium phosphate are well mixed, and adding in grinding equipment carries out ultra-fine grinding, until Grain diameter is distributed in 50 ~ 80nm, sieves, and is dried, you can.

Performance test is carried out to ceramic ink prepared by embodiment 1 ~ 8 and comparative example 1,2, test result shows ink viscosity For 15 ~ 35mPas, surface tension in 25 ~ 40mN/m, even particle size distribution, average grain diameter between 200 ~ 400nm, with good Stability well and Ink Jet Printing Performance.Used cooperatively with paint ink with ceramic ink jet printing, using ink jet printer directly in porcelain Spray printing on adobe body, after burning till, has createed clear orderly, the uneven effect of lines, the solid being a splendid legacy on brick face Sense, feel is fine and smooth, and more common wallpaper class ornament materials has more texture and solid sense.

Embodiment 1 ~ 8 and comparative example 1,2 are carried out into 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 the ceramic tile face for spraying and burning till ceramic ink On, 2h is placed indoors, then bacterium solution sterilized water is eluted in culture medium, 24h is cultivated at 37 DEG C, bacterium number is then detected, Calculate sterilization rate.

Heat endurance is tested：The ceramic tile for spraying and burn till ceramic ink is placed in electric furnace, from room temperature 200 DEG C is raised to, Insulation 20min, rapidly in 25 DEG C of water of input, takes out after 10min and dries, and glaze layer is without temperature shock crackle and tests its sterilization rate.

Wear testing：From the abrasive material that Mohs' hardness is 3～4, rub on by the ceramic tile for spraying and burning till ceramic ink Wipe 1000 times to imitate the effect after paving is used 2 years.

Antifouling test：It is pollutant from chrome green.

Sterilizing Evaluation for Uniformity：100 regions are chosen on glaze modelled after an antique carries out sterilizing test, and the data to measuring are carried out Evenness analysis, by the uniformity=100* (1- standard deviations/mean value).When the uniformity is more than 97%, then be labeled as ▲；When uniform Degree is then labeled as ☆ more than 90% and less than 97%；When the uniformity is less than 90%, then Biao Ji Wei ╳.

Anion burst size：COM-3010PRO types ion detector test anion burst size is produced using Japan, by the sample Product are positioned over 1m³Test box (length is 1m) in, measure air-anion concentration in air（Initial and 24h）；Adopt Tested with Han Wang M1 type haze table, PM2.5 concentration in test box（1h and 24h）；0.1mg formaldehyde is added dropwise in test box, and (formaldehyde is dense Degree 0.1mg/m³), concentration of formaldehyde is measured after 24h.

Deodorizing test：Prepare two 51PVF resin airbags, one piece of sample print is put in an air bag, another tree Fat air bag not setting-out piece.Then 500ppmNH3- air gas mixtures are blown into respectively in two air bags and are sealed.At interval of 30min measures the concentration of NH3 in air bag using gas detecting tube, until terminating after 2 hours of on-test, calculates deodorizing rate.

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

Claims

1. a kind of ceramic ink jet use can sink the preparation method of anti-bacteria ceramic ink, and it is comprised the following steps：

2. ceramic ink jet use according to claim 1 can sink the preparation method of anti-bacteria ceramic ink, it is characterised in that institute The preparation method for stating antibiotic complex is as follows：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mix in beaker, beaker is placed in ice-water bath, while stirring with the speed of 500 ~ 600rpm, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, in slowly adding above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtained GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser 30 ~ 60min of irradiation, laser irradiation power is 0.5~2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；It is added dropwise over 0.5 ~ 1mol/L hydroxides Sodium solution, adjusts pH value to 11, then stands, is centrifuged, and deionized water and ethanol are alternately washed three times, and vacuum drying is obtained GQDs/Ag₂O；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into, adjust pH value be 9 ~ 10, reaction temperature be 20 ~ 25 DEG C, react 30 ~ 60min；Carry out It is centrifuged and is cleaned with acetone and deionized water successively and is precipitated；2 ~ 4h is dried at this is deposited in into 80 ~ 90 DEG C, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Being placed under argon gas atmosphere carries out 500 ~ 800 DEG C of heat 1 ~ 2h is processed, after being cooled to room temperature, be immersed in hydrofluoric acid carries out 10 ~ 15min of ultrasound with 100 ~ 150W of ultrasonic power, removes table Face local silica, is centrifuged and is dried, and obtains antibacterial powder；

3. ceramic ink jet use according to claim 2 can sink the preparation method of anti-bacteria ceramic ink, it is characterised in that step Suddenly（4）With（5）Between increase by a step：Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight Amount is than being 1:1~5；10 ~ 100W, 60 ~ 120min of ultrasound, stand, and deionized water is washed for several times, dry GQDs/Ag₂O/Ag-Zn- Ce/SiO₂/ Graphene antibiosis powder.

4. a kind of ceramic ink jet use can sink the preparation method of anti-bacteria ceramic ink, and it is comprised the following steps：

Then step C, the ink semi-finished product for obtaining step B are vacuumized, high in 80～100 DEG C of constant temperature a mixing bowl Speed vibration, filtration, obtain ink；

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

5. ceramic ink jet use according to claim 4 can sink the preparation method of anti-bacteria ceramic ink, it is characterised in that step Suddenly（3）With（4）Between increase by a step：Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag₂In the O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO is 1:1~5；10 ~ 100W surpasses 60 ~ 120min of sound, stands, and deionized water is washed for several times, dry GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

6. the ceramic ink jet use according to claim 1 or 4 can sink the preparation method of anti-bacteria ceramic ink, and its feature exists In the deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：5%ZrO₂, 10%TiO₂, 16%SiO₂, 4% V₂O₅, 3%K₂O, 2%SnO₂, 2%Cr₂O₃, 13%Al₂O₃, 12%Fe₂O₃, 18%MgO, 8%Na2O, 7%MnO₂, put into PUHLER companies Sand milling is carried out in the big flow circulation horizontal sand mill of exploitation, control particle diameter obtains inorganic oxide between 10 ~ 300nm；By silicon Diatomaceous earth is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, 100 ~ 200W ultrasounds, 100 ~ 300rpm to stir 1 ~ 2h, During nano material is allowed well into diatom soil pores, the cleaning of multiple suction filtration, dry deodorant；Wherein described diatomite with it is inorganic The weight ratio of oxide is 1:1~8.

7. the ceramic ink jet use according to claim 1 or 4 can sink the preparation method of anti-bacteria ceramic ink, and its feature exists In the anion compound preparation method is as follows：By 5 ~ 10% astroies, 10 ~ 15% tourmaline, 20 ~ 35% opals, 1 ~ 5% serpentine, 5 ~ 10% medical stones, 1 ~ 5% Strange ice stone, 1 ~ 5% hokutolite, 1 ~ 5% Doctor king stone, 5 ~ 10% shells, 10 ~ 15% diatomite, 1 ~ 3% di-iron trioxide, 2 ~ 5% alundum (Al2O3)s, 3 ~ 8% zirconium oxides and 1 ~ 5% basic zirconium phosphate are well mixed, and add and enter in grinding equipment Row ultra-fine grinding, until particle diameter distribution is in 50 ~ 80nm, sieves, and is dried, you can the negative ion powder is obtained；Take 5 ~ 10g to bear Ion powder is scattered in 100 ~ 200ml ultra-pure waters, and 1 ~ 2h of water bath sonicator obtains uniform stable dispersion liquid；Will be with 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, roller is rolled around, make this Homogeneous dispersion is scattered in the carbon nanotube mesh film, due to there is hydrophily when CNT is near 8 DEG C, the dispersion liquid It is attracted to multiple net holes of carbon nanotube mesh film；About 25 DEG C are warming up to, CNT has hydrophobicity and catches up with hydrone Walk to leave behind negative ion powder to adsorb in multiple net holes of carbon nanotube mesh film；After drying, the carbon of negative ion powder will be adsorbed with Nanotube reticular membrane scrapes off the substrate, obtains negative ion powder/CNT.

8. a kind of ceramic ink jet use can sink anti-bacteria ceramic ink, it is characterised in that it contains the component of following percentage by weight： 20 ~ 35% sagging glaze, 3 ~ 8% dispersants, 2 ~ 5% surface additives, 0.3 ~ 0.8% defoamer, 1 ~ 3% bonding agents, balance of solvent； Wherein, the 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）, it is 0.5 ~ 5% antibiotic complex, 1 ~ 5% deodorant Agent and 2 ~ 6% anion compounds.