CN106189518A

CN106189518A - A kind of anti-bacteria ceramic ink-jet ink of marble crack effect and preparation method thereof

Info

Publication number: CN106189518A
Application number: CN201610748868.9A
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: 2016-12-07

Abstract

The invention discloses anti-bacteria ceramic ink-jet ink of a kind of marble crack effect and preparation method thereof, this preparation method comprises the following steps: step A, solvent, hyper-dispersant, regulator, defoamer and anti-diffusion agent mix and blend are made into mixed solution, is subsequently adding 0.1 ~ 5% antibiotic complex and stirs；Step B, addition infiltration powder body and photochromic complex, grind and be subsequently adding solvent and anion complex, grind to obtain ink semi-finished product；Step C, filter to obtain ink.Compare with existing ceramic ink, the ceramic ink dispensing science that the present invention manufactures, stable performance, there is natural marble lines, color and texture, improve the decorative effect of ceramic tile further, also extensively can apply in the field such as ceramics and Antique Imitation Tiles；Through reasonably arrange in pairs or groups photochromic complex, anion complex and antimicrobial composite material so that ceramic ink has excellent antibacterial, purifies air and photochromic characteristic, has widened its range of application further.

Description

A kind of anti-bacteria ceramic ink-jet ink of marble crack effect and preparation method thereof

Technical field

The present invention relates to ceramic technology field, particularly relate to the anti-bacteria ceramic ink-jet of a kind of marble crack effect Ink 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.

Photochromic refer to due to cause photochromic of the difference of light source and by reflection, reflect and the physical phenomenon such as interference The color change caused.Photochromic material is divided into organic photochromic material and inorganic photochromic material, wherein to inorganic The research of photochromic material is less, mainly includes transition metal oxide, metal halide and rare earth compounding three kinds.

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.

Marble ceramic tile is a class tile product with natural marble lines, color and texture, part marble porcelain Brick product reaches the lines with recessed effect by complicated silk screen process mode.But rarely have report at present about function The ceramic ink of the marble lines effect of type, therefore technology haves much room for improvement and improves, and needs research and development functional type badly and has Dali The ceramic ink of stone crack effect, such as the function such as antibacterial, antistatic, deodorizer, photochromic, anion, widens it further Range of application.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides the anti-bacteria ceramic spray of a kind of marble crack effect Ink ink and preparation method thereof

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

A kind of preparation method of the anti-bacteria ceramic ink-jet ink of marble crack effect, it comprises the following steps:

Step A, by half solvent, 2 ~ 8% hyper-dispersants, 1 ~ 4% regulator, 0.01 ~ 0.3% defoamer and 0.1 ~ 2% anti-diffusion agent Mix and blend is made into mixed solution, is subsequently adding 0.1 ~ 5% antibiotic complex and stirs, and moves to continue in horizontal sand mill to stir Mix, 3000 ~ 4000 turns/min；

Step B, in horizontal sand mill, it is slowly added to 40 ~ 50% infiltration powder body and 1 ~ 5% anion complex, and follow-up adding Continuous grinding is less than 600nm until ink mean diameter, is subsequently adding second half solvent and 0.3 ~ 4% photochromic complex, continues It is ground to the average size controlling of ink at 200 ~ 400nm, obtains ink semi-finished product；

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.

The anti-bacteria ceramic ink-jet ink of a kind of marble crack effect, consists of the following composition by mass percentage: 40 ~ 50% infiltration powder body, 2 ~ 8% hyper-dispersants, 1 ~ 4% regulator, 0.01 ~ 0.3% defoamer, 0.1 ~ 2% anti-diffusion agent, 0.1 ~ 5% antibacterial Complex, 1 ~ 5% anion complex and 0.3 ~ 4% photochromic complex, surplus is solvent.

In the present invention, described infiltration powder body is V2O5, NH4VO3, BiVO4, CaV2O6, WO3, CaWO4, Bi2W3O12 In one or more.Described hyper-dispersant include Solsperse5000, Solsperse32600, Solsperse54000, Silok®7010、SUP1400.Described regulator is one or more in ethers, alcohols, ketone, specially ethylene glycol bisthioglycolate fourth Ether, butyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol butyl oxide, lauryl alcohol, myristyl alcohol, One or more in phorone, 5-nonanone.Described defoamer is BYK-065, BYK-066N or BYK-088.Described nonproliferation Powder is polypropylene glycol 2000, isomery ten polyoxyethylenated alcohol E-05 or glycerol polyethenoxy ether HSH-330.Described solvent is Hexadecane, pentadecane, abienol, Exxal 12, undecyl alcohol, dibutyl ethylene glycol ether, TRIGLYME, TEG Dimethyl ether, methyl myristate, butyl oleate, butyl stearate, amyl stearate, di-2-ethylhexyl maleate, diethylene adipate and One or more in isopropyl laurate.

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 photochromic complex preparation method is as follows: under nitrogen environment, by concentration be 0.05 ~ The protonic acid solution of 0.5mol/L and the DBSA that concentration is 0.05 ~ 0.5mol/L mix with volume ratio 3:1 ~ 3, with Time add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, photochromic powder and aniline mass ratio are 1:5 ~ 10； After continuously stirred 60 ~ 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；At 20 DEG C～30 DEG C instead Answer 12 ~ 36h；Acetone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；Will 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards And ammonia, it being stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~ 90min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This precipitation is dried, to obtain nanometer polyphenyl Amine/photochromic flour complexes/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove polyaniline, photochromic powder/porous SiO₂, the most photochromic complex.Wherein, institute Stating photochromic powder is MoO3 nano powder and/or rare earth oxide, described rare earth oxide is Nd2O3, Er2O3, Pr2O3, In CeO2, Sm2O3, La2O3, Y2O3, Yb2O3, Ho2O3 at least one.

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) taking 1 ~ 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 100 ~ 200ml 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, dispersion liquid is added concave shape Substrate in, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, due to carbon nanometer Having hydrophilic when pipe is near 8 DEG C, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex absorption and receive at carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial powder complex will be adsorbed with Film scrapes 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) taking 1 ~ 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 100 ~ 200ml 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, dispersion liquid is added concave shape Substrate in, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, due to carbon nanometer Having hydrophilic when pipe is near 8 DEG C, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex absorption and receive at carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial powder complex will be adsorbed with Film scrapes 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 on the carbon nanotubes and fixes antibacterial, not only prevent it Reunite, significantly improve the stability of the antibacterial such as metal nanoparticle so that it is more preferably can be dispersed in low temperature frit, and have more Long-acting antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antibacterial simultaneously, compares Have a more preferable antibacterial effect in single silver nano antibacterial agent, antibacterial persistently；Photochromic complex has photochromic Effect, makes product more rich and varied, and utilizing its Ceramic Tiles produced is that the Ceramic Tiles using conventional colorants to produce cannot compare Intend, the shades of colour that can change along with the difference of irradiation light power, be a splendid legacy, full of magnificent carriage, so that pottery produces Product seem beautiful mystery, pure and fresh elegance, intersperse city night life, increase sentiment and artistic effect to building and interior decoration； Anion complex can efficient continual anion releasing, under having light or no light condition all can uninterrupted anion releasing, Effectively purify the organic gas such as air, decomposing formaldehyde, improve IAQ (indoor air quality), also there is antibacterial effect, be of value to human body Healthy.

Comparing with existing ceramic ink, the ceramic ink dispensing science that the present invention manufactures, preparation is reasonable, and stable performance can Long-time preservation, has good Ink Jet Printing Performance, has natural marble lines, color and texture, improve porcelain further The decorative effect of brick, also extensively can apply in the field such as ceramics and Antique Imitation Tiles；Through photochromic complex of reasonably arranging in pairs or groups, bear Ion complex and antimicrobial composite material so that ceramic ink has excellent antibacterial, purifies air and photochromic characteristic, enters one Step has widened its range of application.

Detailed description of the invention

Technical scheme is further illustrated below by concrete preferred implementation.

Embodiment 1

A kind of anti-bacteria ceramic ink-jet ink of marble crack effect and preparation method thereof, this preparation method comprises the following steps:

Step A, 19% abienol, 6% Solsperse54000,4% lauryl alcohol, 0.2% BYK-088 and 1.4% isomery ten alcohol are gathered Oxygen vinyl Ether E-05 mix and blend is made into mixed solution, is subsequently adding 0.1% antibiotic complex and stirs, moves to horizontal sand milling Machine continues stir, 3500 turns/min；

Step B, be slowly added in horizontal sand mill 45% infiltration powder body (V2O5, BiVO4, WO3, Bi2W3O12 are by weight 2: 1:3:1 mixes) and 5% anion complex, and continue to grind until ink mean diameter is less than 600nm, so after adding Rear addition 19% undecyl alcohol and 0.3% photochromic complex, continue to be ground to the average size controlling of ink at 200 ~ 400nm, Ink semi-finished product；

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 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 photochromic complex preparation method is as follows: under nitrogen environment, is the proton of 0.3mol/L by concentration Acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder (Nd2O3, Er2O3 and Pr2O3 mix by weight 2:1:1), after magnetic agitation 90min, add aniline, photochromic powder and benzene Amine mass ratio is 1:8；After continuously stirred 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；20℃ ～at 30 DEG C, react 20h；Acetone, deionized water wash final vacuum for several times is dried, mill nano polyaniline/photochromic powder is multiple Compound；8g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add volume ratio 4:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate (be 5 with the mass ratio of nano polyaniline/photochromic flour complexes: 2), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and successively with acetone and deionized water Clean and obtain precipitation；This is deposited at 90 DEG C and is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂；Will Nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, light Mutagens toner/porous SiO₂, obtain photochromic complex.

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) taking 1g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 2

Step A, 19% abienol, 5% Solsperse54000,3% lauryl alcohol, 0.2% BYK-088 and 1.3% isomery ten alcohol are gathered Oxygen vinyl Ether E-05 mix and blend is made into mixed solution, is subsequently adding 2.5% antibiotic complex and stirs, moves to horizontal sand milling Machine continues stir, 3500 turns/min；

Step B, be slowly added in horizontal sand mill 44% infiltration powder body (V2O5, BiVO4, WO3, Bi2W3O12 are by weight 2: 1:3:1 mixes) and 3% anion complex, and continue to grind until ink mean diameter is less than 600nm, so after adding Rear addition 19% undecyl alcohol and 3% photochromic complex, continue to be ground to the average size controlling of ink at 200 ~ 400nm, obtain black Water semi-finished product；

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, the preparation method of described photochromic complex is as follows: under nitrogen environment, is the matter of 0.3mol/L by concentration Sub-acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder (MoO3 nano powder), adds aniline after magnetic agitation 90min, photochromic powder and aniline mass ratio are 1:8；Continuously stirred After 90min, 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, nano polyaniline/photochromic flour complexes of milling to obtain；By 8g nano polyaniline/ Photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, after stirring Adding tetraethyl orthosilicate (being 5:2 with the mass ratio of nano polyaniline/photochromic flour complexes), regulation pH value is 9 ~ 10, instead Answering temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；By this precipitation 3h it is dried, to obtain nano polyaniline/photochromic flour complexes/SiO at 90 DEG C₂；By nano polyaniline/photochromic powder Complex/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, photochromic powder/porous SiO₂, to obtain final product Photochromic complex.

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) taking 2g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, it is thus achieved that antibiotic complex.

Embodiment 3

Step A, 19% abienol, 5% Solsperse54000,3% lauryl alcohol, 0.2% BYK-088 and 1.8% isomery ten alcohol are gathered Oxygen vinyl Ether E-05 mix and blend is made into mixed solution, is subsequently adding 5% antibiotic complex and stirs, moves to horizontal sand mill Middle continuation stirs, 3500 turns/min；

Step B, be slowly added in horizontal sand mill 45% infiltration powder body (V2O5, BiVO4, WO3, Bi2W3O12 are by weight 2: 1:3:1 mixes) and 1% anion complex, and continue to grind until ink mean diameter is less than 600nm, so after adding Rear addition 19% undecyl alcohol and 1% photochromic complex, continue to be ground to the average size controlling of ink at 200 ~ 400nm, obtain black Water semi-finished product；

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, the preparation method of described photochromic complex is as follows: under nitrogen environment, is the matter of 0.3mol/L by concentration Sub-acid solution and the DBSA that concentration is 0.3mol/L mix with volume ratio 3:2, are simultaneously introduced photochromic powder (Ho2O3), adding aniline after magnetic agitation 90min, photochromic powder and aniline mass ratio are 1:8；After continuously stirred 90min, 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 to be dried, nano polyaniline/photochromic flour complexes of milling to obtain；By 8g nano polyaniline/photochromic Flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicon Acetoacetic ester (being 5:2 with the mass ratio of nano polyaniline/photochromic flour complexes), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, react 60min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited at 90 DEG C It is dried 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nano polyaniline/photochromic flour complexes/ SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, photochromic powder/porous SiO₂, obtain light-induced variable Color complex.

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) taking 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, 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) taking 1g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, 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) taking 2g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, 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) taking 3g poriferous titanium dioxide/antibacterial powder complex to be scattered in 150ml 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, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to CNT is at 8 DEG C Having hydrophilic time neighbouring, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity being driven away by hydrone and leaves behind poriferous titanium dioxide/antibacterial powder complex and adsorb at carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial powder complex is scraped off this base Plate, 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；Without photochromic complex and anion complex.

Comparative example 2

Preparation method based on embodiment 5, difference is: described antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；Described photochromic complex is MoO3 nano powder；Described anion complex is anion powder, by 8% coral fossil, 12% Tourmaline, 25% opal, 4% serpentine, 7% Maifanitum, 4% rare ice stone, 4% hokutolite, 3% doctor Wang Shi, 8% shell, 12% diatom Soil, 2% iron sesquioxide, 3% aluminium sesquioxide, 5% zirconium oxide and 3% zirconium phosphate mix homogeneously, add in grinding equipment and surpass Finely divided, until particle diameter distribution is at 50 ~ 80nm, sieve, be dried, can be prepared by described anion powder.

The ceramic ink preparing embodiment 1 ~ 8 and comparative example 1,2 carries out performance test, test result display ink viscosity Being 15 ~ 30mPa 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, obtained ceramic tile marble lines is accurate with print pattern para-position, and lines effect is true to nature.

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: the abrasive material selecting Mohs' hardness to be 3～4, rubs spraying and burn till on the ceramic tile of ceramic ink Imitate the effect after paving uses 2 years for 1000 times.

Antifouling test: selection chrome green is pollutant.

Sterilizing Evaluation for Uniformity: spray at same and burn till and choose 100 regions on the ceramic tile of ceramic ink and carry out Sterilizing is tested, and the data recorded is carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When uniformly Degree is more than 97%, then be labeled as ▲；When the uniformity is more than 90% and less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then mark It is designated as.

Anion burst size: use Japan to produce COM-3010PRO type ion detector test anion burst size, will spraying And the ceramic tile burning till ceramic ink is positioned over 1m³Test box (length is 1m) in, record air in air bear from Sub-concentration (initial and 24h)；Use the test of Han Wang M1 type haze table, PM2.5 concentration (initial and 24h) in test box；At test box Interior dropping 0.1mg formaldehyde (concentration of formaldehyde 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. a preparation method for the anti-bacteria ceramic ink-jet ink of marble crack effect, it comprises the following steps:

The preparation method of the anti-bacteria ceramic ink-jet ink of marble crack effect the most according to claim 1, its feature exists In, 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 preparation method of the anti-bacteria ceramic ink-jet ink of marble crack effect the most according to claim 2, its feature exists In, increase by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation and be scattered in aqueous solution, dropwise add Enter GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂'s Weight 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. a preparation method for the anti-bacteria ceramic ink-jet ink of marble crack effect, 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:

5. according to the preparation method of anti-bacteria ceramic ink-jet ink of the marble crack effect described in claim 5, 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 anti-bacteria ceramic ink-jet ink of the marble crack effect described in claim 1 or 4, its feature Being, 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% diatoms Soil, 1 ~ 3% iron sesquioxide, 2 ~ 5% aluminium sesquioxide, 3 ~ 8% zirconium oxides and 1 ~ 5% zirconium phosphate mix homogeneously, add grinding equipment In carry out superfine grinding, until particle diameter distribution is at 50 ~ 80nm, sieve, be dried, can be prepared by described anion powder.Take 5 ~ 10g anion powder is scattered in 100 ~ 200ml ultra-pure water, and water bath sonicator 1 ~ 2h obtains the most even stable dispersion liquid；To have When the substrate of carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around rolling Wheel, makes this homogeneous dispersion be scattered in this carbon nanotube mesh film, owing to there is hydrophilic when CNT is near 8 DEG C, This dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；Being warming up to about 25 DEG C, CNT has hydrophobicity and incites somebody to action Hydrone is driven away and is left behind anion powder absorption in multiple net holes of carbon nanotube mesh film；After drying, will be adsorbed with bear from The carbon nanotube mesh film of sub-powder scrapes off this substrate, it is thus achieved that anion powder/CNT.

7. according to the preparation method of the anti-bacteria ceramic ink-jet ink of the marble crack effect described in claim 1 or 4, its feature Being, described photochromic complex preparation method is as follows: under nitrogen environment, is the Bronsted acid of 0.05 ~ 0.5mol/L by concentration Solution and the DBSA that concentration is 0.05 ~ 0.5mol/L mix with volume ratio 3:1 ~ 3, are simultaneously introduced photochromic Powder, adds aniline after magnetic agitation 60 ~ 120min, photochromic powder and aniline mass ratio are 1:5 ~ 10；Continuously stirred 60 ~ After 90min, dropwise dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Third Ketone, deionized water wash final vacuum for several times is dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nanometer is gathered Aniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1, stirring afterwards Adding tetraethyl orthosilicate after Jun Yun, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged also Clean with acetone and deionized water successively and obtain precipitation；This precipitation is dried, compound to obtain nano polyaniline/photochromic powder Thing/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂Be placed under argon gas atmosphere carry out 800 ~ 1000 DEG C of heat treatments 1 ~ 2h, removes polyaniline, photochromic powder/porous SiO₂, the most photochromic complex.

8. the anti-bacteria ceramic ink-jet ink of a marble crack effect, it is characterised in that it is by mass percentage by following One-tenth is grouped into: 40 ~ 50% infiltration powder body, 2 ~ 8% hyper-dispersants, 1 ~ 4% regulator, 0.01 ~ 0.3% defoamer, 0.1 ~ 2% non-proliferation Agent, 0.1 ~ 5% antibiotic complex, 1 ~ 5% anion complex and 0.3 ~ 4% photochromic complex, surplus is solvent.