CN106189504A - A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps: step A, first 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent are sufficiently mixed after, add 20 ~ 38% ceramic pigments while stirring, dispersion, add 10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, mix homogeneously；Add 0 ~ 5% antibiotic complex and 3 ~ 8% anion complex, mix homogeneously, it is thus achieved that mixed material；Step B, by mixed material grinding distribution, until fineness reaches less than 1 μm；Step C, addition 0.5 ~ 4% water-soluble photoinitiator, after being uniformly dispersed, obtain finished product.Comparing with existing photocuring ceramic ink jet ink, the ink formulations science that the present invention manufactures, preparation is rationally, stable performance, nontoxic do not stimulate, also there is lasting antibacterial characteristics, antifouling self-cleaning function, purify air characteristics, widened the range of application of photocuring ceramic ink jet ink further.

Description

A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof

Technical field

The present invention relates to ceramic technology field, particularly relate to a kind of environment-friendly type aqueous UV photocuring ceramic ink jet oil 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.

Wall brick, no matter household interior decoration, or for commercial production or public place, after meeting outward appearance practicality, How to make it possess more function concerned in terms of health of people guarantee, be also that industry researcher is kept up with the trend of the times and gives birth to Live wind vane and the thinking made.

In the building and ornament materials such as existing wall brick, ceramic ink jet ink receives more and more attention, particularly ultraviolet Light-curable ink.But, in the production of the UV curable ink being currently used for ceramic ink jet, some reactive diluents, to human body Zest relatively big, to producing and using the human body of ink be all likely to result in allergy or burn, need careful use, Er Qietao The UV curable ink of porcelain ink-jet is typically stored the longest with useful life.And, currently also rarely have report specific function type light Solidification ceramic ink, particularly multifunctional light solidification ceramic ink jet ink so that it is application is by bigger limitation.

Summary of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of environment-friendly type aqueous UV photocuring ceramic ink jet Ink and preparation method thereof.

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

A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps:

Step A, first by the most mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent After conjunction, high-speed stirred limit, limit adds 20 ~ 38% ceramic pigments, and then rotating speed doubles, high speed dispersion 30 ~ 60min, adds 10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial compound Thing and 3 ~ 8% anion complex, continue high-speed stirred to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 0.5 ~ 4% water-soluble photoinitiator, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product.

In the present invention, described anion complex preparation method is as follows: take 5 ~ 10g anion powder be scattered in 100 ~ In 200ml ultra-pure water, water bath sonicator 1 ~ 2h obtains the most even stable dispersion liquid；The substrate with carbon nanotube mesh film is put In about 8 DEG C time, dispersion liquid is added in the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in In this carbon nanotube mesh film, owing to having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to CNT Multiple net holes of reticular membrane；Being warming up to about 25 DEG C, CNT has hydrophobicity and is driven away by hydrone and leave behind anion powder Absorption is in multiple net holes of carbon nanotube mesh film；After drying, the carbon nanotube mesh film being adsorbed with anion powder is scraped off This substrate, obtains anion complex.

In the present invention, described deodoriser preparing process is as follows: mix the raw material of following percentage by weight: ZrO₂ 1~ 10%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 3%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 5 ~ 10%, MnO₂5 ~ 10%, put into and sand mill carries out sand milling, control particle diameter Between 10 ~ 500nm, prepare inorganic oxide；By 30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin and 20 ~ 30% inorganic oxides Thing is sufficiently mixed, and adds appropriate butyl acetate and puts in ball mill dispersion dispergation, after discharge, detect, adjust be configured to permissible The slurry of coating；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, it is warmed up to 900 ~ 1000 DEG C, it is incubated 1 ~ 2h；Film is scraped off this substrate, obtains deodorizer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, described water-soluble light trigger is water-soluble selected from the free radical type introducing hydrophilic anions group Property light trigger, or introduce hydrophilic cationic group free radical type water-soluble light trigger, or introduce Hydrophilic nonionic The free radical type water-soluble light trigger of group.Described water-soluble light trigger is further selected from aqueous benzoin derivatives, aqueous Acetophenone derivs, aqueous alpha-alcohol ketone derivant, aqueous α-cracking type light such as amido ketone derivatives, aqueous acylphosphine oxide Initiator system or aqueous benzophenone derivates, aqueous thia anthracyclinone derivatives, aqueous anthraquinone derivative and reactive amines combination One or more in hydrogen-abstraction light initiation system.

Described ceramic pigment is a kind of colorant or of redness, yellow, blueness, ecru, brown, white or black Plant above mixing colorant.

Described ink addition agent is a kind of ink addition agent in defoamer, levelling agent, anti-settling agent and dispersant or one Above mixed ink auxiliary agent.Described dispersant is water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid And any one of derivant.The trade name that dispersant can list include BYK161, BYK163, BYK164, BYK168, EFKA4310, EFKA 4400, EFKA4401, Nuosperse FX9086, Solsperse 24000, Tego710, Tego671, But it is not limited to this.Described levelling agent is polyether modified siloxane, the trade name that levelling agent can list include BYK306, BYK333, Levaslip 8629, but it is not limited to this.Defoamer is the polymer-type defoamer without organosilicon, and defoamer is permissible The trade name listed includes BYK051, BYK052, but is not limited to this.Anti-settling agent be in polyamide wax, oxidic polyethylene extremely Few one, the trade name that anti-settling agent can list includes Disparlon NS-5501, Disparlon 6650, but is not limited to This.

Described solvent is selected from ethylene glycol, propylene glycol, isopropanol, glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol list At least one in butyl ether.

There is advantages that this method loads in carbon nano net and fixes antibacterial, not only prevent it Reunite, significantly improve the stability of the antibacterial such as metal nanoparticle so that it is can more preferably be dispersed in ceramic ink jet ink, and tool There are more efficient antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antibacterial simultaneously, Have a more preferable antibacterial effect compared to single silver nano antibacterial agent, antibacterial persistently；Inorganic oxide main component have magnesium, The trace element that aluminum, ferrum etc. more than 10 kind is favourable to human body, owing to it is the special polarity crystalline solid of a kind of structure, self can grow Phase produces electron ion, and forever discharges negative aeroion, reaches deodorization and purifies the effect of air；Anion complex can the most not The anion releasing being interrupted, under having light or no light condition, the uninterrupted anion releasing of equal energy, effectively purifies air, decomposing formaldehyde Deng organic gas, improve IAQ (indoor air quality), also there is antibacterial effect, be of value to health.With existing photocuring pottery Jetted ink is compared, the ink formulations science that the present invention manufactures, preparation rationally, stable performance, nontoxic do not stimulate, preferably control The viscosity of ink and mobility, make ink show preferable performance when printing；Simultaneously through deodorizer of reasonably arranging in pairs or groups, bear Ion complex and antimicrobial composite material, the synergism of three, make ceramic ink have lasting antibacterial antifouling automatically cleaning merit And air characteristics can be purified, widened the range of application of photocuring ceramic ink jet ink further.

Detailed description of the invention

Technical scheme is further illustrated below by concrete preferred implementation.For convenience of description, Following example all use black pigment as ceramic pigment, but those skilled in the art are readily apparent that, spendable colorant is not It is confined to this.

Embodiment 1

A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps:

Step A, first by 20% water-and acrylate, 20% ethylene glycol and 1% ink addition agent (0.5%Nuosperse FX9086,0.1% Levaslip 8629,0.2%BYK052,0.3%Disparlon 6650) after high speed dispersor is sufficiently mixed, limit high-speed stirred While add 30% ceramic black colorant, then rotating speed doubles, high speed dispersion about 60min, adds 16% water-base epoxy propylene Acid esters and 1% deodorizer, continue high-speed stirred to mix homogeneously；Add 1% antibiotic complex and 10% anion complex, continue Continuous high-speed stirred is to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 1% aqueous alpha-alcohol ketone derivant, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product.

Wherein, described deodoriser preparing process is as follows: mix the raw material of following percentage by weight: ZrO₂5%, TiO₂10%, SiO₂16%, V₂O₅4%, K₂O 3%, SnO₂2%, Cr₂O₃2%, Al₂O₃13%, Fe₂O₃12%, MgO 18%, Na₂O 8%, MnO₂ 7%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and carry out sand milling, control particle diameter 10 ~ 500nm it Between, prepare inorganic oxide；30% epoxy resin, 50% phenolic resin and 20% inorganic oxide are sufficiently mixed, add appropriate Butyl acetate puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This slurry is coated with Spread on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 DEG C, be incubated 1h；Film is scraped off this base Plate, obtains inorganic oxide/holey carbon film.

Wherein, described anion complex preparation method is as follows: 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% kieselguhr, 2% iron sesquioxide, 3% 3 Al 2 O, 5% zirconium oxide and 3% 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 150ml 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, must bear from Sub-complex.

Wherein, described antibiotic complex prepares by the following method:

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

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

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

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

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

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

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

Embodiment 2

A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps:

Step A, first by 24% water-and acrylate, 15% ethylene glycol and 2% ink addition agent (0.5%Nuosperse FX9086,0.5% Levaslip 8629,0.5%BYK052,0.5%Disparlon 6650) after high speed dispersor is sufficiently mixed, limit high-speed stirred While add 25% ceramic black colorant, then rotating speed doubles, high speed dispersion about 60min, adds 20% water-base epoxy propylene Acid esters and 3% deodorizer, continue high-speed stirred to mix homogeneously；Add 3% antibiotic complex and 6% anion complex, continue High-speed stirred is to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 2% aqueous alpha-alcohol ketone derivant, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product.

Wherein, the preparation method of described deodorizer is as follows: mix the raw material of following percentage by weight: ZrO₂5%, TiO₂ 10%, SiO₂16%, V₂O₅4%, K₂O 3%, SnO₂2%, Cr₂O₃2%, Al₂O₃13%, Fe₂O₃12%, MgO 18%, Na₂O 8%, MnO₂ 7%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and carry out sand milling, control particle diameter 10 ~ Between 500nm, prepare inorganic oxide；36% epoxy resin, 40% phenolic resin and 24% inorganic oxide are sufficiently mixed, add Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detect, adjust the slurry being configured to apply；Will This slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 2h；By film Scrape off this substrate, obtain inorganic oxide/holey carbon film.

Wherein, the preparation method of described anion complex is as follows: 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% kieselguhr, 2% iron sesquioxide, 3% Aluminium sesquioxide, 5% zirconium oxide and 3% 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 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, 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, must bear from Sub-complex.

Wherein, described antibiotic complex prepares by the following method:

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

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

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

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

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

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

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

Embodiment 3

A kind of environment-friendly type aqueous UV photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps:

Step A, first by 30% water-and acrylate, 12% ethylene glycol and 3% ink addition agent (1%Nuosperse FX9086,0.3% Levaslip 8629,0.9%BYK052,0.8%Disparlon 6650) after high speed dispersor is sufficiently mixed, limit high-speed stirred While add 28% ceramic black colorant, then rotating speed doubles, high speed dispersion about 60min, adds 10% water-base epoxy propylene Acid esters and 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 5% antibiotic complex and 3% anion complex, continue High-speed stirred is to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 4% aqueous alpha-alcohol ketone derivant, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product.

Wherein, the preparation method of described deodorizer is as follows: mix the raw material of following percentage by weight: ZrO₂5%, TiO₂ 10%, SiO₂16%, V₂O₅4%, K₂O 3%, SnO₂2%, Cr₂O₃2%, Al₂O₃13%, Fe₂O₃12%, MgO 18%, Na₂O 8%, MnO₂ 7%, put in the big flow circulation horizontal sand mill of PUHLER company exploitation and carry out sand milling, control particle diameter 10 ~ Between 500nm, prepare inorganic oxide；40% epoxy resin, 30% phenolic resin and 30% inorganic oxide are sufficiently mixed, add Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detect, adjust the slurry being configured to apply；Will This slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 1000 DEG C, be incubated 1h；By film Scrape off this substrate, obtain inorganic oxide/holey carbon film.

Wherein, the preparation method of described anion complex is as follows: 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% kieselguhr, 2% iron sesquioxide, 3% Aluminium sesquioxide, 5% zirconium oxide and 3% 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 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, 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, must bear from Sub-complex.

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

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

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

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

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

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

Embodiment 4

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

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

Embodiment 5

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

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

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

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

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

Embodiment 6

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

(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 0.005mol/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 aqueous solution；Being added dropwise over concentration is 0.2g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

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

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

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

Embodiment 7

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

(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 0.01mol/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 aqueous solution；Being added dropwise over concentration is 0.05g/100mlZnO quantum dot Aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/ZnO antibacterial powder；

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

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

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

Embodiment 8

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

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.

Comparative example 1

Preparation method based on embodiment 1, difference is: described antibiotic complex is the titanium dioxide carrying metal antibacterial agent Titanium；It is not added with anion complex；The preparation method of described deodorizer 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 in the big flow circulation horizontal sand mill of PUHLER company exploitation and carry out sand milling, control particle diameter 10 ~ Between 500nm, prepare inorganic oxide, i.e. deodorizer.

Comparative example 2

Preparation method based on embodiment 5, difference is: described antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；It is not added with deodorizer；Described anion complex preparation method is as follows: by 5% coral fossil, 15% tourmaline, 20% albumen Stone, 5% serpentine, 5% Maifanitum, 1% rare ice stone, 5% hokutolite, 1% doctor Wang Shi, 10% shell, 15% kieselguhr, 3% 3 oxidation two Ferrum, 2% aluminium sesquioxide, 8% zirconium oxide and 5% zirconium phosphate mix homogeneously, add in grinding equipment and carry out superfine grinding, until Grain diameter Distribution, at 50 ~ 80nm, is sieved, and is dried,.

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

Sterilization rate: use inhibition zone method to check the antibacterial effect of ceramic ink jet ink qualitatively, the strain of employing is golden yellow Portugal Grape coccus and escherichia coli.

Wear testing: the abrasive material selecting Mohs' hardness to be 3～4, rubs on the cured layer formed by this ceramic ink jet ink Wipe and imitate the effect after paving uses 2 years for 1000 times.

Heat stability testing: place 10h under the conditions of ceramic ink jet ink is placed in 60 DEG C.

Antifouling test: selection chrome green is pollutant.

Sterilizing Evaluation for Uniformity: after same ceramic ink jet ink being sprayed in whole piece pottery test piece and solidifying, choose 100 regions carry out sterilizing test, and the data recorded are carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/ Meansigma methods).When the uniformity 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 uniformly Degree less than 90%, is then labeled as.

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

Deodorizing test: prepare two 51PVF resin airbags, put into one piece of sample print in an air bag, another tree Fat air bag not setting-out sheet.Then in two air bags, it is blown into 500ppmNH3-air gas mixture respectively and seals, making after 60min Measure the concentration of NH3 in air bag with gas detecting tube, calculate deodorization rate.

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 (8)

1. a preparation method for environment-friendly type aqueous UV photocuring ceramic ink jet ink, it comprises the following steps:

Step A, first by the most mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent After conjunction, high-speed stirred limit, limit adds 20 ~ 38% ceramic pigments, and then rotating speed doubles, high speed dispersion 30 ~ 60min, adds 10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial compound Thing and 3 ~ 8% anion complex, continue high-speed stirred to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 0.5 ~ 4% water-soluble photoinitiator, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product.

The preparation method of environment-friendly type aqueous UV photocuring ceramic ink jet ink the most according to claim 1, it is characterised in that The preparation method of described antibiotic complex is as follows:

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

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

(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, 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；

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

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

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

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

4. a preparation method for environment-friendly type aqueous UV photocuring ceramic ink jet ink, it comprises the following steps:

Step A, first by the most mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent After conjunction, high-speed stirred limit, limit adds 20 ~ 38% ceramic pigments, and then rotating speed doubles, high speed dispersion 30 ~ 60min, adds 10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial compound Thing and 3 ~ 8% anion complex, continue high-speed stirred to mix homogeneously, it is thus achieved that mixed material；

Step B, mixed material is first carried out preliminary sand milling dispersion through ball mill, then proceeds to the dispersion of sand mill further sand milling, Until the fineness of described ceramic pigment therein reaches less than 300nm；

Step C, add 0.5 ~ 4% water-soluble photoinitiator, agitated be uniformly dispersed after, it is thus achieved that UV photocuring ceramic ink jet ink Finished product；

Wherein, 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；

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

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

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

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

The preparation method of environment-friendly type aqueous UV photocuring ceramic ink jet ink the most according to claim 4, 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 environment-friendly type aqueous UV photocuring ceramic ink jet ink described in claim 1 or 4, its feature exists In, described deodoriser preparing process is as follows: mix the raw material of following percentage by weight: ZrO₂1 ~ 10%, TiO₂5 ~ 15%, SiO₂ 10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 3%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 5 ~ 10%, MnO₂5 ~ 10%, to put into and sand mill carries out sand milling, control particle diameter, between 10 ~ 500nm, prepares nothing Machine oxide；30 ~ 40% epoxy resin, 30 ~ 50% phenolic resin and 20 ~ 30% inorganic oxides are sufficiently mixed, add appropriate Butyl acetate puts into dispersion dispergation in ball mill, after discharge, detects, adjusts the slurry being configured to apply；This slurry is coated with Spread on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped From this substrate, obtain deodorizer.

The preparation method of environment-friendly type aqueous UV photocuring ceramic ink jet ink the most according to claim 6, it is characterised in that Described anion complex preparation method is as follows: takes 5 ~ 10g anion powder and is scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 1 ~ 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 In the substrate of concave shape, meanwhile, roll around roller, make this homogeneous dispersion be scattered in this carbon nanotube mesh film, by Having hydrophilic when CNT is near 8 DEG C, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；Heat up To about 25 DEG C, CNT has hydrophobicity being driven away by hydrone and leaves behind anion powder and adsorb at carbon nanotube mesh film In multiple net holes；After drying, the carbon nanotube mesh film being adsorbed with anion powder is scraped off this substrate, obtains anion complex.

8. an environment-friendly type aqueous UV photocuring ceramic ink jet ink, it contains the component of following percentage by weight: 10 ~ 20% water Property epoxy acrylate, 20 ~ 30% water-and acrylates, 0.5 ~ 4% water-soluble photoinitiator, 20 ~ 38% ceramic pigments, 1 ~ 20% molten Agent, 0.5 ~ 3% ink addition agent, 1 ~ 5% deodorizer and 0 ~ 5% antibiotic complex and 3 ~ 8% anion complex.