CN106349813A - Deodorant aqueous UV light curing ceramics ink-jet ink and preparing method thereof - Google Patents
Deodorant aqueous UV light curing ceramics ink-jet ink and preparing method thereof Download PDFInfo
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- CN106349813A CN106349813A CN201610748978.5A CN201610748978A CN106349813A CN 106349813 A CN106349813 A CN 106349813A CN 201610748978 A CN201610748978 A CN 201610748978A CN 106349813 A CN106349813 A CN 106349813A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention discloses deodorant aqueous UV light curing ceramics ink-jet ink and a preparing method thereof. Thepreparing method comprises the following steps of: step A, after mixing 20-30%of water-based acrylate, 1-20% of solvent and 0.5-3% of ink assistant completely, stirring the mixture and adding 20-38% of ceramic pigment, dispersing the mixture, adding 10-20% of water-base epoxy acrylate and 1-5% of deodorant to be mixed uniformly; adding 0-5% of antimicrobial composite to be mixed uniformly,obtaining the mixed materials; step B, grinding and dispersing the mixed material until the fineness is lower than 1um; step C, adding 0.5-4% of water-soluble photoinitiator to be uniformly dispersed, and then obtaining the finished product. Compared with the current curing ceramics ink-jet ink, the ink provided in the invention has scientific burdening, rational preparation and stable performance without toxic and stimulation; the deodorant and the antibacterial composites have synergistic effect, lasting antibacterial property, anti-fouling and self-cleaning function and deodorant features; and the application range of the curing ceramics ink-jet ink is further widened.
Description
Technical field
The present invention relates to ceramic technology field, a kind of more particularly to deodorization aqueouss uv photocuring ceramic ink jet ink
And preparation method thereof.
Background technology
Antibacterial, mycete has very big harm as pathogen to the mankind and animals and plants, and the health of impact people even jeopardizes life
Life, brings great economic loss.The research of therefore anti-biotic material and its product increasingly causes the concern of people, antibacterial product
Demand will constitute huge market.
Wall brick, no matter household interior decoration, or it is used for commercial production or public place, after meeting outward appearance practicality,
How to make it possess more functions of concerning health of people guarantee aspect, be also that industry researcher is kept up with the trend of the times and given 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 currently used for the UV curable ink of ceramic ink jet, some reactive diluents, to human body
Zest larger, to producing and being all likely to result in allergy using the human body of ink or burn, need careful use, Er Qietao
The general storage of the UV curable ink of porcelain ink-jet and useful life be not long.And, also it is rarely reported specific function type light at present
Solidification ceramic ink, particularly multifunctional light solidification ceramic ink jet ink is so as to application is subject to larger limitation.
Content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of deodorization aqueouss uv photocuring ceramic ink jet is oily
Ink and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of deodorization aqueouss uv photocuring ceramic ink jet ink and preparation method thereof, this preparation method comprises the following steps:
Step a, first will be fully mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent
After conjunction, add 20 ~ 38% ceramic pigments in high-speed stirred, then rotating speed doubles, dispersion 30 ~ 60min, adds at a high speed
10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial to be combined
Thing, continues high-speed stirred to mix homogeneously, obtains 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, obtain uv photocuring ceramic ink jet ink
Finished product.
In the present invention, described deodoriser preparing process is as follows: mixes the raw material of following percentage by weight: zro21~
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 in sand mill, carry out sand milling, control particle diameter
Between 10 ~ 500nm, prepared 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 to put into dispersion dispergation in ball mill, and after discharge, detection, adjustment are 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 be obtained 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
Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead
Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain
Graphene quantum dot (gqds) suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, swashs
Photoirradiation power is 0.5 ~ 2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus
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, adjust ph value to 11, then standing, from
The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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 to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8ml mass fraction is 50%, 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), adjust
Ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Carry out being centrifuged and being cleaned with acetone and deionized water successively
Obtain precipitation；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, 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
In fluoric acid, ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150w, remove surface local silicon dioxide, be centrifuged and be dried, obtain
Antibacterial powder；
(5), under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is the ten of 0.05 ~ 0.5mol/l
Dialkyl benzene sulfonic acids are mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca 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 are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
(6) prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mix homogeneously；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(7) will be fully mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes
Close, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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
Warm 1 ~ 2h；Film is scraped off this substrate, obtains antibiotic complex.
It is preferred that increasing by a step between step (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation to 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 than for 1:1 ~ 5；Ultrasonic 60 ~ the 120min of 10 ~ 100w, standing, 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 be obtained 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
Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead
Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain
Graphene quantum dot (gqds) suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, swashs
Photoirradiation power is 0.5 ~ 2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus
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, adjust ph value to 11, then standing, from
The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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, standing, filter, be washed with deionized for several times,
Vacuum drying, obtains gqds/ag2O/zno antibacterial powder；
(4), under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is the ten of 0.05 ~ 0.5mol/l
Dialkyl benzene sulfonic acids are mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca 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 are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
(5) prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mix homogeneously；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(6) will be fully mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes
Close, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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
Warm 1 ~ 2h；Film is scraped off this substrate, obtains antibiotic complex.
It is preferred that increasing by a step between step (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation to 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, standing, deionized water wash for several times, dry 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 aqueouss benzoin derivatives, aqueouss
The cracking type light such as acetophenone derivs, aqueouss alpha-alcohol ketone derivant, aqueouss α-amido ketone derivatives, aqueouss acylphosphine oxide
Initiator system or aqueouss benzophenone derivates, aqueouss thia anthracyclinone derivatives, aqueouss anthraquinone derivative are combined with reactive amines
One or more of 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 one of defoamer, levelling agent, anti-settling agent and dispersant ink addition agent or one kind
Above mixed ink auxiliary agent.Described dispersant is water solublity and oil-soluble high score subclass, polyacrylic acid and copolymer, benzoic acid
And its any one of derivant.The trade name that dispersant can include include byk161, byk163, byk164, byk168,
Efka4310, efka 4400, efka4401, nuosperse fx9086, solsperse 24000, tego710, tego671,
But not limited to this.Described levelling agent be polyether modified siloxane, the trade name that levelling agent can include include byk306,
Byk333, levaslip 8629, but not limited to this.Defoamer is the polymer-type defoamer without organosilicon, and defoamer is permissible
The trade name including includes byk051, byk052, but not limited to this.Anti-settling agent is polyamide wax, in oxidic polyethylene extremely
Few one kind, the trade name that anti-settling agent can include 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.
The invention has the following beneficial effects: this method loads and fixing antibacterial in carbon nano net, not only prevent it
Reunite, significantly improve the stability of the antibacterial such as metal nanoparticle so as to can more preferably be dispersed in ceramic ink jet ink, and have
There are more efficient antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antibacterial simultaneously,
There is more preferable antibacterial effect compared to single silver nano antibacterial agent, antibacterial is lasting；Inorganic oxide main component have magnesium,
More than 10 kind of aluminum, ferrum etc. trace element favourable to human body, because it is a kind of special polarity crystalline solid of structure, itself can grow
Phase produces electron ion, and forever discharges negative aeroion, reaches the effect of deodorization purify air.With existing photocuring ceramic ink jet
Ink is compared, the ink formulations science that the present invention manufactures, preparation rationally, stable performance, nontoxic do not stimulate, preferably control ink
Viscosity and mobility, make ink printing when show preferable performance；Simultaneously through rational deodorizer and the antibacterial of arranging in pairs or groups
Composite, both synergism, make ceramic ink also have lasting antibacterial characteristics, antifouling self-cleaning function and deodorization
Characteristic, has widened the range of application of photocuring ceramic ink jet ink further.
Specific embodiment
To further illustrate technical scheme below by specific preferred implementation.For convenience of description,
All using black pigment as ceramic pigment, but those skilled in the art are readily apparent that following examples, and spendable colorant is not
It is confined to this.
Embodiment 1
A kind of deodorization aqueouss 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) be sufficiently mixed through high speed dispersor after, side high-speed stirred
Side adds 38% ceramic black colorant, and then rotating speed doubles, and dispersion about 60min, adds 18% water-base epoxy propylene at a high speed
Acid esters and 1% deodorizer, continue high-speed stirred to mix homogeneously；Add 1% antibiotic complex, continue high-speed stirred equal to mixing
Even, obtain 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% aqueouss alpha-alcohol ketone derivant, agitated be uniformly dispersed after, obtain uv photocuring ceramic ink jet ink
Finished product.
Wherein, described deodoriser preparing process is as follows: mixes the raw material of following percentage by weight: zro25%, tio210%,
sio216%, v2o54%, k2O 3%, sno22%, cr2o32%, al2o313%, fe2o312%, mgo 18%, na2O 8%, mno2
7%, carry out sand milling in the big flow circulation horizontal sand mill putting into the exploitation of puhler company, control particle diameter 10 ~ 500nm it
Between, prepared 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, and after discharge, detection, adjustment are configured to the slurry that can apply；This slurry is applied
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 antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic to be stirred
Mix, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass to divide
The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain
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), adjust ph value for 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will
This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put
Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w
Sound 10min, removes surface local silicon dioxide, is centrifuged and is dried, obtains antibacterial powder；
(5) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(6) prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti-
Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
(7) 30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 2
A kind of deodorization aqueouss 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) be sufficiently mixed through high speed dispersor after, side high-speed stirred
Side adds 31% ceramic black colorant, and then rotating speed doubles, and dispersion about 60min, adds 20% water-base epoxy propylene at a high speed
Acid esters and 3% deodorizer, continue high-speed stirred to mix homogeneously；Add 3% antibiotic complex, continue high-speed stirred equal to mixing
Even, obtain 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% aqueouss alpha-alcohol ketone derivant, agitated be uniformly dispersed after, obtain uv photocuring ceramic ink jet ink
Finished product.
Wherein, the preparation method of described deodorizer is as follows: mixes the raw material of following percentage by weight: zro25%, tio2
10%, sio216%, v2o54%, k2O 3%, sno22%, cr2o32%, al2o313%, fe2o312%, mgo 18%, na2O 8%,
mno27%, carry out sand milling in the big flow circulation horizontal sand mill putting into the exploitation of puhler company, control particle diameter 10 ~
Between 500nm, prepared inorganic oxide；36% epoxy resin, 40% phenolic resin and 24% inorganic oxide are sufficiently mixed, plus
Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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, described antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 2ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic to be stirred
Mix, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass to divide
The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain
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), adjust ph value for 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will
This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put
Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w
Sound 12min, removes surface local silicon dioxide, is centrifuged and is dried, obtains antibacterial powder；
(5) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(6) prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti-
Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
(7) 45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 3
A kind of deodorization aqueouss 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) be sufficiently mixed through high speed dispersor after, side high-speed stirred
Side adds 28% ceramic black colorant, and then rotating speed doubles, and dispersion about 60min, adds 13% water-base epoxy propylene at a high speed
Acid esters and 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 5% antibiotic complex, continue high-speed stirred equal to mixing
Even, obtain 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% aqueouss alpha-alcohol ketone derivant, agitated be uniformly dispersed after, obtain uv photocuring ceramic ink jet ink
Finished product.
Wherein, the preparation method of described deodorizer is as follows: mixes the raw material of following percentage by weight: zro25%, tio2
10%, sio216%, v2o54%, k2O 3%, sno22%, cr2o32%, al2o313%, fe2o312%, mgo 18%, na2O 8%,
mno27%, carry out sand milling in the big flow circulation horizontal sand mill putting into the exploitation of puhler company, control particle diameter 10 ~
Between 500nm, prepared inorganic oxide；40% epoxy resin, 30% phenolic resin and 30% inorganic oxide are sufficiently mixed, plus
Enter appropriate butyl acetate and put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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, antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 3ggqds/ag2O 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；Continue ultrasonic agitation, regulation mixed solution ph value to 7.0；Side is ultrasonic
Stirring, side adds the hydrazine hydrate that 6ml mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45ml mass
Fraction is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain
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), adjust ph value for 9 ~
10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will
This is deposited in and 3h is dried at 90 DEG C, to obtain gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2Put
Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in Fluohydric acid. and surpassed with ultrasonic power 100w
Sound 15min, removes surface local silicon dioxide, is centrifuged and is dried, obtains antibacterial powder；
(5) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(6) prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/
Antibacterial flour complexes, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained complex after milling
Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(7) 40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 4
Based on the preparation method of embodiment 2, difference is: increases 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 than for 1:3；The ultrasonic 90min of 50w, standing, deionized water
Washing for several times, dry gqds/ag2o/ag-zn-ce/sio2/ Graphene antibiosis powder.
Three-dimensional sponge shape graphene preparation method is as follows: by 3g graphite 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 to go
Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% h2o2 with unnecessary kmno4,
The color of mixed solution is brown color, filtered while hot, and deionized water cyclic washing obtains go to neutrality, ultrasonic disperse；Take
200ml mass fraction is that the graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, 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
Based on the preparation method of embodiment 1, difference is: described antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 1ggqds/ag2O 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, standing, filter, be washed with deionized for several times, vacuum drying,
Obtain gqds/ag2O/zno antibacterial powder；
(4) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:18 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(5) prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti-
Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
(6) 30% epoxy resin, 50% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 6
Based on the preparation method of embodiment 2, difference is: described antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 2ggqds/ag2O 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, standing, filter, be washed with deionized for several times, vacuum drying,
Obtain gqds/ag2O/zno antibacterial powder；
(4) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:15 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(5) prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti-
Mycopowder complex, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained complex after milling
1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；
(6) 45% epoxy resin, 35% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 7
Based on the preparation method of embodiment 3, difference is: described antibiotic complex is obtained 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
Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder,
Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add
Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot (gqds) and hang
Supernatant liquid；100rpm speed stirs gqds suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1w；Standby；
(2) ultrasonic agitation 60mlgqds suspension, Deca 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；It is added dropwise over 1mol/l sodium hydroxide solution, regulation ph value to 11, then standing, centrifugation, deionized water and ethanol
Alternately washing three times, vacuum drying, obtain gqds/ag2o；
(3) take 3ggqds/ag2O 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, standing, filter, be washed with deionized for several times, vacuum drying,
Obtain gqds/ag2O/zno antibacterial powder；
(4) under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/l for the protonic acid solution and concentration for 0.2mol/l for the concentration
Acid, with the mixing of volume ratio 3:2, is simultaneously introduced the antibacterial powder that step (4) is obtained, and adds aniline, antibacterial powder after magnetic agitation 100min
After being the continuously stirred 90min of 2:12 with aniline mass ratio, dropwise Deca 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 are vacuum dried for several times afterwards, mill nano polyaniline/antibacterial powder is multiple
Compound；
(5) prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/
Antibacterial flour complexes, mix homogeneously；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained complex after milling
Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(6) 40% epoxy resin, 40% phenolic resin and 20% poriferous titanium dioxide/antibacterial flour complexes are sufficiently mixed, add suitable
The butyl acetate of amount puts into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to the slurry that can 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, obtain antibiotic complex.
Embodiment 8
Based on the preparation method of embodiment 6, difference is: increases 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
Black alkene and gqds/ag2The weight of o/zno is than for 1:3；The ultrasonic 90min of 50w, standing, deionized water wash is for several times, dry
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 to go
Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% h2o2 with unnecessary kmno4,
The color of mixed solution is brown color, filtered while hot, and deionized water cyclic washing obtains go to neutrality, ultrasonic disperse；Take
200ml mass fraction is that the graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, 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
Based on the preparation method of embodiment 1, difference is: described antibiotic complex is the titanium dioxide carrying metal antibacterial agent
Titanium；It is not added with deodorizer.
Comparative example 2
Based on the preparation method of embodiment 5, difference is: described antibiotic complex is the mixing of zinc oxide and titanium dioxide
Thing；Described deodorizer is inorganic oxide, is obtained by the following method: mixes the raw material of following percentage by weight: zro25%,
tio210%, sio216%, v2o54%, k2O 3%, sno22%, cr2o32%, al2o313%, fe2o312%, mgo 18%,
na2O 8%, mno27%, carry out sand milling in the big flow circulation horizontal sand mill putting into the exploitation of puhler company, control particle diameter
Between 10 ~ 500nm, prepared inorganic oxide.
Embodiment 1 ~ 8 and comparative example 1,2 are carried out performance test, test result is as follows:
Sterilization rate: qualitatively check the antibacterial effect of ceramic ink jet ink using inhibition zone method, the strain of employing is golden yellow Portugal
Grape coccus and escherichia coli.
Wear testing: the abrasive material being 3～4 from Mohs' hardness, rubs on the cured layer being formed by this ceramic ink jet ink
Wipe 1000 times to imitate the effect after paving uses 2 years.
Heat stability testing: place 10h under the conditions of ceramic ink jet ink is placed in 60 DEG C.
Antifouling test: be pollutant from chrome green.
Sterilizing Evaluation for Uniformity: after same ceramic ink jet ink is sprayed in whole piece pottery test piece and solidifies, choose
100 regions carry out sterilizing test, carry out Uniformity Analysis to the data recording, by the uniformity=100* (1- standard deviation/
Meansigma methodss).When the uniformity is more than 97%, then be labeled as ▲；When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When uniform
Degree is less than 90%, then be labeled as.
Deodorizing test: prepare two 51pvf resin airbags, an air bag is put into one piece of sample print, another tree
Fat air bag not setting-out piece.Then it is blown into 500ppmnh3- air gas mixture in two air bags respectively and seals, make after 60min
Measure the concentration of nh3 in air bag with gas detecting tube, calculate deodorizing rate.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (7)
1. a kind of preparation method of deodorization aqueouss uv photocuring ceramic ink jet ink, it comprises the following steps:
Step a, first will be fully mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent
After conjunction, add 20 ~ 38% ceramic pigments in high-speed stirred, then rotating speed doubles, dispersion 30 ~ 60min, adds at a high speed
10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial to be combined
Thing, continues high-speed stirred to mix homogeneously, obtains 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, obtain uv photocuring ceramic ink jet ink
Finished product.
2. the preparation method of deodorization aqueouss uv photocuring ceramic ink jet ink according to claim 1 is it is characterised in that institute
The preparation method stating 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
Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead
Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain
Gqds suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is
0.5~2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus
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, adjusts ph value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain
gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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 to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8ml mass fraction is 50%, 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, adjust ph value be 9 ~ 10, reaction temperature be 20 ~ 25 DEG C, react 30 ~ 60min；Carry out
Centrifugation simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, to obtain
gqds/ag2o/ag-zn-ce/sio2；By gqds/ag2o/ag-zn-ce/sio2It is placed under argon gas atmosphere and carry out 500 ~ 800 DEG C of heat
Process 1 ~ 2h, after being cooled to room temperature, be immersed in Fluohydric acid. and ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150w, remove table
Face local silicon dioxide, is centrifuged and is dried, obtain antibacterial powder；
(5), under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is the ten of 0.05 ~ 0.5mol/l
Dialkyl benzene sulfonic acids are mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca 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 are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
(6) prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mix homogeneously；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(7) will be fully mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes
Close, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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
Warm 1 ~ 2h；Film is scraped off this substrate, obtains antibiotic complex.
3. the preparation method of deodorization aqueouss uv photocuring ceramic ink jet ink according to claim 2 is it is characterised in that walk
Suddenly increase by a step between (4) and (5): take three-dimensional sponge shape Graphene ultrasonic agitation to 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, standing, deionized water wash for several times, dry gqds/ag2o/ag-zn-
ce/sio2/ Graphene antibiosis powder.
4. a kind of preparation method of deodorization aqueouss uv photocuring ceramic ink jet ink, it comprises the following steps:
Step a, first will be fully mixed through high speed dispersor to 20 ~ 30% water-and acrylates, 1 ~ 20% solvent and 0.5 ~ 3% ink addition agent
After conjunction, add 20 ~ 38% ceramic pigments in high-speed stirred, then rotating speed doubles, dispersion 30 ~ 60min, adds at a high speed
10 ~ 20% waterborne epoxy acrylates and 1 ~ 5% deodorizer, continue high-speed stirred to mix homogeneously；Add 0 ~ 5% antibacterial to be combined
Thing, continues high-speed stirred to mix homogeneously, obtains 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, obtain 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
Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high
Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead
Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain
Gqds suspension；100 ~ 150rpm speed stirs gqds suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is
0.5~2w；Standby；
(2) ultrasonic agitation 50 ~ 60mlgqds suspension, Deca concentration is 0.001 ~ 0.01mol/l silver nitrate aqueous solution；Dropwise plus
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, adjusts ph value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain
gqds/ag2o；
(3) take 1 ~ 3ggqds/ag2O 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, standing, filter, be washed with deionized for several times,
Vacuum drying, obtains gqds/ag2O/zno antibacterial powder；
(4), under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is the ten of 0.05 ~ 0.5mol/l
Dialkyl benzene sulfonic acids are mixed with volume ratio 2 ~ 4:2, are simultaneously introduced the antibacterial powder that step (4) is obtained, after magnetic agitation 60 ~ 120min
Add aniline, antibacterial powder and aniline mass ratio are 2:12 ~ 18；After continuously stirred 60 ~ 90min, dropwise Deca 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 are vacuum dried for several times afterwards,
Mill to obtain nano polyaniline/antibacterial flour complexes；
(5) prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol
Amine/antibacterial flour complexes, mix homogeneously；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple
Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；
(6) will be fully mixed to 30 ~ 45% epoxy resin, 35 ~ 50% phenolic resin and 8 ~ 20% poriferous titanium dioxides/antibacterial flour complexes
Close, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to the slurry that can 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
Warm 1 ~ 2h；Film is scraped off this substrate, obtains antibiotic complex.
5. the preparation method of deodorization aqueouss uv photocuring ceramic ink jet ink according to claim 4 is it is characterised in that walk
Suddenly increase by a step between (3) and (4): take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in aqueous solution, be added dropwise over
gqds/ag2In o/zno aqueous solution, three-dimensional sponge shape Graphene and gqds/ag2The weight of o/zno is than for 1:1 ~ 5；10 ~ 100w surpasses
Sound 60 ~ 120min, standing, deionized water wash for several times, dry gqds/ag2O/zno/ Graphene antibiosis powder.
6. the preparation method of the deodorization aqueouss uv photocuring ceramic ink jet ink according to 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%, put into and in sand mill, carry out sand milling, control particle diameter between 10 ~ 500nm, be obtained no
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, and after discharge, detection, adjustment are configured to the slurry that can apply；This slurry is applied
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.
7. a kind of deodorization aqueouss uv photocuring ceramic ink jet ink, it contains the component of following percentage by weight: 10 ~ 20% aqueouss
Epoxy acrylate, 20 ~ 30% water-and acrylates, 0.5 ~ 4% water-soluble photoinitiator, 20 ~ 38% ceramic pigments, 1 ~ 20% solvent,
0.5 ~ 3% ink addition agent, 1 ~ 5% deodorizer and 0 ~ 5% antibiotic complex.
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