CN106084999A - A kind of preparation method of water solublity deodorization ink - Google Patents
A kind of preparation method of water solublity deodorization ink Download PDFInfo
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- CN106084999A CN106084999A CN201610748844.3A CN201610748844A CN106084999A CN 106084999 A CN106084999 A CN 106084999A CN 201610748844 A CN201610748844 A CN 201610748844A CN 106084999 A CN106084999 A CN 106084999A
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- quantum dot
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- kieselguhr
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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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses the preparation method of a kind of water solublity deodorization ink, it comprises the following steps: (1) prepares kieselguhr/antibiotic complex；(2) in container, add styrene-acrylic emulsion, drip kieselguhr/antibiotic complex aqueous solution while stirring；Stir to obtain antibacterial dispersion liquid；(3) in container, add EVA emulsion, drip kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring 30 ~ 60min, prepare except formaldehyde dispersion liquid；(4) mix antibacterial dispersion liquid and except formaldehyde dispersion liquid, add in deionized water, alcohol ester 12, PE water-borne wax, varnish, aqueous levelling agent, aqueous defoamer, nonionic surfactant input Scattered Kettle, stirring, prepare water solublity deodorization ink.The present invention is through kieselguhr/antimicrobial composite material and the kieselguhr/inorganic oxide of reasonably arranging in pairs or groups, synergism between functional additive, make ink have excellent antibacterial and anti-formaldehyde and deodorization properties, meet multi-functional demand, widen the application of ink further.
Description
Technical field
The present invention relates to technical field of ink, particularly relate to the preparation method of a kind of water solublity deodorization ink.
Background technology
Ink is the important materials for packaging material printing, and it is by printing by pattern, literal table the most on the substrate
Ink includes main component and auxiliary element, and they mix equably and form a kind of viscosity colloidal fluid through repeat-rolling.
It is made up of pigment, link stuff and auxiliary agent etc..For various printings such as books and periodicals, packing and decorating, building decorations.Along with social need increases
Greatly, ink kind and yield also respective extension and growth.But the function singleness of tradition ink, can not meet the polynary need of people
Ask.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of water solublity deodorization ink.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of water solublity deodorization ink, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, ultrasonic agitation limit, limit dropping 3 ~ 8mL concentration is 0.001 ~ 0.01mol/L
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) under 30 ~ 40 DEG C of temperature conditionss, in container add 25 ~ 30 parts of styrene-acrylic emulsions, 800 ~ 1200rpm stirring 30 ~
60min；Dropping concentration is 0.1 ~ 3g/L kieselguhr/antibiotic complex aqueous solution while stirring；Continue stirring 30 ~ 60min, prepare
Antibacterial dispersion liquid；
(3) under 30 ~ 40 DEG C of temperature conditionss, in container add 10 ~ 12 parts of EVA emulsions, 800 ~ 1200rpm stirring 30 ~
60min；Dropping concentration is 0.1 ~ 3g/L kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring 30 ~ 60min, add
1 ~ 3 part of anophelifuge granule；Continue stirring 30 ~ 60min, prepare anophelifuge deodorization dispersion liquid；Described kieselguhr/inorganic oxide preparation side
Method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2
3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, put into the exploitation of PUHLER company
Big flow circulation horizontal sand mill is ground, controls particle diameter between 10 ~ 300nm；Kieselguhr is dispersed in the water of 120ml
In solution, adding inorganic oxide, the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h, allows nano material well into kieselguhr hole
In gap, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr and the weight ratio of inorganic oxide
It is 1 ~ 2:5；
(4) under 30 ~ 40 DEG C of temperature conditionss, mix antibacterial dispersion liquid and anophelifuge deodorization dispersion liquid by 1:1 volume ratio, and add
15 ~ 20 parts of deionized waters, 1 ~ 5 part of alcohol ester-12,3 ~ 5 parts of PE water-borne wax, 1 ~ 2 part of varnish, 1 ~ 3 part of aqueous levelling agent, 0.5 ~ 2
Part aqueous defoamer, 0.1 ~ 1 portion of nonionic surfactant put in Scattered Kettle, and 800 ~ 1200rpm stirs 60 ~ 90min, prepares
Water solublity antibacterial ink.
Styrene-acrylic emulsion uses the styrene-acrylic emulsion of the HYDRO-REZ 1830 of Lauth OY of the U.S.；EVA emulsion uses Guangzhou
The EVA707 of Qi Sheng Chemical trade company limited；PE water-borne wax uses the PE water-borne wax of the Aquatec4101 of Lauth OY of the U.S.；
Aqueous levelling agent uses the aqueous levelling agent of the 455 of TaiWan, China De Qian company；Aqueous defoamer uses the modest public affairs of TaiWan, China moral
The aqueous defoamer of the 0506 of department.
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2
The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic merit of 500 ~ 1000W
Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide,
Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti-
Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes Nano silver grain and zinc oxide have more efficient
Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously
Agent has a more preferable antibacterial effect, antibacterial persistently；
The inorganic oxide main component that the present invention uses has more than the 10 kind of trace element favourable to human body such as magnesium, aluminum, ferrum, by
Being the special polarity crystalline solid of a kind of structure in it, self can produce electron ion for a long time, and forever discharge negative aeroion, reach
Deodorization purifies the effect of air.After being ground by inorganic oxide and be immersed in inside kieselguhr, can effectively improve it stable
Property, kieselguhr can also adsorb harmful gas particularly formaldehyde in air simultaneously, improves the effect purifying air further；
The present invention is through kieselguhr/antimicrobial composite material and the kieselguhr/inorganic oxide of reasonably arranging in pairs or groups, between functional additive
Synergism so that ink has excellent antibacterial and anti-formaldehyde and deodorization properties, meets multi-functional demand, widens further
The application of ink.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
Photoirradiation power is 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, dropping step (1) prepare one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.1g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot that surface processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves
To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g C60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash
Photoirradiation power is 1W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water；
Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that dropping step (1) prepares
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide
Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined
In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
110 DEG C, after reaction 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide
Graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load silver/titanium dioxide Graphene
Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~
6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan
Base sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, dropping concentration is
0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium,
Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, MIC) method of testing (Xiang Cai, Shaozao Tan, Aili Yu,
Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.Chemistry-An Asian Journal. 2012,7 (7): 1664-1670.), first weigh with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute
Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL,
Then shaken cultivation 24h at 37 DEG C, observes its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite material
Embodiment 4
A kind of preparation method of water solublity antibacterial ink, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 3 parts of kieselguhr, ultrasonic agitation limit, limit dropping 5mL concentration is 0.006ol/L's
Embodiment 2 antibiotic complex aqueous dispersions；Standing 90min, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) under 40 DEG C of temperature conditionss, in container, the phenylpropyl alcohol breast of the HYDRO-REZ 1830 of 30 parts of Lauth OY of the U.S. is added
Liquid, 1000rpm stirs 30min；Dropping concentration is 0.1g/L kieselguhr/antibiotic complex aqueous solution while stirring；Continue stirring
60min, prepares antibacterial dispersion liquid；
(3) under 40 DEG C of temperature conditionss, in container, the EVA707 of 10 parts of Guangzhou Qi Sheng Chemical trade company limiteies is added,
1000rpm stirs 30min；Dropping concentration is 3g/L kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring 60min,
Add 3 parts of anophelifuge granules；Continue stirring 60min, prepare anophelifuge deodorization dispersion liquid；
Described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2
8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%,
Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 300rpm of 200W stirs
Mixing 2h, allow nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein
Described kieselguhr is 2:5 with the weight ratio of inorganic oxide；
(4) under 40 DEG C of temperature conditionss, mix antibacterial dispersion liquid and anophelifuge deodorization dispersion liquid by 1:1 volume ratio, and add 20
Part deionized water, 3 parts of alcohol ester-12, the PE water-borne wax of Aquatec4101 of 4 parts of Lauth OY of the U.S., 1 part of varnish, in 2 parts
The aqueous levelling agent of the 455 of Taiwan De Qian company of state, 1 part of TaiWan, China De Qian company 0506 aqueous defoamer, 0.5 part non-
Ionic surface active agent puts in Scattered Kettle, and 1000rpm stirs 60min, prepares water solublity antibacterial ink.
Embodiment 5
A kind of preparation method of water solublity antibacterial ink, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 3 parts of kieselguhr, ultrasonic agitation limit, limit dropping 5mL concentration is 0.006mol/L's
Embodiment 2 antibiotic complex aqueous dispersions；Standing 90min, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) under 40 DEG C of temperature conditionss, in container, the phenylpropyl alcohol breast of the HYDRO-REZ 1830 of 30 parts of Lauth OY of the U.S. is added
Liquid, 1000rpm stirs 30min；Dropping concentration is 1.2g/L kieselguhr/antibiotic complex aqueous solution while stirring；Continue stirring
60min, prepares antibacterial dispersion liquid；
(3) under 40 DEG C of temperature conditionss, in container, the EVA707 of 10 parts of Guangzhou Qi Sheng Chemical trade company limiteies is added,
1000rpm stirs 30min；Dropping concentration is 1.5g/L kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring
60min, adds 3 parts of anophelifuge granules；Continue stirring 60min, prepare anophelifuge deodorization dispersion liquid；
Described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2
8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%,
Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 300rpm of 200W stirs
Mixing 2h, allow nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein
Described kieselguhr is 2:5 with the weight ratio of inorganic oxide；
(4) under 40 DEG C of temperature conditionss, mix antibacterial dispersion liquid and anophelifuge deodorization dispersion liquid by 1:1 volume ratio, and add 20
Part deionized water, 3 parts of alcohol ester-12, the PE water-borne wax of Aquatec4101 of 4 parts of Lauth OY of the U.S., 1 part of varnish, in 2 parts
The aqueous levelling agent of the 455 of Taiwan De Qian company of state, 1 part of TaiWan, China De Qian company 0506 aqueous defoamer, 0.5 part non-
Ionic surface active agent puts in Scattered Kettle, and 1000rpm stirs 60min, prepares water solublity antibacterial ink.
Embodiment 6
A kind of preparation method of water solublity antibacterial ink, it comprises the following steps:
(1) being dispersed in the aqueous solution of 120ml by 3 parts of kieselguhr, ultrasonic agitation limit, limit dropping 5mL concentration is 0.006mol/L's
Embodiment 2 antibiotic complex aqueous dispersions；Standing 90min, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) under 40 DEG C of temperature conditionss, in container, the phenylpropyl alcohol breast of the HYDRO-REZ 1830 of 30 parts of Lauth OY of the U.S. is added
Liquid, 1000rpm stirs 30min；Dropping concentration is 3g/L kieselguhr/antibiotic complex aqueous solution while stirring；Continue stirring
60min, prepares antibacterial dispersion liquid；
(3) under 40 DEG C of temperature conditionss, in container, the EVA707 of 10 parts of Guangzhou Qi Sheng Chemical trade company limiteies is added,
1000rpm stirs 30min；Dropping concentration is 0.5g/L kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring
60min, adds 3 parts of anophelifuge granules；Continue stirring 60min, prepare anophelifuge deodorization dispersion liquid；
Described kieselguhr/inorganic oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2
8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%,
Na2O8%, MnO2 7%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 300rpm of 200W stirs
Mixing 2h, allow nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein
Described kieselguhr is 2:5 with the weight ratio of inorganic oxide；
(4) under 40 DEG C of temperature conditionss, mix antibacterial dispersion liquid and anophelifuge deodorization dispersion liquid by 1:1 volume ratio, and add 20
Part deionized water, 3 parts of alcohol ester-12, the PE water-borne wax of Aquatec4101 of 4 parts of Lauth OY of the U.S., 1 part of varnish, in 2 parts
The aqueous levelling agent of the 455 of Taiwan De Qian company of state, 1 part of TaiWan, China De Qian company 0506 aqueous defoamer, 0.5 part non-
Ionic surface active agent puts in Scattered Kettle, and 1000rpm stirs 60min, prepares water solublity antibacterial ink.
Comparative example 3
Preparation method based on embodiment 6, difference is: be not added with antibiotic complex.
Comparative example 4
Preparation method based on embodiment 6, difference is: be not added with kieselguhr/inorganic oxide.
The key technical indexes of embodiment 4 ~ 6 and comparative example 3,4 is as follows:
Antibacterial Evaluation for Uniformity: be sprayed on by ink on glass or ceramic wafer, chooses 100 regions and carries out sterilizing test, to survey
The data obtained carry 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 the uniformity is less than 90%, then it is labeled as.
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 (7)
1. a preparation method for water solublity deodorization ink, it comprises the following steps:
(1) being scattered in aqueous solution by 2 ~ 5 parts of kieselguhr, ultrasonic agitation limit, limit dropping 3 ~ 8mL concentration is 0.001 ~ 0.01mol/L
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；
(2) under 30 ~ 40 DEG C of temperature conditionss, in container add 25 ~ 30 parts of styrene-acrylic emulsions, 800 ~ 1200rpm stirring 30 ~
60min；Dropping concentration is 0.1 ~ 3g/L kieselguhr/antibiotic complex aqueous solution while stirring；Continue stirring 30 ~ 60min, prepare
Antibacterial dispersion liquid；
(3) under 30 ~ 40 DEG C of temperature conditionss, in container add 10 ~ 12 parts of EVA emulsions, 800 ~ 1200rpm stirring 30 ~
60min；Dropping concentration is 0.1 ~ 3g/L kieselguhr/inorganic oxide aqueous solution while stirring；Continue stirring 30 ~ 60min, add
1 ~ 3 part of anophelifuge granule；Continue stirring 30 ~ 60min, prepare anophelifuge deodorization dispersion liquid；
(4) under 30 ~ 40 DEG C of temperature conditionss, mix antibacterial dispersion liquid and anophelifuge deodorization dispersion liquid by 1:1 volume ratio, and add
15 ~ 20 parts of deionized waters, 1 ~ 5 part of alcohol ester-12,3 ~ 5 parts of PE water-borne wax, 1 ~ 2 part of varnish, 1 ~ 3 part of aqueous levelling agent, 0.5 ~ 2
Part aqueous defoamer, 0.1 ~ 1 portion of nonionic surfactant put in Scattered Kettle, and 800 ~ 1200rpm stirs 60 ~ 90min, prepares
Water solublity antibacterial ink.
The preparation method of water solublity deodorization ink the most according to claim 1, it is characterised in that described kieselguhr/inorganic
Oxide preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%,
K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%, put into
The big flow circulation horizontal sand mill of PUHLER company exploitation is ground, controls particle diameter between 10 ~ 300nm；By diatom
Soil is dispersed in the aqueous solution of 120ml, adds inorganic oxide, and the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h, allows nanometer material
Expect that repeatedly sucking filtration cleans well in kieselguhr hole, be dried to obtain kieselguhr/inorganic oxide；Wherein said kieselguhr with
The weight ratio of inorganic oxide is 2:5.
The preparation method of water solublity deodorization ink the most according to claim 1, it is characterised in that described antibiotic complex leads to
Cross following methods to prepare:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of water solublity deodorization ink the most according to claim 3, it is characterised in that described graphene quantum dot
The preparation method of suspension is as follows: weigh 0.5 ~ 0.8g C60 powder, measures the concentrated sulphuric acid that 50 ~ 100ml mass fraction is 98%,
C60 powder and concentrated sulphuric acid being mixed in beaker, beaker is placed in ice-water bath, stirs with the speed of 300 ~ 500rpm simultaneously,
Mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, protect
Water holding bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, be then 1000 with molecular cut off
Bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, swashs simultaneously
Photoirradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of water solublity deodorization ink the most according to claim 3, it is characterised in that ink alkene is 2 ~ 5 layers, Kong great
Little about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of polylactic acid antibacterial matrices the most according to claim 5, it is characterised in that described load silver/titanium dioxide
The surface of titanium graphene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL, super
Sound stirs and adds 0.1 ~ 0.3g and carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, and moving to liner is
In the microwave hydrothermal reaction kettle of politef, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~
400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/titanium dioxide Graphene amount
Sub-point.
The preparation method of water solublity deodorization ink the most according to claim 3, it is characterised in that described load zinc oxide
The surface of graphene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL, ultrasonic
Stirring and add the graphene quantum dot of 0.1 ~ 0.3g load zinc oxide, continue ultrasonic agitation 10 ~ 30min, it is poly-for moving to liner
In the microwave hydrothermal reaction kettle of tetrafluoroethene, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W,
60 ~ 90min is reacted at 200 ~ 240 DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
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