CN106318025A - Antibacterial gravure water-borne ink and preparing method thereof - Google Patents
Antibacterial gravure water-borne ink and preparing method thereof Download PDFInfo
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- CN106318025A CN106318025A CN201610748598.1A CN201610748598A CN106318025A CN 106318025 A CN106318025 A CN 106318025A CN 201610748598 A CN201610748598 A CN 201610748598A CN 106318025 A CN106318025 A CN 106318025A
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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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
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
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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
Abstract
The invention discloses an antibacterial gravure water-borne ink and a preparing method thereof. The ink is prepared from, by percentage of weight, 70-75% water soluble resin, 10-15% deionized water, 5-10% water-borne organic pigment, 3-6% ethyl alcohol, 0.5-1% kieselguhr/antibacterial composite, 1-2% dispersant, 0-1% drying retarder, 0.5-1% water-borne flatting agent, 0.5-1% water-borne wax emulsion, 0-1% kieselguhr/porous carbon, 0.5-1% organic amine, 0.5-1% defoamer. A reasonable match of kieselguhr/antibacterial composite and kieselguhr/porous as well as cooperation of functional additives enables excellent properties of antibiosis, anti-formaldehyde and deodorization of the ink, meets multi-functional demand and further widens application of the ink.
Description
Technical field
The present invention relates to technical field of ink, particularly relate to a kind of antibacterial gravure water color ink and preparation side thereof
Method.
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
Increase, ink kind and yield also respective extension and growth.Gravure water color ink, is a kind of low toxicity, non-stimulated taste, does not fires, saves
The novel ink of energy environmental protection, but common water color ink has not had anti-microbial property, the health growing for meeting people
Demand, it is provided that a kind of gravure water color ink with high-efficiency antimicrobial performance, can give the antibacterial aqueous ink printing of use out
Printing there is efficient anti-microbial property, people contact these printings just to above infection process, have effectively cut off disease
The route of transmission of bacterium, ensures the health of people.The function singleness of tradition ink, can not meet the multi-demands of people simultaneously.
Summary of the invention
The technical problem to be solved there is provided a kind of antibacterial gravure water color ink and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibacterial gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, keep temperature 55～65 DEG C, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), it is sequentially added into deionized water, ethanol and dispersant and carries out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stirring
Defoamer is added after 30～60min；Continuing stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) in standby color paste, deionized water, ethanol, water-borne wax emulsion, aqueous levelling agent and drying retardant it are sequentially added into, 1200
After stirring under the rotating speed of ~ 1500r/min, being slowly added to organic amine regulation PH is 8.0～9.5, is ground by three-roll grinder
Mill dispersion makes up to the fineness of 10～20 μm；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6.
Described antibacterial gravure water color ink is prepared by following components: water-soluble resin 70～
75%, deionized water 10～15%, aqueous organic pigment 5～10%, ethanol 3～6%, kieselguhr/antibiotic complex 0.5～1%, point
Powder 1～2%, drying retardant 0～1%, aqueous levelling agent 0.5～1%, water-borne wax emulsion 0.5～1%, kieselguhr/porous carbon 0 ~ 1%,
Organic amine 0.5～1%, defoamer 0.5～1%.
Described water-soluble resin is arbitrary in water-borne acrylic resin, aqueous epoxy resins, water soluble alkyd resin etc.
Plant or multiple combination；Aqueous organic pigment is appointing in the aqueous organic pigments such as benzidine yellow, transparent yellow, Dracocephalum moldabium, the purplish red F2R of phthalein
A kind of；Organic amine be in N-octadecyl trimethylene diamine and N-cyclohexyl trimethylene diamine any one, keep ink
PH value is 8.0～9.5, and the too low meeting of pH value delays oxidation polymerization and the formation effect of the firm ink film that volatilizees, the pH value of water color ink
Too high meeting causes wet inside and dry outside to affect adhesive force；Defoamer is any one in tributyl phosphate, dibutylphosphoric acid ester, silicone oil
Kind, it is used for eliminating bubble.Described aqueous levelling agent is aqueous levelling agent HP-855；Water-borne wax emulsion is the water-borne wax of E-340FM
Emulsion, the most above-mentioned drying retardant is propylene glycol monomethyl ether.Described dispersant is sodium hexametaphosphate, and ink can be prevented in storage and fortune
Defeated middle coalescence.
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, ultrasonic agitation limit, limit
Dropping antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr with
The weight ratio of antibiotic complex is 1 ~ 3:4 ~ 6.
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water add
Enter in 100ml water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, forge under the air atmosphere of 900 DEG C
Burn 1h, obtain porous carbon；3 ~ 5 parts of nano silicone diatomaceous earth are dispersed in the aqueous solution of 120ml, immerse porous carbon 2h, allow nanometer
Material is well in duct, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/porous carbon, and kieselguhr with the weight ratio of porous carbon is
5:1。
Described antibiotic complex prepares by the following method:
(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) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue 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
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) 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.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and 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 silver, continues ultrasonic agitation 10 ~ 30min, moves to the microwave hydrothermal that liner is politef
In reactor (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filter, dry surface process SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the SiO that step (4) prepares2Cladding carries silver
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C, be incubated 15
~30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Described antibiotic complex prepares by the following method:
(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) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue 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
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) 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.
(4) 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 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after be aged 6 hours, clean, be dried, obtain carrying silver-colored/
Titanium dioxide graphene quantum dot.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide that step (5) prepares
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C, be incubated 15
~30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Described antibiotic complex prepares by the following method:
(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) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the prepared load zinc oxide of step (3)
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1 ~ 3) that graphene quantum dot and step (7) prepare is ultrasonic to be stirred
Mix 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C, be incubated 15 ~ 30min；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
Antibiotic complex method of the present invention uses the graphene quantum dot after laser irradiation as the carrier of antibacterial, surface
Reason, is finally attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevent it from reuniting,
Significantly improve the stability of antibacterial so that it is there is more efficient antibacterial activity；Kieselguhr can also adsorb in air simultaneously has
Evil gas particularly formaldehyde, then there is under antibacterial action the effect with purification air；The present invention is through diatom of reasonably arranging in pairs or groups
Soil/antimicrobial composite material and kieselguhr/porous carbon, the synergism between functional additive so that ink has excellent antibacterial
With anti-formaldehyde and deodorization properties, meet multi-functional demand, widen the application of ink further.
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 porous graphene Ag-carried antibacterial composite, 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 0.5g 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 saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
30min, laser irradiation power is 1W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.08mol/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 3:2:2.
(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 5:1 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 3 hours；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.005g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.3g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 90min at 240 DEG C；Cooling, filters, dries to obtain surface
The SiO of reason2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the SiO that step (4) 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.
Embodiment 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g 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 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 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 40min, swash
Photoirradiation power is 1.3W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.05mol/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 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (800W ultrasonic power, 500rpm mixing speed) point of 0.3g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of ink alkene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 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.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.008g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.2g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the SiO that step (4) 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.
Embodiment 3
A kind of preparation method of porous graphene Ag-carried antibacterial composite, 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 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 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 30min, swash
Photoirradiation power is 2W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
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 4:3:2.
(3) by the graphene quantum dot ultrasonic agitation (500W ultrasonic power, 500rpm mixing speed) point of 0.5g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of ink alkene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.01g graphite oxide joins the dispersion of 10mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.1g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 90min at 200 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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) 80ml graphene dispersion solution, add the SiO that step (4) 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 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps: weigh porous graphene (2 ~
5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent
For water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion is molten
Liquid, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Ageing, cleans, dries to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) compound concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, the volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is 3:2；Afterwards
Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into the tetraethyl orthosilicate (quality with the graphene quantum dot of load silver
Ratio is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged and successively with acetone and going
Ionized water cleans and obtains precipitation；This is deposited in 90o3h it is dried, to obtain Ag/SiO under C2。
(2) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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) 80ml graphene dispersion solution, add the Ag/SiO that step (2) prepares2, ultrasonic agitation 30min, then
Move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clean, dry to obtain antibacterial composite wood
Material.
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 antibacterial gravure water color ink, it comprises the following steps:
(1) 72% water-soluble resin and 0.8% kieselguhr/antibiotic complex are put in reactor, holding temperature 60 C,
The rotating speed of 900r/min；
(2) under conditions of step (1), be sequentially added into 6% deionized water, 2% ethanol and 1% dispersant carry out mix and blend 30 ~
60min；
(3) add 8% organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stir
0.5% defoamer is added after mixing 30～60min；Continue stirring 60～90min, by three-roll grinder grind to form fineness be 20～
The standby color paste of 30 μm；
(4) be sequentially added in standby color paste 6% deionized water, 1% ethanol, 1% water-borne wax emulsion, 0.5% aqueous levelling agent and
0.4% drying retardant, after stirring, is slowly added to 0.8% organic amine regulation PH, by three under the rotating speed of 1200 ~ 1500r/min
Roller mill grinding distribution makes up to the fineness of 10～20 μm；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Embodiment 2 antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described diatom
Soil is 2:5 with the weight ratio of antibiotic complex.
Embodiment 5
Preparation method based on embodiment 4, difference is: the preparation method of described antibiotic complex is as follows:
(1) prepare graphene quantum dot suspension: weigh 0.6g C60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric 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,
Mixed liquor；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 7h；Rapidly join 200ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
45min, laser irradiation power is 1.2W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.05mol/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 3:3:2.
(3) 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.
(4) 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 (3) 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.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the load silver/titanium dioxide graphene quantum dot that step (5) prepares,
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.
Embodiment 6
A kind of preparation method of antibacterial gravure water color ink, it comprises the following steps:
(1) 72% water-soluble resin and 0.8% kieselguhr/antibiotic complex are put in reactor, holding temperature 60 C,
The rotating speed of 900r/min；
(2) under conditions of step (1), be sequentially added into 6% deionized water, 2% ethanol and 1% dispersant carry out mix and blend 30 ~
60min；
(3) add 8% organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stir
0.5% defoamer is added after mixing 30～60min；Continue stirring 60～90min, by three-roll grinder grind to form fineness be 20～
The standby color paste of 30 μm；
(4) be sequentially added in standby color paste 6% deionized water, 1% ethanol, 0.5% water-borne wax emulsion, 0.5% aqueous levelling agent,
0.8% kieselguhr/porous carbon and 0.1% drying retardant, after stirring, be slowly added to 0.8% under the rotating speed of 1200 ~ 1500r/min
Organic amine regulation PH, makes up to the fineness of 10～20 μm by three-roll grinder grinding distribution；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join
In 100ml water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Entering in duct, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/porous carbon, and kieselguhr is 5:1 with the weight ratio of porous carbon.
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, ultrasonic agitation limit, limit
Dropping antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr with
The weight ratio of antibiotic complex is 2:5；
Described antibiotic complex preparation method is as follows:
(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 about 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.
Comparative example 3
Preparation method based on embodiment 4, difference is: be not added with kieselguhr.
Comparative example 4
Preparation method based on embodiment 4, difference is: described kieselguhr/antibiotic complex replaces with by following weight
Amount part component: 10% nano-ZnO, the antibacterial of 90% nm level CaCO_3 composition.
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 (4)
1. a preparation method for gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, keep temperature 55～65 DEG C, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), it is sequentially added into deionized water, ethanol and dispersant and carries out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stirring
Defoamer is added after 30～60min；Continuing stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) in standby color paste, it is sequentially added into deionized water, ethanol, water-borne wax emulsion, kieselguhr/porous carbon, aqueous levelling agent
And drying retardant, after stirring under the rotating speed of 1200 ~ 1500r/min, being slowly added to organic amine regulation PH is 8.0～9.5, logical
Cross three-roll grinder to grind
Mill dispersion makes up to the fineness of 10～20 μm；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join
In 100ml water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine
1h, obtains porous carbon；3 ~ 5 parts of nano silicone diatomaceous earth are dispersed in the aqueous solution of 120ml, immerse porous carbon 2h, allow nanometer material
Expecting that repeatedly sucking filtration cleans well in duct, be dried to obtain kieselguhr/porous carbon, kieselguhr is 5 with the weight ratio of porous carbon:
1；
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate
Solution, 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；
(2) 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；This is deposited in 90o3h it is dried, to obtain under C
SiO2The graphene quantum dot of the load silver of cladding；
(3) SiO2Cladding carries the surface of silver graphene quantum dot and processes；
(4) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the SiO that step (3) prepares2Cladding carries silver Graphene
Quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~
30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
2. a preparation method for antibacterial gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, keep temperature 55～65 DEG C, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), it is sequentially added into deionized water, ethanol and dispersant and carries out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stirring
Defoamer is added after 30～60min；Continuing stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) in standby color paste, it is sequentially added into deionized water, ethanol, water-borne wax emulsion, kieselguhr/porous carbon, aqueous levelling agent
And drying retardant, after stirring under the rotating speed of 1200 ~ 1500r/min, being slowly added to organic amine regulation PH is 8.0～9.5, logical
Cross three-roll grinder to grind
Mill dispersion makes up to the fineness of 10～20 μm；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join
In 100ml water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine
1h, obtains porous carbon；3 ~ 5 parts of nano silicone diatomaceous earth are dispersed in the aqueous solution of 120ml, immerse porous carbon 2h, allow nanometer material
Expecting that repeatedly sucking filtration cleans well in duct, be dried to obtain kieselguhr/porous carbon, kieselguhr is 5 with the weight ratio of porous carbon:
1；
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, and dropping continues ultrasonic agitation 60 ~ 120min；Ageing, cleans, and dries to obtain load silver
Graphene quantum dot；
(2) 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, obtains SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(3) 0.1 ~ 0.3mol/L titanium source is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add what step (2) prepared
SiO2Cladding 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, old
Change, clean, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) surface carrying silver/titanium dioxide graphene quantum dot processes；
(5) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) prepares
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~
30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
3. a preparation method for antibacterial gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, keep temperature 55～65 DEG C, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), it is sequentially added into deionized water, ethanol and dispersant and carries out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, adding organic pigment while stirring, stirring
Defoamer is added after 30～60min；Continuing stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) in standby color paste, it is sequentially added into deionized water, ethanol, water-borne wax emulsion, kieselguhr/porous carbon, aqueous levelling agent
And drying retardant, after stirring under the rotating speed of 1200 ~ 1500r/min, being slowly added to organic amine regulation PH is 8.0～9.5, logical
Cross three-roll grinder to grind
Mill dispersion makes up to the fineness of 10～20 μm；
(5) mixture prepared by step (4) is filtered and packaged, complete preparation；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join
In 100ml water heating kettle, in 180 DEG C of baking ovens seal reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine
1h, obtains porous carbon；3 ~ 5 parts of nano silicone diatomaceous earth are dispersed in the aqueous solution of 120ml, immerse porous carbon 2h, allow nanometer material
Expecting that repeatedly sucking filtration cleans well in duct, be dried to obtain kieselguhr/porous carbon, kieselguhr is 5 with the weight ratio of porous carbon:
1；
The preparation method of described antibiotic complex is as follows:
(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: 0.005 ~ 0.01g graphite oxide is joined 5 ~ 10mL
Dispersant in, ultrasonic agitation also adds 0.1 ~ 0.3g and carries silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, seals and is 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/bis-
Titanium oxide graphene quantum dot；
(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.
4. an antibacterial gravure water color ink, it is characterised in that described antibacterial gravure water color ink by following by weight percentage
The composition of meter prepares: water-soluble resin 70～75%, deionized water 10～15%, aqueous organic pigment 5～10%, ethanol 3～
6%, kieselguhr/antibiotic complex 0.5～1%, dispersant 1～2%, drying retardant 0～1%, aqueous levelling agent 0.5～1%, water-borne wax
Emulsion 0.5～1%, kieselguhr/porous carbon 0 ~ 1%, organic amine 0.5～1%, defoamer 0.5～1%.
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| CN112063229A (en) * | 2020-10-21 | 2020-12-11 | 赵元梅 | Antibacterial heat-resistant environment-friendly printing ink and preparation method thereof |
| CN115636985A (en) * | 2022-09-08 | 2023-01-24 | 广西大学 | Preparation method and application of antibacterial breathable biomass-based packaging film |
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| CN102942821A (en) * | 2012-10-30 | 2013-02-27 | 广东壮丽彩印股份有限公司 | Nano-antibacterial gravure aqueous printing ink and preparation method thereof |
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| CN104941643A (en) * | 2015-06-16 | 2015-09-30 | 北京科技大学 | Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst |
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| CN102070957A (en) * | 2010-12-30 | 2011-05-25 | 东莞市华立实业股份有限公司 | Water-soluble antibacterial ink and antibacterial floorboard manufactured by using same |
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| CN115636985A (en) * | 2022-09-08 | 2023-01-24 | 广西大学 | Preparation method and application of antibacterial breathable biomass-based packaging film |
| CN115636985B (en) * | 2022-09-08 | 2023-08-04 | 广西大学 | Preparation method and application of antibacterial breathable biomass-based packaging film |
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