CN106366758A - Gravure water-based ink and preparation method thereof - Google Patents
Gravure water-based ink and preparation method thereof Download PDFInfo
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- CN106366758A CN106366758A CN201610748899.4A CN201610748899A CN106366758A CN 106366758 A CN106366758 A CN 106366758A CN 201610748899 A CN201610748899 A CN 201610748899A CN 106366758 A CN106366758 A CN 106366758A
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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
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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
-
- 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
Abstract
The invention discloses gravure water-based ink and a preparation method thereof. The gravure water-based ink is prepared from, in weight percentage, 70-75% of water-soluble resin, 10-15% of deionized water, 5-10% of water-based organic pigments, 3-6% of ethyl alcohol, 0.5-1% of diatomite/antimicrobial composite, 1-2% of dispersing agents, 0-1% of slow-dry agent, 0.5-1% of water-based flatting agent, 0.5-1% of water-based wax emulsion, 0-1% of diatomite/porous carbon, 0.5-1% of organic amine and 0.5-1% of defoaming agent. According to the gravure water-based ink, the diatomite/antimicrobial composite and the diatomite/porous carbon are reasonably matched, the ink has excellent antibacterial, anti-formaldehyde and deodorization characteristics by the aid of synergistic effects between functional additives, multifunctional demands are met, and application of the ink is widened.
Description
Technical field
The present invention relates to technical field of ink, a kind of more particularly to gravure water color ink and preparation method thereof.
Background technology
Ink is the important materials for packaging material printing, and it is shown pattern, word on stock by printing
Ink includes main component and auxiliary element, and they equably mix and form a kind of viscosity colloidal fluid through repeat-rolling；
It is made up of pigment, link stuff and auxiliary agent etc.；For the various printing such as books and periodicals, packing and decorating, building decoration.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 fire, saves
Can environmental protection novel ink, but common water color ink has not had anti-microbial property, the health growing for meeting people
Demand, is provided a kind of gravure water color ink with high-efficiency antimicrobial performance, can give and being printed using antibacterial aqueous ink
Printing there is efficient anti-microbial property, people contact these printings just to infection process above, have effectively cut off disease
The route of transmission of bacterium, ensures the health of people.The single function of traditional ink simultaneously, can not meet the multi-demandses of people.
Content of the invention
The technical problem to be solved there is provided a kind of 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 gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, 55～65 DEG C of keeping temperature, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), sequentially add deionized water, ethanol and dispersant and carry out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, add organic pigment, stirring while stirring
Defoamer is added after 30～60min；Continue stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) deionized water, ethanol, aqueouss wax emulsion, aqueous levelling agent and drying retardant are sequentially added in standby color paste, 1200
After stirring under the rotating speed of ~ 1500r/min, being slowly added to organic amine and adjusting ph is 8.0～9.5, is ground by three-roll grinder
Mill dispersion makes up to 10～20 μm of fineness；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6.
Described gravure water color ink is prepared by following components: water-soluble resin 70～75%,
Deionized water 10～15%, aqueouss 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%, aqueouss 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；Aqueouss organic pigment is appointing in the aqueouss organic pigment such as benzidine yellow, transparent yellow, blue or green blue, purplish red f2r
A kind of；Organic amine is any one in n- octadecyl trimethylene diamine and n- cyclohexyl trimethylene diamine, keeps ink
Ph value is in the formation effect of the too low oxidation polymerization that can delay water color ink of 8.0～9.5, ph value and the firm ink film that volatilizees, ph value
Too high wet inside and dry outside can be led to affect adhesive force；Defoamer is tributyl phosphate, dibutylphosphoric acid ester, any one in silicone oil
Kind, for eliminating bubble.Described aqueous levelling agent is aqueous levelling agent hp-855；Aqueouss wax emulsion is the water-borne wax of e-340fm
Emulsion, preferably above-mentioned drying retardant is propylene glycol monomethyl ether.Described dispersant is sodium hexametaphosphate, can prevent ink from storage and transporting
Defeated middle coalescence.
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, in ultrasonic agitation
Deca antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr with
The weight of antibiotic complex is than for 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, sealing reaction 10h, after cleaned drying, forges under 900 DEG C of air atmosphere
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 well in duct, multiple sucking filtration cleaning, dry kieselguhr/porous carbon, kieselguhr with the weight ratio of porous carbon is
5:1.
Described antibiotic complex is obtained by the following method:
(1) prepare 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, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, 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, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load 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
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c
Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 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), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filters, dries the sio that must be surface-treated2Cladding carries silver-colored 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) is obtained2Cladding carries silver
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(1) prepare 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, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, 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, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load 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
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry 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) is obtained2Cladding carries silver-colored graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, cleaning, be dried, obtain carrying silver/
Titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 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), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(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) is obtained
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(1) prepare 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, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) weigh 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, Deca walks
Suddenly the half graphene quantum dot suspension that (1) is obtained, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g loads the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, and dries the graphene quantum dot of the load zinc oxide that must be surface-treated.
(4) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction temperature
Spend for 45 ~ 60 DEG C, Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleaning, dry the graphene quantum dot that must load 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
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry 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) is obtained2Cladding carries silver-colored 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) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 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), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(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) are obtained is ultrasonic to be stirred
Mix 10 ~ 30min, then move in the reactor of politef, be incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly
Wash, dry to obtain antimicrobial composite material.
The invention has the following beneficial effects:
Antibiotic complex method of the present invention adopt laser irradiation after graphene quantum dot as antibacterial carrier, at surface
Reason, is finally attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevents its reunion,
Significantly improve the stability of antibacterial so as to have more efficient antibacterial activity；Kieselguhr can also adsorb in the air and have simultaneously
Evil gas particularly formaldehyde, then there is the effect under antibacterial action with purify air；The present invention is through rational diatom of arranging in pairs or groups
Soil/antimicrobial composite material and kieselguhr/porous carbon, the synergism between functional additive is so that ink has excellent antibacterial
With anti-formaldehyde and deodorization properties, meet multi-functional demand, widen the application of ink further.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 0.5g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
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, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load 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 adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.005g graphite oxide is added to the dispersion of 5ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.3g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, reacts 90min at 240 DEG C；Cooling, filters, dry at surface
The sio of reason2Cladding carries silver-colored 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) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 40min simultaneously, swashs
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, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load 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 black alkene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.008g graphite oxide is added to the dispersion of 8ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.2g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300w, reacts 60min at 220 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored 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) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs
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, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load 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 black alkene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 10ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.1g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, reacts 90min at 200 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored 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) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
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, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l bis- water
Close trisodium citrate, continue ultrasonic agitation 90min；Ageing, cleaning, dry 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 Deca concentration is 0.01mol/l
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, silver nitrate solution is 3:2 with the volume ratio of two citric acid monohydrate trisodiums；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
For 1:1, adjust ph value is 9 ~ 10 to ratio, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged and successively with acetone and going
Ionized water cleaning obtains precipitation；This is deposited in 90o3h 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) is obtained2, ultrasonic agitation 30min, then
Move in the reactor of politef, be incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antibacterial composite wood
Material.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses 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 weighed with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again
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 as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 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 materials
Embodiment 4
A kind of preparation method of gravure water color ink, it comprises the following steps:
(1) 72% water-soluble resin and 0.8% kieselguhr/antibiotic complex are put in reactor, 60 DEG C of keeping temperature,
The rotating speed of 900r/min；
(2) under conditions of step (1), sequentially add 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, add 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～
30 μm of standby color paste；
(4) sequentially add in standby color paste 6% deionized water, 1% ethanol, 1% aqueouss wax emulsion, 0.5% aqueous levelling agent and
0.4% drying retardant, after stirring, is slowly added to 0.8% organic amine and adjusts ph, by three under the rotating speed of 1200 ~ 1500r/min
Roller mill grinding distribution makes up to 10～20 μm of fineness；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Embodiment 2 antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described diatom
Soil and the weight of antibiotic complex ratio is for 2:5.
Embodiment 5
Based on the preparation method of 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains
Mixed liquor；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 7h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
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, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load 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 adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(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) is obtained,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 6
A kind of preparation method of gravure water color ink, it comprises the following steps:
(1) 72% water-soluble resin and 0.8% kieselguhr/antibiotic complex are put in reactor, 60 DEG C of keeping temperature,
The rotating speed of 900r/min；
(2) under conditions of step (1), sequentially add 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, add 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～
30 μm of standby color paste；
(4) sequentially add in standby color paste 6% deionized water, 1% ethanol, 0.5% aqueouss wax emulsion, 0.5% aqueous levelling agent,
0.8% kieselguhr/porous carbon and 0.1% drying retardant, after stirring, are slowly added to 0.8% under the rotating speed of 1200 ~ 1500r/min
Organic amine adjusts ph, makes up to 10～20 μm of fineness by three-roll grinder grinding distribution；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, in ultrasonic agitation
Deca antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr with
The weight of antibiotic complex is than for 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs
Photoirradiation power is 1.5w.
(2) weigh 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, Deca step (1) is obtained
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load 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 adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(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) be obtained 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) is obtained, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Comparative example 3
Based on the preparation method of embodiment 4, difference is: is not added with kieselguhr and antibiotic complex.
Comparative example 4
Based on the preparation method of embodiment 4, difference is: described kieselguhr/antibiotic complex replaces with by following weight
Amount part component: 10% nanometer of zno, the antibacterial of 90% nanometer of caco3 composition.
The key technical indexes of embodiment 4 ~ 6 and comparative example 3,4 is as follows:
Antibacterial Evaluation for Uniformity: ink is sprayed on glass or ceramic wafer, chooses 100 regions and carry out sterilizing test, to survey
The data obtaining carries out Uniformity Analysis, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than 97%, then
Be labeled as ▲；When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (4)
1. a kind of preparation method of gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, 55～65 DEG C of keeping temperature, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), sequentially add deionized water, ethanol and dispersant and carry out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, add organic pigment, stirring while stirring
Defoamer is added after 30～60min；Continue stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) deionized water, ethanol, aqueouss wax emulsion, aqueous levelling agent and drying retardant are sequentially added in standby color paste, 1200
After stirring under the rotating speed of ~ 1500r/min, being slowly added to organic amine and adjusting ph is 8.0～9.5, is ground by three-roll grinder
Mill dispersion makes up to 10～20 μm of fineness；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
Described antibiotic complex preparation method is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry the graphene quantum dot that must load 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, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain under c
sio2The graphene quantum dot of the load silver of cladding；
(3) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot；
(4) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the sio that step (3) is obtained2Cladding carries silver-colored Graphene
Quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
2. a kind of preparation method of gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, 55～65 DEG C of keeping temperature, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), sequentially add deionized water, ethanol and dispersant and carry out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, add organic pigment, stirring while stirring
Defoamer is added after 30～60min；Continue stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) deionized water, ethanol, aqueouss wax emulsion, aqueous levelling agent and drying retardant are sequentially added in standby color paste, 1200
After stirring under the rotating speed of ~ 1500r/min, being slowly added to organic amine and adjusting ph is 8.0～9.5, is ground by three-roll grinder
Mill dispersion makes up to 10～20 μm of fineness；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
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, Deca silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca, continues ultrasonic agitation 60 ~ 120min；Ageing, cleaning, dry and must 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, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried, obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(3) 0.1 ~ 0.3mol/l titanium source is added in 1 mol/l sulfuric acid solution, mix homogeneously；Step (2) is added to be obtained
sio2Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, old
Change, cleaning, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(5) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) is obtained
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
3. a kind of preparation method of gravure water color ink, it comprises the following steps:
(1) water-soluble resin and kieselguhr/antibiotic complex are put in reactor, 55～65 DEG C of keeping temperature, 800 ~
The rotating speed of 1000r/min；
(2) under conditions of step (1), sequentially add deionized water, ethanol and dispersant and carry out mix and blend 30 ~ 60min；
(3) add organic pigment and mixing speed is adjusted to 1200 ~ 1500r/min, add organic pigment, stirring while stirring
Defoamer is added after 30～60min；Continue stirring 60～90min, grinding to form fineness by three-roll grinder is 20～30 μm
Standby color paste；
(4) deionized water, ethanol, aqueouss wax emulsion, aqueous levelling agent and drying retardant are sequentially added in standby color paste, 1200
After stirring under the rotating speed of ~ 1500r/min, being slowly added to organic amine and adjusting ph is 8.0～9.5, is ground by three-roll grinder
Mill dispersion makes up to 10～20 μm of fineness；
(5) mixture preparing step (4) is filtered and packaged, and completes to prepare；Wherein,
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
The preparation method of described antibiotic complex is as follows:
(1) prepare graphene quantum dot suspension: 100rpm speed stirring graphene quantum dot suspension, laser irradiation 30 simultaneously
~ 60min, laser irradiation power is 1 ~ 2w；
(2) weigh 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 Deca step (1) is obtained, continue ultrasonic agitation 30 ~
60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface treatment of the graphene quantum dot of load zinc oxide；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, Deca silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry the graphene quantum dot that must load 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, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried to obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(6) 0.1 ~ 0.3mol/l titanium source is added in 1mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2
Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, is aged, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~ 10ml
Dispersant in, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, is placed in microwave assisted hydrothermal synthesis apparatus after sealing,
Microwave power is 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries load silver/bis- that must be surface-treated
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 load zinc oxide that addition step (3) is obtained and step (7) are obtained
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
It is incubated 15 ~ 30min at 120 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
4. a kind of gravure water color ink is it is characterised in that described gravure water color ink is by following components
Prepare: water-soluble resin 70～75%, deionized water 10～15%, aqueouss organic pigment 5～10%, ethanol 3～6%, diatom
Soil/antibiotic complex 0.5～1%, dispersant 1～2%, drying retardant 0～1%, aqueous levelling agent 0.5～1%, aqueouss wax emulsion 0.5
～1%, kieselguhr/porous carbon 0 ~ 1%, organic amine 0.5～1%, defoamer 0.5～1%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102845471A (en) * | 2012-07-27 | 2013-01-02 | 烟台大学 | Silver-based composite particle, preparation method of the silver-based composite particle and antibacterial agent containing the silver-based composite particle |
| 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 |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102845471A (en) * | 2012-07-27 | 2013-01-02 | 烟台大学 | Silver-based composite particle, preparation method of the silver-based composite particle and antibacterial agent containing the silver-based composite particle |
| 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 |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| 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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