CN106243936A - A kind of wash resistant coating and preparation method thereof - Google Patents
A kind of wash resistant coating and preparation method thereof Download PDFInfo
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- CN106243936A CN106243936A CN201610748622.1A CN201610748622A CN106243936A CN 106243936 A CN106243936 A CN 106243936A CN 201610748622 A CN201610748622 A CN 201610748622A CN 106243936 A CN106243936 A CN 106243936A
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of wash resistant coating and preparation method thereof, the method comprises the following steps: 40 ~ 50 parts of film forming matters are dissolved in 20 ~ 30 parts of solvents by (1), prepares film forming matter solution；(2) take 10 ~ 20 parts of antimicrobial composite materials to add in 1/3 film forming matter solution, obtain antibacterial dispersion liquid；(3) take 10 ~ 20 parts of conductive fillers to add in 1/3 film forming matter solution, obtain conductive dispersions；(4) take 5 ~ 10 parts of inorganic oxides to add in 1/3 film forming matter solution, obtain deodorization dispersion liquid；(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, sequentially add 3 ~ 5 parts of dispersants, 1 ~ 5 part of levelling agent, 1 ~ 3 part of defoamer and 1 ~ 5 portion of anti-settling agent, after being uniformly dispersed, obtain wash resistant coating.The present invention is by scientific compatibility antibiotic complex, conductive filler and inorganic oxide, mutual synergism between raw material so that coating not only has wash resistant characteristic, also has the function of antibacterial, antistatic and deodorization, has widened the range of application of coating further.
Description
Technical field
The present invention relates to a kind of wash resistant coating and preparation method thereof.
Background technology
The accumulation of static electricity on the non-metal items surfaces such as macromolecular material reaches to a certain degree will discharge, and causes various precision
Instrument, precise electronic components and parts puncture and scrap, and even cause inflammable and explosive substances on fire or blast, cause huge life and wealth
Produce loss.It addition, be accumulated in the electrostatic of surface of plastic products due to dust suction serious and be difficult to purify, thus affect plastic
Outward appearance and the application in super-clean environment (such as operating room, computer room, precision instrument etc.).Existing anti-static coatings need to carry
Its antistatic property high and stability.
Meanwhile, existing coating function is more single, such as antibiotic paint, anti-static coatings or except methanal paint etc., often
It is to reach multifunctional characteristics by the coating of mixing several functions, but is relatively inaccessible to desired effect.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of wash resistant coating.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of wash resistant coating, it comprises the following steps:
(1) 40 ~ 50 parts of film forming matters are dissolved in 20 ~ 30 parts of solvents, after mix homogeneously, prepare film forming matter solution；Described film forming matter
It is saturated polyester resin or polyurethane resin；
(2) take 10 ~ 20 parts of antimicrobial composite materials and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain antibacterial dispersion
Liquid；
(3) take 10 ~ 20 parts of conductive fillers and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain conductive dispersions；
Described conductive filler is made up of porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing；
Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join 100ml
In 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, obtain
Porous carbon；CNT, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant
Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, so
After sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain conductive filler under vacuum；
(4) take 5 ~ 10 parts of inorganic oxides and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain deodorization dispersion liquid；
Inorganic oxide preparation method is as follows: add the raw material of following percentage by weight: ZrO2 5%, TiO2 8% in grinding groove,
SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%,
MnO2 7%；Put into grinder to be ground, control particle diameter between 10 ~ 30 μm.
(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, high speed dispersion 60 ~ 90min, then add successively
Entering 3 ~ 5 parts of dispersants, 1 ~ 5 part of levelling agent, 1 ~ 3 part of defoamer and 1 ~ 5 portion of anti-settling agent, high speed dispersion prepares wash resistant the most afterwards and is coated with
Material.
In the present invention, described defoamer is organic siliconresin class defoamer, modified organic silicone resin class defoamer and two
At least two of the mixing species defoamer of silicon oxide and organic siliconresin；Described anti-settling agent is wax class anti-settling agent, silicon dioxide
At least one of class anti-settling agent and polyureas anti-settling agent；Described levelling agent is solvent levelling agent, acrylic compounds levelling agent and has
At least one of machine silicon class levelling agent.Described dispersant is natural polymer subclass dispersant, synthesis high score subclass dispersant, multivalence
At least one of carboxylic acids dispersant, block macromolecular copolymer analog dispersant and special ethylenic polymer species dispersant；Institute
Stating the mixture that solvent is esters solvent and ketones solvent, described esters solvent is ethyl acetate or butyl acetate, described ketone
Solvent is cyclohexanone, N-Methyl pyrrolidone, butanone or methyl iso-butyl ketone (MIBK).
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2
The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic merit of 500 ~ 1000W
Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide,
Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti-
Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes Nano silver grain and zinc oxide have more efficient
Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously
Agent has a more preferable antibacterial effect, antibacterial persistently；
Conductive filler used in the present invention makes the conductive structure of ink finer and close, forms good interlayer UNICOM structure, conduction
Passage is more smooth and easy, thus improves conductivity and stability further, overcomes again pure carbon black conductive ink electric conductivity not
Stable defect；
The present invention is by scientific compatibility antibiotic complex, conductive filler and inorganic oxide, and between raw material, mutual synergism, makes
Obtain coating and not only there is wash resistant characteristic, also there is the function of antibacterial, antistatic and deodorization, widen answering of coating further
Use scope.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
Photoirradiation power is 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, dropping step (1) prepare one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.1g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot that surface processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves
To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g C60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash
Photoirradiation power is 1W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water；
Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that dropping step (1) prepares
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide
Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined
In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
110 DEG C, after reaction 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide
Graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load silver/titanium dioxide Graphene
Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 100ml graphene dispersion solution, add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~
6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan
Base sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, dropping concentration is
0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium,
Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, MIC) method of testing (Xiang Cai, Shaozao Tan, Aili Yu,
Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.Chemistry-An Asian Journal. 2012,7 (7): 1664-1670.), first weigh with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute
Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL,
Then shaken cultivation 24h at 37 DEG C, observes its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite material
Embodiment 4
A kind of preparation method of wash resistant coating, it comprises the following steps:
(1) 50 parts of film forming matters are dissolved in 30 parts of solvents, after mix homogeneously, prepare film forming matter solution；Described film forming matter is saturated
Polyester resin；
(2) take 10 parts of embodiment 2 antimicrobial composite materials and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain antibacterial point
Dissipate liquid；
(3) take 15 parts of conductive fillers and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain conductive dispersions；Described lead
Electricity filler is made up of porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing；
Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join 100ml
In 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, obtain
Porous carbon；CNT, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant
Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, so
After sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain conductive filler under vacuum；
(4) take 8 parts of inorganic oxides and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain deodorization dispersion liquid；Inorganic oxygen
Compound preparation method is as follows: add the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16% in grinding groove,
V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Throw
Enter and be ground to grinder, control particle diameter between 10 ~ 30 μm.
(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, high speed dispersion 90min, sequentially add 4
Part dispersant, 3 parts of levelling agents, 2 parts of defoamer and 1 portion of anti-settling agent, high speed dispersion prepares wash resistant coating the most afterwards.
Embodiment 5
A kind of preparation method of wash resistant coating, it comprises the following steps:
(1) 50 parts of film forming matters are dissolved in 30 parts of solvents, after mix homogeneously, prepare film forming matter solution；Described film forming matter is saturated
Polyester resin；
(2) take 20 parts of embodiment 2 antimicrobial composite materials and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain antibacterial point
Dissipate liquid；
(3) take 10 parts of conductive fillers and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain conductive dispersions；Described lead
Electricity filler is made up of porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing；
Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join 100ml
In 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, obtain
Porous carbon；CNT, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant
Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, so
After sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain conductive filler under vacuum；
(4) take 5 parts of inorganic oxides and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain deodorization dispersion liquid；Inorganic oxygen
Compound preparation method is as follows: add the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16% in grinding groove,
V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Throw
Enter and be ground to grinder, control particle diameter between 10 ~ 30 μm.
(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, high speed dispersion 90min, sequentially add 4
Part dispersant, 3 parts of levelling agents, 2 parts of defoamer and 1 portion of anti-settling agent, high speed dispersion prepares wash resistant coating the most afterwards.
Embodiment 6
A kind of preparation method of wash resistant coating, it comprises the following steps:
(1) 50 parts of film forming matters are dissolved in 30 parts of solvents, after mix homogeneously, prepare film forming matter solution；Described film forming matter is saturated
Polyester resin；
(2) take 15 parts of embodiment 2 antimicrobial composite materials and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain antibacterial point
Dissipate liquid；
(3) take 0 part of conductive filler and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain conductive dispersions；Described conduction
Filler is made up of porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing；
Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join 100ml
In 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, obtain
Porous carbon；CNT, nanometer aluminium powder are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant
Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, so
After sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain conductive filler under vacuum；
(4) take 10 parts of inorganic oxides and add in 1/3 film forming matter solution, high speed dispersion 90min, obtain deodorization dispersion liquid；Inorganic
Oxide preparation method is as follows: add the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 in grinding groove
16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2
7%；Put into grinder to be ground, control particle diameter between 10 ~ 30 μm.
(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, high speed dispersion 90min, sequentially add 4
Part dispersant, 3 parts of levelling agents, 2 parts of defoamer and 1 portion of anti-settling agent, high speed dispersion prepares wash resistant coating the most afterwards.
Comparative example 3
Preparation method based on embodiment 6, difference is: be not added with antibiotic complex.
Comparative example 4
Preparation method based on embodiment 6, difference is: be not added with conductive filler.
Comparative example 5
Preparation method based on embodiment 6, difference is: be not added with inorganic oxide.
Comparative example 6
Preparation method based on embodiment 6, difference is: be not added with antibiotic complex and inorganic oxide.
Testing the antibiotic antistatic coating of embodiment 4 ~ 6 and comparative example 3 ~ 6, result is as follows:
Wash resistant is tested: by coatings on PET sheet surface, prepares antistatic film after oven for drying.Then will have
The PET sheet material of this layer film is immersed in water or alcohols solvent (such as ethanol), ultrasonic waves for cleaning 6 times, each 10 points
Clock, tests the surface resistivity change of film after drying.
Antibacterial Evaluation for Uniformity: be coated uniformly on by coating on glass or ceramic wafer, chooses 100 regions and carries out sterilizing survey
The data recorded are carried out Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods) by examination.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
╳。
Deodorizing test: prepare two 51PVF resin airbags, put into one piece of sample print in an air bag, another tree
Fat air bag not setting-out sheet.Then in two air bags, it is blown into 500ppmNH3-air gas mixture respectively and seals.At interval of 30
The concentration of NH3 in air bag measured by minute use gas detecting tube, until terminating after 2 hours on-tests.
Hundred lattice tests: as reference standard, specifically survey with " scratch experiment of GBT 9286-1998 paint and varnish paint film "
Examination flow process is as follows: draw the small grid of 10 × 10 (100) 1mm × 1mm on test sample surface with cross-cut tester, each
Line should deeply and paint bottom；With hairbrush, the fragment of test zone is cleaned down；With 3M600 gummed paper or equal efficiency
Gummed paper firmly clings tested small grid, and exerts oneself wiping adhesive tape with erasing rubber, to strengthen the contact surface of adhesive tape and tested region
Amass and dynamics；Holding adhesive tape one end, shut down rapidly gummed paper in vertical direction (90 °), same position carries out 2 identical examinations
Test.Wherein, the quantity sticked by adhesive tape accounts for the result that the percentage ratio (i.e. come off percentage ratio) of hundred lattice quantity is hundred lattice tests.
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 (9)
1. a preparation method for wash resistant coating, it comprises the following steps:
(1) 40 ~ 50 parts of film forming matters are dissolved in 20 ~ 30 parts of solvents, after mix homogeneously, prepare film forming matter solution；
(2) take 10 ~ 20 parts of antimicrobial composite materials and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain antibacterial dispersion
Liquid；
(3) take 10 ~ 20 parts of conductive fillers and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain conductive dispersions；
Described conductive filler is made up of porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder 4:2:1:2:2 in mass ratio mixing；
(4) take 5 ~ 10 parts of inorganic oxides and add in 1/3 film forming matter solution, high speed dispersion 60 ~ 90min, obtain deodorization dispersion liquid；
(5) antibacterial dispersion liquid, conductive dispersions and deodorization dispersion liquid are mixed, high speed dispersion 60 ~ 90min, sequentially add 3 ~ 5
Part dispersant, 1 ~ 5 part of levelling agent, 1 ~ 3 part of defoamer and 1 ~ 5 portion of anti-settling agent, high speed dispersion prepares wash resistant coating the most afterwards.
The preparation method of wash resistant coating the most according to claim 1, it is characterised in that described inorganic oxide preparation side
Method is as follows: add the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4% in grinding groove,
K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into grinding
Machine is ground, and controls particle diameter between 10 ~ 30 μm.
The preparation method of wash resistant coating the most according to claim 1, it is characterised in that described conductive filler preparation method
As follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water join in 100ml water heating kettle, close in 180 DEG C of baking ovens
Envelope reaction 10h, cleaned after drying, under the air atmosphere of 900 DEG C calcine 1h, obtain porous carbon；By CNT, nano aluminum
Powder is dispersed in the aqueous solution of 120ml, immerses porous carbon 1 ~ 2h, allow nano material well in duct, then sucking filtration；Sucking filtration
The filter cake of gained is immersed in 50ml white carbon black and graphene aqueous solution, 30 ~ 60min, the most again sucking filtration；Sucking filtration gained again
Filter cake distilled water wash, 120 DEG C of drying, obtain conductive filler under vacuum.
4. according to the preparation method of the arbitrary described wash resistant coating of claims 1 to 3, it is characterised in that described antibacterial compound
Thing prepares by the following method:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of wash resistant coating the most according to claim 4, it is characterised in that described graphene quantum dot suspends
The preparation method of liquid is as follows: weigh 0.5 ~ 0.8g C60 powder, measures the concentrated sulphuric acid that 50 ~ 100ml mass fraction is 98%, will
C60 powder and concentrated sulphuric acid mix in beaker, and beaker is placed in ice-water bath, stir with the speed of 300 ~ 500rpm simultaneously, obtain mixed
Close liquid；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep
Bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, be then 1000 with molecular cut off
Bag filter is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser
Irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of wash resistant coating the most according to claim 4, it is characterised in that ink alkene is 2 ~ 5 layers, and hole size is about
3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of wash resistant coating the most according to claim 4, it is characterised in that described load silver/titanium dioxide stone
The surface of ink alkene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL, ultrasonic stirs
Mixing and add 0.1 ~ 0.3g and carry silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, moving to liner is poly-four
In the microwave hydrothermal reaction kettle of fluorothene, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W,
60 ~ 90min is reacted at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
The preparation method of wash resistant coating the most according to claim 4, it is characterised in that the graphite of described load zinc oxide
The surface of alkene quantum dot processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL, ultrasonic agitation
And add 0.1 ~ 0.3g load zinc oxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, moving to liner is polytetrafluoro
In the microwave hydrothermal reaction kettle of ethylene, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~
60 ~ 90min is reacted at 240 DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
9. a wash resistant coating, it is made up of the raw material of following weight portion: 40 ~ 50 parts of film forming matters, 20 ~ 30 parts of solvents, 10 ~ 20
Part antimicrobial composite material, 10 ~ 20 parts of conductive fillers, 5 ~ 10 parts of inorganic oxides, 3 ~ 5 parts of dispersants, 1 ~ 5 part of levelling agent, 1 ~ 3 part
Defoamer and 1 ~ 5 portion of anti-settling agent；Described conductive filler is pressed quality by porous carbon, CNT, white carbon black, Graphene and nanometer aluminium powder
Than 4:2:1:2:2 mixing composition.
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| CN109852744A (en) * | 2019-01-24 | 2019-06-07 | 南京天诗蓝盾生物科技有限公司 | A kind of antibacterial treatment process of leather |
| CN116143418A (en) * | 2023-04-21 | 2023-05-23 | 山东孟友新材料科技有限责任公司 | Antibacterial toughened glass and preparation method thereof |
| CN116143418B (en) * | 2023-04-21 | 2023-08-18 | 山东孟友新材料科技有限责任公司 | Antibacterial toughened glass and preparation method thereof |
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Application publication date: 20161221 |