CN109370315A - A kind of application of the preparation method of microplate graphene electric heating ink, the preparation method of electric heating wall paper and electric heating wall paper - Google Patents
A kind of application of the preparation method of microplate graphene electric heating ink, the preparation method of electric heating wall paper and electric heating wall paper Download PDFInfo
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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
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- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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Abstract
The application of a kind of preparation method of microplate graphene electric heating ink, the preparation method of electric heating wall paper and electric heating wall paper, the preparation of microplate graphene electric heating ink: the preparation of nano-silver thread；The preparation of few layer microplate graphene filter cake；The preparation of microplate graphene electric heating ink.The microplate graphene electric heating ink of this method preparation has many advantages, such as uniform dispersibility and high conductivity.The preparation of electric heating wall paper: the preparation of microplate graphene electric heating ink is compounded with diluent；It is pumped to the spray head out of ink of cylinder printing equipment by pipeline, under the pressure of pump, equably send to cylinder inner cylinder, adjusts depth, the angles and positions of cylinder printing scraper, ink is made uniformly to squeeze out printing out of cylinder to substrate；It send to toasting in baking oven, obtains electric heating wall paper semi-finished product in printing silver electrode；It is this method simple process, easy to operate, it can solve limitation of the traditional printing mode to substrate material.The application of electric heating wall paper: electric heating wall skin is applied to the electromagnetic shield cloth of computer room.
Description
Technical field
The present invention relates to thermo electric material preparation technical fields, and in particular to a kind of preparation side of microplate graphene electric heating ink
The application of method, the preparation method of electric heating wall paper and electric heating wall paper.
Background technique
Under the policy support of national " coal changes electricity ", the whole nation has been widelyd popularize the exploitation of " coal changes electricity " technology and product and has been made
With encouragement resident cleans heating, gradually bans traditional coal-fired arcola, slows down the generation of haze disaster, to promote energy-saving and emission-reduction.
The market development of electric heating is rapid, requires the product quality of electric heating also higher and higher.
By the development of more than ten years, electricity floor heating heating system is gradually received and is approved by the majority of consumers.Print electric heating wall
The usual manner of cloth is the fever carbon-coating a thin layer of in polyester PET thin film surface printing, in early days based on silk-screen printing, the later period
The mode being developed into based on intaglio printing slowly, and become the mainstream production method of modern printing electric heating wall paper.Screen printing
Brush is a major advantage that and can be printed on different substrates, such as fexible film PET, hard epoxy glass mat.But
It is to need Hui Mo again after often printing unit pattern, interval printing, there are production efficiency deficiencies, greatly limit screen printing
The development in electric heating wall paper field is brushed, meanwhile, printing scraper returns black phenomenon after printing pattern, results in the fever of printing
Layer is in uneven thickness, easily causes the non-uniform quality problems of film layer fever.It is low in order to solve silk-screen printing bring production efficiency
Under problem, engineers attempt to carry out production electric heating wall paper using intaglio printing, and this mode substantially increases production efficiency,
But it can only be printed on flexible parent metal (PET film) surface, which also limits the selections of printing element.Intaglio printing is to ink
Selectivity it is higher, and traditional ink color is dim, and dispersibility and poorly conductive, in addition, its adhesive force is bad, water resistance
Difference is also not suitable with the requirement of printing process levelability, and therefore, traditional ink must be printed under specific viscosity, and
Ink after-tacks the efficiency of phenomena impair printing ink transfer to substrate in transfer process, to influence the thickness of film layer, can also make
At the non-uniform quality problems of heating layer fever.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of preparation sides of microplate graphene electric heating ink
Method, the black compound electro-thermal ink of oiliness graphene/carbon of this method preparation have uniform dispersibility, high conductivity, bright color
The advantages that, adhesive force is good, water-tolerant, is adapted to the levelability of printing process, can help to the fever for improving electric heating wall paper
The uniformity of thickness degree.
To achieve the goals above, the present invention provides a kind of preparation method of microplate graphene electric heating ink, including as follows
Step:
A kind of preparation method of microplate graphene electric heating ink, includes the following steps:
S1: the preparation of nano-Ag particles, nano-silver thread:
A1: using chemical reduction method, in deionized water, restores silver salt solution by reducing agent and prepares nano silver colloid,
The pH value of colloid is adjusted by pH adjusting agent, and dispersing agent is added, obtains the spherical silver particles of different grain size size, and add stabilization
The nano-Ag particles that agent is stored for a long time；
Wherein, deionized water, silver salt, pH adjusting agent, reducing agent and stabilizer volume ratio 0.1~80:0.1~20:0.1~
5:0.1~20:0.1~20；
A2: with solvent stability and reducing agent, silver salt is restored under the high temperature conditions and prepares elemental silver；Using crystal seed growth stimulator tune
Save crystal seed growth；Regulate and control the nano-silver thread that the silver-colored crystal seed direction of growth prepares different draw ratios by high molecular polymer；
S2: the preparation of few layer microplate graphene filter cake:
B1: ammonium persulfate is added in concentrated sulfuric acid and is slowly stirred dissolution, graphite powder is added, continues to stir, and dioxygen is added dropwise
Water after standing, obtains micron order graphite aggregation, is washed to neutrality, dries；
Wherein, 0.1~4:0.1 of mass ratio~50:0.1~8:0.1 of graphite powder, the concentrated sulfuric acid, ammonium persulfate and hydrogen peroxide
~10；
B2: micron order graphite aggregation is removed into the graphene microchip at few layer using in powder crushing plant, then will be lacked
The graphene microchip of layer is sent to high-temperature expansion in high temperature carbonization furnace and obtains few layer graphenes aggregations, and powder is made；
B3: few layer graphenes aggregations, aqueous dispersion and deionized water are deployed into aqueous stone by physical dispersion method
Black alkene dispersion liquid；
Wherein, the mass ratio of few layer graphenes aggregations, aqueous dispersion and deionized water is 0.1~20:0.1~10:
0.1~90；
B4: separating watersoluble plumbago alkene dispersion liquid by separation method and obtain few layer microplate graphene filter cake, spare；
S3: the preparation of microplate graphene electric heating ink:
By few layer of microplate graphene filter cake, macromolecule dispersing agent, levelling agent, size, preservative, nano-Ag particles, receive
Rice silver wire and binding material resin solution and defoaming agent are mixed, and utilize macromolecule dispersing agent by nano silver in whipping process
Grain, nano-silver thread are dispersed as nanodispersion in resin, and nanodispersion grain is punctured into few layer of microplate graphene sheet layer
In space, graphene microchip/nano silver electric heating ink, i.e. microplate graphene electric heating ink are obtained；
Wherein, few layer microplate graphene filter cake, macromolecule dispersing agent, levelling agent, size, preservative, nano-Ag particles,
The mass ratio of nano-silver thread and binding material resin solution and defoaming agent is 0.1~50:0.1~10:0.1~1%:0.1~1:0.1
~1:0.1~1:0.01~0.2:0.1~60.
Further, in the a1 in S1, deionized water, silver salt, pH adjusting agent, reducing agent and stabilizer volume ratio be 50~
70:7~15:0.1~2:8~13:7~15；
In the b1 of S2, graphite powder, the concentrated sulfuric acid, ammonium persulfate and hydrogen peroxide mass ratio be 2~3:40~50:4~8:5
~10；
In b3 in S2, the mass ratio of few layer graphenes aggregations, aqueous dispersion and deionized water is 14~18:7
~10:72~85.
Further, in the a1 in S1, silver salt is one of silver nitrate and silver sulfate or two kinds of mixing, and pH is adjusted
Agent is KOH, and reducing agent is the mixed of one or more of ascorbic acid, sodium citrate, glucose, sodium borohydride or amino acid
It closes, stabilizer is the mixing of one or more of polyurethane, acrylic acid or styrene-acrylic emulsion；
In a2 in S1, solvent stability and reducing agent are one of ethylene glycol, propylene glycol or isopropanol or more
The mixing of kind, silver salt are one of silver nitrate and silver sulfate or two kinds of mixing, and crystal seed growth stimulator is vulcanized sodium, potassium sulfide
One or more of mixing, high molecular polymer be PVP K-30 or K-90；
In b3 in S2, aqueous dispersion is one of BYK190 and Digao dispersing agent or two kinds of mixing；
In S3, macromolecule dispersing agent is one of anionic, quaternary ammonium salts, non-ionic or supermolecule dispersant
Or a variety of mixing, levelling agent are BYK-333 or BYK-349, size is Digao 270, preservative KD-3000, in S3
In, binding material resin is the mixture of thermoplastic resin and thermosetting resin.
Further, in the a1 in S1, reducing agent sodium citrate or amino acid, stabilizer are polyaminoester emulsion；
In a2 in S1, solvent stability and reducing agent are ethylene glycol, and silver salt is silver nitrate, and high molecular polymer is poly- second
Alkene pyrrolidone K-30, crystal seed growth stimulator are nine water vulcanized sodium, and the volume of nine water vulcanized sodium is 0.1-500 μ L, ethylene glycol, poly- second
The volume ratio of alkene pyrrolidone K-30 and silver nitrate is 0.1~40:0.1~10:0.1~4, and reaction temperature is 120-160 DEG C, instead
It is 0.1-2 hours between seasonable；
In S3, the mass ratio of thermoplastic resin and thermosetting resin is 0.1~1.
Further, in the a1 of S1, nano-Ag particles granule size obtained is 10~100nm；
In the a2 of S1, nano-silver thread draw ratio obtained is 0.1~100, microplate graphene electric heating ink obtained
Viscosity is 3000~12000mPa.s, granularity is 0.1~20 μm, adhesive force is 0 grade；
In the b1 of S2, the specific surface area of required graphite powder is 0.1~50m2/ g, micron order graphite aggregation obtained
Specific surface area is 0.1~120m2/g；
In the b2 of S2, the specific surface area of the graphene microchip of few layer obtained is 0.1~320m2/g；
In b3 in S2, the specific surface area of few layer graphenes aggregations is 0.1~600m2/g；
In S3, the oil absorbency of few layer graphene is 0.1~600m2/g.
Further, in the b2 in S2, used powder crushing plant is airslide disintegrating mill, in ultrasonic oscillator
One kind, used high temperature carbonization furnace select inert gas shielding, inert gas N2Or Ar2, the high temperature of high temperature carbonization furnace is swollen
800~1200 DEG C of swollen temperature；
In b3 in S2, physical dispersion method is one of ultrasound removing, sand mill grinding or micro-fluidic removing；
In b4 in S2, separation method is one of filter press filters pressing, industrial centrifugal machine centrifugation.
Further, in the b2 in S2, used powder crushing plant is airslide disintegrating mill, inert gas N2, high
500~1200 DEG C of the high-temperature expansion temperature of warm carbide furnace；
In b3 in S2, physical dispersion method is sand mill grinding；
In b4 in S2, separation method is industrial centrifugal machine centrifugation.
The present invention prepares few layer graphenes aggregations using chemical room temperature intercalation-two layers of Mechanical Crushing-high temperature expansion process,
Process is simple, technical maturity, stability are high and easy to operate, and gained lacks layer graphenes aggregations good conductivity, large specific surface area.
The few vermiform (within 100 layers) of the number of plies is presented in prepared graphenes aggregations, convenient for removing more completely to obtain
The few grapheme material of lamella.The zero dimension ag material (nano-Ag particles) of chemical reduction method preparation is dispersible granule in deionized water
Son is punctured into inside the graphenes aggregations of sheet connection, on the one hand can improve electric conductivity, can improve fever uniformity, also mention
The high safety in utilization and service life of product；Another aspect zero dimension ag material (nano-Ag particles) is that barrier is punctured into stone
Black alkene piece interlayer can prevent its graphitization.Crystal seed growth is adjusted using short vulcanization object, polyhydroxy high temperature reduction method prepares monocrystalline
Nano-silver thread；On the one hand one-dimensional silver nanowires, zero dimension Argent grain and flake graphite alkene can arrange in pairs or groups to form three-dimensional conductive network, in turn
The conductive stability of ink can be improved；Another aspect silver nanowires has excellent draw ratio, by silver nanowires lateral length
Excellent access enables the graphene film interlayer of big spacing to complete access by putting up a bridge, can prevent the reunion of graphene, also can
The stability for ensureing ink conduction, improves the service life of ink, moreover it is possible to improve the safety in utilization and service life of product；Change
It learns room temperature intercalation-two layers of Mechanical Crushing-high temperature expansion process and prepares few layer graphene, have both the graphene number of plies of chemical method preparation
Few feature, and have both physical method and prepare the good advantage of graphene conductive.Compared to chemical method, the pressure of environmental protection can be effectively reduced
Power compares physical method, can significantly reduce energy consumption.The binding material resin for preparing water-based electric heating ink is thermoplastic resin and thermosetting property
Resin compound, the lower glass transition temperature of thermoplastic resin can improve the flexibility of paint film, the characteristics such as adhesive force of paint film.
Substantially increase the safety of the use process of film layer.Binding material resin is weather-proof after thermosetting resin raising ink is powered
Property, temperature tolerance and surface hardness.Have by microplate graphene electric heating ink obtained by this method uniformly dispersed, highly conductive
Property, bright color the advantages that, and adhesive force is good, and water-fast, alcohol resistance can be good, is able to satisfy the levelability requirement of printing, greatly improves
The thickness uniformity of the heating layer of electric heating wall paper keeps the excellent rate of the product produced high, also can be convenient for improving product export
Safety.The slow curing of ink does not gamble the performance of mesh, provides convenience for the clear cylinder of cylinder technique, convenient for large-scale production electricity
Heat conversion film.
It is this method simple process, easy to operate the present invention also provides a kind of preparation method of electric heating wall paper, it can solve traditional print
Limitation of the brush mode to substrate material, and the production efficiency of electric heating wall paper can be significantly improved, the electric heating wall as made from this method
Cloth heating layer thickness uniformly and heating effect more evenly.
To achieve the goals above, the present invention provides a kind of preparation methods of electric heating wall paper, print electric heating using cylinder
Wall paper technique, specifically comprises the following steps:
D1: a kind of described in any item preparations of microplate graphene electric heating ink of claim 1 to 8 will be passed through with diluent
Microplate graphene electric heating ink made from method is compounded to the viscosity of 3000cps cylinder printing technology；
Microplate graphene electric heating ink after compounding: being pumped to the spray head out of ink of cylinder printing equipment by d2 by pipeline,
It under pump pressure, uniformly send to cylinder inner cylinder, adjusts cylinder printing scraper depth, angles and positions keep ink uniform out of cylinder
Extrusion print to substrate, the position of adjustable supporting roll regulates and controls the thickness and the thickness uniformity of ink printing；
D3: the ink printed is sent to toasting in baking oven, obtains electric heating wall paper semi-finished product in printing silver electrode；
D4: electric heating wall paper semi-finished product, copper sheathing, rubber protective layer are combined into electric heating wall paper by compounding machine high temperature.
In d2, cylinder material is one of polyurethane net, steel wire, nickel screen, and cylinder printing net inner diameter of steel flue is 0.1
~640mm, 80~300 mesh of cylinder mesh mesh number, sprinkler pressure are 0.1~0.5MPa, and scraper material is ordinary steel, in polyurethane
One kind, scraper angle is 60~85 °, 0.1~20 ° of support roller and scraper point of contact angle, substrate support rod and cylinder spacing 0.1
~300 μm, printing carbon layers having thicknesses are 0.1~20 μm, and print speed printing speed is 0.1~15m/min, and baking temperature is 60~150 DEG C, are dried
The roasting time is 5~30 minutes.
The present invention is suitble to the new electrically heating ink of cylinder printing using microplate graphene electric heating ink formulation, prints for cylinder
Electric heating wall paper provides possibility.Electric heating wall paper, which is printed, by cylinder opens a kind of new electric heating wall paper production technology.Pass through circle
Wire mark brush electric heating wall paper, thoroughly solves that silk-screen printing production efficiency is low, in the presence of the problem for returning black phenomenon when printing, also solves
Intaglio printing can only select the shortcomings that soft base material, realize the continous way production of even print, greatly improve production effect
Rate, and the carbon-coating fever printed is uniformly, significantly improves the quality of electric heating wall paper product, also significantly improves the excellent of product
Etc. rates, so that the safety of product in use has been obtained effective raising.It is this method simple process, easy to operate, pass through
Electric heating conversion film obtained by this method is applied to resident's electric heating, health physical therapy, greenhouse plantation, airport ground snow removing etc.
There is extraordinary application prospect in field.In addition, the electric heating metope is able to satisfy the demand in electromagnetic shielding.
The present invention also provides a kind of applications of electric heating wall paper, and electric heating wall paper obtained is applied to electromagnetic shield cloth.
Less than 10 Ω/, the shield effectiveness in 5kHz~10GHz frequency range is greater than the sheet resistance of the electric heating wall paper
40dB, absorbing property is excellent, meets the requirement of commercial 35dB.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of nano-Ag particles in the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of nano-silver thread in the present invention.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings.
A kind of preparation method of microplate graphene electric heating ink, includes the following steps:
S1: the preparation of nano-Ag particles, nano-silver thread:
A1: using chemical reduction method, in deionized water, restores silver salt solution by reducing agent and prepares nano silver colloid,
The pH value of colloid is adjusted by pH adjusting agent, and dispersing agent is added, obtains the spherical silver particles of different grain size size, and add stabilization
The nano-Ag particles that agent is stored for a long time；Wherein, deionized water, silver salt, pH adjusting agent, reducing agent and stabilizer volume ratio
0.1~80:0.1~20:0.1~5:0.1~20:0.1~20；Silver salt is one of silver nitrate and silver sulfate or two kinds
Mixing, preferably silver nitrate；PH adjusting agent is KOH, and pH value is 7~10, preferably 10；Reducing agent is ascorbic acid, citric acid
The mixing of one or more of sodium, glucose, sodium borohydride or amino acid (including tyrosine, aspartic acid etc.), preferably
It is reducing agent for the sodium citrate or amino acid (including tyrosine, aspartic acid etc.) of economic and environment-friendly type；Stabilizer be polyurethane,
The mixing of one or more of acrylic acid or styrene-acrylic emulsion, preferably triturable low-viscosity polyurethane lotion.Such as Fig. 1 and
Fig. 2 is respectively the scanning electron microscope (SEM) photograph of nano-Ag particles and nano-silver thread.
A2: with solvent stability and reducing agent, silver salt is restored under the high temperature conditions and prepares elemental silver, solvent stability and reducing agent
For the mixing of one or more of ethylene glycol, propylene glycol or isopropanol, preferably ethylene glycol, ethylene glycol under the high temperature conditions
Hydroxyls dehydrate become aldehyde radical, reduction silver salt prepares elemental silver；Crystal seed growth is adjusted using crystal seed growth stimulator, crystal seed growth stimulator is
The mixing of one or more of vulcanized sodium, potassium sulfide, preferably nine water vulcanized sodium, the volume of nine water vulcanized sodium are 0.1-500 μ
L is (using ethylene glycol as solvent, concentration 3mM)；Regulate and control the silver-colored crystal seed direction of growth by high molecular polymer and prepares different draw ratios
Nano-silver thread, high molecular polymer be PVP K-30 or K-90, preferably K-30；Wherein, solvent stability and
Reducing agent is ethylene glycol；The volume ratio of ethylene glycol, polyvinylpyrrolidone and silver nitrate is 0.1~40:0.1~10:0.1~4；
Reaction temperature is 120-160 DEG C, preferably 145-160 DEG C；Reaction time is 0.1-2 hours.
S2: the preparation of few layer microplate graphene filter cake:
B1: in the concentrated sulfuric acid (H2SO4) in be added ammonium persulfate ((NH4)2S2O8) it is slowly stirred dissolution, graphite powder is added
(C0), continue to stir, and hydrogen peroxide (H is added dropwise2O2), after standing, obtain micron order graphite aggregation (C1), it is washed to neutrality, is dried
It is dry；Wherein, 0.1~4:0.1 of mass ratio~50:0.1~8:0.1~10 of graphite powder, the concentrated sulfuric acid, ammonium persulfate and hydrogen peroxide,
Preferably 2~3:40~50:4~8:5~10.Required graphite powder (C0) specific surface area (BET) be 0.1~50m2/ g, preferably 30
~50m2/ g, micron order graphite aggregation (C obtained1) specific surface area (BET) be 0.1~120m2/ g, preferably 80~
120m2/g；
B2: it utilizes graphite aggregation (C in powder crushing plant1) further removing is at few layer of graphene microchip (C2),
Graphene microchip (the C of few layer obtained2) specific surface area (BET) be 0.1~320m2/ g, preferably 200~320m2/g；Again
By few layer of graphene microchip (C2) give to high-temperature expansion in high temperature carbonization furnace and obtain few layer graphenes aggregations (C3), it is obtained
Few layer graphenes aggregations (C3) specific surface area (BET) be 0.1~600m2Powder is made in/g；Used powder is broken to be set
Standby is one of airslide disintegrating mill, ultrasonic oscillator, preferably airslide disintegrating mill；Used high temperature carbonization furnace selection is lazy
Property gas shield, inert gas N2Or Ar2, preferably N2, 500~1200 DEG C of the high-temperature expansion temperature of high temperature carbonization furnace is excellent
It is selected as 800~1200 DEG C.
B3: by few layer graphenes aggregations (C3), aqueous dispersion and deionized water pass through physical dispersion method allotment water outlet
Property graphene dispersing solution；Few layer graphenes aggregations (C3), the mass ratio of aqueous dispersion and deionized water be 0.1~20:0.1
~10:0.1~90；It is preferred that 14~18:7~10:72~85；Few layer graphenes aggregations (C3) specific surface area (BET) be 0.1
~600m2/g；Aqueous dispersion is one of BYK190 and Digao dispersing agent or two kinds of mixing, preferably BYK190.
Physical dispersion method is one of ultrasound removing, sand mill grinding or micro-fluidic removing, and preferably sand mill is ground, and is sanded
Machine grinding cylinder temperature control at 10~35 DEG C, preferably 20~30 DEG C, sand mill mill ball be zirconium ball, granularity be 0.1~
0.8mm, preferably 0.6~0.8mm, discharging-material size is less than 20 μm.
B4: separating watersoluble plumbago alkene dispersion liquid by separation method and obtain few layer microplate graphene filter cake, spare；Separation side
Method is one of filter press filters pressing, industrial centrifugal machine centrifugation, preferably industrial centrifugal machine.Obtained high solids content graphene filter
Cake solid content 15-20%, preferably 17%.
S3: the preparation of microplate graphene electric heating ink:
By few layer of microplate graphene filter cake, macromolecule dispersing agent, levelling agent, size, preservative, nano-Ag particles, receive
Rice silver wire and binding material resin solution and defoaming agent are mixed, few layer microplate graphene filter cake, macromolecule dispersing agent, levelling
The mass ratio of agent, size, preservative, nano-Ag particles, nano-silver thread and binding material resin solution and defoaming agent be 0.1~
50:0.1~10:0.1~1%:0.1~1:0.1~1:0.1~1:0.01~0.2:0.1~60, the oil absorbency of few layer graphene
For 0.1~600m2/g；Macromolecule dispersing agent is one of anionic, quaternary ammonium salts, non-ionic or supermolecule dispersant
Or a variety of mixing, preferably quaternary ammonium salts and supermolecule dispersant compound, compound proportion 0.1~40:60~100；Levelling
Agent is BYK-333 or BYK-349；Size is Digao 270, and addition ground size is generation when defoaming agent is added in order to prevent
Shrinkage cavity phenomenon；Preservative is KD-3000；Binding material resin is the mixture of thermoplastic resin and thermosetting resin, thermoplasticity
The mass ratio of resin and thermosetting resin is 0.1~1, and thermoplastic resin is aqueous acrylic emulsion, styrene-acrylic emulsion, aqueous poly- ammonia
One or more of ester, preferably aqueous polyurethane emulsion, glass transition temperature (Tg) be 0.1~105 DEG C, preferably 40~
70 DEG C, lower glass transition temperature Tg improves the flexibility of paint film, the characteristics such as adhesive force of paint film, and thermosetting resin is aqueous
One or more of amino resins, aqueous epoxy resins and aqueous polyurethane, preferably waterborne polyurethane resin.Thermosetting property tree
Rouge improves weatherability, temperature tolerance and surface hardness after ink is powered.Nano-Ag particles granule size is 10~100nm, preferably
For 50~80nm；Nano-silver thread draw ratio is 0.1~100, preferably 20~60, and mixing time is 0.1~1 hour, stirred
Nano-Ag particles, nano-silver thread are dispersed as nanodispersion, nanometer fraction in resin using macromolecule dispersing agent in journey
Granular media grain is punctured into few layer of microplate graphene film sheaf space, obtains graphene microchip/nano silver electric heating ink, i.e. microplate graphite
Alkene electric heating ink.The viscosity of microplate graphene electric heating ink obtained is 3000~12000mPa.s, granularity is 0.1~20 μm,
Adhesive force is 0 grade.
A kind of preparation method of electric heating wall paper is printed electric heating wall paper technique using cylinder, is specifically comprised the following steps:
D1: a kind of described in any item preparations of microplate graphene electric heating ink of claim 1 to 8 will be passed through with diluent
Microplate graphene electric heating ink made from method is compounded to the viscosity of 3000cps cylinder printing technology；
Microplate graphene electric heating ink after compounding: being pumped to the spray head out of ink of cylinder printing equipment by d2 by pipeline,
It under pump pressure, uniformly send to cylinder inner cylinder, adjusts cylinder printing scraper depth, angles and positions keep ink uniform out of cylinder
Extrusion print to substrate, the position of adjustable supporting roll regulates and controls the thickness and the thickness uniformity of ink printing；Wherein cylinder
Printing equipment includes cylinder printing net, scraper, scraper adjuster, ink feed pump, ink spray head out of ink and substrate support roller group
At.Cylinder material is one of polyurethane net, steel wire, nickel screen, and cylinder printing net inner diameter of steel flue is 0.1~640mm, preferably
For 300~500mm, 80~300 mesh of cylinder mesh mesh number, preferably 80~200 mesh, sprinkler pressure is 0.1~0.5MPa, scraper
Material is one of ordinary steel, polyurethane, and scraper angle is 60~85 °, 0.1~20 ° of support roller and scraper point of contact angle, base
Material supporting stick and 0.1~300 μm of cylinder spacing, preferably 190~250 μm.Print carbon layers having thicknesses be 0.1~20 μm, preferably 8
~15 μm, print speed printing speed is 0.1~15m/min, and baking temperature is 60~150 DEG C, and preferably 100~130 DEG C, baking time is
5~30 minutes.
D3: the ink printed is sent to toasting in baking oven, obtains electric heating wall paper semi-finished product in printing silver electrode；
D4: electric heating wall paper semi-finished product, copper sheathing, rubber protective layer are combined into electric heating wall paper by compounding machine high temperature.Finished product
Electric heating wall paper resistance is 0.1~300 Ω/m2。
The diluent is the mixture of one or more of ethyl acetate, cyclohexanone.
Electric heating wall paper obtained is applied to electromagnetic shield cloth by a kind of application of electric heating wall paper, can be used for computer room, office
The separate spaces such as room carry out electromagnetic shielding use.Its wall paper sheet resistance is less than 10 Ω/.In frequency range: the screen of 5kHz~10GHz
Efficiency is covered greater than 40dB.Absorbing property is excellent, meets the requirement of commercial 35dB.
Embodiment 1:
One, the preparation method of one of the present embodiment microplate graphene electric heating ink, includes the following steps:
S1: the preparation of nano-Ag particles, nano-silver thread:
The tyrosine of 10mL is added in the deionized water of a1:70mL, oil bath is warming up to 90 DEG C, stirs half an hour, removes
The silver nitrate (0.5mM) of 10mL is added under stirring for extra tyrosine in ionized water, and rear color becomes light yellow, stirs
The KOH (1M) of 1mL is added under state, persistently stirs 1 hour, solution colour becomes grey black by light yellow, stops stirring, is down to
After room temperature, 10mL aqueous polyurethane emulsion is added, half an hour is stirred at room temperature, for use；
The ethylene glycol oil bath heating of a2:30mL continues heated at constant temperature 1 hour to 160 DEG C under stirring, 420 μ L are added
Nine water vulcanized sodium (solvent is ethylene glycol, 3mM), after five minutes, the polyvinylpyrrolidone of 7.5mL is added, and (k30, solvent are
EG, 180mM) and 2.5mL silver salt (284mM), in 160 DEG C of whipping process, the color of solution successively by it is colourless become claret,
Khaki eventually becomes milky.Stop heating, is down to room temperature, for use.
S2: the preparation of few layer microplate graphene filter cake:
B1: in the 400mL concentrated sulfuric acid (H2SO4) in be added 60g ammonium persulfate ((NH4)2S2O8) it is slowly stirred dissolution, it is added
20g graphite powder (C0, carbon content is greater than 99%, and lateral dimension is 10~120 μm, specific surface area 50m2/ g), continue to stir, stir
Mixing revolving speed is 600rpm, and the H of 60mL is slowly added dropwise2O2, after standing, obtain 20g micron order graphite aggregation (C1), it is washed to
Neutrality, drying；
B2: it is removed 0.5 hour, feed pressure 0.1MPa, operating pressure 0.8MPa using air-flow powder machine air-flow crushing, work
It is compressed air as medium, obtains the graphene microchip (C of few layer2)；It send to high temperature carbonization furnace, N2Under protective condition, 950 DEG C
High-temperature expansion 30 seconds, obtain few layer graphenes aggregations (C3, specific surface 450m2/ g) powder.
B3: by 17 parts of graphenes aggregations, 8 parts of BYK-190,75 parts of deionized water stirring half an hour obtain graphene aggregation
Liquid solution send to machine drum body (effective volume 30L) is sanded and is ground, and the control of sand mill barrel temperature is at 20~30 DEG C, zirconium ball
Granularity is 0.6~0.8mm, and zirconium ball loading 70% is ground to discharging-material size less than 20 μm.It send to centrifuge and is centrifuged, consolidate
The graphene filter cake of content 17%, for use.
S3: the preparation of microplate graphene electric heating ink:
Take 62.4 parts of aqueous polyurethane emulsions (thermoplasticity: thermosetting property mass ratio=1:2), 5 parts of macromolecule dispersing agent cores
Chemical S19 and Digao 760W mixture (compound proportion 30:70), 0.5 part of defoaming agent are mixed, and speed of agitator 800rpm is held
30 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of Digao are slowly added in continuous whipping process
270 ground sizes, 0.5 part of preservative KD3000,0.5 part of nano-Ag particles, 0.1 part of nano-silver thread, stirring obtain for 0.5 hour
Graphene microchip/nano silver electric heating ink, the i.e. preparation of microplate graphene electric heating ink.
Two, the preparation method of one of the present embodiment electric heating wall paper prints electric heating wall paper technique using cylinder, specific to wrap
Include following steps:
Microplate graphene electric heating ink obtained is compounded to the viscosity of 3000cps cylinder printing technology with diluent,
The sheet resistance of the middle black compound electro-thermal ink of graphene/carbon is 400 Ω/；
Microplate graphene electric heating ink is sent by pumping to cylinder printing to get to know, cylinder printing net is nickel screen, prints mesh number
200 mesh, cylinder diameter 640mm, sprinkler pressure 0.2MPa, scraper angle are 85 °, support roller with 10 ° of scraper angle, adjust printing
10 μm of carbon layers having thicknesses, print speed printing speed 10m/min, 130 degrees Celsius of baking temperature, baking time 5 minutes.Print silver electrode, baking
150 degrees Celsius of temperature, baking time 5 minutes.Silver electrode width 10mm, compound copper bar, glue film obtain 220W/m2Electric heating wall
Cloth.
Embodiment 2:
One, the step S1 and S2 in the preparation method of one of the present embodiment microplate graphene electric heating ink with implementation
S1 and S2 in example 1 is identical；
Step S3 particular content in the preparation method of one of the present embodiment microplate graphene electric heating ink are as follows:
Take 43 parts of aqueous polyurethane emulsions (thermoplasticity: thermosetting property mass ratio=1:2), 5 parts of macromolecule dispersing agent cores
S19 and Digao 760W mixture (compound proportion 30:70) are learned, 0.5 part of defoaming agent is mixed, and speed of agitator 800rpm continues
40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of Digao 270 are slowly added in whipping process
Ground size, 0.5 part of preservative KD3000,5 parts of nano-Ag particles, 5 parts of nano-silver threads, stirring obtain graphene in 0.5 hour
Microplate/nano silver electric heating ink, the i.e. preparation of microplate graphene electric heating ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of the present embodiment electric heating wall paper electric heating wall paper
Method is identical.
Embodiment 3:
One, step S1, S2 in the preparation method of one of the present embodiment microplate graphene electric heating ink with implementation
S1 and S2 in example 1 is identical；
Step S3 particular content in the preparation method of one of the present embodiment microplate graphene electric heating ink are as follows:
Take 43 parts of aqueous polyurethane emulsions (thermoplasticity: thermosetting property mass ratio=1:2), 5 parts of macromolecule dispersing agent cores
S19 and Digao 760W mixture (compound proportion 30:70) are learned, 0.5 part of defoaming agent is mixed, and speed of agitator 800rpm continues
40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of Digao 270 are slowly added in whipping process
Ground size, 0.5 part of preservative KD3000,10 parts of nano-Ag particles, stirring obtain graphene microchip/nano silver in 0.5 hour
Electric heating ink, the i.e. preparation of microplate graphene electric heating ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of the present embodiment electric heating wall paper electric heating wall paper
Method is identical.
Embodiment 4:
One, the step S1 and S2 in the preparation method of one of the present embodiment microplate graphene electric heating ink with implementation
S1 and S2 in example 1 is identical；
Step S3 particular content in the preparation method of one of the present embodiment microplate graphene electric heating ink are as follows:
Take 43 parts of aqueous polyurethane emulsions (thermoplasticity: thermosetting property mass ratio=1:2), 5 parts of macromolecule dispersing agent cores
S19 and Digao 760W mixture (compound proportion 30:70) are learned, 0.5 part of defoaming agent is mixed, and speed of agitator 800rpm continues
40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of Digao 270 are slowly added in whipping process
Ground size, 0.5 part of preservative KD3000,10 parts of nano-silver threads, stirring obtain graphene microchip/nano silver electricity for 0.5 hour
Hot oil ink, i.e. the preparation of microplate graphene electric heating ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of the present embodiment electric heating wall paper electric heating wall paper
Method is identical.
Comparative example 1:
One, the step S1 and S2 in the preparation method of one of this comparative example 1 microplate graphene electric heating ink with reality
The S1 and S2 applied in example 1 is identical；Step S3 in the preparation method of one of comparative example 1 microplate graphene electric heating ink is specific
Content is as follows:
Take 53 parts of aqueous polyurethane emulsions (thermoplasticity: thermosetting property mass ratio=1:2), 5 parts of macromolecule dispersing agent cores
S19 and Digao 760W mixture (compound proportion 30:70) are learned, 0.5 part of defoaming agent is mixed, and speed of agitator 800rpm continues
40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of Digao 270 are slowly added in whipping process
Ground size, 0.5 part of preservative KD3000, stirring obtain graphene microchip/nano silver electric heating ink, i.e. microplate in 0.5 hour
The preparation of graphene electric heating ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of this comparative example 1 electric heating wall paper electric heating wall paper
Method is identical.
Comparative example 2:
One, the step S1 and S2 in the preparation method of one of this comparative example 2 microplate graphene electric heating ink and implementation
S1 and S2 in example 1 is identical；Step S3 in the preparation method of one of this comparative example 2 microplate graphene electric heating ink is specific
Content is as follows:
Take 43 parts of aqueous thermoplastic polyurethane lotions (solid content 60%, Tg:32 DEG C of glass transition temperature), 5 parts of high scores
Sub- dispersing agent core chemistry S19 and Digao 760W mixture (compound proportion 30:70), 0.5 part of defoaming agent are mixed, and stirring turns
Fast 800rpm continues to be slowly added to 40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349 in whipping process,
0.5 part of 270 ground size of Digao, 0.5 part of preservative KD3000, stirring obtain graphene microchip/nano silver electric heating in 0.5 hour
Ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of this comparative example 2 electric heating wall paper electric heating wall paper
Method is identical.
Comparative example 3:
One, the step S1 and S2 in the preparation method of one of this comparative example 2 microplate graphene electric heating ink and implementation
S1 and S2 in example 1 is identical；Step S3 in the preparation method of one of this comparative example 2 microplate graphene electric heating ink is specific
Content is as follows:
Take 43 parts of aqueous thermosetting polyurethane resins (solid content 60%), 5 parts of macromolecule dispersing agent core chemistry S19 and enlightening
High 760W mixture (compound proportion 30:70), 0.5 part of defoaming agent are mixed, and speed of agitator 800rpm continues in whipping process
It is slowly added to 40 parts of graphene filter cakes (solid content 17%), 0.5 part of levelling agent BYK-349,0.5 part of 270 ground size of Digao,
0.5 part of preservative KD3000,5 parts of nano-Ag particles, 5 parts of nano-silver threads, stirring obtain graphene microchip/nano silver in 0.5 hour
Electric heating ink.
Two, the preparation of one of preparation method Yu embodiment 1 of one of this comparative example 2 electric heating wall paper electric heating wall paper
Method is identical.
Comparative example 4:
One, one of preparation method and embodiment 1 of one of this comparative example 2 microplate graphene electric heating ink microplate
The preparation method of graphene electric heating ink is identical；
Two, the preparation method particular content of one of this comparative example 2 electric heating wall paper is as follows.
Microplate graphene electric heating ink obtained is compounded to the viscosity of 3000cps cylinder printing technology with diluent,
The sheet resistance of the middle black compound electro-thermal ink of graphene/carbon is 400 Ω/；
400 Ω of sheet resistance/ ink is sent to silk-screen printing and is got to know, silk-screen printing net is poly- ammonia web material, prints mesh number 200
Mesh, effective printed patterns area are printed with cylinder, and shore scraper angle is 70 °, print 10 μm of carbon layers having thicknesses, print speed printing speed 5m/
Min, 120 degrees Celsius of baking temperature, baking time 10 minutes.Printing silver electrode, 140 degrees Celsius of baking temperature, baking time 10
Minute, silver electrode width 10mm, compound copper bar, glue film obtain the electric heating wall paper of 220W/m2.
By microplate obtained by microplate graphene electric heating ink obtained by embodiment 1-4 and electric heating wall paper comparative example 1-4
Graphene electric heating ink and electric heating wall paper compare performance test, as a result shown in table 1:
Table 1: micro- obtained by microplate graphene electric heating ink obtained by embodiment 1-4 and electric heating wall paper comparative example 1-4
Piece graphene electric heating ink and electric heating wall paper performance comparison table
The accounting of embodiment 1-4 difference graphene, nano-Ag particles and nano-silver thread, on the sheet resistance of finished product ink influence compared with
Greatly.Directly affect the electromagnet shield effect within the scope of diaphragm 5kHz~10GHz.
Embodiment 1 and comparative example 1 inhibit decaying as it can be seen that nano-Ag particles and nano-silver thread have graphene ink, slow down
The effect that graphene is reunited.
Embodiment 1 and comparative example 2, comparative example 3 is as it can be seen that thermoplasticity and thermosetting resin collocation are high using the service life of rear ink
In single thermoplasticity or heat cured resin.Thermoplasticity and thermosetting resin collocation are using improving the adhesive force of film layer and resistance to
It waits, temperature-resistance characteristic.
Embodiment 1 and comparative example 4 are as it can be seen that the electric heating film thickness using cylinder mode of printing prints fever temperature than flat bed screen
It spends more uniform.The safety of film layer also can be more preferable.
The accounting of embodiment 2-4 difference graphene, nano-Ag particles and nano-silver thread is as it can be seen that the electromagnetism that nano-silver thread is arranged in pairs or groups
Shielding properties is best, may be attributed to the draw ratio of the characteristic of nano-silver thread, and easy bridging forms electronics access.
By table 1 it is found that the sheet resistance of ink is remarkably decreased, film layer after the ratio for improving nano-Ag particles, nano-silver thread
Electromagnet shield effect significantly improve, wherein up to 69dB when highest, the shielding effect of any material in daily life can be met
Therefore fruit can be suitably used for computer room and use as electromagnetic shield cloth.
Process of the present invention is simple, technical maturity, stability are high and microplate graphene electric heating ink easy to operate, obtained
Sheet resistance is controllable, and adhesive force is good, and water-fast, alcohol resistance can be good, and the electric heating wall paper thickness printed with cylinder is more uniform, and heating temperature is not
The uniformity substantially increases the security performance of electric heating products less than 2 DEG C.Electric heating wall paper heating effect obtained by it is good, thickness
Uniformly, it is suitable for the fields such as resident's electric heating, greenhouse plantation, there is extraordinary application prospect.Meanwhile being also applied for computer room
Electromagnetic shield cloth use.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of microplate graphene electric heating ink, which comprises the steps of:
S1: the preparation of nano-Ag particles, nano-silver thread:
A1: using chemical reduction method, in deionized water, restores silver salt solution by reducing agent and prepares nano silver colloid, pass through
PH adjusting agent adjusts the pH value of colloid, and dispersing agent is added, obtains the spherical silver particles of different grain size size, and add stabilizer and obtain
To the nano-Ag particles stored for a long time；
Wherein, deionized water, silver salt, pH adjusting agent, reducing agent and stabilizer volume ratio 0.1~80:0.1~20:0.1~5:
0.1~20:0.1~20；
A2: with solvent stability and reducing agent, silver salt is restored under the high temperature conditions and prepares elemental silver；It is adjusted using crystal seed growth stimulator brilliant
Kind growth；Regulate and control the nano-silver thread that the silver-colored crystal seed direction of growth prepares different draw ratios by high molecular polymer；
S2: the preparation of few layer microplate graphene filter cake:
B1: ammonium persulfate being added in concentrated sulfuric acid and is slowly stirred dissolution, graphite powder is added, continues to stir, and hydrogen peroxide is added dropwise, quiet
It postpones, obtains micron order graphite aggregation, be washed to neutrality, dry；
Wherein, 0.1~4:0.1 of mass ratio~50:0.1~8:0.1~10 of graphite powder, the concentrated sulfuric acid, ammonium persulfate and hydrogen peroxide；
B2: micron order graphite aggregation is removed into the graphene microchip at few layer using in powder crushing plant, then by few layer
Graphene microchip is sent to high-temperature expansion in high temperature carbonization furnace and obtains few layer graphenes aggregations, and powder is made；
B3: few layer of graphenes aggregations, aqueous dispersion and deionized water are mixed into watersoluble plumbago alkene by physical dispersion method
Dispersion liquid；
Wherein, the mass ratio of few layer graphenes aggregations, aqueous dispersion and deionized water be 0.1~20:0.1~10:0.1~
90；
B4: separating watersoluble plumbago alkene dispersion liquid by separation method and obtain few layer microplate graphene filter cake, spare；
S3: the preparation of microplate graphene electric heating ink:
It will few layer microplate graphene filter cake, macromolecule dispersing agent, levelling agent, size, preservative, nano-Ag particles, nano silver
Line and binding material resin solution and defoaming agent are mixed, in whipping process using macromolecule dispersing agent by nano-Ag particles, receive
Rice silver wire is dispersed as nanodispersion in resin, and nanodispersion grain is punctured into few layer of microplate graphene film sheaf space
It is interior, obtain graphene microchip/nano silver electric heating ink, i.e. microplate graphene electric heating ink；
Wherein, few layer microplate graphene filter cake, macromolecule dispersing agent, levelling agent, size, preservative, nano-Ag particles, nanometer
The mass ratio of silver wire and binding material resin solution and defoaming agent is 0.1~50:0.1~10:0.1~1%:0.1~1:0.1~1:
0.1~1:0.01~0.2:0.1~60.
2. a kind of preparation method of microplate graphene electric heating ink according to claim 1, which is characterized in that
In a1 in S1, deionized water, silver salt, pH adjusting agent, reducing agent and stabilizer volume ratio are 50~70:7~15:
0.1~2:8~13:7~15；
In the b1 of S2, graphite powder, the concentrated sulfuric acid, ammonium persulfate and hydrogen peroxide mass ratio be 2~3:40~50:4~8:5~
10；
In b3 in S2, the mass ratio of few layer graphenes aggregations, aqueous dispersion and deionized water is 14~18:7~10:
72~85.
3. a kind of preparation method of microplate graphene electric heating ink according to claim 2, which is characterized in that
In a1 in S1, silver salt is one of silver nitrate and silver sulfate or two kinds of mixing, and pH adjusting agent KOH is gone back
Former agent is the mixing of one or more of ascorbic acid, sodium citrate, glucose, sodium borohydride or amino acid, stabilizer
For the mixing of one or more of polyurethane, acrylic acid or styrene-acrylic emulsion；
In a2 in S1, solvent stability and reducing agent are one or more of ethylene glycol, propylene glycol or isopropanol
Mixing, silver salt are one of silver nitrate and silver sulfate or two kinds of mixing, and crystal seed growth stimulator is vulcanized sodium, in potassium sulfide
One or more kinds of mixing, high molecular polymer are PVP K-30 or K-90；
In b3 in S2, aqueous dispersion is one of BYK190 and Digao dispersing agent or two kinds of mixing；
In S3, macromolecule dispersing agent be one of anionic, quaternary ammonium salts, non-ionic or supermolecule dispersant or
A variety of mixing, levelling agent are BYK-333 or BYK-349, and size is Digao 270, and preservative KD-3000 glues in S3
Ramming material resin is the mixture of thermoplastic resin and thermosetting resin.
4. a kind of preparation method of microplate graphene electric heating ink according to claim 3, which is characterized in that
In a1 in S1, reducing agent sodium citrate or amino acid, stabilizer are polyaminoester emulsion；
In a2 in S1, solvent stability and reducing agent are ethylene glycol, and silver salt is silver nitrate, and high molecular polymer is polyethylene pyrrole
Pyrrolidone K-30, crystal seed growth stimulator are nine water vulcanized sodium, and the volume of nine water vulcanized sodium is 0.1-500 μ L, ethylene glycol, polyethylene pyrrole
The volume ratio of pyrrolidone K-30 and silver nitrate is 0.1~40:0.1~10:0.1~4, and reaction temperature is 120-160 DEG C, when reaction
Between be 0.1-2 hours；
In S3, the mass ratio of thermoplastic resin and thermosetting resin is 0.1~1.
5. a kind of electric heating wall paper preparation method according to claim 4, which is characterized in that
In the a1 of S1, nano-Ag particles granule size obtained is 10~100nm；
In the a2 of S1, nano-silver thread draw ratio obtained is 0.1~100, the viscosity of microplate graphene electric heating ink obtained
For 3000~12000mPa.s, granularity be 0.1~20 μm, adhesive force is 0 grade；
In the b1 of S2, the specific surface area of required graphite powder is 0.1~50m2/ g, the ratio table of micron order graphite aggregation obtained
Area is 0.1~120m2/g；
In the b2 of S2, the specific surface area of the graphene microchip of few layer obtained is 0.1~320m2/g；
In b3 in S2, the specific surface area of few layer graphenes aggregations is 0.1~600m2/g；
In S3, the oil absorbency of few layer graphene is 0.1~600m2/g.
6. a kind of electric heating wall paper preparation method according to claim 5, which is characterized in that
In b2 in S2, used powder crushing plant is one of airslide disintegrating mill, ultrasonic oscillator, is used
High temperature carbonization furnace select inert gas shielding, inert gas N2Or Ar2, the high-temperature expansion temperature 800 of high temperature carbonization furnace~
1200℃；
In b3 in S2, physical dispersion method is one of ultrasound removing, sand mill grinding or micro-fluidic removing；
In b4 in S2, separation method is one of filter press filters pressing, industrial centrifugal machine centrifugation.
7. a kind of electric heating wall paper preparation method according to claim 6, which is characterized in that
In b2 in S2, used powder crushing plant is airslide disintegrating mill, inert gas N2, the height of high temperature carbonization furnace
500~1200 DEG C of warm expansion temperature；
In b3 in S2, physical dispersion method is sand mill grinding；
In b4 in S2, separation method is industrial centrifugal machine centrifugation.
8. a kind of preparation method of electric heating wall paper, which is characterized in that print electric heating wall paper technique using cylinder, specifically include as follows
Step:
D1: a kind of described in any item preparation methods of microplate graphene electric heating ink of claim 1 to 8 will be passed through with diluent
Microplate graphene electric heating ink obtained is compounded to the viscosity of 3000cps cylinder printing technology；
D2: the microplate graphene electric heating ink after compounding is pumped to the spray head out of ink of cylinder printing equipment by pipeline, is being pumped
It under pressure, uniformly send to cylinder inner cylinder, adjusts cylinder printing scraper depth, angles and positions squeeze ink uniformly out of cylinder
It prints out to substrate, the position of adjustable supporting roll regulates and controls the thickness and the thickness uniformity of ink printing；
D3: the ink printed is sent to toasting in baking oven, obtains electric heating wall paper semi-finished product in printing silver electrode；
D4: electric heating wall paper semi-finished product, copper sheathing, rubber protective layer are combined into electric heating wall paper by compounding machine high temperature.
9. a kind of preparation method of electric heating wall paper according to claim 8, which is characterized in that in d2, cylinder material is
One of polyurethane net, steel wire, nickel screen, cylinder printing net inner diameter of steel flue be 0.1~640mm, cylinder mesh mesh number 80~
300 mesh, sprinkler pressure be 0.1~0.5MPa, scraper material be one of ordinary steel, polyurethane, scraper angle be 60~
85 °, 0.1~20 ° of support roller and scraper point of contact angle, substrate support rod with 0.1~300 μm of cylinder spacing, print carbon layers having thicknesses
It is 0.1~20 μm, print speed printing speed is 0.1~15m/min, and baking temperature is 60~150 DEG C, and baking time is 5~30 minutes.
10. a kind of application of electric heating wall paper, which is characterized in that a kind of system of electric heating wall paper described in claim 8 or 9 will be passed through
Electric heating wall paper made from Preparation Method is applied to electromagnetic shield cloth.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294960A (en) * | 2019-07-30 | 2019-10-01 | 高碑店市隆泰丰博石墨烯有限公司 | Freezing point is starched and preparation method in -20 DEG C or less anti-freeze type watersoluble plumbago alkene electric heating |
| CN113604112A (en) * | 2021-08-31 | 2021-11-05 | 深圳清研皓隆科技有限公司 | Electrothermal coating and preparation method thereof |
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