CN106998597A - Electric heating device and device and preparation method thereof - Google Patents

Electric heating device and device and preparation method thereof Download PDF

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Publication number
CN106998597A
CN106998597A CN201710167035.8A CN201710167035A CN106998597A CN 106998597 A CN106998597 A CN 106998597A CN 201710167035 A CN201710167035 A CN 201710167035A CN 106998597 A CN106998597 A CN 106998597A
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China
Prior art keywords
graphene
heating device
electric heating
conductive ink
electrically conductive
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CN201710167035.8A
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Chinese (zh)
Inventor
李青
孙金梅
李赫然
王忠辉
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Beijing Xutan New Material Science & Technology Co Ltd
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Beijing Xutan New Material Science & Technology Co Ltd
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Priority to CN201710478928.4A priority Critical patent/CN107197546A/en
Priority to CN201710167035.8A priority patent/CN106998597A/en
Publication of CN106998597A publication Critical patent/CN106998597A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145Carbon only, e.g. carbon black, graphite
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/52Electrically conductive inks

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses electric heating device and device and preparation method thereof, belong to electrically conductive ink field, described electric heating device includes insulating body, watersoluble plumbago alkene electrically conductive ink heating layer, electrode and insulating protective film successively from down to up;Described watersoluble plumbago alkene electrically conductive ink heating layer by percentage to the quality, including following component:Resin 13%~74%, graphene 0.3~5%, conducting particles 1.5~24%, auxiliary agent 5.3~28%.Electric heating device of the present invention has good electric conductivity and long-time stability.

Description

Electric heating device and device and preparation method thereof
Technical field
The present invention relates to electrically conductive ink field, and in particular to a kind of electric heating device and device and preparation method thereof.
Background technology
In recent years, Electric radiant Heating Film is obtained in fields such as building, industry, agricultural, military affairs, household supplies and is widely applied, Particularly in terms of building and heating.Electric radiant Heating Film/plate in the market has two kinds, and one kind is one kind using carbon fiber as heater It is that resistance heater is used as using solvent-borne type conductive carbon paste;Both Electric radiant Heating Films/plate generally existing resistance is unstable, it is irregular to generate heat, The problem of long-time uses power attenuation, service life is short, while the problem of there is environmental pollution, constrains its electric heating significantly The application and development of film/plate.
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom, with high electron mobility and Electric conductivity, can be as high-quality conducting function unit, while graphene has fabulous heat conductivility, thermal conductivity factor is high, as Electrically heated heating function unit has very excellent performance and development prospect.
Graphene Electric radiant Heating Film in the market, its preparation method is prepared by chemical vapour deposition technique, and cost is high, system Standby area is small, product unification and industrial automation production are difficult.
The content of the invention
The embodiment of the present invention provides a kind of electric heating device and device and preparation method thereof, and the electrothermal structure has resistance steady The fixed, advantage of long lifespan.
In a first aspect, the embodiments of the invention provide a kind of electric heating device, described electric heating device includes exhausted successively Edge matrix, watersoluble plumbago alkene electrically conductive ink heating layer, electrode and insulating protective film;
Described watersoluble plumbago alkene electrically conductive ink heating layer by percentage to the quality, including following component:Resin 13%~ 74%, graphene 0.3~5%, conducting particles 1.5~24%, auxiliary agent 5.3~28%.
Further, watersoluble plumbago alkene electrically conductive ink heating layer causes film to obtain by watersoluble plumbago alkene electrically conductive ink is dry, institute The watersoluble plumbago alkene electrically conductive ink stated includes following component by percentage to the quality:Graphene:0.09%-6.40%, water: 8.10%-63.36%, abrasive media:3.00%-24.00%, conducting particles:1.50%-24.00%, the second auxiliary agent: 3.00%-8.00%, resinoid bond:10.00%-50.00%, the first auxiliary agent:5.00%-20.00%;Described first helps Agent includes dispersant and defoamer;The pH value of described watersoluble plumbago alkene electrically conductive ink be 8-10, viscosity be 3000~ 30000mPaS, sheet resistance is 100~5000 Ω;Described conducting particles be spherical conductive particle and rod conductive particle according to Mass ratio is 3-5:1 is mixed to get..
Further, the surface heat temperature of described electric heating device is 35~100 DEG C, power density 150~ 2000W;Working life >=30000h.
Further, described insulating body is polyester film, epoxy resin fiberglass plate or polyimide film;It is described Electrode be silver electrode and/or copper electrode;Described insulating protective film is to scribble the polyester film of adhesive, scribble adhesive Polyimide film, epoxy resin fiberglass plate.
Second aspect, the embodiment of the present invention provides a kind of preparation method of electric heating device, comprises the following steps:
By watersoluble plumbago alkene electrically conductive ink by silk-screen printing or intaglio printing on insulating body, drying form aqueous stone Black alkene electrically conductive ink heating layer of ink, covers electrode, then with insulation above described watersoluble plumbago alkene electrically conductive ink heating layer of ink Diaphragm hot pressing is compounded to form described electric heating device.
Further, described watersoluble plumbago alkene electrically conductive ink includes following component by percentage to the quality:Graphene: 0.09%-6.40%, water:8.10%-63.36%, abrasive media:3.00%-24.00%, conducting particles:1.50%- 24.00%, the second auxiliary agent:3.00%-8.00%, resinoid bond:10.00%-50.00%, the first auxiliary agent:5.00%- 20.00%;The first described auxiliary agent includes dispersant and defoamer;The pH value of described watersoluble plumbago alkene electrically conductive ink is 8- 10, viscosity is 3000~30000mPaS, and sheet resistance is 100~5000 Ω.
Further, the preparation of watersoluble plumbago alkene electrically conductive ink comprises the following steps:
(1) described abrasive media, water-based graphite alkene slurry and the first auxiliary agent are uniformly mixed so as to obtain the first mixture;
(2) described conducting particles is mixed with the first mixture, it is scattered to stir, obtain the second mixture;
(3) the second described mixture is ground to solid content particle diameter therein less than 5 μm, is filtrated to get graphene conductive Black wash;
(4) graphene conductive black wash, resinoid bond and the first auxiliary agent are disperseed after stirring to obtain watersoluble plumbago alkene Electrically conductive ink.
Further, described conducting particles is included in conductive black, carbon black, conductive zinc oxide and conductive titanium dioxide extremely Few one kind.
Further, described conducting particles is that spherical conductive particle and rod conductive particle are 3-5 according to mass ratio:1 It is mixed to get.Further, the second described auxiliary agent includes at least one of wetting agent, dispersant and defoamer.
Further, described resinoid bond is the resinoid bond crossed through amination treatment.
Further, described resinoid bond is emulsion acrylic resin, aqueous acrylic resin dispersion, acrylic acid tree At least one of the fat aqueous solution, aqueous polyurethane dispersion and styrene-acrylic emulsion.
Further, the first described auxiliary agent also includes pH adjusting agent, film forming agent, levelling agent, thickener, coupling agent and profit At least one of humectant.
Further, described dispersant be high molecular polymer, it is polycarboxylic acids ammonium salt class dispersant, polysiloxane-based scattered At least one of agent, polycarboxylate sodium's class dispersant, copolymer analog dispersant and Sulfonates dispersant;The defoamer is At least one of polysiloxane-based defoamer, organic silicon defoamer, silicone oil defoamer and polyethers defoamer;The pH Conditioning agent be amine nertralizer and/or alkaline matter, wherein, the amine nertralizer can be N, N- dimethylethanolamines and/ Or triethanolamine, the alkaline matter can be ammoniacal liquor and/or sodium hydroxide;The film forming agent is alkoxide and/or alcohol ethers; The thickener is at least one of polyurethanes copolymer, cellulose family and silica;The levelling agent is acrylic acid At least one of class, organic silicon and fluorocarbons class;The coupling agent is that silane coupler and/or titanate esters are coupled Agent;The wetting agent is organic silicon surface modifier.
The third aspect, the embodiment of the present invention provides a kind of electric heater unit, and described electric heater unit includes above-mentioned electricity Heating arrangement.
Further, described electric heater unit includes graphene heating wall, graphene heating pipeline, graphene electric heating wall Picture, graphene electric heater, graphene heating floor and graphene electric pad.
By such scheme, the present invention has the advantages that:
The watersoluble plumbago alkene electrically conductive ink layer of ink of the present invention, is that watersoluble plumbago alkene electrically conductive ink is printed on insulating substrate, Form high uniformity densification, the ultra-thin conductive heating coating of high adhesion force.Pass through graphene and the carbon nanomaterial of different scale It is compound, form 3-D nano, structure layer and stable skeleton conductive network, the SP2 carbon atomic layers of graphene film layer surface can be with It is in close contact with conducting particles, highest contacting efficiency is shown, while avoiding graphene between layers in the work of external force With the tomography of lower appearance, the quantity of conductive net path is added, conductive network structure is improved;Under electric field action, mutually rub Wipe, collide, make " Brownian motion ", produce substantial amounts of heat, and radiated with far infrared mode, realize efficient electric heating Conversion, heater heating is uniform, and system is stable, solves power attenuation in the prior art, the problem of service life is short.
Graphene Electric radiant Heating Film/plate of the present invention, by by watersoluble plumbago alkene electrically conductive ink silk-screen printing and/or intaglio printing On insulating substrate, new material new technology is combined with traditional handicraft, cost is low, homogeneity of product degree is high, efficiency high, it is real Existing auto industrialization production.
Overcome carbon printing ink and pollute the problems such as environment, resistance are big, poor adhesive force, electrical property are decayed, make up solution and prepare stone The influence for the electrical property that imperfect tape during black alkene comes.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.
A kind of electric heating device, described electric heating device includes insulating body, watersoluble plumbago alkene successively from down to up leads Electric ink heating layer, electrode and insulating protective film;Described watersoluble plumbago alkene electrically conductive ink heating layer by percentage to the quality, is wrapped Include following component:Resin 13%~74%, graphene 0.3~5%, conducting particles 1.5~24%, auxiliary agent 5.3~28%.
Preferably, described watersoluble plumbago alkene electrically conductive ink includes following component by percentage to the quality:Graphene: 0.09%-6.40%, water:8.10%-63.36%, abrasive media:3.00%-24.00%, conducting particles:1.50%- 24.00%, the second auxiliary agent:3.00%-8.00%, resinoid bond:10.00%-50.00%, the first auxiliary agent:5.00%- 20.00%;The first described auxiliary agent includes dispersant and defoamer;The pH value of described watersoluble plumbago alkene electrically conductive ink is 8- 10, viscosity is 3000~30000mPaS, and sheet resistance is 100~5000 Ω;Described conducting particles is spherical conductive particle and rod Shape conducting particles is 3-5 according to mass ratio:1 is mixed to get.
Preferably, the surface heat temperature of described electric heating device is 35~100 DEG C, power density 150~ 2000W;Working life >=30000h.
Preferably, described insulating body is polyester film, epoxy resin fiberglass plate or polyimide film.
To note here is that:Insulating body is by base material wetting and sided corona treatment mistake.
Preferably, described electrode is silver electrode and/or copper electrode.
Preferably, described insulating protective film is the polyester film for scribbling adhesive, the polyimides for scribbling adhesive Film, epoxy resin fiberglass plate.
A kind of preparation method of electric heating device, comprises the following steps:
By watersoluble plumbago alkene electrically conductive ink by silk-screen printing or intaglio printing on insulating body, drying form aqueous stone Black alkene electrically conductive ink heating layer of ink, covers electrode, then with insulation above described watersoluble plumbago alkene electrically conductive ink heating layer of ink Diaphragm hot pressing is compounded to form described electric heating device.
Preferably, described watersoluble plumbago alkene electrically conductive ink includes following component by percentage to the quality:Graphene: 0.09%-6.40%, water:8.10%-63.36%, abrasive media:3.00%-24.00%, conducting particles:1.50%- 24.00%, the second auxiliary agent:3.00%-8.00%, resinoid bond:10.00%-50.00%, the first auxiliary agent:5.00%- 20.00%;The first described auxiliary agent includes dispersant and defoamer;The pH value of described watersoluble plumbago alkene electrically conductive ink is 8- 10, viscosity is 3000~30000mPaS, and sheet resistance is 100~5000 Ω.
Preferably, the preparation of watersoluble plumbago alkene electrically conductive ink comprises the following steps:
(1) graphene, water, abrasive media, conducting particles, the second auxiliary agent, resin are weighed according to above-mentioned mass percent Binding agent, the first auxiliary agent;
(2) described abrasive media, water-based graphite alkene slurry and the first auxiliary agent are uniformly mixed so as to obtain the first mixture;
(3) described conducting particles is mixed with the first mixture, it is scattered to stir, obtain the second mixture;
(4) the second described mixture is ground to solid content particle diameter therein less than 5 μm, is filtrated to get graphene conductive Black wash.
(5) graphene conductive black wash, resinoid bond and the first auxiliary agent are disperseed after stirring to obtain watersoluble plumbago alkene Electrically conductive ink.
Preferably, described conducting particles is included in conductive black, carbon black, conductive zinc oxide and conductive titanium dioxide extremely Few one kind.
Preferably, it is 3-5 according to mass ratio that described conducting particles, which is spherical conductive particle and rod conductive particle,:1 It is mixed to get.
Preferably, the second described auxiliary agent includes at least one of wetting agent, dispersant and defoamer.
Preferably, described resinoid bond is the resinoid bond crossed through amination treatment.
Preferably, described resinoid bond is emulsion acrylic resin, aqueous acrylic resin dispersion, acrylic acid tree At least one of the fat aqueous solution, aqueous polyurethane dispersion and styrene-acrylic emulsion.It will be clear that when described resin is viscous When knot agent is two or more, the mass percent for any two kinds of resinoid bonds selected is not particularly limited.
Preferably, the first described auxiliary agent also includes pH adjusting agent, film forming agent, levelling agent, thickener, coupling agent and profit At least one of humectant.
Preferably, described dispersant be high molecular polymer, it is polycarboxylic acids ammonium salt class dispersant, polysiloxane-based scattered At least one of agent, polycarboxylate sodium's class dispersant, copolymer analog dispersant and Sulfonates dispersant;
To note here is that:Specifically, the high molecular polymerization species dispersant can be purchased from dimension Persian new material The dispersant of company, model 4900;Described polycarboxylic acids ammonium salt class dispersant can be purchased from the scattered of Sheng Nuopuke companies Agent, model SN-5027;Described copolymer analog dispersant can be the dispersant purchased from Di Gao companies and Bi Ke chemistry, type Number be Dego-752W, Dego-760W, BYK190.When described dispersant is two or more, that selectes is any The mass percent of two kinds of dispersants is not particularly limited.
The defoamer is polysiloxane-based defoamer, organic silicon defoamer, silicone oil defoamer and polyethers froth breaking At least one of agent;
To note here is that:The defoamer is preferably polysiloxane-based defoamer, specifically, can be high purchased from enlightening Company and the defoamer of Bi Ke chemistry, model Dego-901W, BYK-024, BYK-028.
The pH adjusting agent be amine nertralizer and/or alkaline matter, wherein, the amine nertralizer can be N, N- bis- Methylethanolamine and/or triethanolamine;The alkaline matter can be ammoniacal liquor and/or sodium hydroxide;
To note here is that:Specifically, the pH adjusting agent can be to be neutralized purchased from the entitled amine of this company of hamming Agent DMAE;The content of the pH adjusting agent is not particularly limited, as long as the pH value of the watersoluble plumbago alkene electrically conductive ink is controlled In above range.
The film forming agent is alkoxide and/or alcohol ethers;To note here is that:Specifically, the alkoxide can be Lauryl Alcohol ester, the alcohol ethers can be butyl glycol ether and/or propane diols phenylate;
The thickener is at least one of polyurethanes copolymer, cellulose family and silica;
To note here is that:The thickener can be to increase purchased from the entitled polyurethanes copolymer of Rhom and Hass Thick dose, model RM-8W, or hydroxyethyl ether cellulose, model 250HBR.The content of the thickener is not specific Limit, as long as the viscosity of the watersoluble plumbago alkene electrically conductive ink is controlled in above range.
The levelling agent is at least one of acrylic compounds, organic silicon and fluorocarbons class;
Specifically, described levelling agent can be the levelling agent purchased from Bi Ke chemistry, model BYK-381, BYK-340.
The coupling agent is silane coupler and/or titanate coupling agent;Wherein, preferably coupling agent is silane coupler, Specifically, it can be KH-550.
The wetting agent is organic silicon surface modifier.Specifically, described wetting agent can be purchased from Bi Ke chemistry Organosilyl surface auxiliary agent, model BYK-349.
To note here is that:The dispersant, defoamer, pH adjusting agent, film forming agent, levelling agent, thickener, coupling agent It is not particularly limited with the respective content of wetting agent, can is the conventional selection of those skilled in the art.
A kind of electric heater unit, described electric heater unit includes above-mentioned electric heating device.
To note here is that:Performance parameter on electrically conductive ink can be determined in the following way:By watersoluble plumbago alkene On the glass substrate, it is 25 μm to make its thickness of dry film to conductive ink application, and after after its drying, sample is placed on into tester operation Platform, operation probe station pressure probe, turn-on current, selection sheet resistance classification is tested;
Viscosity parameter is tested by U.S.'s Brookfield rotation viscometers;
Attachment force parameter passes through GB 1720-89《Paint film adhesion determination method》Measure;
Electric performance stablity parameter has by a certain temperature, placing the sheet resistance rate of change after certain time to judge Body examination method for testing is as follows:
By watersoluble plumbago alkene conductive ink application on the glass substrate, it is 25 μm to make its thickness of dry film, after after its drying, is led to Cross the double electrical measurement four-point probes of RTS-9 and test its sheet resistance, record initial sheet resistance R;Then sample is placed on to 80 DEG C of baking oven In, after baking 360h, test sample sheet resistance, records final sheet resistance R again', then calculate sheet resistance rate of change R%=(R′- R)/R
Printing adaptability parameter by by watersoluble plumbago alkene electrically conductive ink silk-screen printing or intaglio printing on certain base material, Investigate its outward appearance, whether printed matter clearly judges.
The water-based graphite alkene slurry being previously mentioned in the present invention is the dispersion liquid of graphene and surfactant, wherein, surface The weight/mass percentage composition of activating agent is not higher than 1%, and solvent is water.
Here is specific embodiment:
Embodiment 1
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
(1) by 100g water-based acrylic resins, 700g water-based graphite alkene slurry (solid quality percentage composition 3%, wherein Contain surfactant 3.5g), 10g dispersants SN-5027,20g dispersant 760W, 5g wetting agent BYK-349,15g defoamer 901W is added in grinding pot, and stirring 2h is disperseed under 1000rpm rotating speeds, then adds 150g spherical conductive carbon black, in 1500rpm Disperse stirring 2h under rotating speed;Then 0.8~1.0 μm of zirconium oxide bead is added in step (1) mixture, is ground to particle diameter and is less than 5 μm, discharging obtains graphene conductive black wash;
(2) 500g graphene conductives black wash, 400g water-based acrylic resins emulsion, 20g dispersant Bs YK190,15g are disappeared Infusion BYK-024,40g film forming agent, 15g levelling agents, 10g coupling agents KH550 are added in dispersion tank, under 1000rpm rotating speeds Scattered stirring 3h, while adding pH adjusting agent DMAE and thickener RM8W, regulation pH value is 9, and viscosity is 10000mPaS.Go out Material both obtains watersoluble plumbago alkene electrically conductive ink Ink1;
As a result the Ink1 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 2
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
(1) by 150g water-based acrylic resins, 600g water-based graphite alkene slurry (solid quality percentage composition 5%, wherein Contain surfactant 6g), 10g dispersants SN-5027,20g dispersant 760W, 5g wetting agent BYK-349,15g defoamer 901W is added in grinding pot, and stirring 2h is disperseed under 1000rpm rotating speeds, then adds 200g bar-shaped zinc oxide, is turned in 1500rpm The lower scattered stirring 2h of speed;Then 0.8~1.0 μm of zirconium oxide bead is added in step (1) mixture, is ground to particle diameter less than 5 μ M, discharging obtains graphene conductive black wash;
(2) 600g graphene conductives black wash, 300g water-based acrylic resins emulsion, 20g dispersant Bs YK190,15g are disappeared Infusion BYK-024,40g film forming agent, 15g levelling agents, 10g coupling agents KH550 are added in dispersion tank, under 1000rpm rotating speeds Scattered stirring 3h, while adding pH adjusting agent DMAE and thickener RM8W, regulation pH value is 9, and viscosity is 15000mPaS.Go out Material both obtains watersoluble plumbago alkene electrically conductive ink Ink2;
As a result the Ink2 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 3
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
(1) by 250g water-based acrylic resins, 450g water-based graphite alkene slurry (solid quality percentage composition 8%, wherein Contain surfactant 4.2g), 10g dispersants SN-5027,20g dispersant 760W, 5g wetting agent BYK-349,15g defoamer 901W is added in grinding pot, the scattered stirring 2h under 1000rpm rotating speeds, Ran Houjia, 250g spherical conductive titanium dioxide, Disperse stirring 2h under 1500rpm rotating speeds;Then 0.8~1.0 μm of zirconium oxide bead is added in step (1) mixture, be ground to Particle diameter is less than 5 μm, and discharging obtains graphene conductive black wash;
(2) 700g graphene conductives black wash, 200g water-based acrylic resins emulsion, 20g dispersant Bs YK190,15g are disappeared Infusion BYK-024,40g film forming agent, 15g levelling agents, 10g coupling agents KH550 are added in dispersion tank, under 1000rpm rotating speeds Scattered stirring 3h, while adding pH adjusting agent DMAE and thickener RM8W, regulation pH value is 9, and viscosity is 25000mPaS.Go out Material both obtains watersoluble plumbago alkene electrically conductive ink Ink3;
As a result the Ink3 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 4
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 1 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 2 Property Graphene conductive ink, i.e. Ink4.
As a result the Ink4 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 5
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 1 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 3 Property Graphene conductive ink, i.e. Ink5.
As a result the Ink5 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 6
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 2 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 1 Property Graphene conductive ink, i.e. Ink6.
As a result the Ink6 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 7
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 2 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 3 Property Graphene conductive ink, i.e. Ink7.
As a result the Ink7 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 8
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 3 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 1 Property Graphene conductive ink, i.e. Ink8.
As a result the Ink8 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 9
The present embodiment is used for illustrating preparing watersoluble plumbago alkene electrically conductive ink using the method for the present invention.
Method according to (1) in embodiment 3 prepares graphene conductive black wash, and water is prepared according to the method for (2) in embodiment 2 Property Graphene conductive ink, i.e. Ink9.
As a result the Ink9 of above-mentioned preparation is respectively coated on tinplate, on glass plate, while being screen printed onto PET On film, wherein, thickness of dry film is 25 μm;
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 10
The difference of the present embodiment and embodiment 1 is that the conducting particles that the present embodiment is selected is spherical conductive carbon black What 120g and bar-shaped zinc oxide 30g was uniformly mixed to get.
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 11
Be with the difference of embodiment 2, the conducting particles that the present embodiment is used for spherical conductive titanium dioxide 150g and Bar-shaped zinc oxide 50g mixture.
Then the sheet resistance and the stability of electrical property of the dry film of test coating on a glass, are coated on tinplate and do The adhesive force of film, tests the viscosity and printing adaptability of watersoluble plumbago alkene electrically conductive ink sample, as shown in table 1.
Embodiment 10 and 11 is from conducting particles and rod conductive particle according to certain mass ratio (3-5:1) mixing, Bar-shaped zinc oxide can form skeleton between layers in graphene, prevent the relative slip of ball contact, make graphene layer with Contact between layer is more firm;And bar-shaped zinc oxide can connect multi-layer graphene, make contact between layers more It is stable;But the ratio of rod conductive particle can not be too big, resistance between layers otherwise can be increased, and conducting particles and rod Shape conducting particles is used cooperatively so that while the stability of the contact between ensureing graphene layer, moreover it is possible to ensure electric conductivity Energy.
To note here is that:Graphene conductive layer of ink (conductive ink application dry after, there are fractions to vapor away) by Graphene, conducting particles, resin, auxiliary agent (including the first auxiliary agent and second auxiliary agent) composition, its content are as follows:Resin 13%~ 74%, graphene 0.3~5%, conducting particles 1.5~24%, auxiliary agent 5.3~28%.Specific insulation:0.001~0.09 Ω·cm。
Table 1 is embodiment 1-11 watersoluble plumbago alkene electrically conductive ink performance parameter tables, the performance parameter such as institute of table 1 of electrically conductive ink Show.
The watersoluble plumbago alkene electrically conductive ink performance parameter table of table 1
It can be seen that from above-described embodiment 1-11 test result:The watersoluble plumbago alkene prepared using the method for the present invention is led Electric ink adhesion is excellent, and sheet resistance and viscosity are adjustable, it is most important that after baking 360h 80 degree long-term resistance variations it is micro- its It is micro-, wherein where may having the reason for measurement error causes resistance variations.The watersoluble plumbago alkene prepared using the inventive method is led Electric ink, stable conductive network structure, the SP of graphene film layer surface are formed by adding conducting particles and graphene2Carbon is former Sublayer can be in close contact with conducting particles, show highest contacting efficiency, be existed between layers while avoiding graphene The tomography occurred in the presence of external force, adds the quantity of conductive net path, improves conductive network structure, the test number of table 1 Long-time stability according to the electric conductivity for indicating the watersoluble plumbago alkene electrically conductive ink are excellent.
Used it can be seen from the measurement result of embodiment 10 and 11 using conducting particles and rod conductive mix particles, The performance of electrically conductive ink, which is substantially better than, uses merely spherical or rod conductive particle ink, it is recognised that spherical and bar-shaped lead There is certain synergy between charged particle, add the stability and electric conductivity of electrically conductive ink, and adhesive force also has Certain lifting.
Watersoluble plumbago alkene electrically conductive ink printing adaptability is prepared using the method for the present invention excellent, printed matter is fine and smooth, clear, And water-base resin is used, and it is environment friendly and pollution-free, prepare graphene heating film or graphene electric heating for the watersoluble plumbago alkene electrically conductive ink Plate, and then graphene Electrical heating fresco, graphene electric heater, graphene heating floor, graphene electric heating are prepared by product design The products such as pad, applied to constructure heatings such as family, public building, agriculture cultivations, pipe insulation, ground device for melting snow, far red The fields such as outer health-care physical therapy provide theoretical foundation and practical basis.
Graphene Electric radiant Heating Film/the plate prepared by above-mentioned watersoluble plumbago alkene electrically conductive ink can be adjusted according to different application Scenario Design Its performance parameter is saved, wherein surface heat temperature is 35~100 DEG C adjustable, and 150~2000W of power density is adjustable;Its work longevity Life >=30000h, programming rate is fast, and 1~3min is the surface temperature that can reach design.
To note here is that:Typically by watersoluble plumbago alkene electrically conductive ink silk-screen printing or intaglio printing in insulating body On, uniform conductive exothermal film layer is formed, its thicknesses of layers is 10 μm~50 μm.Insulating body can make polyester film, epoxy Plexiglas fiberboard or polyimide film, its thickness are 0.1~20mm.Electrode can be silver electrode and/or copper electrode, be used for Switch on power.Insulating protective film can be scribbled the polyester film of adhesive, scribble the polyimide film or asphalt mixtures modified by epoxy resin of adhesive Fat glass mat.
By sheet resistance be 500 Ω, viscosity be 4000~6000mPaS, adhesive force be 1 grade, the watersoluble plumbago of fineness≤15 μm Alkene electrically conductive ink is printed on PET film by the way of intaglio printing, forms the watersoluble plumbago alkene electrically conductive ink that thickness is 15 μm and sends out Hot layer of ink, after 120 DEG C of oven dryings, silver electrode is printed in both sides, is toasted through 120 DEG C of baking ovens, after silver electrode is dried, thereon Copper electrode is covered in side, then forms graphene Electric radiant Heating Film after 80 DEG C of hot pressing are compound with scribbling the polyester film of adhesive.Performance is surveyed Test result is as shown in table 2 (1 group).
Be respectively 200 Ω, 500 Ω, 1000 Ω by sheet resistance, viscosity be 15000~20000mPaS, adhesive force be 1 grade, The watersoluble plumbago alkene electrically conductive ink of fineness≤15 μm is mixed by a certain percentage according to power setting, using the side of silk-screen printing Formula is printed on epoxy resin fiberglass plate, the watersoluble plumbago alkene electrically conductive ink heating layer of ink that thickness is 15 μm is formed, through 120 After DEG C oven drying, copper electrode is covered above it, after then hot pressing is compound at a temperature of 300 DEG C with epoxy resin fiberglass plate Form graphene electric hot plate.The performance test results are as shown in table 2 (2 groups).
After graphene Electric radiant Heating Film and graphene electric hot plate switch on power, it is brought rapidly up, reaches the surface temperature of design, simultaneously Trigger itself and produce far infrared, heat is sent into space in the form of far infrared heat energy is radiated, human body and object is experienced It is warm, naturally uniform rise indoor temperature.It is applied to prepare graphene Electrical heating fresco, graphene electric heating by product design The products such as device, graphene heating floor, graphene electric pad.Graphene Electric radiant Heating Film and graphene electric hot plate and application graphite electricity Hot product can be widely applied to the constructure heatings such as family, public building, agriculture cultivations, pipe insulation, ground device for melting snow, far The fields such as infrared health physiotherapy.
Table 2
It can be seen that from above-mentioned test result:The graphene Electric radiant Heating Film and graphene electric heating prepared using the method for the present invention Plate, the temperature difference is small, and quick heating, service life is long, and changed power is small, substantially undamped.The test data of table 1 indicates the graphene The excellent performance of Electric radiant Heating Film and graphene electric hot plate.
Graphene Electric radiant Heating Film is prepared using the method for the present invention and the heating of graphene electric hot plate is uniform, the temperature difference is small, uses the longevity Life length, electric performance stablity, power is substantially undamped, rapid to rise after the graphene Electric radiant Heating Film and graphene electric hot plate switch on power Temperature, reaches the surface temperature of design, while triggering itself produces far infrared, heat is sent in the form of far infrared heat energy is radiated Enter space, experience human body and object warm, naturally uniform rise indoor temperature.It is applied to prepare stone by product design The products such as black alkene Electrical heating fresco, graphene electric heater, graphene heating floor, graphene electric pad.For graphene Electric radiant Heating Film and Graphene electric hot plate and using graphite electric heating products be widely used in the constructure heatings such as family, public building, agricultural cultivate, The fields such as pipe insulation, ground device for melting snow, far infrared health care physiotherapy provide theoretical foundation and practical basis.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.
Above example is only the exemplary embodiment of the present invention, is not used in the limitation present invention, protection scope of the present invention It is defined by the claims.Those skilled in the art can make respectively in the essence and protection domain of the present invention to the present invention Modification or equivalent substitution are planted, this modification or equivalent substitution also should be regarded as being within the scope of the present invention.

Claims (16)

1. a kind of electric heating device, it is characterised in that described electric heating device includes insulating body, watersoluble plumbago alkene successively leads Electric ink heating layer, electrode and insulating protective film;
Described watersoluble plumbago alkene electrically conductive ink heating layer by percentage to the quality, including following component:Resin 13%~74%, Graphene 0.3~5%, conducting particles 1.5~24%, auxiliary agent 5.3~28%.
2. electric heating device according to claim 1, it is characterised in that watersoluble plumbago alkene electrically conductive ink heating layer is by aqueous Graphene conductive ink is dry to cause film to obtain, and described watersoluble plumbago alkene electrically conductive ink includes such as the following group by percentage to the quality Point:Graphene:0.09%-6.40%, water:8.10%-63.36%, abrasive media:3.00%-24.00%, conducting particles: 1.50%-24.00%, the second auxiliary agent:3.00%-8.00%, resinoid bond:10.00%-50.00%, the first auxiliary agent: 5.00%-20.00%;The first described auxiliary agent includes dispersant and defoamer;The pH of described watersoluble plumbago alkene electrically conductive ink It is worth for 8-10, viscosity is 3000~30000mPaS, sheet resistance is 100~5000 Ω;Described conducting particles is spherical conductive grain Son and rod conductive particle are 3-5 according to mass ratio:1 is mixed to get.
3. electric heating device according to claim 1, it is characterised in that the surface heat temperature of described electric heating device For 35~100 DEG C, 150~2000W of power density;Working life >=30000h.
4. electric heating device according to claim 1, it is characterised in that described insulating body is polyester film, epoxy Plexiglas fiberboard or polyimide film;Described electrode is silver electrode and/or copper electrode;Described insulating protective film is painting Polyester film, the polyimide film for scribbling adhesive, the epoxy resin fiberglass plate for having adhesive.
5. a kind of preparation method of electric heating device, it is characterised in that comprise the following steps:
By watersoluble plumbago alkene electrically conductive ink by silk-screen printing or intaglio printing on insulating body, drying form watersoluble plumbago alkene Electrically conductive ink heating layer of ink, covers electrode, then with insulation protection above described watersoluble plumbago alkene electrically conductive ink heating layer of ink Film hot pressing is compounded to form described electric heating device.
6. the preparation method of electric heating device according to claim 5, it is characterised in that described watersoluble plumbago alkene is conductive Ink includes following component by percentage to the quality:Graphene:0.09%-6.40%, water:8.10%-63.36%, grinding medium Matter:3.00%-24.00%, conducting particles:1.50%-24.00%, the second auxiliary agent:3.00%-8.00%, resinoid bond: 10.00%-50.00%, the first auxiliary agent:5.00%-20.00%;The first described auxiliary agent includes dispersant and defoamer;It is described Watersoluble plumbago alkene electrically conductive ink pH value be 8-10, viscosity be 3000~30000mPaS, sheet resistance be 100~5000 Ω.
7. the preparation method of electric heating device according to claim 6, it is characterised in that watersoluble plumbago alkene electrically conductive ink Preparation comprises the following steps:
(1) described abrasive media, water-based graphite alkene slurry and the first auxiliary agent are uniformly mixed so as to obtain the first mixture;
(2) described conducting particles is mixed with the first mixture, it is scattered to stir, obtain the second mixture;
(3) the second described mixture is ground to solid content particle diameter therein less than 5 μm, is filtrated to get graphene conductive black Slurry;
(4) graphene conductive black wash, resinoid bond and the first auxiliary agent are disperseed to obtain watersoluble plumbago alkene conduction after stirring Ink.
8. the preparation method of electric heating device according to claim 6, it is characterised in that described conducting particles includes leading At least one of electric carbon black, carbon black, conductive zinc oxide and conductive titanium dioxide.
9. the preparation method of electric heating device according to claim 8, it is characterised in that described conducting particles is spherical Conducting particles and rod conductive particle are 3-5 according to mass ratio:1 is mixed to get.
10. the preparation method of electric heating device according to claim 6, it is characterised in that the second described auxiliary agent includes At least one of wetting agent, dispersant and defoamer.
11. the preparation method of electric heating device according to claim 6, it is characterised in that described resinoid bond is The resinoid bond crossed through amination treatment.
12. the preparation method of electric heating device according to claim 11, it is characterised in that described resinoid bond is Emulsion acrylic resin, aqueous acrylic resin dispersion, acrylic resin aqueous solution, aqueous polyurethane dispersion and styrene-acrylic emulsion At least one of.
13. the preparation method of electric heating device according to claim 6, it is characterised in that the first described auxiliary agent is also wrapped Include at least one of pH adjusting agent, film forming agent, levelling agent, thickener, coupling agent and wetting agent.
14. the preparation method of electric heating device according to claim 13, it is characterised in that described dispersant is high score Sub- polymer, polycarboxylic acids ammonium salt class dispersant, polysiloxane-based dispersant, polycarboxylate sodium's class dispersant, copolymer analog disperse At least one of agent and Sulfonates dispersant;The defoamer is polysiloxane-based defoamer, organic silicon defoamer, silicon At least one of oils defoamer and polyethers defoamer;The pH adjusting agent be amine nertralizer and/or alkaline matter, its In, the amine nertralizer can be N, N- dimethylethanolamines and/or triethanolamine, and the alkaline matter can be ammoniacal liquor And/or sodium hydroxide;The film forming agent is alkoxide and/or alcohol ethers;The thickener is polyurethanes copolymer, cellulose At least one of class and silica;The levelling agent be acrylic compounds, organic silicon and fluorocarbons class at least It is a kind of;The coupling agent is silane coupler and/or titanate coupling agent;The wetting agent is organic silicon surface modifier.
15. a kind of electric heater unit, it is characterised in that described electric heater unit is included described in claim any one of 1-4 Electric heating device.
16. electric heater unit according to claim 15, it is characterised in that described electric heater unit is sent out including graphene Hot wall, graphene heating pipeline, graphene Electrical heating fresco, graphene electric heater, graphene heating floor and graphene electric pad.
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