CN107236382A - The Electric radiant Heating Film that water-based electric heating coating is prepared with composition and water-based electric heating coating and preparation method thereof and by it - Google Patents
The Electric radiant Heating Film that water-based electric heating coating is prepared with composition and water-based electric heating coating and preparation method thereof and by it Download PDFInfo
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- CN107236382A CN107236382A CN201710462979.8A CN201710462979A CN107236382A CN 107236382 A CN107236382 A CN 107236382A CN 201710462979 A CN201710462979 A CN 201710462979A CN 107236382 A CN107236382 A CN 107236382A
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- water
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- electric heating
- aqueous dispersion
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000010438 heat treatment Methods 0.000 title claims abstract description 74
- 238000005485 electric heating Methods 0.000 title claims abstract description 71
- 238000000576 coating method Methods 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- 239000006185 dispersion Substances 0.000 claims abstract description 40
- 239000006229 carbon black Substances 0.000 claims abstract description 31
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 27
- 239000008199 coating composition Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000000227 grinding Methods 0.000 claims description 34
- 239000013530 defoamer Substances 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000002562 thickening agent Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 17
- 239000003002 pH adjusting agent Substances 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- -1 oxygen alkanes Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 229940043237 diethanolamine Drugs 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000029219 regulation of pH Effects 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 239000005439 thermosphere Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 240000003936 Plumbago auriculata Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating 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
- H05B3/14—Heating 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- 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)
Abstract
The present invention relates to paint field, and in particular to the Electric radiant Heating Film that water-based electric heating coating is prepared with composition and water-based electric heating coating and preparation method thereof and by it.The water-based electric heating coating composition contains aqueous dispersion resin, CNT, graphene and nano carbon black, wherein, the aqueous dispersion resin, the CNT, the weight ratio of the content of the graphene and the nano carbon black are 1：0.09‑0.4：0.08‑0.3：0.1‑0.7.During Electric radiant Heating Film is prepared by water-based electric heating coating, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive network is built in heating layer, the problems such as Electric radiant Heating Film power attenuation, production and application are discharged fundamentally is solved.
Description
Technical field
The present invention relates to paint field, and in particular to water-based electric heating coating composition and water-based electric heating coating and its preparation
Method and the Electric radiant Heating Film prepared by it.
Background technology
Electric radiant Heating Film, Electrical heating fresco, electric pad etc. are that a kind of can be generated heat after energization film makes, by by electrically-conducting paint
It is printed on film, is aided with the materials such as metal current-carrying bar, conductive silver paste and is made.By the development of decades, the application of Electric radiant Heating Film
Scope is more and more wider, and the multiple fields such as heating, industry, agricultural are covered extensively, and in air pollution serious today, Electric radiant Heating Film is made
Without discharge heating mode, to there is extensive development space.Electric radiant Heating Film can give off far infrared by coating, reasonable to human body
Health-care efficacy is treated, body-sensing is comfortable.Coordinate intelligence control system, Electric radiant Heating Film can be truly realized energy-conserving and environment-protective.
The core heater of Electric radiant Heating Film is electric-heating coatings, and the quality of its quality directly determines the product capability of Electric radiant Heating Film.Mesh
Electric radiant Heating Film on preceding domestic market is generally South Korea's technology, using coating such as carbon crystal, carbon slurries, has power attenuation seriously, production makes
And have VOC (VOC (volatile organic compounds)) discharge etc. critical defect.
Therefore, a kind of water-based electric heating coating composition and water-based electric heating coating are researched and developed, and is applied in Electric radiant Heating Film
On have important practical significance.
The content of the invention
The invention aims to the drawbacks described above for overcoming prior art presence, there is provided a kind of water-based electric heating coating group
Compound and water-based electric heating coating and preparation method thereof and the Electric radiant Heating Film prepared by it.Electric heating is being prepared by water-based electric heating coating
During film, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive net is built in heating layer
Network, fundamentally solves the problems such as Electric radiant Heating Film power attenuation, production and application are discharged.
To achieve these goals, one aspect of the present invention provides a kind of water-based electric heating coating composition, wherein, its
In, the aqueous dispersion resin, the CNT, the weight ratio of the content of the graphene and the nano carbon black can be
1：0.09-0.4：0.08-0.3：0.1-0.7.
Preferably, the content of the aqueous dispersion resin, the CNT, the graphene and the nano carbon black
Weight ratio is 1：0.1-0.3：0.1-0.2：0.3-0.5.
Preferably, the aqueous dispersion resin is water-based acrylic resin, waterborne polyurethane resin and water-based fluorocarbon resin
In one or more；
Preferably, the CNT is one kind in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube
Or it is a variety of；
Preferably, the graphene is the single-layer graphene and/or multi-layer graphene prepared using physics stripping method, described
The number of plies of multi-layer graphene is 1-10 layers.
Preferably, the composition also contains resin aqueous emulsion, wherein, the aqueous dispersion resin and the aqueous tree
The weight ratio of the content of fat liquor is 1：0.4-1.
Preferably, the composition also contains auxiliary agent, the auxiliary agent be selected from defoamer, dispersant, deaeration agent, levelling agent,
One or more in thickener and pH adjusting agent；
Preferably, the aqueous dispersion resin, the defoamer, the dispersant, the deaeration agent, the levelling agent,
The weight ratio of the content of the thickener and the pH adjusting agent is 1：0.01-0.1：0.2-1：0.01-0.1：0.05-0.2：
0.3-1：0.02-0.2.
Present invention also offers a kind of water-based electric heating coating, the coating is by the coating combination described in above-mentioned any one
What each component in thing was obtained by mixing.
Present invention also offers a kind of preparation method of above-mentioned water-based electric heating coating, wherein, this method comprises the following steps：
(1) CNT, graphene, nano carbon black and aqueous dispersion resin are mixed and ground；
(2) mixed slurry for obtaining step (1) is mixed with resin aqueous emulsion；
Wherein, auxiliary agent is alternatively introduced in step (1) and/or step (2).
Preferably, in step (1), the process of the grinding includes the first process of lapping and the second process of lapping, described
The condition of first process of lapping includes：The speed of grinding is 700-800rpm, and the time of grinding is 50-70min, and described second grinds
The condition of honed journey includes：The speed of grinding is 2000-4000rpm.
Preferably, the particle diameter of the mixed slurry obtained after step (1) processing is 500nm-3 μm.
Preferably, the pH value of the mixture mixed process of step (2) obtained is adjusted to 8-10.
Another aspect of the present invention additionally provides a kind of Electric radiant Heating Film, wherein, the Electric radiant Heating Film is by above-mentioned water-based electric heating painting
Material or the water-based electric heating coating prepared by the preparation method of above-mentioned water-based electric heating coating are prepared.
Using the water-based electric heating coating or water-based electric heating coating of the present invention during Electric radiant Heating Film is prepared, by by carbon
Nanotube, graphene and nano carbon black Application of composite, three-dimensional conductive network is built in heating layer, Electric radiant Heating Film is fundamentally solved
Power attenuation problem, and due in preparation process, due to being unfavorable for the material of environmental protection without introducing, and preparing
There is no volatile materials effusion in journey, the problems such as being discharged beneficial to reduction production and application.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the three-dimensional manometer conductive network in the Electric radiant Heating Film that the water-based electric heating coating prepared by embodiment 1 is prepared
SEM photograph；
Fig. 2 is the three-dimensional manometer conductive network in the Electric radiant Heating Film that the water-based electric heating coating prepared by embodiment 2 is prepared
SEM photograph；
Fig. 3 is the power attenuation datagram for the Electric radiant Heating Film that the water-based electric heating coating prepared by embodiment 1 is prepared.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In the present invention there is provided a kind of water-based electric heating coating composition, wherein, the composition contains aqueous dispersion
Resin, CNT, graphene and nano carbon black；Wherein, the aqueous dispersion resin, the CNT, the graphene
Weight ratio with the content of the nano carbon black is 1：0.09-0.4：0.08-0.3：0.1-0.7.
Preferably, the content of the aqueous dispersion resin, the CNT, the graphene and the nano carbon black
Weight ratio is 1：0.1-0.3：0.1-0.2：0.3-0.5.
According to the present invention, the aqueous dispersion resin is water-based acrylic resin, waterborne polyurethane resin and water-based fluorocarbon
One or more in resin；Preferably, the aqueous dispersion resin is water-based acrylic resin and/or aqueous polyurethane tree
Fat.
According to the present invention, the CNT refers to the seamless nanotube by individual layer or the curling of Multi-layer graphite piece.
The CNT can be the one or more in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube；It is preferred that
Ground, the CNT can be single-walled carbon nanotube or multi-walled carbon nanotube；It is highly preferred that the CNT is many wall carbon
Nanotube.The CNT internal diameter ID can be 2-15nm, and external diameter OD≤30nm, length of carbon nanotube can be 5-30 μm,
Preferably, the CNT internal diameter ID is 10-15nm, and external diameter OD≤30nm, length of carbon nanotube is 10-30 μm.
According to the present invention, the graphene is the single-layer graphene and/or multi-layer graphene prepared using physics stripping method,
The number of plies of the multi-layer graphene is 1-10 layers.
According to the present invention, the composition also contains resin aqueous emulsion, wherein, the aqueous dispersion resin and the water
Property resin emulsion content weight ratio can be 1：0.4-1；Under preferable case, the aqueous dispersion resin and the aqueous tree
The weight ratio of the content of fat liquor is 1：0.5-0.7；Preferably, the resin aqueous emulsion is selected from aqueous acrylic emulsion and water
One or more in property dispersions of polyurethanes.
According to the present invention, the composition also contains auxiliary agent, and the auxiliary agent is selected from defoamer, dispersant, deaeration agent, levelling
One or more in agent, thickener and pH adjusting agent；In the present invention, the content of the auxiliary agent is not particularly limited, preferably
Ground, the weight ratio of the total content of the aqueous dispersion resin and the auxiliary agent can be 1：0.59-2.6, preferably 1：1.07-
1.75；Wherein, when the auxiliary agent is any in defoamer, dispersant, deaeration agent, levelling agent, thickener and pH adjusting agent
When a kind of, " total content of the auxiliary agent " is referred in defoamer, dispersant, deaeration agent, levelling agent, thickener and pH adjusting agent
Any one auxiliary agent content；When the auxiliary agent is selected from defoamer, dispersant, deaeration agent, levelling agent, thickener and pH regulations
During a variety of in agent, " total content of the auxiliary agent " refers to that defoamer, dispersant, deaeration agent, levelling agent, thickener and pH are adjusted
Save the total content of two or more any auxiliary agent in agent；
Preferably, the aqueous dispersion resin, the defoamer, the dispersant, the deaeration agent, the levelling agent,
The weight ratio of the content of the thickener and the pH adjusting agent is 1：0.01-0.1：0.2-1：0.01-0.1：0.05-0.2：
0.3-1：0.02-0.2；It is highly preferred that the aqueous dispersion resin, the defoamer, the dispersant, the deaeration agent, institute
The weight ratio for stating the content of levelling agent, the thickener and the pH adjusting agent is 1：0.05-0.08：0.3-0.5：0.02-
0.07：0.1-0.15：0.5-0.8：0.1-0.15.
, according to the invention it is preferred in the case of, composition of the invention also contains defoamer, and the defoamer can be this
Various defoamers well known to field, for example, can be waterborne organic silicon class defoamer, polyether-modified silicon class defoamer and poly- silicon
One or more in oxygen alkanes defoamer；
Wherein, the organic silicon defoamer for example can be dimethyl silicone polymer, polyether-modified polydimethylsiloxanes
One or more in alkane and organic silicon emulsion；
Wherein, the polyether-modified silicon class defoamer for example can be the one or more in BYK-019 and BYK-024；
Wherein, the polysiloxane-based defoamer for example can be the one or more in BYK-017 and BYK-020.
, according to the invention it is preferred in the case of, composition of the invention also contains dispersant, and the dispersant can be poly-
Ethers dispersant and/or polyesters dispersant.
, according to the invention it is preferred in the case of, composition also agent containing deaeration of the invention, the deaeration agent can be organic
Silicon and silica composite.
, according to the invention it is preferred in the case of, composition of the invention also contains levelling agent, and the levelling agent can be ion
Type polyacrylate solution, wherein, one that the ionic polyacrylate solution can be in BYK-249 and BYK-381
Plant or a variety of.
, according to the invention it is preferred in the case of, composition of the invention also contains thickener, and the thickener can be poly- ammonia
Type thickener, wherein, the one or more that the polyurethanes thickener can be in RM-8W and RM-2020.
, according to the invention it is preferred in the case of, composition of the invention also contains pH adjusting agent, and the pH adjusting agent can be
Diethanol amine；In the present invention, there is no particular limitation for the content of the pH adjusting agent, preferably in the case of, pH regulation
The content of agent is the consumption when pH of the whole system to be adjusted to pH=9-10.
Present invention also offers a kind of water-based electric heating coating, the coating is by the coating combination described in above-mentioned any one
What each component in thing was obtained by mixing.
Present invention also offers a kind of preparation method of above-mentioned water-based electric heating coating, wherein, this method includes following step
Suddenly：
(1) CNT, graphene, nano carbon black and aqueous dispersion resin are mixed and ground；
(2) mixed slurry for obtaining step (1) is mixed with resin aqueous emulsion；
Wherein, auxiliary agent is alternatively introduced in step (1) and/or step (2).
According to the present invention, there is no particular limitation for the condition of grinding, can be the normal condition of this area.For example, grinding
Temperature can be room temperature (be, for example, 5-45 DEG C)；
Wherein, in step (1), the process of the grinding includes the first process of lapping and the second process of lapping, and described the
The condition of one process of lapping includes：The speed of grinding can be 700-800rpm, and the time of grinding can be 50-70min, described
The condition of second process of lapping includes：The speed of grinding can be 2000-4000rpm.
Wherein, the particle diameter of the mixed slurry obtained after step (1) processing is 500nm-3 μm.
Wherein, the pH value of the mixture mixed process of step (2) obtained is adjusted to 8-10.
In the present invention, the particle diameter of the mixed slurry obtained through step (1) can be 500nm-3 μm, preferably 800nm-
2.5 μm, more preferably 1 μm -2 μm；
Preferably, assisted milling is carried out from zirconium pearl in process of lapping, wherein, the consumption of the zirconium pearl can be grinding kettle
The 55%-70% of kettle chamber volume, preferably 60%-65%.
Preferably, carried out in process of lapping under conditions of stirring, wherein, the condition of stirring is：Stir speed (S.S.) can be with
For 700-900rpm, mixing time can be 20-40min, it is preferable that stir speed (S.S.) is 750-850rpm, and mixing time is 25-
35min。
According to the present invention it is possible to by coating or slurry coating containing the water-based electric heating coating composition in heating element
On part, wherein, coating or slurry containing the water-based electric heating coating composition can by by the present invention water-based electric heating
Coating composition is obtained by mixing with deionized water, wherein, the weight of the consumption of the aqueous dispersion resin and the deionized water
It can be 1 to measure ratio：4-7；Under preferable case, the weight ratio of the consumption of the aqueous dispersion resin and the deionized water is 1：5-
6；In addition, being coated with the coating of water-based electric heating coating composition or the heater members of slurry containing the present invention has resistance
Rate is low, safety and environmental protection, power stability, high infrared emittance the advantages of.
Present invention also offers a kind of Electric radiant Heating Film, wherein, the Electric radiant Heating Film is by water-based electric heating coating group described above
Compound or the water-based electric heating coating prepared by method described above are prepared.
In the present invention, by during the water-based electric heating coating of the present invention prepares Electric radiant Heating Film, by by CNT, stone
Black alkene and nano carbon black Application of composite, builds three-dimensional conductive network in heating layer, fundamentally solve Electric radiant Heating Film power attenuation,
The problems such as production and application is discharged.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, unless otherwise instructed, each material and reagent can be by commercially available.
CNT is purchased from KUMHO PETROCHEMICAL, and graphene is purchased from new material limited company of precious ACE Semi, received
Rice carbon black is purchased from TIMCAL；
Zirconium pearl is purchased from Zibo Ying Chi ceramic new materials Co., Ltd, and material is 95% iridium stabilizing zirconia, and particle diameter is
0.3-1mm；And
Aqueous dispersion resin, auxiliary agent and aqueous dispersion emulsion etc. are purchased from Foshan with moral Chemical Co., Ltd..
In following examples and comparative example, the accelerated aging test of Electric radiant Heating Film is determined according to GB/T7287-2008.
SEM figures are measured using the SEM of HITACHI companies S-3400N models.
Embodiment 1
The present embodiment is used for water-based electric heating coating composition and water-based electric heating coating and its preparation side for illustrating the present invention
Method and the Electric radiant Heating Film prepared by it
(1) by aqueous dispersion resin (water-based acrylic resin) 1000g, defoamer (polyether-modified dimethyl silicone polymer)
10g, dispersant (polyethers dispersant) 200g, deaeration agent (organosilicon and silica composite) 10g, deionized water 4000g
It is put into grinding kettle and 30min is stirred with 800rpm rotating speed, is prepared into mixed solution；Again by graphene powder 100g, carbon nanometer
Pipe powder (multi-walled carbon nanotube) 100g, conductive black powder 300g are added in the mixed solution, and grinding kettle is with 800rpm's
Rotating speed grinding stirring 60min, obtains the dispersion liquid containing CNT, graphene and nano carbon black；
(2) zirconium pearl is added in the dispersion liquid of step (1) and is configured to mixed slurry, wherein, the consumption of zirconium pearl is grinding
The 60% of kettle kettle chamber volume, adjustment rotating speed to 2500rpm, grinding, in process of lapping, every 30min test mixed once slurries
The particle diameter of material, when reaching 1 μm, stops grinding；
(3) mixed slurry for obtaining step (2), and by resin aqueous emulsion (water-based acrylic resin emulsion)
500g, levelling agent (BYK-349) 50g, defoamer (polysiloxane-based defoamer) 10g, thickener (RM-8W) 300g, pH regulations
Agent (diethanol amine) 20g, which is added in Scattered Kettle, stirs 1h, and regulation pH is 9, obtains water-based electric heating coating.
The water-based electric heating coating prepared using embodiment 1 prepares Electric radiant Heating Film.
The SEM figures of the Electric radiant Heating Film, the water-based electric heating prepared it can be seen from SEM photograph by embodiment 1 are surveyed as shown in Figure 1
The Electric radiant Heating Film that coating preparation is obtained is in three-dimensional manometer conductive network；
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by embodiment 1 is determined and prepares
The decay power of obtained Electric radiant Heating Film, the power attenuation datagram of Electric radiant Heating Film as shown in Figure 3；Wherein, it is designated 1 in Fig. 3
Solid line is the change curve of power against time with the dotted line for being designated 2, and 3 solid line is designated in Fig. 3 and 4 dotted line is designated
For the change curve of current-vs-time；As shown in Figure 3：The power for being fitted initial value is 43.9W, and the power of fitting end value is
43.27W, the power of attenuation rate is 1.44%.
Therefore, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive net is built in heating layer
Network, the problem of can fundamentally solving Electric radiant Heating Film power attenuation.
Embodiment 2
The present embodiment is used for water-based electric heating coating composition and water-based electric heating coating and its preparation side for illustrating the present invention
Method and the Electric radiant Heating Film prepared by it
(1) by aqueous dispersion resin (waterborne polyurethane resin) 1000g, defoamer (BYK-017) 50g, dispersant (polyester
Class dispersant) 1000g, deaeration agent (organosilicon and silica composite) 100g, deionized water 7000g be put into grinding kettle with
800rpm rotating speed stirring 30min, is prepared into mixed solution, then by graphene powder 200g, carbon nanotube dust 300g, conduction
Carbon black powder 500g is added in the mixed solution, and grinding kettle obtains receiving containing carbon with 800rpm rotating speed grinding stirring 60min
The dispersion liquid of mitron, graphene and nano carbon black；
(2) zirconium pearl is added in the dispersion liquid of step (1) and is configured to mixed slurry, wherein, the consumption of zirconium pearl is grinding
The 65% of kettle kettle chamber volume, adjustment rotating speed to 3000rpm, grinding, in process of lapping, every 30min test mixed once slurries
The particle diameter of material, when reaching 2 μm, stops grinding；
(3) mixed slurry for obtaining step (2), and by resin aqueous emulsion (aqueous polyurethane emulsion) 1000g, stream
Flat agent (BYK-381) 200g, defoamer (polysiloxane-based defoamer) 50g, thickener (RM-2020) 1000g, pH adjusting agent
(diethanol amine) 200g, which is added in Scattered Kettle, stirs 1h, and regulation pH is 10, obtains watersoluble plumbago olefinic carbon nanotube electric-heating coatings.
The water-based electric heating coating prepared using embodiment 2 prepares Electric radiant Heating Film.
The SEM figures of the Electric radiant Heating Film, the water-based electric heating prepared it can be seen from SEM photograph by embodiment 1 are surveyed as shown in Figure 2
The Electric radiant Heating Film that coating preparation is obtained is in three-dimensional manometer conductive network；
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by embodiment 2 is determined and prepares
The decay power of obtained Electric radiant Heating Film is 1.2%.
Therefore, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive net is built in heating layer
Network, the problem of can fundamentally solving Electric radiant Heating Film power attenuation.
Embodiment 3
The present embodiment is used for water-based electric heating coating composition and water-based electric heating coating and its preparation side for illustrating the present invention
Method and the Electric radiant Heating Film prepared by it
(1) by aqueous dispersion resin (polyether resin) 1000g, defoamer (organic silicon emulsion) 30g, dispersant (polyethers
Dispersant) 650g, deaeration agent (organosilicon and silica composite) 30g, deionized water 6000g be put into grinding kettle with
800rpm rotating speed stirring 30min, is prepared into mixed solution, then by graphene powder 150g, carbon nanotube dust 200g, conduction
Carbon black powder 400g is added in the mixed solution, and grinding kettle obtains receiving containing carbon with 800rpm rotating speed grinding stirring 60min
The dispersion liquid of mitron, graphene and nano carbon black；
(2) zirconium pearl is added in the dispersion liquid of step (1) and is configured to mixed slurry, wherein, the consumption of zirconium pearl is grinding
The 65% of kettle kettle chamber volume, adjustment rotating speed to 3000rpm, grinding, in process of lapping, every 30min test mixed once slurries
The particle diameter of material, when reaching 2 μm, stops grinding；
(3) mixed slurry for obtaining step (2), and by resin aqueous emulsion (aqueous acrylic emulsion) 800g, stream
Flat agent (BYK-381) 100g, defoamer (organic silicon defoamer) 30g, thickener (RM-8W) 500g, pH adjusting agent (diethanol
Amine) 120g is added in Scattered Kettle and stirs 1h, and regulation pH is 10, obtains watersoluble plumbago olefinic carbon nanotube electric-heating coatings.
The water-based electric heating coating prepared using embodiment 3 prepares Electric radiant Heating Film.
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by embodiment 3 is determined and prepares
The decay power of obtained Electric radiant Heating Film is 0.9%.
Therefore, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive net is built in heating layer
Network, the problem of can fundamentally solving Electric radiant Heating Film power attenuation.
Comparative example 1
Method according to embodiment 1 prepare water-based electric heating coating composition and water-based electric heating coating and preparation method thereof and
The Electric radiant Heating Film prepared by it, institute's difference is：In step (1), graphene powder is not added.
The water-based electric heating coating prepared using comparative example 1 prepares Electric radiant Heating Film.
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by comparative example 1 is determined and prepares
The decay power of obtained Electric radiant Heating Film is 9.54%.
Therefore, because not by CNT, graphene and nano carbon black Application of composite in comparative example 1, and then in hair
The problem of can not building three-dimensional conductive network in thermosphere, and then can not fundamentally solve Electric radiant Heating Film power attenuation.
Comparative example 2
Method according to embodiment 1 prepare water-based electric heating coating composition and water-based electric heating coating and preparation method thereof and
The Electric radiant Heating Film prepared by it, institute's difference is：In step (1), CNT is not added.
The water-based electric heating coating prepared using comparative example 2 prepares Electric radiant Heating Film.
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by comparative example 2 is determined and prepares
The decay power of obtained Electric radiant Heating Film is 10.03%.
Therefore, because not by CNT, graphene and nano carbon black Application of composite in comparative example 2, and then in hair
The problem of can not building three-dimensional conductive network in thermosphere, and then can not fundamentally solve Electric radiant Heating Film power attenuation.
Comparative example 3
Method according to embodiment 1 prepare water-based electric heating coating composition and water-based electric heating coating and preparation method thereof and
The Electric radiant Heating Film prepared by it, institute's difference is：In step (1), nano carbon black is not added.
The water-based electric heating coating prepared using comparative example 3 prepares Electric radiant Heating Film.
Accelerated aging test is carried out according to GB/T7287-2008, the water-based electric heating coating prepared by comparative example 3 is determined and prepares
The decay power of obtained Electric radiant Heating Film is 11.51%.
Therefore, because not by CNT, graphene and nano carbon black Application of composite in comparative example 3, and then in hair
The problem of can not building three-dimensional conductive network in thermosphere, and then can not fundamentally solve Electric radiant Heating Film power attenuation.
It can be seen from embodiment 1-3 and comparative example 1-3 experimental result：The mistake of Electric radiant Heating Film is being prepared by water-based electric heating coating
Cheng Zhong, by the way that by CNT, graphene and nano carbon black Application of composite, three-dimensional conductive network is built in heating layer, from root
The problem of Electric radiant Heating Film power attenuation being solved in sheet.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
1. a kind of water-based electric heating coating composition, it is characterised in that the coating composition contains aqueous dispersion resin, carbon
Nanotube, graphene and nano carbon black；Wherein, the aqueous dispersion resin, the CNT, the graphene and described receive
The weight ratio of the content of rice carbon black is 1：0.09-0.4：0.08-0.3：0.1-0.7.
2. coating composition according to claim 1, wherein, it is the aqueous dispersion resin, the CNT, described
The weight ratio of the content of graphene and the nano carbon black is 1：0.1-0.3：0.1-0.2：0.3-0.5.
3. coating composition according to claim 1 or 2, wherein, the aqueous dispersion resin is water soluble acrylic acid tree
One or more in fat, waterborne polyurethane resin and water-based fluorocarbon resin；The CNT is single-walled carbon nanotube and many
One or more in wall carbon nano tube；The graphene is the single-layer graphene and/or multilayer prepared using physics stripping method
Graphene, the number of plies of the multi-layer graphene is 1-10 layers.
4. coating composition according to claim 1, wherein, the coating composition is also containing water-base resin breast
Liquid, wherein, the weight ratio of the content of the aqueous dispersion resin and the resin aqueous emulsion is 1：0.4-1.
5. the coating composition according to claim 1 or 4, wherein, the coating composition also contains auxiliary agent, described
One or more of the auxiliary agent in defoamer, dispersant, deaeration agent, levelling agent, thickener and pH adjusting agent；
Preferably, the aqueous dispersion resin, defoamer, the dispersant, the deaeration agent, the levelling agent, described
The weight ratio of the content of thickener and the pH adjusting agent is 1：0.01-0.1：0.2-1：0.01-0.1：0.05-0.2：0.3-1：
0.02-0.2。
6. the aqueous electricity that each component in coating composition in a kind of claim 1-5 described in any one is obtained by mixing
The preparation method of hot coating, wherein, this method comprises the following steps：
(1) CNT, graphene, nano carbon black and aqueous dispersion resin are mixed and ground；
(2) mixed slurry for obtaining step (1) is mixed with resin aqueous emulsion；
Wherein, auxiliary agent is alternatively introduced in step (1) and/or step (2).
7. preparation method according to claim 6, wherein, in step (1), the process of the grinding includes the first grinding
Process and the second process of lapping, the condition of first process of lapping include：The speed of grinding be 700-800rpm, grinding when
Between be 50-70min, the condition of second process of lapping includes：The speed of grinding is 2000-4000rpm.
8. the preparation method according to claim 6 or 7, wherein, the grain of the mixed slurry obtained after step (1) processing
Footpath is 500nm-3 μm.
9. the preparation method according to claim 6 or 7, wherein, the pH for the mixture that the mixed process of step (2) is obtained
Value is adjusted to 8-10.
10. a kind of Electric radiant Heating Film, it is characterised in that the Electric radiant Heating Film is as the coating group described in any one in claim 1-5
Water-based electric heating coating that each component in compound is obtained by mixing or as the method system described in any one in claim 6-9
Standby water-based electric heating coating is prepared.
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