CN107592688B - Electrothermal film and preparation method and application thereof - Google Patents
Electrothermal film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrothermal film and a preparation method and application thereof. The electrothermal film comprises a waterproof layer, an insulating layer, an electrothermal layer, an electrode, an insulating layer, a heat insulating layer, a waterproof layer and the like, wherein the electrothermal layer comprises a fiber substrate fabric, a high-conductivity nano-carbon material and a functional auxiliary agent, and the high-conductivity nano-carbon material is adsorbed on the surface of the fiber substrate fabric or in gaps of the fiber substrate fabric. The preparation method comprises the following steps: taking a fiber substrate fabric as a bearing substrate of a high-conductivity nano carbon material, firstly soaking a hydrophilic treatment solution, baking and curing, then coating a soaking nano carbon aqueous dispersion solution, baking and curing to obtain an electric heating layer; then, the electric heating film is bonded with the insulating layer, the heat insulation layer, the waterproof layer and the electrode through hot melt adhesive to form the electric heating film. The electrothermal film of the invention does not need binder resin, remarkably avoids the problem of electric heating performance attenuation caused by resin aging, integrates the performances of electric heating, water resistance, heat insulation, reflection and the like, and can be widely applied to the industries of household heating, floor heating, heat preservation, industrial heating and the like.
Description
Technical Field
The invention relates to an electrothermal film and a preparation method thereof, in particular to a nano carbon material electrothermal film and a preparation method and application thereof, belonging to the technical field of electric heating.
Background
The electric heating technology is a heat energy providing means which is widely used at present, and is particularly widely applied in the fields of home heating, industrial and agricultural heat preservation protection and the like. The existing electric heating technology mostly adopts heating elements such as metal resistance wires and the like, for example, the metal resistance wires, carbon fiber heating cables and the like adopted by the existing electric floor heating, electric blanket and the like. The heating through the cable is finally converted into planar heating, but the contact area from the wire rod-shaped heating element to the planar heating surface is small, so that the wire rod-shaped heating element is a typical unfavorable interface structure for heat conduction, huge contact thermal resistance is formed, and the utilization rate of heat energy is greatly hindered. Therefore, the planar heating element becomes an important solution, and is increasingly emphasized and developed.
At present, a planar electrothermal film is mainly made of electrothermal ink, wherein a high-conductivity carbon material is mainly added as a filling material to form a conductive network, and a large-area electrothermal film is prepared by utilizing the high electrothermal conversion efficiency of the carbon material. Of course, the prior art also has several core problems which always troubles the further popularization of the electrothermal ink technology, and the product life and energy consumption in the practical engineering application are the most concerned problems of consumers and are the bottleneck links for determining the deep development of the electrothermal ink technology. Tracing, the problems are directly related to the aging of the electrothermal ink, and the aging is mainly caused by the contact resistance formed by the lap joint of the conductive networks formed by the conductive fillers, and when current passes through the contact resistance, high temperature which is far higher than the temperature of the actual electrothermal ink is generated at the interface, so that the high-temperature accelerated aging of the ink bonding resin is caused. The solution idea can be started from multiple aspects: firstly, the adhesive resin with more excellent high-temperature resistance is selected, but the prior art is remedied, and the overheating phenomenon of a micro interface cannot be fundamentally improved; secondly, the use amount of bonding is reduced, a more direct conductive filler contact network is constructed, and the aging factor of resin is overcome; and thirdly, the contact resistance of the micro interface is reduced, the contact area and the density of the conductive network can be improved, and the conductive threshold is reduced to form a more effective conductive network. Comprehensive analysis can find that the problems of resin aging and interface resistance can be simultaneously avoided by adopting the electrothermal film structure without glue and with less glue. Chinese patent 201510234167.9 discloses a new type of planar electrothermal material, which is made up of a fabric as carrier, a collector, a substrate and an electrothermal material, wherein the collector is fixed firmly by penetrating into the fabric. The Chinese invention patent 201310062282.3 discloses a carbon nanotube-water soluble polymer composite flexible electric heating film, a preparation method and application thereof, wherein the carbon nanotube is dispersed in water soluble resin to prepare water-based electric heating paint. Chinese patent 201410158405.8 discloses a composition for water-based electrothermal nano-coating, a preparation method and an application technology thereof, wherein the water-based electrothermal coating is prepared by using the composite addition of graphene and carbon nano-tubes.
However, the above prior art still can not meet the current research needs, and can not completely avoid the problems of resin aging, organic solvent and other pollution, so the industry needs to develop a novel electrothermal film and a preparation method thereof to avoid the defects of the prior art.
Disclosure of Invention
The invention mainly aims to provide an electrothermal film, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention also provides a preparation method of the electrothermal film, which comprises the following steps:
(1) uniformly dispersing a high-conductivity nano carbon material and a dispersing agent in water to form a nano carbon water dispersion liquid, wherein the nano carbon water dispersion liquid contains 0.05-10 wt% of the nano carbon material and 0.02-5 wt% of the dispersing agent;
(2) uniformly mixing 20-50 parts of hydrophilic resin, 1-10 parts of wetting agent, 1-10 parts of dispersing agent, 1-8 parts of cosolvent and 50-90 parts of water to form a fabric hydrophilic treatment solution;
(3) soaking a fiber substrate fabric with the fabric hydrophilic treatment solution, and then drying at 50-90 ℃ to obtain a hydrophilic fabric;
(4) soaking the hydrophilic fabric by using the nano-carbon aqueous dispersion solution, and then drying at 50-90 ℃ to obtain an electric heating layer;
(5) arranging electrodes in the electrothermal layer;
(6) the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, hot melt adhesive is adopted between layers for separation, and the layers are bonded into a whole under the conditions that the temperature is 50-150 ℃ and the pressure is 1-50 MPa, so that the electric heating film is obtained.
The embodiment of the invention also provides the electrothermal film prepared by the preparation method.
The embodiment of the present invention further provides an electrothermal film, which includes:
the electrothermal layer comprises fiber substrate fabrics, high-conductivity nano-carbon materials and functional auxiliaries, wherein the high-conductivity nano-carbon materials are adsorbed on the surfaces of the fiber substrate fabrics and/or gaps among the fiber substrate fabrics;
the insulating layers are arranged on two opposite sides of the electric heating layer; and the number of the first and second groups,
and the electrodes are arranged at two ends of the electric heating layer.
The embodiment of the invention also provides the application of the electrothermal film in the fields of household heating, heat preservation or industrial heating.
For example, the embodiment of the invention also provides a household heating device which comprises the electric heating film.
Preferably, the household heating device comprises a floor heating device.
Compared with the prior art, the invention has the advantages that:
1) the high-conductivity nano carbon material in the electric heating layer in the electric heating film provided by the invention is directly attached to the fiber substrate fabric or between the fiber substrate fabrics, so that the electric heating layer without glue and glue is obtained, binder resin is not needed, the problem of electric heating performance attenuation caused by resin aging is obviously avoided, and the service life of the electric heating film is greatly prolonged;
2) according to the preparation method of the electrothermal film, the fiber base fabric is pretreated by the hydrophilic resin, so that the electrothermal film has good hydrophilic property, the subsequent load of the nano-carbon aqueous dispersion liquid is realized, and the pollution problems of organic solvents and the like are avoided;
3) the preparation method of the electrothermal film provided by the invention has full water-based process, is simple and convenient, is easy to continuously coat and is suitable for large-scale production;
4) the electrothermal film provided by the invention has a multilayer composite structure, integrates the performances of electric heating, water resistance, heat insulation, reflection and the like, has high heat utilization rate, obviously improves the service performance, can be widely applied to the industrial fields of home heating, floor heating, heat preservation, industrial heating and the like, and has wide application prospect and commercial value.
Drawings
Fig. 1 is a schematic structural diagram of an electrothermal film according to an exemplary embodiment of the present invention.
Description of reference numerals: 1-waterproof layer, 2-insulating layer, 3-electrothermal layer, 4-heat-insulating layer and 5-electrode.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
One aspect of the embodiment of the invention provides a preparation method of an electrothermal film, which mainly takes a fiber substrate fabric as a bearing substrate of a high-conductivity nano carbon material, firstly adopts a coating technology to soak hydrophilic treatment fluid, and then coats and soaks nano carbon aqueous dispersion liquid after baking and curing, and an electrothermal layer of the electrothermal film is prepared after baking and curing; then the electric heating film is combined with the insulating layer, the heat-insulating layer, the waterproof layer and the electrode through hot melt adhesive at a certain temperature and pressure to form an integral electric heating film.
Specifically, the preparation method comprises the following steps:
(1) uniformly dispersing a high-conductivity nano carbon material and a dispersing agent in water to form a nano carbon water dispersion liquid, wherein the nano carbon water dispersion liquid contains 0.05-10 wt% of the nano carbon material and 0.02-5 wt% of the dispersing agent;
(2) uniformly mixing 20-50 parts of hydrophilic resin, 1-10 parts of wetting agent, 1-10 parts of dispersing agent, 1-8 parts of cosolvent and 50-90 parts of water to form a fabric hydrophilic treatment solution;
(3) soaking a fiber substrate fabric with the fabric hydrophilic treatment solution, and then drying at 50-90 ℃ to obtain a hydrophilic fabric;
(4) soaking the hydrophilic fabric by using the nano-carbon aqueous dispersion solution, and then drying at 50-90 ℃ to obtain an electric heating layer;
(5) arranging electrodes in the electrothermal layer;
(6) the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, hot melt adhesive is adopted between layers for separation, and the layers are bonded into a whole under the conditions that the temperature is 50-150 ℃ and the pressure is 1-50 MPa, so that the electric heating film is obtained.
In some embodiments, the preparation method may specifically comprise the following steps:
(1) preparing nano-carbon aqueous dispersion liquid, wherein the content of the nano-carbon material is 0.05-10 wt%, the content of the dispersing agent is 0.02-5 wt%, preparing the uniformly dispersed dispersion liquid by adopting the processes of ultrasound, grinding, high-speed shearing, high-pressure homogenization and the like, and standing for defoaming for later use;
(2) preparing fabric hydrophilic treatment liquid, uniformly mixing 20-50 parts of hydrophilic resin, 1-10 parts of wetting agent, 1-10 parts of dispersing agent, 1-8 parts of cosolvent and 50-90 parts of water in a high-speed dispersion machine, and standing for defoaming for later use;
(3) soaking the fiber substrate fabric in a fabric hydrophilic treatment solution by adopting processes such as dip coating, curtain coating, spray coating, roll coating and the like, and drying at 50-90 ℃ to obtain a hydrophilic fabric;
(4) soaking the hydrophilic fabric into the nano-carbon aqueous dispersion by adopting processes of dip coating, curtain coating, spray coating, roll coating and the like, and drying at 50-90 ℃ to obtain an electric heating layer;
(5) attaching or sewing the copper electrode in the electric heating layer;
(6) the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, hot melt adhesive is adopted between layers for separation, and the layers are bonded into a whole under the conditions that the temperature is 50-150 ℃ and the pressure is 1-50 MPa, so that a final electric heating film product is obtained.
Further, in the step (1), the dispersant may be any one or a combination of two or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant, a water-soluble polymer dispersant, and the like, and is preferably a combination of a sulfate surfactant and a polyoxyethylene ether nonionic surfactant, but not limited thereto, and the mass ratio of the sulfate surfactant to the polyoxyethylene ether nonionic surfactant is 1: 10-5: 1.
further, the hydrophilic resin in the step (2) is a water-soluble polymer resin, and may be any one or a combination of two or more of polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide-modified aqueous acrylic acid, polyethylene glycol-modified aqueous acrylic acid, and the like, but is not limited thereto.
Further, the wetting agent is a sulfonate polymer, and is preferably any one or a combination of two or more of secondary alkyl sodium sulfonate, allyloxy hydroxypropyl sodium sulfonate, polystyrene sodium sulfonate, sodium lignin sulfonate, and the like, but is not limited thereto.
Further, the dispersant may be any one or a combination of two or more of cationic, anionic, nonionic surfactant, water-soluble polymer dispersant, and the like, but is not limited thereto.
Further, the cosolvent is any one or a combination of two or more of ethanol, isopropanol, acetone, alcohol ether solvents, and the like, but is not limited thereto.
Further, the hot melt adhesive in step (6) may be any one or a combination of two or more of polyurethane, polyacrylic acid, ethylene-vinyl acetate copolymer, polyethylacrylate, polyoxymethylene, polycaprolactone, and the like, but is not limited thereto.
Preferably, the processing temperature of the hot melt adhesive is 60-120 ℃.
In the preparation method of the present invention, the highly conductive nanocarbon material may be any one or a combination of two or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, nanocarbon fibers, and the like, and is preferably a single-walled carbon nanotube, but not limited thereto.
Further, the fiber base fabric may be any one of woven, knitted, and nonwoven fabrics of natural fibers or artificial fibers, and is preferably a nonwoven fabric of flame retardant grade polypropylene, nylon, polyester, acrylic, or the like, but is not limited thereto.
Further, the insulating layer is any one of woven, knitted, and nonwoven fabrics of natural fibers or artificial fibers, and is preferably a nonwoven fabric of flame retardant grade polypropylene, nylon, polyester, acrylic, or the like, but is not limited thereto.
Further, the heat insulation layer is a composite aluminum-plastic heat insulation reflection heat insulation plate composed of an aluminum foil and foam heat insulation plates of flame retardant grade polyester, polystyrene, polyvinyl chloride, melamine, polyurethane and the like, but is not limited thereto.
Further, the waterproof layer is any one or a combination of two or more of films such as polypropylene, polyethylene, polyester, polystyrene, polyvinyl chloride, polyamide, polyimide and the like, but is not limited thereto.
Further, the electrode may be a copper foil, a copper sheet, or a copper wire, but is not limited thereto.
Another aspect of the embodiment of the present invention provides an electrothermal film prepared by the foregoing preparation method.
Another aspect of the embodiments of the present invention also provides an electrothermal film, which includes:
the electrothermal layer comprises fiber substrate fabrics, high-conductivity nano-carbon materials and functional auxiliaries, wherein the high-conductivity nano-carbon materials are adsorbed on the surfaces of the fiber substrate fabrics and/or gaps among the fiber substrate fabrics;
the insulating layers are arranged on two opposite sides of the electric heating layer; and the number of the first and second groups,
and the electrodes are arranged at two ends of the electric heating layer.
In some embodiments, the electrothermal layer has first and second opposing surfaces, the insulating layer is disposed on the first and second surfaces, respectively, and the electrode is disposed on the first surface.
In some embodiments, a waterproof layer is further arranged on one side of the insulating layer, which is far away from the electric heating layer, and a heat insulation layer is further arranged between the waterproof layer and the insulating layer.
In some embodiments, the fiber base fabric used in the electrothermal layer may be any one of woven fabric, knitted fabric, non-woven fabric and the like of natural fiber or artificial fiber, preferably non-woven fabric of flame retardant grade polypropylene, nylon, terylene, acrylic and the like, but is not limited thereto, and the thickness thereof is 10 to 100 g/m.
Further, the highly conductive nano carbon material used in the electric heating layer may be any one or a combination of two or more of a single-walled carbon nanotube, a multi-walled carbon nanotube, graphene, a carbon nanofiber and the like, and is preferably a single-walled carbon nanotube, but not limited thereto, and the loading amount of the carbon material on the fiber substrate fabric is 0.5 to 25 g/m.
Further, the insulating layer is any one of woven fabric, knitted fabric and non-woven fabric of natural fiber or artificial fiber, preferably non-woven fabric of flame retardant grade polypropylene fiber, nylon, terylene, acrylic fiber and the like, but is not limited to the above, and the thickness of the insulating layer is 20-150 g/square meter.
Further, the heat insulation layer is a composite aluminum-plastic heat insulation reflection heat insulation plate composed of aluminum foil and foam heat insulation plates of flame retardant grade polyester, polystyrene, polyvinyl chloride, melamine, polyurethane and the like, but is not limited to the above, and the thickness of the heat insulation layer is 0.5 mm-2 cm.
Further, the waterproof layer is any one or a combination of two or more of films of polypropylene, polyethylene, polyester, polystyrene, polyvinyl chloride, polyamide, polyimide and the like, but is not limited thereto, and the thickness of the waterproof layer is 2-100 μm.
Furthermore, the electrodes can be copper foils, copper sheets or copper wires which are respectively positioned at two parallel ends of the electric heating layer, wherein the copper foil and the copper sheets can be directly attached to the surface of the electric heating layer, the copper wires are directly sewn in the electric heating layer by adopting a sewing process, and conductive silver adhesive can be further coated between the copper electrodes and the electric heating layer to reduce the contact resistance.
Furthermore, the electrothermal film consists of an electrothermal layer, an insulating layer, a heat insulating layer, a waterproof layer and electrodes, and the layers are bonded by a hot melt adhesive.
The embodiment of the invention also provides application of the electric heating film in the fields of household heating, heat preservation or industrial heating.
For example, the embodiment of the invention also provides a household heating device which comprises the electric heating film.
Preferably, the household heating device includes a floor heating device, but is not limited thereto.
The technical solution of the present invention is further explained below with reference to several embodiments and the accompanying drawings.
Fig. 1 is a schematic structural diagram of an electrothermal film according to an exemplary embodiment of the present invention, which mainly includes an electrothermal layer 3, an insulating layer 2, a thermal insulating layer 4, a waterproof layer 1 and electrodes 5, wherein the layers are bonded by a hot melt adhesive. The electric heating layer 3 comprises fiber substrate fabrics, high-conductivity nano carbon materials and functional auxiliary agents, wherein the high-conductivity nano carbon materials are adsorbed on the surfaces of the fiber substrate fabrics and/or gaps among the fiber substrate fabrics. The thickness of the fiber substrate fabric is 10-100 g/square meter, the loading capacity of the high-conductivity nano carbon material on the fiber substrate fabric is 0.5-25 g/square meter, the thickness of the insulating layer is 20-150 g/square meter, the thickness of the heat insulating layer is 0.5-2 cm, and the thickness of the waterproof layer is 2-100 mu m.
The following describes the technical solution of the present invention with reference to several embodiments for the preparation method of the electric heating film.
Example 1
Firstly, preparing nano-carbon aqueous dispersion liquid, wherein the content of a multi-walled carbon nano-tube is 2 wt%, the content of a sulfate surfactant, namely a sodium dodecyl sulfate dispersing agent is 1 wt%, preparing the uniformly dispersed nano-carbon aqueous dispersion liquid by adopting an ultrasonic dispersion process, and standing for defoaming for later use. Meanwhile, preparing fabric hydrophilic treatment liquid, uniformly mixing 30 parts of acrylamide modified water-based acrylic resin, 2 parts of secondary alkyl sodium sulfonate, 2 parts of anionic surfactant dispersant, 5 parts of ethanol cosolvent and 61 parts of water in a high-speed dispersion machine, and standing for defoaming for later use. And then, soaking the fiber substrate fabric into fabric hydrophilic treatment liquid by adopting a dip coating process, and drying at 70 ℃ to obtain the hydrophilic fabric. And then soaking the hydrophilic fabric into the nano-carbon aqueous dispersion liquid by adopting a dip-coating process, and drying at 70 ℃ to obtain the electrothermal layer. Further, the copper electrode is attached to the electric heating layer, the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, ethylene-vinyl acetate copolymer hot melt adhesives are adopted between the layers at intervals, and the layers are attached into a whole under the temperature of 100 ℃ and the pressure of 20MPa, so that the final electric heating film product is obtained. The materials and specification parameters for the various layers involved are listed in table 1 below:
table 1 materials and specification parameters for the layers referred to in example 1
Example 2
Firstly, preparing nano-carbon aqueous dispersion liquid, wherein the content of a multi-wall carbon nano tube is 3 wt%, the content of a polyoxyethylene ether AEO-10P dispersing agent is 1 wt%, preparing the nano-carbon aqueous dispersion liquid with uniform dispersion by adopting an ultrasonic dispersion process, and standing and defoaming for later use. Meanwhile, preparing fabric hydrophilic treatment liquid, uniformly mixing 20 parts of polyethylene glycol modified waterborne acrylic resin, 2 parts of secondary alkyl sodium sulfonate, 2 parts of anionic surfactant dispersant, 5 parts of ethanol cosolvent and 61 parts of water in a high-speed dispersion machine, and standing for defoaming for later use. And then, soaking the fiber substrate fabric into the hydrophilic treatment solution by adopting a dip coating process, and drying at 50 ℃ to obtain the hydrophilic fabric. And then soaking the hydrophilic fabric into the nano-carbon aqueous dispersion liquid by adopting a dip-coating process, and drying at 50 ℃ to obtain the electrothermal layer. Further, the copper electrode is attached to the electric heating layer, the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, ethylene-vinyl acetate copolymer hot melt adhesives are adopted between the layers at intervals, and the layers are attached into a whole under the temperature of 100 ℃ and the pressure of 20MPa, so that the final electric heating film product is obtained. The materials and specification parameters for the various layers involved are listed in table 2 below:
table 2 materials and specification parameters for the layers referred to in example 2
Example 3
Firstly, preparing nano-carbon aqueous dispersion liquid, wherein the content of graphene is 10wt%, the content of polyoxyethylene ether OP-10 dispersant is 1 wt%, preparing uniformly dispersed nano-carbon dispersion liquid by adopting an ultrasonic dispersion process, and standing for defoaming for later use. Meanwhile, preparing a fabric hydrophilic treatment solution, uniformly mixing 30 parts of polyvinyl alcohol resin, 2 parts of secondary alkyl sodium sulfonate, 2 parts of anionic surfactant dispersant, 5 parts of ethanol cosolvent and 61 parts of water in a high-speed dispersion machine, and standing for defoaming for later use. And then, soaking the fiber substrate fabric into the hydrophilic treatment solution by adopting a dip coating process, and drying at 70 ℃ to obtain the hydrophilic fabric. And then soaking the hydrophilic fabric into the nano-carbon aqueous dispersion liquid by adopting a dip-coating process, and drying at 70 ℃ to obtain the electrothermal layer. Further, the copper electrode is attached to the electric heating layer, the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, ethylene-vinyl acetate copolymer hot melt adhesives are adopted between the layers at intervals, and the layers are attached into a whole under the temperature of 50 ℃ and the pressure of 50MPa, so that the final electric heating film product is obtained. The materials and specification parameters for the various layers involved are listed in table 3 below:
table 3 materials and specification parameters for the layers referred to in example 3
Example 4
Firstly, preparing nano-carbon aqueous dispersion liquid, wherein the content of a single-walled carbon nanotube is 0.05 wt%, the content of a polyoxyethylene ether TX-100 dispersing agent is 0.5 wt%, preparing the uniformly dispersed nano-carbon aqueous dispersion liquid by adopting an ultrasonic dispersion process, and standing for defoaming for later use. Meanwhile, preparing fabric hydrophilic treatment liquid, uniformly mixing 30 parts of polyvinylpyrrolidone, 2 parts of secondary alkyl sodium sulfonate, 2 parts of anionic surfactant dispersant, 5 parts of ethanol cosolvent and 61 parts of water in a high-speed dispersion machine, and standing for defoaming for later use. And then, soaking the fiber substrate fabric into the hydrophilic treatment solution by adopting a dip coating process, and drying at 70 ℃ to obtain the hydrophilic fabric. And then soaking the hydrophilic fabric into the nano-carbon aqueous dispersion liquid by adopting a dip-coating process, and drying at 70 ℃ to obtain the electrothermal layer. Further, the copper electrode is attached to the electric heating layer, the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, ethylene-vinyl acetate copolymer hot melt adhesives are adopted between the layers at intervals, and the layers are attached into a whole under the temperature of 150 ℃ and the pressure of 1MPa, so that the final electric heating film product is obtained. The materials and specification parameters for the various layers involved are listed in table 4 below:
table 4 materials and specification parameters for the layers referred to in example 4
Example 5
Firstly, preparing nano-carbon aqueous dispersion liquid, wherein the content of nano-carbon fibers is 10wt%, the content of polyoxyethylene ether TWEEN-80 dispersant is 1 wt%, preparing the uniformly dispersed nano-carbon aqueous dispersion liquid by adopting an ultrasonic dispersion process, and standing and defoaming for later use. Meanwhile, preparing fabric hydrophilic treatment liquid, uniformly mixing 50 parts of acrylamide modified water-based acrylic resin, 2 parts of secondary alkyl sodium sulfonate, 2 parts of anionic surfactant dispersant, 5 parts of ethanol cosolvent and 61 parts of water in a high-speed dispersion machine, and standing for defoaming for later use. And then, soaking the fiber substrate fabric into the hydrophilic treatment solution by adopting a dip coating process, and drying at 90 ℃ to obtain the hydrophilic fabric. And then soaking the hydrophilic fabric into the nano-carbon aqueous dispersion liquid by adopting a dip-coating process, and drying at 90 ℃ to obtain the electrothermal layer. Further, the copper electrode is attached to the electric heating layer, the waterproof layer, the insulating layer, the electric heating layer, the insulating layer, the heat insulating layer and the waterproof layer are sequentially stacked, ethylene-vinyl acetate copolymer hot melt adhesives are adopted between the layers at intervals, and the layers are attached into a whole under the temperature of 100 ℃ and the pressure of 20MPa, so that the final electric heating film product is obtained. The materials and specification parameters for the various layers involved are listed in table 5 below:
table 5 materials and specification parameters for the layers referred to in example 5
The electric heating film obtained in the above examples 1 to 5 was electrified at 220V, after the temperature thereof was stabilized, the surface and back surface temperatures thereof were measured by using an infrared thermometer, and the resistance changes of both electrodes thereof were measured after continuous electrification for 30 days, and the results thereof are respectively shown in the following table 6:
TABLE 6 test Properties of the electrothermal films obtained in examples 1 to 5
As can be seen from table 6, the electrothermal layer based on the nanocarbon material of the present invention still has good stability after being electrified for 30 days, and the thermal insulation layer obtains good thermal insulation effect to prevent heat from being transferred downward.
Comparative example 1
The high-conductivity carbon black Keqin carbon black KBEC-300J is used as a conductive agent, and the carbon black type electrothermal film is prepared by adopting the process flow same as that of the embodiment 1.
Comparative example 2
The high-conductivity 300-mesh ball-milled carbon fiber powder is used as a conductive agent, a three-roll grinder, polyurethane resin, a dispersing agent, a cosolvent and the like are used for grinding and dispersing the high-conductivity 300-mesh ball-milled carbon fiber powder to the fineness of 10 micrometers, a screen printing process is adopted to prepare the ink type electrothermal film, wherein the carbon fiber powder accounts for 50% of the solid component content, the thickness of a coating electrode is 10 micrometers, the size of a heating electrode is 1.5cm x 25cm, the distance is 1cm, and then the ink type electrothermal film is prepared by compounding the carbon fiber powder, an insulating layer, a heat preservation layer.
The electric heating film prepared in comparative example 1-2 was electrified at 220V, after the temperature was stabilized, the surface and back surface temperatures were measured using an infrared thermometer, and the resistance changes of the two electrodes were measured after continuous electrification for 30 days, the results of which are shown in table 7 below, respectively.
TABLE 7 test Properties of electric heating films obtained in comparative examples 1-2
As can be seen from Table 7, the resistance value of the comparative example electrothermal film changes by about 5% after being electrified for 30 days, and the difference is large, so that the service life of the comparative example electrothermal film is seriously influenced.
In conclusion, by the technical scheme, the high-conductivity nano carbon material in the electric heating layer is directly attached to or between the fiber base fabrics, so that the electric heating layer without glue and less glue is obtained, binder resin is not needed, the problem of electric heating performance attenuation caused by resin aging is remarkably solved, and the service life of the electric heating film is greatly prolonged; meanwhile, the preparation method has full water-based flow, is simple and convenient, is easy to continuously coat and is suitable for large-scale production; the obtained electrothermal film has a multilayer composite structure, integrates the performances of electric heating, water resistance, heat insulation, reflection and the like, has high heat utilization rate, obviously improves the service performance, can be widely applied to the industrial fields of home heating, floor heating, heat preservation, industrial heating and the like, and has wide application prospect and commercial value.
In addition, the inventor also refers to the modes of the examples 1-5, tests are carried out by using other raw materials, conditions and the like listed in the specification, and an electrothermal film which has good electrothermal performance and integrates the performances of electric heating, water resistance, heat insulation, reflection and the like is also prepared.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (34)
1. A preparation method of an electrothermal film is characterized by comprising the following steps:
(1) uniformly dispersing a high-conductivity nano carbon material and a dispersing agent in water to form a nano carbon water dispersion liquid, wherein the nano carbon water dispersion liquid contains 0.05-10 wt% of the nano carbon material and 0.02-5 wt% of the dispersing agent;
(2) uniformly mixing 20-50 parts of hydrophilic resin, 1-10 parts of wetting agent, 1-10 parts of dispersing agent, 1-8 parts of cosolvent and 50-90 parts of water to form a fabric hydrophilic treatment solution;
(3) soaking a fiber substrate fabric with the fabric hydrophilic treatment solution, and then drying at 50-90 ℃ to obtain a hydrophilic fabric;
(4) soaking the hydrophilic fabric by using the nano-carbon aqueous dispersion solution, and then drying at 50-90 ℃ to obtain an electric heating layer;
(5) arranging electrodes in the electrothermal layer;
(6) sequentially stacking a waterproof layer, an insulating layer, an electric heating layer, an insulating layer, a heat insulating layer and a waterproof layer, wherein hot melt adhesives are adopted between the layers for separation, and the layers are bonded into a whole under the conditions that the temperature is 50-150 ℃ and the pressure is 1-50 MPa to obtain an electric heating film;
the electric heating film includes:
the electrothermal layer comprises fiber substrate fabrics, high-conductivity nano-carbon materials and functional auxiliaries, wherein the high-conductivity nano-carbon materials are adsorbed on the surfaces of the fiber substrate fabrics and/or gaps among the fiber substrate fabrics;
the insulating layers are arranged on two opposite sides of the electric heating layer; and the number of the first and second groups,
electrodes arranged at two parallel ends of the electric heating layer;
the surface, far away from the electric heating layer, of the insulating layer is further provided with a waterproof layer, a heat insulation layer is further arranged between the waterproof layer and the insulating layer, the layers in the electric heating layer, the insulating layer, the heat insulation layer, the waterproof layer and the electrodes are bonded through a hot melt adhesive, and the capacity of the high-conductivity nano carbon material on the fiber substrate fabric is 0.5-25 g/square meter.
2. The method of claim 1, wherein: the dispersant in the step (1) is selected from any one or the combination of more than two of cationic surfactant, anionic surfactant and nonionic surfactant.
3. The method of claim 2, wherein: the dispersant is selected from the group consisting of sulfate surfactants and polyoxyethylene ether nonionic surfactants.
4. The production method according to claim 3, characterized in that: the mass ratio of the sulfate surfactant to the polyoxyethylene ether nonionic surfactant is 1: 10-5: 1.
5. the method of claim 1, wherein: the hydrophilic resin in the step (2) is selected from water-soluble high polymer resin.
6. The method of claim 5, wherein: the hydrophilic resin is selected from one or the combination of more than two of polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide modified water-based acrylic acid and polyethylene glycol modified water-based acrylic acid.
7. The method of claim 1, wherein: in the step (2), the wetting agent is selected from sulfonate polymers.
8. The method of claim 7, wherein: the wetting agent is selected from any one or the combination of more than two of secondary alkyl sodium sulfonate, allyloxy hydroxypropyl sodium sulfonate, sodium polystyrene sulfonate and sodium lignin sulfonate.
9. The method of claim 1, wherein: the dispersant in the step (2) is selected from any one or the combination of more than two of cationic surfactant, anionic surfactant and nonionic surfactant.
10. The method of claim 1, wherein: in the step (2), the cosolvent is selected from any one or a combination of more than two of ethanol, isopropanol, acetone and alcohol ether solvents.
11. The method of claim 1, wherein: the impregnation is any one mode selected from dip coating, curtain coating, spray coating and roll coating.
12. The method of claim 1, wherein: the hot melt adhesive is selected from any one or the combination of more than two of polyurethane, polyacrylic acid, ethylene-vinyl acetate copolymer, polyethylacrylate, polyformaldehyde and polycaprolactone.
13. The method of claim 1, wherein: the processing temperature of the hot melt adhesive is 60-120 ℃.
14. The production method according to any one of claims 1 to 13, characterized in that: the high-conductivity nano carbon material is selected from any one or a combination of more than two of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene and nano carbon fibers.
15. The method of claim 14, wherein: the high-conductivity nano carbon material is a single-wall carbon nano tube.
16. The method of claim 1, wherein: the fiber base fabric is selected from any one of woven, knitted and non-woven fabrics of natural fibers and/or artificial fibers.
17. The method of manufacturing according to claim 16, wherein: the non-woven fabric is selected from any one of flame-retardant polypropylene fiber, chinlon, terylene and acrylic fiber.
18. The method of claim 1, wherein: the material of the insulating layer is selected from any one of woven fabric, knitted fabric and non-woven fabric of natural fiber and/or artificial fiber.
19. The method of claim 18, wherein: the non-woven fabric is selected from any one of flame-retardant polypropylene fiber, chinlon, terylene and acrylic fiber.
20. The method of claim 1, wherein: the heat insulation layer is a composite aluminum-plastic heat insulation reflection heat insulation plate.
21. The method of claim 20, wherein: the composite aluminum-plastic heat-insulation reflective insulation board is selected from an aluminum foil and a foam insulation board.
22. The method of manufacturing according to claim 21, wherein: the foam insulation board is made of any one or a combination of more than two of flame-retardant polyester, polystyrene, polyvinyl chloride, melamine and polyurethane.
23. The method of claim 1, wherein: the waterproof layer is made of any one or a combination of more than two of polypropylene, polyethylene, polyester, polystyrene, polyvinyl chloride, polyamide and polyimide.
24. The method of claim 1, wherein: the electrode is selected from any one of copper foil, copper sheet and copper wire.
25. The method of claim 1, wherein: the electric heating layer is provided with a first surface and a second surface which are opposite, the insulating layers are respectively arranged on the first surface and the second surface, and the electrodes are arranged on the first surface.
26. The method of manufacturing according to claim 16, wherein: the thickness of the fiber base fabric is 10-100 g/m.
27. The method of claim 18, wherein: the thickness of the insulating layer is 20-150 g/m.
28. The method of claim 20, wherein: the thickness of the heat insulation layer is 0.5 mm-2 cm.
29. The method of claim 23, wherein: the waterproof layer is in the form of a film.
30. The method of claim 23, wherein: the thickness of the waterproof layer is 2-100 mu m.
31. The method of claim 24, wherein: the copper foil or the copper sheet is attached to the surface of the electric heating layer.
32. The method of claim 24, wherein: the copper wire is sewn in the electric heating layer.
33. The method of claim 1, wherein: and conductive silver adhesive is arranged between the electrode and the electric heating layer.
34. Use of an electrothermal film prepared by the process of any one of claims 1 to 33 in the field of home heating, insulation or industrial heating.
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Effective date of registration: 20200811 Address after: No. 1129, Gaoxin Avenue, Nanchang high tech Industrial Development Zone, Nanchang City, Jiangxi Province Applicant after: Jiangxi Jiangtong carbon nano material Co., Ltd Address before: Linquan Street Industrial Park of Suzhou city in Jiangsu province 215000 No. 608 building 17 room 1401 Applicant before: Chen Minghai |