Preparation method of aqueous carbon nanotube electrothermal films
阅读说明：本技术 一种水性碳纳米管电热膜的制备方法 (Preparation method of aqueous carbon nanotube electrothermal films ) 是由 陈名海 戴辉 邵苗苗 于 2019-10-12 设计创作，主要内容包括：本发明属于新材料技术领域,涉及电热膜材料,特别涉及一种含碳纳米管的水性碳纳米管电热膜的制备方法,该方法的步骤为：将碳纳米管水性分散液喷涂于加热的转印辊表面,水分挥发后形成连续碳纳米管膜,随后将其通过热压转印至带有热熔胶的塑料基材表面,进一步通过等离子或者电弧刻蚀工艺,将碳纳米管膜表面的分散剂清理刻蚀,获得高导电的碳纳米管层,最后印制银浆电极并贴合铜箔集流体,使用热熔胶封装成成品电热膜。由于采用本发明方法制备得到的电热膜的发热层中无粘结树脂,且经过等离子/电弧处理进一步清理小分子表面活性剂,具有优异的导电性及稳定性,可实现长寿命运行,且全流程水性化无溶剂,绿色环保,具有重要商业应用价值。(The invention belongs to the technical field of new materials, and relates to an electrothermal film material, in particular to a preparation method of carbon nanotube-containing waterborne carbon nanotube electrothermal films, which comprises the steps of spraying a carbon nanotube waterborne dispersion liquid on the surface of a heated transfer roller, volatilizing moisture to form a continuous carbon nanotube film, then transferring the continuous carbon nanotube film to the surface of a plastic substrate with hot melt adhesive through hot pressing, cleaning and etching a dispersing agent on the surface of the carbon nanotube film through a plasma or arc etching process in a step to obtain a highly conductive carbon nanotube layer, finally printing a silver paste electrode, attaching a copper foil to the silver paste electrode, and packaging the silver paste electrode into a finished electrothermal film by using the hot melt adhesive.)
The preparation method of the water-based carbon nanotube electrothermal film is characterized by comprising the following steps:
s1) mixing the carbon nano tube, the dispersing agent and the wetting agent, and dispersing to obtain uniform carbon nano tube dispersion liquid;
s2) spraying the carbon nano tube dispersion liquid obtained in the S1) on the surface of the transfer roller, and drying to form a carbon nano tube film;
s3) transferring the carbon nanotube film obtained in S2) to the surface of the plastic substrate precoated with the hot melt adhesive by hot pressing;
s4) etching the carbon nanotube film on the surface of the plastic substrate by adopting a physical cleaning process;
s5) printing silver paste electrodes on the edges of the carbon nanotube film, covering a copper foil current collector, and laminating the carbon nanotube film and a plastic substrate into a whole by adopting a hot melt adhesive to obtain a finished product of the electric heating film.
2. The preparation method according to claim 1, wherein the specific steps of S1) are as follows:
s1.1) mixing the following raw materials in percentage by mass: carbon nanotube: 0.1-20%, dispersant: 0.2-10%, wetting agent: 0.1-3 percent of the total weight of the raw materials and the balance of water are uniformly mixed to obtain a mixed material;
s1.2) carrying out ultrasonic, high-speed shearing, ball milling, nano grinding and high-pressure homogenizing and dispersing on the mixed material obtained in the step S1.1) to obtain uniform and stable dispersion liquid.
3. The method as claimed in claim 2, wherein the carbon nanotubes in S1) are or more of single-walled carbon nanotubes, few-walled carbon nanotubes and multi-walled carbon nanotubes, and have a tube diameter of 0.4-100 nm and a length of 0.5-500 μm.
4. The method according to claim 2, wherein the dispersant in S1) is a surfactant comprising or more selected from sodium dodecylbenzene sulfonate, sodium dodecylsulfate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, triton, polyoxyethylene ether surfactant, polyoxypropylene ether surfactant, alkylsulfonate, alkylol sulfonate, and alkylbenzenesulfonic acid.
5. The method according to claim 2, wherein the wetting agent in S1) is an aqueous wetting agent, and the aqueous wetting agent is BYK151, BYK154, BYK180, BYK184, BYK187, BYK190, BYK191, BYK192, BYK194, BYK2010, or BYK 2015.
6. The method according to claim 1, wherein in S2): the transfer roller is a stainless steel roller, the interior of the transfer roller is heated, the surface temperature is 70-120 ℃, the surface of the transfer roller is coated with a release agent which is easy for material transfer printing, the rotating speed is 0.5-60 r/min, and a carbon nanotube film with the dry film thickness of 1-50 microns is formed on the surface of the transfer roller.
7. The method according to claim 1, wherein in S3): the hot-pressing transfer printing uses a stainless steel roller as a hot-pressing roller, the interior is heated, and the surface temperature is 120-; the hot melt adhesive is a reactive hot melt adhesive; the plastic base material is polyethylene terephthalate, polystyrene, polyimide or polyvinyl chloride, and the thickness of the plastic base material is 10-500 micrometers.
8. The preparation method of claim 7, wherein the reactive hot melt adhesive is a moisture-curable reactive polyurethane hot melt adhesive, and the adhesive thickness is 1-50 microns.
9. The method as recited in claim 1, wherein the physical cleaning process in S4) is plasma cleaning or arc cleaning.
10. The preparation method of claim 1, wherein the surface resistance of the electrothermal film is 5-8 ohm/square.
Technical Field
The invention belongs to the technical field of new materials, relates to an electrothermal film material, and particularly relates to a preparation method of aqueous carbon nanotube electrothermal films containing carbon nanotubes.
Background
The electrothermal film is planar heating sources obtained by printing electrothermal ink on an insulating substrate, and has the characteristics of uniform heating, high infrared radiation rate, energy conservation and environmental protection.
Chinese invention patent 201810378166.5 discloses a method for preparing ultra-soft alkene-carbon electrothermal films, which comprises printing conductive ink on a substrate by a printing method, and further packaging the substrate into an electrothermal film, Chinese invention patent 201610491552.6 discloses a method for preparing graphene aqueous electrothermal films, wherein graphene is subjected to hydrophilic treatment, is dispersed in water under the auxiliary action of a dispersing agent, and then is mixed with bonding resin to prepare the conductive ink which is coated on a substrate to obtain the electrothermal film, Chinese invention patent 201910149657.7 discloses gravure electrothermal film printing equipment and an electrothermal film printing method, and the continuous production of the electrothermal film is realized by adopting an improved gravure printing technology.
Disclosure of Invention
The invention discloses a preparation method of aqueous carbon nanotube electrothermal films, which aims to solve any problem in the above and other potential problems in the prior art.
In order to achieve the aim, the technical scheme of the invention is that the preparation method of aqueous carbon nanotube electrothermal films specifically comprises the following steps:
s1) mixing the carbon nano tube, the dispersing agent and the wetting agent, and dispersing to obtain uniform carbon nano tube dispersion liquid;
s2) spraying the carbon nano tube dispersion liquid obtained in the S1) on the surface of the transfer roller, and drying to form a carbon nano tube film;
s3) transferring the carbon nanotube film obtained in S2) to the surface of the plastic substrate precoated with the hot melt adhesive by hot pressing;
s4) etching the carbon nanotube film on the surface of the plastic substrate by adopting a physical cleaning process;
s5) printing silver paste electrodes on the edges of the carbon nanotube film, covering a copper foil current collector, and laminating the carbon nanotube film and a plastic substrate into a whole by adopting a hot melt adhesive to obtain a finished product of the electric heating film.
, the S1) comprises the following steps:
s1.1, the mass percentage of each raw material is as follows: carbon nanotube: 0.1-20%, dispersant: 0.2-10%, wetting agent: 0.1-3 percent of the total weight of the mixture and the balance of water are evenly mixed;
s1.2) carrying out ultrasonic, high-speed shearing, ball milling, nano grinding and high-pressure homogenizing and dispersing on the mixed material obtained in the S1.1 to obtain uniform and stable dispersion liquid.
, the carbon nano-tube in S1) is or more of single-wall carbon nano-tube, few-wall carbon nano-tube or multi-wall carbon nano-tube, the tube diameter is 0.4-100 nm, and the length is 0.5-500 μm.
, the dispersant in S1) is surfactant, and the surfactant comprises or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, triton, polyoxyethylene ether surfactant, polyoxypropylene ether surfactant, alkyl sulfonate alcohol ether and alkyl benzene sulfonic acid.
, the wetting agent in S1) is an aqueous wetting agent, and the aqueous wetting agent is BYK151, BYK154, BYK180, BYK184, BYK187, BYK190, BYK191, BYK192, BYK194, BYK2010 or BYK 2015.
, the S2) that the transfer roller is a stainless steel roller, the inside is heated, the surface temperature is 70-120 ℃, the surface is coated with a release agent which is easy to transfer materials, the rotating speed is 0.5-60 r/min, and a carbon nanotube film with the dry film thickness of 1-50 microns is formed on the surface of the transfer roller.
, in the step S3), the hot-press transfer printing uses a stainless steel roller, the inside is heated, the surface temperature is 120 ℃. The hot-melt adhesive is a reactive hot-melt adhesive, and the plastic base material is polyethylene terephthalate, polystyrene, polyimide or polyvinyl chloride, and the thickness is 10 microns to 500 microns.
, the reactive hot melt adhesive is moisture curing reactive polyurethane hot melt adhesive with thickness of 1-50 μm.
Further , the physical cleaning process in S4) is plasma cleaning or arc cleaning.
And , the surface resistance of the electric heating film is 5-8 ohm/square.
Compared with the prior art, the invention has the advantages that:
(1) the carbon nano tube dispersion liquid is adopted to directly form a film and assist subsequent plasma/arc etching, and the small molecular polymer in the carbon nano tube dispersion liquid is removed as much as possible, so that the whole electrothermal film has no resin binder, the content of the bulk-enhanced polymer is low, the carbon nano tubes are lapped without the resin binder, and the electrothermal film has excellent conductivity and electrical stability, and has excellent long-life and non-attenuation characteristics.
(2) Adopt reaction type polyurethane hot melt adhesive, encapsulate immediately after the rubber coating, the carbon nanotube membrane electric heat layer that forms before can obtain excellent interface bonding strength in partly imbedding the hot melt adhesive to can be high temperature resistant, overcome the drawback that traditional hot melt adhesive heat softened and brought, make the electric heat membrane have outstanding electrical safety, avoid the electric leakage hidden danger.
(3) The whole processing technology has no organic solvent, is a full-aqueous processing technology, has no VOC emission, and has the obvious advantages of environmental protection and safety.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing an aqueous carbon nanotube electrothermal film of the present invention.
FIG. 2 is a schematic surface topography of a scanning electron microscope for carbon nanotube film after drying and scanning a transfer roll to a plastic substrate in example 1 of the present invention.
Fig. 3 is a schematic view of the surface topography of the carbon nanotube film after plasma etching in
In the figure:
1. precoating with hot melt adhesive; 2. a thermal transfer roller; 3, a carbon nanotube dispersion liquid; 4. a carbon nanotube film; 5. transferring the carbon nanotube film; 6. a hot press roll; 7. plasma/arc treatment of carbon nanotube film; 8. printing silver paste electrodes; 9. a copper foil current collector; 10. a plastic substrate; 11. precoating with hot melt adhesive; 12. and (6) fitting and packaging.
Detailed Description
The technical solution of the present invention is further illustrated in step with reference to specific examples.
As shown in figure 1, a uniform carbon nanotube dispersion liquid is obtained through high-pressure homogeneous dispersion, then a PUR
The preparation method specifically comprises the following steps:
s1) mixing the carbon nano tube, the dispersing agent and the wetting agent, and dispersing to obtain uniform carbon nano tube dispersion liquid;
s2) spraying the carbon nano tube dispersion liquid obtained in the S1) on the surface of the transfer roller, and drying to form a carbon nano tube film;
s3) transferring the carbon nanotube film obtained in S2) to the surface of the plastic substrate precoated with the hot melt adhesive by hot pressing;
s4) etching the carbon nanotube film on the surface of the plastic substrate by adopting a physical cleaning process;
s5) printing silver paste electrodes on the edges of the carbon nanotube film, covering a copper foil current collector, and laminating the carbon nanotube film and a plastic substrate into a whole by adopting a hot melt adhesive to obtain a finished product of the electric heating film.
, the S1) comprises the following steps:
s1.1) mixing the following raw materials in percentage by mass: carbon nanotube: 0.1-20%, dispersant: 0.2-10%, wetting agent: 0.1-3 percent of the total weight of the mixture and the balance of water are evenly mixed;
s1.2) carrying out ultrasonic, high-speed shearing, ball milling, nano grinding and high-pressure homogenizing and dispersing on the mixed material obtained in the step S1.1) to obtain uniform and stable dispersion liquid.
, the carbon nano-tube in S1) is or more of single-wall carbon nano-tube, few-wall carbon nano-tube or multi-wall carbon nano-tube, the tube diameter is 0.4-100 nm, and the length is 0.5-500 μm.
, the dispersant in S1) is surfactant, and the surfactant comprises or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, triton, polyoxyethylene ether surfactant, polyoxypropylene ether surfactant, alkyl sulfonate alcohol ether and alkyl benzene sulfonic acid.
, the wetting agent in S1) is an aqueous wetting agent, and the aqueous wetting agent is BYK151, BYK154, BYK180, BYK184, BYK187, BYK190, BYK191, BYK192, BYK194, BYK2010 or BYK 2015.
, the S2) that the transfer roller is a stainless steel roller, the inside is heated, the surface temperature is 70-120 ℃, the surface is coated with a release agent which is easy to transfer materials, the rotating speed is 0.5-60 r/min, and a carbon nanotube film with the dry film thickness of 1-50 microns is formed on the surface of the transfer roller.
, in the step S3), the hot-press transfer printing uses a stainless steel roller, the inside is heated, the surface temperature is 120 ℃. The hot-melt adhesive is a reactive hot-melt adhesive, and the plastic base material is polyethylene terephthalate, polystyrene, polyimide or polyvinyl chloride, and the thickness is 10 microns to 500 microns.
, the reactive hot melt adhesive is moisture curing reactive polyurethane hot melt adhesive with thickness of 1-50 μm.
Further , the physical cleaning process in S4) is plasma cleaning or arc cleaning.
And , the surface resistance of the electric heating film is 5-8 ohm/square.
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