WO2022120565A1 - Graphene heating ink, preparation method therefor, and application thereof - Google Patents

Graphene heating ink, preparation method therefor, and application thereof Download PDF

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Publication number
WO2022120565A1
WO2022120565A1 PCT/CN2020/134513 CN2020134513W WO2022120565A1 WO 2022120565 A1 WO2022120565 A1 WO 2022120565A1 CN 2020134513 W CN2020134513 W CN 2020134513W WO 2022120565 A1 WO2022120565 A1 WO 2022120565A1
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Prior art keywords
graphene
polysilazane
heating ink
graphene heating
agent
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PCT/CN2020/134513
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French (fr)
Chinese (zh)
Inventor
蔺洪振
程双
王健
李麟阁
李付锦
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苏州烯时代材料科技有限公司
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Priority to PCT/CN2020/134513 priority Critical patent/WO2022120565A1/en
Publication of WO2022120565A1 publication Critical patent/WO2022120565A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • 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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater 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—Heater 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
    • 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
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs

Definitions

  • the invention belongs to the field of electric heating materials, in particular to a graphene electric heating film, and in particular to a graphene heating ink and a preparation method and application thereof.
  • the heating principle of the electric heating film is: under the action of the electric field, the carbon molecules in the heating body produce "Brownian motion", and the carbon molecules undergo severe friction and collision, and the generated heat energy is in the form of far-infrared radiation and convection to the outside world.
  • the conversion rate of electric energy and heat energy is as high as 98%.
  • the action of the carbon molecules rapidly heats the surface of the system.
  • the electric heating film heating system is installed on the wall (ground), the heat energy will be continuously and evenly transmitted to every corner of the room.
  • the reason why the electric heating film can rapidly heat up the space is that all its electrical energy input is effectively converted into more than 60% of far-infrared radiation energy and more than 30% of convective heat energy.
  • graphene has good electrical conductivity, fast electron mobility, fast heating speed, more energy saving and environmental protection, and graphene heating principle is "life light" 8-15 ⁇ m far-infrared heating, which has a good health care effect on the human body, so graphene heating Ink in far-infrared electric heating film, infrared heating equipment, far-infrared heating clothing, heating cap, heating insole, far-infrared electric blanket, steam room, self-heating floor, far-infrared electric mural, far-infrared drying box, incubator, far-infrared barbecue It has a wide range of applications in many fields such as boards.
  • the prior art of the Chinese Patent Announcement No. CN103338538A discloses a graphene radiation heating film and its preparation method and application on October 2, 2013.
  • the patent improves the electrothermal conversion efficiency, high power and high hardness of the electrothermal film.
  • the non-folding and other aspects have been significantly improved, but the heating film has the following problems: once the surface of the heating film is covered during use, the heat cannot be dissipated in time, which will inevitably lead to excessive local temperature and excessive potential risk factors.
  • the prior art of the Chinese Patent Bulletin No. CN103607795A discloses a preparation method of a graphene heating film on February 26, 2014.
  • the patent prepares a graphene heating film with low voltage and adjustable size through a simple and easy-to-control method , in a relatively small area, the heating is very uniform, but in a relatively large heating area or when there is a covering, the heat cannot be dissipated in time, which will cause the local temperature to be too high, which is likely to cause safety hazards.
  • the prior art of the Chinese Patent Bulletin No. CN107446408A discloses a PTC graphene heating ink and its preparation method, and a heating film prepared thereon on December 08, 2017, comprising 50-70% of a binder, a solvent of 9% -21%, auxiliary agent 1-3%, conductive filler 10-20%, PTC functional material 5-20%; the PTC functional material is barium carbonate oxide, lead oxide oxide, niobium oxide oxide, Bi oxide , La oxide, Y oxide, Nb oxide, Sb oxide, one of sintering aids or a plurality of mixtures in any proportion.
  • this patent increases the PTC function of the graphene heating film, because the PTC functional materials used are either highly toxic, or use lanthanide, actinide and other group elements, the price is relatively expensive, and the powder is not easy to be dispersed in the ink. , there is a serious dispersion instability problem, and this patent only adopts the conventional stirring method, which has the problem of batch instability, which is not conducive to industrial application.
  • the technical problem to be solved by the present invention is to overcome one or more deficiencies in the prior art, and to provide an improved graphene heating ink. , the resistance is greatly improved at high temperature and self-limiting temperature is realized. At the same time, the most important thing is that the resistance value of the material does not change much when it returns to normal temperature, and the reversibility is good, thus improving the cycle performance of the electrothermal film. Safety for use in special fields.
  • the present invention also provides a preparation method of the above graphene heating ink.
  • the invention also provides an electric heating film.
  • a graphene heating ink which comprises a resin matrix, a conductive filler, an auxiliary agent and a solvent
  • the conductive filler comprises graphene
  • the resin matrix is composed of an organic polymer and a polysilazane in a mass ratio of 1:0.08-1.5
  • the graphene heating ink also contains a crosslinking agent.
  • the polymer film, the ceramicized polymer film can not only make the polymer itself in a more orderly state, which is conducive to the effective bridging of conductive fillers, which is conducive to conducting electricity;
  • the deformation is more localized, which makes it easier to restore the original shape when returning to normal temperature, and makes the bridge of the conductive filler particles easier to restore, so the reversibility is good and the recycling performance is better.
  • the polysilazane has a weight average molecular weight of 600-1300; further preferably, the polysilazane has a weight average molecular weight of 800-1000. According to a specific aspect of the present invention, the polysilazane has a weight average molecular weight of 900. The polysilazane of this molecular weight can obtain more excellent ceramic quality.
  • the mass ratio of the organic polymer to the polysilazane is 1:0.1-1. Further preferably, the mass ratio of the organic polymer to the polysilazane is 1:0.1-0.8. In some embodiments of the present invention, the mass ratio of the organic polymer to the polysilazane is 1:0.2-0.6.
  • the auxiliary agent includes at least a silicon-containing dispersant and a thickening agent.
  • the graphene accounts for 3-20%, and the organic polymer accounts for 3-20%. 3-10%, polysilazane 0.95-3.1%, crosslinking agent 1-2.5%, silicon-containing dispersant 0.1-0.6%, thickener 0.2-1.3%, solvent 63-90%.
  • the organic polymer is a polyurethane resin and/or an acrylic resin
  • the cross-linking agent is a combination of one or more selected from cross-linking agents containing amine groups
  • the amine group-containing crosslinking agent includes, but is not limited to, modified polycarbodiimide crosslinking agent, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, and the like.
  • the silicon-containing dispersant is a combination of one or more selected from the group consisting of polyether-modified silicone oil, silicone resin, silicone rubber and silane coupling agent.
  • the thickener is a combination of one or more selected from hydrophobically modified cellulose thickener and polyacrylate.
  • the introduction of polysilazane into the graphene ink improves the safety and cycle reversible performance, and at the same time, on the basis of polysilazane and organic polymers, a cross-linking reaction capable of cross-linking reaction with organic polymers is further combined It ensures that the basic properties of the ink product are better guaranteed, such as better and firmer adhesion and better film-forming properties.
  • the present invention further combines silicon-containing dispersants and thickeners as auxiliary agents. On the one hand, the dispersibility of polysilazane in the ink system is greatly improved, so that the ink is not prone to phase separation.
  • the increase of silicon content improves the thermal stability and mechanical properties of the film-forming layer; on the other hand, the viscosity of the ink system added with polysilazane is better improved, so that it is suitable for ink coating or screen printing Other processes can also obtain better film-forming properties.
  • the organic combination of the above-mentioned composite resin matrix, cross-linking agent, silicon-containing dispersant and thickener not only realizes the unexpectedly good self-limiting temperature, It has the characteristics of reversibility, and has a good promotion effect on the basic properties of the ink, including but not limited to adhesion, film formation, stability, dispersion, and electrical conductivity.
  • the adjuvant optionally further comprises a combination of one or more selected from polyvinylpyrrolidone and cetyltrimethylammonium bromide.
  • the solvent is a combination of one or more selected from N,N-dimethylformamide, dichloromethane, dimethylsulfoxide, chloroform and n-hexane.
  • a defoamer or the like may also be added to the graphene heating ink.
  • a preparation method of the above-mentioned graphene heating ink comprises: using graphene powder in powder form for graphene, and polysilazane in solution form for polysilazane
  • the azane solution firstly, the graphene powder and the polysilazane solution are stirred and dispersed so as to be fully mixed, and after the mixing is uniform, the remaining raw materials are added under stirring to prepare the graphene heating ink.
  • the graphene powder is obtained by mixing and dispersing graphene with water to form a homogeneous and stable graphene aqueous solution, then drying the graphene aqueous solution and pulverizing with a pulverizer.
  • the D50 of the graphene powder is 5-10 ⁇ m.
  • the mass percentage of polysilazane in the polysilazane solution is 6-10%. According to a specific aspect of the present invention, the mass percentage of polysilazane in the polysilazane solution is 8%, which can be obtained commercially.
  • an electric heating film comprising a base body and an electric heating film layer covered on the base body, the electric heating film layer is obtained by coating the above-mentioned graphene heating ink on The ceramic polymer film formed by crosslinking and curing on the substrate and heated to 140-150°C.
  • the working principle of the electric heating film made of graphene heating ink is that under the excitation of electricity, "Brownian motion" is generated by graphene carbon molecular clusters, which are generated by the mutual collision and friction between graphene carbon molecules. heat energy and generate a lot of infrared radiation.
  • the ceramized polymer film formed can be conducive to making the polymer itself in a more orderly state, which is conducive to the effective overlapping of conductive fillers to form bridges, and is conducive to conducting electricity, thereby obtaining Excellent heating effect;
  • the polymer chain is deformed, so that the link of the conductive filler (conductive particle) is damaged to a certain extent, so that the resistance increases, the power is reduced, and the self-limiting temperature is achieved; with this
  • the deformation of the polymer chain can become more localized in the process of being subjected to a high temperature impact, thereby facilitating the recovery of the polymer chain from the high temperature to the normal temperature, making the conductive filler particles easier to recover.
  • the bridge is also easier to recover, so the reversibility is good, and the cycle performance is better, which solves the problem that the existing polymer PTC materials are prone to thermal fatigue, that is, the conductive filler particle chain (bridge) is not very good when it is returned to normal working temperature after being subjected to high temperature.
  • the substrate may be a PET film (polyethylene terephthalate film) or a PI film (polyimide film) or the like.
  • the present invention has the following advantages compared with the prior art:
  • the present invention innovatively proposes an improved graphene heating ink.
  • the heating ink selects a specific composite resin matrix, and the organic polymer contained in the composite resin matrix is cross-linked and cured by cooperating with a cross-linking agent.
  • the polysilazane contained in the composite resin matrix undergoes ceramization transformation, so that the heating ink of the present application can directly obtain a ceramized polymer film during curing, and the ceramized polymer film not only has excellent low-temperature conductivity It also has the characteristics of increasing high temperature resistance, realizing self-limiting temperature and improving the safety of use; at the same time, it is especially critical that even if it is subjected to multiple high temperature shocks, if it returns to normal temperature, it can still make the internal conductive filler.
  • the particle bridge is easy to restore to its original state, thereby achieving good reversibility and improving the recycling performance, which solves the problem that the existing polymer PTC materials are easily thermally fatigued and difficult to restore to their original state, resulting
  • the raw materials used in the heating ink of the present application are easy to obtain, and the price is moderate, the preparation process is simple, the preparation process is controllable, the components are simple, the physical and mechanical properties such as ideal viscosity, etc.
  • the electrothermal film in the prior art has more excellent comprehensive performance and is convenient for industrial production.
  • the polysilazane solution was purchased from Anhui Aiyota Silicon Oil, the brand name was IOTA-9108, the mass percentage of polysilazane was 8%, the dispersing solvent was chloroform, and the weight-average molecular weight of polysilazane was 900.
  • Polyvinylpyrrolidone PVP was purchased from Aladdin under the designation P110567.
  • the hydrophobic modified cellulose thickener was purchased from Shanghai Kane under the brand name BYK-032.
  • the modified polycarbodiimide crosslinking agent was purchased from Shanghai Kaiyin under the trade name EBECRYL-0071.
  • Polyurethane resin was purchased from Hengke, the brand name was PU3645; polyether modified silicone oil was purchased from Maclean, the brand name was P875564.
  • Graphene (purchased from Suzhou Graphene Times Materials Technology Co., Ltd., the number of graphene layers is 1-10 layers) is mixed and dispersed with water to form a uniform and stable graphene aqueous solution, and then the graphene aqueous solution is dried , using a pulverizer to pulverize and treat for later use, and the average diameter of the graphene powder obtained after pulverization is 6 ⁇ m.
  • This embodiment provides a graphene heating ink.
  • the raw materials include: graphene powder 18%, polysilazane solution 30%, polyvinylpyrrolidone PVP 1.0%, hydrophobic modified cellulose Thickener 0.7%, modified polycarbodiimide crosslinking agent 1.8%, polyurethane resin 5%, polyether modified silicone oil 0.3%, and the balance is N,N-dimethylformamide.
  • the preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, after the mixing is uniform, respectively adding polyvinylpyrrolidone PVP and hydrophobic modified cellulose in the stirring process. Thickener, modified polycarbodiimide crosslinking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand for 30 minutes. The described graphene heating ink.
  • This embodiment provides a graphene heating ink.
  • the raw materials include: 15% of graphene powder, 30% of polysilazane solution, 1.2% of cetyltrimethylammonium bromide, Hydrophobic modified cellulose thickener 0.8%, modified polycarbodiimide crosslinking agent 1.8%, polyurethane resin 6%, polyether modified silicone oil 0.5%, the balance is N,N-dimethylformamide .
  • the preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, and after the mixing is uniform, sequentially adding cetyltrimethylammonium bromide in the stirring process, Hydrophobic modified cellulose thickener, modified polycarbodiimide cross-linking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand After 30 minutes, the graphene heating ink was obtained.
  • This embodiment provides a graphene heating ink, in terms of mass percentage, the raw materials include: 10% of graphene powder, 30% of polysilazane solution, 1.5% of polyvinylpyrrolidone PVP, hydrophobic modified cellulose Thickener 1.0%, modified polycarbodiimide crosslinking agent 2.0%, polyurethane resin 8%, polyether modified silicone oil 0.6%, and the balance is N,N-dimethylformamide.
  • the preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, after the mixing is uniform, respectively adding polyvinylpyrrolidone PVP and hydrophobic modified cellulose in the stirring process. Thickener, modified polycarbodiimide crosslinking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand for 30 minutes. The described graphene heating ink.
  • Example 2 Basically the same as Example 1, the difference is only that polysilazane is not added, and the content of the solvent is adjusted accordingly.
  • Example 2 Basically the same as Example 1, the only difference is that: no polyether modified silicone oil is added, and the content of polyvinylpyrrolidone PVP is increased to 1.3%.
  • Example 2 Basically the same as Example 1, the only difference is: no thickener is added, and the content of polyurethane resin is increased to 12.6% (the total content of polyurethane resin and polysilazane is 15%), and the content of solvent is correspondingly reduced.
  • the obtained graphene heating ink is evenly coated on the PET film, baked at 145 ⁇ 5 degrees Celsius for 2 minutes, then rolled up, and then placed in an oven for cross-linking and curing, and the curing time is 4 hours to obtain Graphene electric heating film can be used in heating and other fields.
  • the electric-thermal radiation conversion efficiency is tested according to the standard GB/T 7287-2008 "Infrared Radiation Heater Test Method", and the thermal image measurement method (B method) in the standard is adopted.
  • the power density is set to 200-500W/m 2 , and after the heating temperature is stabilized after electrification, the electric heating films made of the graphene heating inks of Example 1-3 and Comparative Example 1-3 are tested, according to the formula:
  • Example 1 Example 2
  • Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 S 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 T1 322.6 322.8 326 302.1 310.3 316 T 0 298.8 299.3 299.8 299.6 299.3 298.6 Pe 30.5 30.1 32.8 26.6 28.6 29.4 n 79% 80% 83% 54% 60% 62%

Abstract

Disclosed in the present invention are a graphene heating ink, a preparation method therefor, and an application thereof. The graphene heating ink comprises a resin matrix, a conductive filler, an auxiliary agent, and a solvent. The conductive filler comprises graphene; the resin matrix consists of an organic polymer and polysilazane according to a mass ratio of 1:0.08-1.5. The graphene heating ink further comprises a crosslinking agent. The preparation method comprises: using graphene powder; using a polysilazane solution; first stirring and dispersing the graphene powder and the polysilazane solution to fully mix same; and after uniform mixing, adding the remaining raw materials under stirring to make the graphene heating ink. An electric heating film prepared from the ink is provided. By means of the electric heating film, excellent electrical conductivity is ensured at a lower temperature, resistance is greatly improved at a high temperature, and self-limiting of the temperature is realized; moreover, there is little material resistance change when the temperature restores to a normal temperature, and the reversibility is good, thereby improving the recycling performance and safety of the electric heating film.

Description

一种石墨烯发热油墨及其制备方法和应用A kind of graphene heating ink and preparation method and application thereof 技术领域technical field
本发明属于电热材料领域，尤其涉及石墨烯电热膜，具体涉及一种石墨烯发热油墨及其制备方法和应用。The invention belongs to the field of electric heating materials, in particular to a graphene electric heating film, and in particular to a graphene heating ink and a preparation method and application thereof.
背景技术Background technique
社会的快速发展是建立在对自然资源的严重消耗基础之上，随着人们对生活品质追求提出越来越高的要求，例如：供暖效果好、安全性高、节能环保等等。目前主要有两种供暖方式，其一为煤炭取暖，其二为电热取暖。近二十年来，环境污染的加剧已经严重影响了我们的生活，危害到我们的身体健康，所以电热取暖可以有效降低对煤炭资源的消耗，同时也保护了我们的安全和环境。但在满足人们取暖需求的同时，需要不断改进电热取暖的施工技术和改良电热的材料。The rapid development of society is based on the serious consumption of natural resources. As people put forward higher and higher requirements for the pursuit of quality of life, such as: good heating effect, high safety, energy saving and environmental protection, etc. At present, there are two main heating methods, one is coal heating and the other is electric heating. In the past two decades, the aggravation of environmental pollution has seriously affected our lives and endangered our health. Therefore, electric heating can effectively reduce the consumption of coal resources, while also protecting our safety and the environment. However, while meeting people's heating needs, it is necessary to continuously improve the construction technology of electric heating and improve the materials of electric heating.
电热膜制热原理是：产品在电场的作用下，发热体中的碳分子团产生“布朗运动”，碳分子之间发生剧烈的摩擦和撞击，产生的热能以远红外辐射和对流的形式对外传递，其电能与热能的转换率高达98％以上。碳分子的作用使***表面迅速升温。将电热膜暖采暖***安装在墙(地)面上，热能就会源源不断地均匀传递到房间的每一个角落。电热膜之所以能够对空间起到迅速升温的作用，就在于其全部的电能输入被有效地转换成了超过六成多的远红外辐射能和三成多的对流热能。The heating principle of the electric heating film is: under the action of the electric field, the carbon molecules in the heating body produce "Brownian motion", and the carbon molecules undergo severe friction and collision, and the generated heat energy is in the form of far-infrared radiation and convection to the outside world. The conversion rate of electric energy and heat energy is as high as 98%. The action of the carbon molecules rapidly heats the surface of the system. When the electric heating film heating system is installed on the wall (ground), the heat energy will be continuously and evenly transmitted to every corner of the room. The reason why the electric heating film can rapidly heat up the space is that all its electrical energy input is effectively converted into more than 60% of far-infrared radiation energy and more than 30% of convective heat energy.
由于石墨烯导电性能好，电子迁移率快，发热速度快，更加节能环保，并且石墨烯发热原理是“生命光线”8-15μm远红外发热，对人体有很好的保健作用，因此石墨烯发热油墨在远红外电热膜、红外取暖设备、远红外发热衣物、发热帽、发热鞋垫、远红外电热毯、汗蒸房、自发热地板、远红外电热壁画、远红外干燥箱、孵化器、远红外烧烤板等诸多领域都有及其广阔的应用。Because graphene has good electrical conductivity, fast electron mobility, fast heating speed, more energy saving and environmental protection, and graphene heating principle is "life light" 8-15μm far-infrared heating, which has a good health care effect on the human body, so graphene heating Ink in far-infrared electric heating film, infrared heating equipment, far-infrared heating clothing, heating cap, heating insole, far-infrared electric blanket, steam room, self-heating floor, far-infrared electric mural, far-infrared drying box, incubator, far-infrared barbecue It has a wide range of applications in many fields such as boards.
目前，涉及到石墨烯发热膜的现有技术很多，例如：At present, there are many existing technologies related to graphene heating films, such as:
中国专利公告号为CN103338538A的现有技术在2013年10月2日公开了一种石墨烯辐射发热膜及其制备方法和应用，该专利在改善电热膜的电热转换效率、功率偏大以及硬度高不可折叠等方面得到明显改善，但该发热膜存在如下问题：该发热膜在使用过程中，一旦表面被覆盖，热量不能及时散热出去，则必然导致局部温度过高，潜在危险因素过大。The prior art of the Chinese Patent Announcement No. CN103338538A discloses a graphene radiation heating film and its preparation method and application on October 2, 2013. The patent improves the electrothermal conversion efficiency, high power and high hardness of the electrothermal film. The non-folding and other aspects have been significantly improved, but the heating film has the following problems: once the surface of the heating film is covered during use, the heat cannot be dissipated in time, which will inevitably lead to excessive local temperature and excessive potential risk factors.
中国专利公告号为CN103607795A的现有技术在2014年2月26日公开了一种石墨烯发热薄膜的制备方法，该专利通过简单易控的方法制备了低电压、尺寸可调的石墨烯发热膜，在相对较小的面积按下其发热很均匀，但是在相对较大的发热面积下或者有覆盖物的情况下，存在热量不能及时散热出去，进而导致局部温度过高，容易造成安全隐患。The prior art of the Chinese Patent Bulletin No. CN103607795A discloses a preparation method of a graphene heating film on February 26, 2014. The patent prepares a graphene heating film with low voltage and adjustable size through a simple and easy-to-control method , in a relatively small area, the heating is very uniform, but in a relatively large heating area or when there is a covering, the heat cannot be dissipated in time, which will cause the local temperature to be too high, which is likely to cause safety hazards.
中国专利公告号为CN103476158A的现有技术在2015年6月3日公开了PTC复合材料发热膜及其制备方法和应用，该专利通过导电填料与结晶或者半结晶高分子复合材料进行复合得到PTC特性复合材料，但由于采用了结晶或半结晶高分子材料，因此其依靠高分子材料本身的热胀冷缩调节电阻，受有机聚合物材质及构造机理所决定，每次经过流冲击后，阻值变大，不能恢复到原值，可逆性不好，且当高压大电流脉冲冲击时，外包封易炸裂，大大缩短发热膜的使用寿命。The prior art of Chinese Patent Announcement No. CN103476158A discloses PTC composite material heating film and its preparation method and application on June 3, 2015. This patent obtains PTC characteristics by compounding conductive filler and crystalline or semi-crystalline polymer composite material Composite materials, but because of the use of crystalline or semi-crystalline polymer materials, the resistance is adjusted by the thermal expansion and contraction of the polymer material itself, which is determined by the organic polymer material and structural mechanism. If it becomes larger, it cannot be restored to the original value, and the reversibility is not good. When the high-voltage and high-current pulse is impacted, the outer package is easy to burst, which greatly shortens the service life of the heating film.
中国专利公告号为CN107446408A的现有技术在2017年12月08日公开了一种PTC石墨烯发热油墨及其制备方法、及其制备的发热膜，其包括粘结剂50-70％，溶剂9-21％，助剂1-3％，导电填料10-20％，PTC功能材料5-20％；所述PTC功能材料为碳酸钡氧化物、氧化铅氧化物、氧化铌氧化物、Bi氧化物、La氧化物、Y氧化物、Nb氧化物、Sb氧化物、烧结助剂中的一种或按任意比例混合的多种。该专利虽然增加了石墨烯发热膜的PTC功能，但由于采用的PTC功能材料要么存在毒性大，要么使用了镧系、锕系等族元素，价格较贵，且属于粉体不易在油墨中分散，存在着严重的分散不稳定性问题，而此专利中仅仅采用了常规的搅拌方式，存在着批次性不稳定的问题，不利于工业化应用。The prior art of the Chinese Patent Bulletin No. CN107446408A discloses a PTC graphene heating ink and its preparation method, and a heating film prepared thereon on December 08, 2017, comprising 50-70% of a binder, a solvent of 9% -21%, auxiliary agent 1-3%, conductive filler 10-20%, PTC functional material 5-20%; the PTC functional material is barium carbonate oxide, lead oxide oxide, niobium oxide oxide, Bi oxide , La oxide, Y oxide, Nb oxide, Sb oxide, one of sintering aids or a plurality of mixtures in any proportion. Although this patent increases the PTC function of the graphene heating film, because the PTC functional materials used are either highly toxic, or use lanthanide, actinide and other group elements, the price is relatively expensive, and the powder is not easy to be dispersed in the ink. , there is a serious dispersion instability problem, and this patent only adopts the conventional stirring method, which has the problem of batch instability, which is not conducive to industrial application.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是克服现有技术中的一个或多个不足，提供一种改进的石墨烯发热油墨，该发热油墨制成的发热膜在保证较低温度下优异导电性的前提下，实现了在高温下电阻大幅度提升的特性进而实现自限温，同时尤为关键的是其恢复到正常温度时材料阻值变化不大，可逆性好，从而提高了电热膜的循环使用性能以及在特殊领域使用的安全性。The technical problem to be solved by the present invention is to overcome one or more deficiencies in the prior art, and to provide an improved graphene heating ink. , the resistance is greatly improved at high temperature and self-limiting temperature is realized. At the same time, the most important thing is that the resistance value of the material does not change much when it returns to normal temperature, and the reversibility is good, thus improving the cycle performance of the electrothermal film. Safety for use in special fields.
本发明同时还提供了一种上述石墨烯发热油墨的制备方法。The present invention also provides a preparation method of the above graphene heating ink.
本发明同时还提供了一种电发热膜。The invention also provides an electric heating film.
为解决以上技术问题，本发明采取的一种技术方案如下：In order to solve the above technical problems, a kind of technical scheme adopted by the present invention is as follows:
一种石墨烯发热油墨，其包含树脂基体、导电填料、助剂和溶剂，所述导电填料包括石墨烯，所述树脂基体由有机聚合物与聚硅氮烷按照质量比1：0.08-1.5组成，所述石墨烯发热油墨还包含交联剂。该石墨烯发热油墨经涂布后并被加热至一定温度时，所述树脂基体在交联剂的作用下发生交联化反应且其中的聚硅氮烷发生陶瓷化转变，进而得到陶瓷化的高分子膜，该陶瓷化的高分子膜，既可以使高分子本身处于更有序的状态，有利于导电填料有效搭接成桥，利于导电；又可以使得在高温冲击时，高分子链的变形更局域，进而促使回到正常温度时更容易恢复原状，使导电填料粒子桥也更易恢复，因此可逆性好，循环使用性能更佳。A graphene heating ink, which comprises a resin matrix, a conductive filler, an auxiliary agent and a solvent, the conductive filler comprises graphene, and the resin matrix is composed of an organic polymer and a polysilazane in a mass ratio of 1:0.08-1.5 , the graphene heating ink also contains a crosslinking agent. After the graphene heating ink is coated and heated to a certain temperature, the resin matrix undergoes a cross-linking reaction under the action of a cross-linking agent, and the polysilazane in it undergoes a ceramization transformation, thereby obtaining a ceramization. The polymer film, the ceramicized polymer film, can not only make the polymer itself in a more orderly state, which is conducive to the effective bridging of conductive fillers, which is conducive to conducting electricity; The deformation is more localized, which makes it easier to restore the original shape when returning to normal temperature, and makes the bridge of the conductive filler particles easier to restore, so the reversibility is good and the recycling performance is better.
根据本发明的一些优选方面，所述聚硅氮烷的重均分子量为600-1300；进一步优选地，所述聚硅氮烷的重均分子量为800-1000。根据本发明的一个具体方面，所述聚硅氮烷的重均分子量为900。该分子量的聚硅氮烷能够获得更为优异的陶瓷化质量。According to some preferred aspects of the present invention, the polysilazane has a weight average molecular weight of 600-1300; further preferably, the polysilazane has a weight average molecular weight of 800-1000. According to a specific aspect of the present invention, the polysilazane has a weight average molecular weight of 900. The polysilazane of this molecular weight can obtain more excellent ceramic quality.
根据本发明的一些优选方面，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.1-1。进一步优选地，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.1-0.8。在本发明的一些实施方式中，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.2-0.6。According to some preferred aspects of the present invention, the mass ratio of the organic polymer to the polysilazane is 1:0.1-1. Further preferably, the mass ratio of the organic polymer to the polysilazane is 1:0.1-0.8. In some embodiments of the present invention, the mass ratio of the organic polymer to the polysilazane is 1:0.2-0.6.
根据本发明的一些优选方面，所述助剂至少包括含硅分散剂、增稠剂，以质量百分含量计，石墨烯发热油墨中，所述石墨烯占3-20％、有机聚合物占3-10％、聚硅氮烷占0.95-3.1％、交联剂占1-2.5％、含硅分散剂0.1-0.6％、增稠剂占0.2-1.3％，溶剂占63-90％。According to some preferred aspects of the present invention, the auxiliary agent includes at least a silicon-containing dispersant and a thickening agent. In terms of mass percentage, in the graphene heating ink, the graphene accounts for 3-20%, and the organic polymer accounts for 3-20%. 3-10%, polysilazane 0.95-3.1%, crosslinking agent 1-2.5%, silicon-containing dispersant 0.1-0.6%, thickener 0.2-1.3%, solvent 63-90%.
根据本发明的一些具体且优选的方面，所述有机聚合物为聚氨酯树脂和/或丙烯酸树脂，所述交联剂为选自含有胺基的交联剂中的一种或多种的组合，所述含有胺基的交联剂包括但不限于改性聚碳二亚胺交联剂、二亚乙基三胺、三亚乙基四胺、二甲胺基丙胺及二乙胺基丙胺等。According to some specific and preferred aspects of the present invention, the organic polymer is a polyurethane resin and/or an acrylic resin, and the cross-linking agent is a combination of one or more selected from cross-linking agents containing amine groups, The amine group-containing crosslinking agent includes, but is not limited to, modified polycarbodiimide crosslinking agent, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, diethylaminopropylamine, and the like.
根据本发明的一些具体且优选的方面，所述含硅分散剂为选自聚醚改性硅油、硅树脂、硅橡胶和硅烷偶联剂中的一种或多种的组合。According to some specific and preferred aspects of the present invention, the silicon-containing dispersant is a combination of one or more selected from the group consisting of polyether-modified silicone oil, silicone resin, silicone rubber and silane coupling agent.
根据本发明的一些具体且优选的方面，所述增稠剂为选自憎水改性纤维素增稠剂、聚丙烯酸酯中的一种或多种的组合。According to some specific and preferred aspects of the present invention, the thickener is a combination of one or more selected from hydrophobically modified cellulose thickener and polyacrylate.
本发明中，在石墨烯油墨中引入聚硅氮烷提升了安全性和循环可逆性能等，同时在聚硅氮烷、有机聚合物的基础上进一步结合能够与有机聚合物交联反应的交联剂，确保了该油墨产品的基本性能得到较好的保障，例如粘结性更好更牢固、成膜性更优等。与此同时，本发明中进一步结合含硅分散剂和增稠剂作为助剂，一方面，极大地提升了聚硅氮烷在油墨体系中的分散性，使得该油墨不易发生相分离的现象，而硅含量的提升又提升了成膜膜层的热稳定性和力学性能；另一方面，较好地改善了添加有聚硅氮烷的油墨体系的粘度，以便适于油墨的涂布或丝印等工艺，也可以获得更好的成膜性等性能。显然，对于本发明的石墨烯发热油墨而言，上述复合的树脂基体、交联剂、含硅分散剂与增稠剂的有机结合，不仅实现了成膜膜层出人意料的好的自限温、可逆性特点，而且对于油墨的基础性能，包括但不限于粘结性、成膜性、稳定性、分散性、导电性等均具有较好的促进作用。In the present invention, the introduction of polysilazane into the graphene ink improves the safety and cycle reversible performance, and at the same time, on the basis of polysilazane and organic polymers, a cross-linking reaction capable of cross-linking reaction with organic polymers is further combined It ensures that the basic properties of the ink product are better guaranteed, such as better and firmer adhesion and better film-forming properties. At the same time, the present invention further combines silicon-containing dispersants and thickeners as auxiliary agents. On the one hand, the dispersibility of polysilazane in the ink system is greatly improved, so that the ink is not prone to phase separation. The increase of silicon content improves the thermal stability and mechanical properties of the film-forming layer; on the other hand, the viscosity of the ink system added with polysilazane is better improved, so that it is suitable for ink coating or screen printing Other processes can also obtain better film-forming properties. Obviously, for the graphene heating ink of the present invention, the organic combination of the above-mentioned composite resin matrix, cross-linking agent, silicon-containing dispersant and thickener not only realizes the unexpectedly good self-limiting temperature, It has the characteristics of reversibility, and has a good promotion effect on the basic properties of the ink, including but not limited to adhesion, film formation, stability, dispersion, and electrical conductivity.
根据本发明的一些具体且优选的方面，所述的助剂还选择性地包含有选自聚乙烯吡咯烷酮、十六烷基三甲基溴化铵中的一种或多种的组合。According to some specific and preferred aspects of the present invention, the adjuvant optionally further comprises a combination of one or more selected from polyvinylpyrrolidone and cetyltrimethylammonium bromide.
根据本发明的一些优选方面，所述溶剂为选自N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜、氯仿和正己烷中的一种或多种的组合。According to some preferred aspects of the present invention, the solvent is a combination of one or more selected from N,N-dimethylformamide, dichloromethane, dimethylsulfoxide, chloroform and n-hexane.
在本发明的一些实施方式中，所述石墨烯发热油墨中还可以添加消泡剂等。In some embodiments of the present invention, a defoamer or the like may also be added to the graphene heating ink.
本发明提供的又一技术方案：一种上述所述的石墨烯发热油墨的制备方法，该制备方法包括：石墨烯采用粉体形式的石墨烯粉体，聚硅氮烷采 用溶液形式的聚硅氮烷溶液，首先将石墨烯粉体和聚硅氮烷溶液进行搅拌分散，使充分混合，待混合均匀后，在搅拌下加入剩余原料，制成所述石墨烯发热油墨。Another technical solution provided by the present invention: a preparation method of the above-mentioned graphene heating ink, the preparation method comprises: using graphene powder in powder form for graphene, and polysilazane in solution form for polysilazane For the azane solution, firstly, the graphene powder and the polysilazane solution are stirred and dispersed so as to be fully mixed, and after the mixing is uniform, the remaining raw materials are added under stirring to prepare the graphene heating ink.
根据本发明的一些优选且具体的方面，所述石墨烯粉体通过将石墨烯与水混合分散形成均一稳定的石墨烯水溶液，然后将石墨烯水溶液烘干，利用粉碎机进行粉碎而得。According to some preferred and specific aspects of the present invention, the graphene powder is obtained by mixing and dispersing graphene with water to form a homogeneous and stable graphene aqueous solution, then drying the graphene aqueous solution and pulverizing with a pulverizer.
根据本发明的一些具体且优选的方面，所述石墨烯粉体的D50为5-10μm。According to some specific and preferred aspects of the present invention, the D50 of the graphene powder is 5-10 μm.
根据本发明的一些优选且具体的方面，所述聚硅氮烷溶液中聚硅氮烷的质量百分含量为6-10％。根据本发明的一个具体方面，所述聚硅氮烷溶液中聚硅氮烷的质量百分含量为8％，可通过商购获得。According to some preferred and specific aspects of the present invention, the mass percentage of polysilazane in the polysilazane solution is 6-10%. According to a specific aspect of the present invention, the mass percentage of polysilazane in the polysilazane solution is 8%, which can be obtained commercially.
本发明提供的又一技术方案：一种电发热膜，包括基体以及覆设在所述基体上的电发热膜层，该电发热膜层是通过将上述所述的石墨烯发热油墨涂布在所述基体上并加热至140～150℃交联固化形成的陶瓷化的高分子膜。Another technical solution provided by the present invention: an electric heating film, comprising a base body and an electric heating film layer covered on the base body, the electric heating film layer is obtained by coating the above-mentioned graphene heating ink on The ceramic polymer film formed by crosslinking and curing on the substrate and heated to 140-150°C.
本发明中，石墨烯发热油墨制成的电发热膜的工作原理是在电的引发激励下，通过石墨烯碳分子团产生“布朗运动”，由石墨烯碳分子间的互相撞击和摩擦从而产生热能，并产生大量的红外线辐射。其中，本发明的电发热膜层在常温时，形成的陶瓷化的高分子膜可以有利于使高分子本身处于更有序的状态，有利于导电填料有效搭接成桥，利于导电，从而获得极好的发热效果；同时还可在受到高温冲击时，高分子链产生形变，使导电填料(导电粒子)的链接受到一定程度破坏，从而电阻升高，降低功率而达到自限温；与此同时，在本发明中，在此遭受高温冲击的过程中，高分子链的变形可以变得更局域性，进而促使从高温回到正常温度时高分子链更容易恢复原状，使导电填料粒子桥也更易恢复，因此可逆性好，循环使用性能也更佳，解决了现有高分子PTC材料容易热疲劳，即受高温后再回到正常工作温度时导电填料粒子链(桥)并不能很好地恢复到原来的状态而出现的可逆性不好的问题。In the present invention, the working principle of the electric heating film made of graphene heating ink is that under the excitation of electricity, "Brownian motion" is generated by graphene carbon molecular clusters, which are generated by the mutual collision and friction between graphene carbon molecules. heat energy and generate a lot of infrared radiation. Among them, when the electric heating film layer of the present invention is at room temperature, the ceramized polymer film formed can be conducive to making the polymer itself in a more orderly state, which is conducive to the effective overlapping of conductive fillers to form bridges, and is conducive to conducting electricity, thereby obtaining Excellent heating effect; at the same time, when subjected to high temperature impact, the polymer chain is deformed, so that the link of the conductive filler (conductive particle) is damaged to a certain extent, so that the resistance increases, the power is reduced, and the self-limiting temperature is achieved; with this At the same time, in the present invention, the deformation of the polymer chain can become more localized in the process of being subjected to a high temperature impact, thereby facilitating the recovery of the polymer chain from the high temperature to the normal temperature, making the conductive filler particles easier to recover. The bridge is also easier to recover, so the reversibility is good, and the cycle performance is better, which solves the problem that the existing polymer PTC materials are prone to thermal fatigue, that is, the conductive filler particle chain (bridge) is not very good when it is returned to normal working temperature after being subjected to high temperature. The problem of poor reversibility that occurs when it is restored to its original state.
在本发明的一些实施方式中，所述基体可以为PET膜(聚对苯二甲酸乙二醇酯薄膜)或PI膜(聚酰亚胺薄膜)等。In some embodiments of the present invention, the substrate may be a PET film (polyethylene terephthalate film) or a PI film (polyimide film) or the like.
由于以上技术方案的采用，本发明与现有技术相比具有如下优点：Due to the adoption of the above technical solutions, the present invention has the following advantages compared with the prior art:
本发明创新地提出了一种改进的石墨烯发热油墨，该发热油墨通过选择特定的复合树脂基体，该复合树脂基体包含的有机聚合物通过与交联剂的配合实现交联固化，而与此同时该复合树脂基体包含的聚硅氮烷发生了陶瓷化转变，进而使得本申请的发热油墨能够在固化时直接得到陶瓷化的高分子膜，该陶瓷化的高分子膜不仅具有优异的低温导电性而且还具有高温电阻变大的特性，实现自限温，提升了使用安全性；同时尤其关键的是其即使遭受多次高温冲击，但是若恢复到正常温度时，其仍然能够使得内部导电填料粒子桥容易恢复原状，进而实现了可逆性好，循环使用性能得以提升，解决了现有高分子PTC材料容易热疲劳而难以恢复原状而造成发热性能不好的问题。The present invention innovatively proposes an improved graphene heating ink. The heating ink selects a specific composite resin matrix, and the organic polymer contained in the composite resin matrix is cross-linked and cured by cooperating with a cross-linking agent. At the same time, the polysilazane contained in the composite resin matrix undergoes ceramization transformation, so that the heating ink of the present application can directly obtain a ceramized polymer film during curing, and the ceramized polymer film not only has excellent low-temperature conductivity It also has the characteristics of increasing high temperature resistance, realizing self-limiting temperature and improving the safety of use; at the same time, it is especially critical that even if it is subjected to multiple high temperature shocks, if it returns to normal temperature, it can still make the internal conductive filler. The particle bridge is easy to restore to its original state, thereby achieving good reversibility and improving the recycling performance, which solves the problem that the existing polymer PTC materials are easily thermally fatigued and difficult to restore to their original state, resulting in poor heat generation performance.
此外，本申请的发热油墨所采用的原料均易获得，且价格适中，制备流程简单，制备工艺可控，组分简单并具有理想的粘度等物理力学性质，成膜性好，相比于现有技术中的电热膜具有更优异的综合性能，便于产业化生产。In addition, the raw materials used in the heating ink of the present application are easy to obtain, and the price is moderate, the preparation process is simple, the preparation process is controllable, the components are simple, the physical and mechanical properties such as ideal viscosity, etc. The electrothermal film in the prior art has more excellent comprehensive performance and is convenient for industrial production.
具体实施方式Detailed ways
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。The above scheme will be further described below in conjunction with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following examples; The implementation conditions can be further adjusted according to specific requirements, and the unspecified implementation conditions are usually those in routine experiments.
下述中，如无特殊说明，所有的原料均来自于商购或者通过本领域的常规方法制备而得。In the following, unless otherwise specified, all raw materials are commercially available or prepared by conventional methods in the art.
聚硅氮烷溶液购自安徽艾约塔硅油，牌号为IOTA-9108，聚硅氮烷的质量百分数为8％，分散溶剂是氯仿，聚硅氮烷的重均分子量为900。The polysilazane solution was purchased from Anhui Aiyota Silicon Oil, the brand name was IOTA-9108, the mass percentage of polysilazane was 8%, the dispersing solvent was chloroform, and the weight-average molecular weight of polysilazane was 900.
聚乙烯吡咯烷酮PVP购自Aladdin，牌号为P110567。Polyvinylpyrrolidone PVP was purchased from Aladdin under the designation P110567.
憎水改性纤维素增稠剂购自上海凯茵，牌号为BYK-032。The hydrophobic modified cellulose thickener was purchased from Shanghai Kane under the brand name BYK-032.
改性聚碳二亚胺交联剂购自上海凯茵，牌号为EBECRYL-0071。The modified polycarbodiimide crosslinking agent was purchased from Shanghai Kaiyin under the trade name EBECRYL-0071.
聚氨酯树脂购自亨缌克，牌号为PU3645；聚醚改性硅油购自麦克林，牌号为P875564。Polyurethane resin was purchased from Hengke, the brand name was PU3645; polyether modified silicone oil was purchased from Maclean, the brand name was P875564.
石墨烯粉体的配制：将石墨烯(购自苏州烯时代材料科技有限公司，石墨烯层数为1-10层)与水混合分散形成均一稳定的石墨烯水溶液，然后将石墨烯水溶液烘干，利用粉碎机进行粉碎处理后备用，粉碎后所得石墨烯粉体的平均直径为6μm。Preparation of graphene powder: Graphene (purchased from Suzhou Graphene Times Materials Technology Co., Ltd., the number of graphene layers is 1-10 layers) is mixed and dispersed with water to form a uniform and stable graphene aqueous solution, and then the graphene aqueous solution is dried , using a pulverizer to pulverize and treat for later use, and the average diameter of the graphene powder obtained after pulverization is 6 μm.
实施例1Example 1
本实施例提供一种石墨烯发热油墨，以质量百分含量计，其原料包括：石墨烯粉体18％、聚硅氮烷溶液30％、聚乙烯吡咯烷酮PVP 1.0％、憎水改性纤维素增稠剂0.7％、改性聚碳二亚胺交联剂1.8％、聚氨酯树脂5％、聚醚改性硅油0.3％，余量为N,N-二甲基甲酰胺。This embodiment provides a graphene heating ink. In terms of mass percentage, the raw materials include: graphene powder 18%, polysilazane solution 30%, polyvinylpyrrolidone PVP 1.0%, hydrophobic modified cellulose Thickener 0.7%, modified polycarbodiimide crosslinking agent 1.8%, polyurethane resin 5%, polyether modified silicone oil 0.3%, and the balance is N,N-dimethylformamide.
其制备方法包括：按配方称取各原料，先将石墨烯粉体与聚硅氮烷溶液充分搅拌混合，混合均匀后，在搅拌过程中依次分别加入聚乙烯吡咯烷酮PVP，憎水改性纤维素增稠剂，改性聚碳二亚胺交联剂，聚氨酯树脂，聚醚改性硅油，剩余质量百分比量的N,N-二甲基甲酰胺，充分搅拌，静置30分钟，即得所述的石墨烯发热油墨。The preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, after the mixing is uniform, respectively adding polyvinylpyrrolidone PVP and hydrophobic modified cellulose in the stirring process. Thickener, modified polycarbodiimide crosslinking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand for 30 minutes. The described graphene heating ink.
实施例2Example 2
本实施例提供一种石墨烯发热油墨，以质量百分含量计，其原料包括：石墨烯粉体15％、聚硅氮烷溶液30％、十六烷基三甲基溴化铵1.2％、憎水改性纤维素增稠剂0.8％、改性聚碳二亚胺交联剂1.8％、聚氨酯树脂6％、聚醚改性硅油0.5％，余量为N,N-二甲基甲酰胺。This embodiment provides a graphene heating ink. In terms of mass percentage, the raw materials include: 15% of graphene powder, 30% of polysilazane solution, 1.2% of cetyltrimethylammonium bromide, Hydrophobic modified cellulose thickener 0.8%, modified polycarbodiimide crosslinking agent 1.8%, polyurethane resin 6%, polyether modified silicone oil 0.5%, the balance is N,N-dimethylformamide .
其制备方法包括：按配方称取各原料，先将石墨烯粉体与聚硅氮烷溶液充分搅拌混合，混合均匀后，在搅拌过程中依次分别加入十六烷基三甲基溴化铵，憎水改性纤维素增稠剂，改性聚碳二亚胺交联剂，聚氨酯树脂，聚醚改性硅油，剩余质量百分比量的N,N-二甲基甲酰胺，充分搅拌，静置30分钟，即得所述的石墨烯发热油墨。The preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, and after the mixing is uniform, sequentially adding cetyltrimethylammonium bromide in the stirring process, Hydrophobic modified cellulose thickener, modified polycarbodiimide cross-linking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand After 30 minutes, the graphene heating ink was obtained.
实施例3Example 3
本实施例提供一种石墨烯发热油墨，以质量百分含量计，其原料包括：石墨烯粉体10％、聚硅氮烷溶液30％、聚乙烯吡咯烷酮PVP 1.5％、 憎水改性纤维素增稠剂1.0％、改性聚碳二亚胺交联剂2.0％、聚氨酯树脂8％、聚醚改性硅油0.6％，余量为N,N-二甲基甲酰胺。This embodiment provides a graphene heating ink, in terms of mass percentage, the raw materials include: 10% of graphene powder, 30% of polysilazane solution, 1.5% of polyvinylpyrrolidone PVP, hydrophobic modified cellulose Thickener 1.0%, modified polycarbodiimide crosslinking agent 2.0%, polyurethane resin 8%, polyether modified silicone oil 0.6%, and the balance is N,N-dimethylformamide.
其制备方法包括：按配方称取各原料，先将石墨烯粉体与聚硅氮烷溶液充分搅拌混合，混合均匀后，在搅拌过程中依次分别加入聚乙烯吡咯烷酮PVP，憎水改性纤维素增稠剂，改性聚碳二亚胺交联剂，聚氨酯树脂，聚醚改性硅油，剩余质量百分比量的N,N-二甲基甲酰胺，充分搅拌，静置30分钟，即得所述的石墨烯发热油墨。The preparation method includes: weighing each raw material according to the formula, first fully stirring and mixing the graphene powder and the polysilazane solution, after the mixing is uniform, respectively adding polyvinylpyrrolidone PVP and hydrophobic modified cellulose in the stirring process. Thickener, modified polycarbodiimide crosslinking agent, polyurethane resin, polyether modified silicone oil, the remaining mass percentage of N,N-dimethylformamide, fully stirred, and allowed to stand for 30 minutes. The described graphene heating ink.
对比例1Comparative Example 1
基本同实施例1，其区别仅在于：不加聚硅氮烷，相应调整溶剂的含量。Basically the same as Example 1, the difference is only that polysilazane is not added, and the content of the solvent is adjusted accordingly.
对比例2Comparative Example 2
基本同实施例1，其区别仅在于：不加聚醚改性硅油，并且将聚乙烯吡咯烷酮PVP的含量提升至1.3％。Basically the same as Example 1, the only difference is that: no polyether modified silicone oil is added, and the content of polyvinylpyrrolidone PVP is increased to 1.3%.
对比例3Comparative Example 3
基本同实施例1，其区别仅在于：不加增稠剂，并且将聚氨酯树脂的含量提升至12.6％(聚氨酯树脂和聚硅氮烷的总含量为15％)，相应减少溶剂的含量。Basically the same as Example 1, the only difference is: no thickener is added, and the content of polyurethane resin is increased to 12.6% (the total content of polyurethane resin and polysilazane is 15%), and the content of solvent is correspondingly reduced.
实施例4Example 4
将制得的所述石墨烯发热油墨均匀涂布在PET薄膜上，145±5摄氏度下烘烤2分钟后收卷，再放入烘箱中进行交联固化，固化时间为4小时，即可得到石墨烯电发热膜，可应用于取暖等领域。The obtained graphene heating ink is evenly coated on the PET film, baked at 145±5 degrees Celsius for 2 minutes, then rolled up, and then placed in an oven for cross-linking and curing, and the curing time is 4 hours to obtain Graphene electric heating film can be used in heating and other fields.
本发明中，依据标准GB/T 7287—2008《红外辐射加热器试验方法》测试电-热辐射转换效率，采用标准中的热像测量法(B方法)。功率密度设定200～500W/m 2，通电发热温度稳定后，对采用实施例1-3和对比例1-3的石墨烯发热油墨制成的电发热膜进行测试，按照公式： In the present invention, the electric-thermal radiation conversion efficiency is tested according to the standard GB/T 7287-2008 "Infrared Radiation Heater Test Method", and the thermal image measurement method (B method) in the standard is adopted. The power density is set to 200-500W/m 2 , and after the heating temperature is stabilized after electrification, the electric heating films made of the graphene heating inks of Example 1-3 and Comparative Example 1-3 are tested, according to the formula:
η＝Sσ(T 1 4-T 0 4)/P e*100 η=Sσ(T 1 4 -T 0 4 )/P e *100
式中：η为电-热辐射转换效率(％)；P e为实测电功率(W)；T 1为平均辐射温度(K)；T 0为环境温度(K)；S为辐射面面积(m 3)；σ为斯特潘-玻尔兹曼常(5.67×10 -8W·m -2·K -4)。 In the formula: η is the electric-thermal radiation conversion efficiency (%); P e is the measured electric power (W); T 1 is the average radiation temperature (K); T 0 is the ambient temperature (K); S is the radiation surface area (m 3 ); σ is the Stepan-Boltzmann constant (5.67×10 -8 W·m -2 ·K -4 ).
测试数据得到如下表1所示：The test data are shown in Table 1 below:
表1Table 1
   实施例1Example 1 实施例2Example 2 实施例3Example 3 对比例1Comparative Example 1 对比例2Comparative Example 2 对比例3Comparative Example 3
SS 0.150.15 0.150.15 0.150.15 0.150.15 0.150.15 0.150.15
T 1 T1 322.6322.6 322.8322.8 326326 302.1302.1 310.3310.3 316316
T 0 T 0 298.8298.8 299.3299.3 299.8299.8 299.6299.6 299.3299.3 298.6298.6
P e Pe 30.530.5 30.130.1 32.832.8 26.626.6 28.628.6 29.429.4
ηn 79％79% 80％80% 83％83% 54％54% 60％60% 62％62%
同时经过十万次过流之后阻值变化不明显且仍具有自限温特性，具体结果参见表2所示。At the same time, after 100,000 overcurrents, the resistance value does not change significantly and still has self-limiting temperature characteristics. The specific results are shown in Table 2.
表2Table 2
Figure PCTCN2020134513-appb-000001
Figure PCTCN2020134513-appb-000001
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those who are familiar with the art to understand the content of the present invention and implement them accordingly, and cannot limit the scope of protection of the present invention with this. Equivalent changes or modifications made in the spirit and spirit should all be included within the protection scope of the present invention.

Claims (15)

  1. 一种石墨烯发热油墨，其包含树脂基体、导电填料、助剂和溶剂，所述导电填料包括石墨烯，其特征在于，所述树脂基体由有机聚合物与聚硅氮烷按照质量比1：0.08-1.5组成，所述石墨烯发热油墨还包含交联剂；A kind of graphene heating ink, it comprises resin matrix, conductive filler, auxiliary agent and solvent, described conductive filler comprises graphene, it is characterized in that, described resin matrix is made of organic polymer and polysilazane according to mass ratio 1: 0.08-1.5 composition, the graphene heating ink also includes a crosslinking agent;
    其中，所述助剂包括含硅分散剂、增稠剂，以质量百分含量计，石墨烯发热油墨中，所述石墨烯占3-20％、有机聚合物占3-10％、聚硅氮烷占0.95-3.1％、交联剂占1-2.5％、含硅分散剂占0.1-0.6％、增稠剂占0.2-1.3％，溶剂占63-90％；Wherein, the auxiliary agent includes a silicon-containing dispersant and a thickening agent. In terms of mass percentage, in the graphene heating ink, the graphene accounts for 3-20%, the organic polymer accounts for 3-10%, the polysilicon Azane accounts for 0.95-3.1%, cross-linking agent accounts for 1-2.5%, silicon-containing dispersant accounts for 0.1-0.6%, thickener accounts for 0.2-1.3%, and solvent accounts for 63-90%;
    所述聚硅氮烷的重均分子量为600-1300，所述有机聚合物为聚氨酯树脂和/或丙烯酸树脂，所述交联剂为选自含有胺基的交联剂中的一种或多种的组合，所述含有胺基的交联剂为选自改性聚碳二亚胺交联剂、二亚乙基三胺、三亚乙基四胺、二甲胺基丙胺和二乙胺基丙胺中的一种或多种的组合，所述含硅分散剂为选自聚醚改性硅油、硅树脂、硅橡胶和硅烷偶联剂中的一种或多种的组合，所述增稠剂为选自憎水改性纤维素增稠剂、聚丙烯酸酯中的一种或多种的组合。The weight-average molecular weight of the polysilazane is 600-1300, the organic polymer is a polyurethane resin and/or an acrylic resin, and the cross-linking agent is one or more selected from cross-linking agents containing amine groups. The combination, the crosslinking agent containing amine group is selected from modified polycarbodiimide crosslinking agent, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine and diethylamine The combination of one or more in propylamine, the silicon-containing dispersant is a combination of one or more selected from polyether-modified silicone oil, silicone resin, silicone rubber and silane coupling agent, the thickening The agent is a combination of one or more selected from hydrophobic modified cellulose thickener and polyacrylate.
  2. 一种石墨烯发热油墨，其包含树脂基体、导电填料、助剂和溶剂，所述导电填料包括石墨烯，其特征在于，所述树脂基体由有机聚合物与聚硅氮烷按照质量比1：0.08-1.5组成，所述石墨烯发热油墨还包含交联剂。A kind of graphene heating ink, it comprises resin matrix, conductive filler, auxiliary agent and solvent, described conductive filler comprises graphene, it is characterized in that, described resin matrix is made of organic polymer and polysilazane according to mass ratio 1: 0.08-1.5 composition, the graphene heating ink also contains a crosslinking agent.
  3. 根据权利要求2所述的石墨烯发热油墨，其特征在于，所述聚硅氮烷的重均分子量为600-1300。The graphene heating ink according to claim 2, wherein the weight average molecular weight of the polysilazane is 600-1300.
  4. 根据权利要求3所述的石墨烯发热油墨，其特征在于，所述聚硅氮烷的重均分子量为800-1000。The graphene heating ink according to claim 3, wherein the weight average molecular weight of the polysilazane is 800-1000.
  5. 根据权利要求1或2或3或4所述的石墨烯发热油墨，其特征在于，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.1-1。The graphene heating ink according to claim 1 or 2 or 3 or 4, wherein the mass ratio of the organic polymer to the polysilazane is 1:0.1-1.
  6. 根据权利要求5所述的石墨烯发热油墨，其特征在于，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.1-0.8。The graphene heating ink according to claim 5, wherein the mass ratio of the organic polymer to the polysilazane is 1:0.1-0.8.
  7. 根据权利要求6所述的石墨烯发热油墨，其特征在于，所述有机聚合物与所述聚硅氮烷的投料质量比为1：0.2-0.6。The graphene heating ink according to claim 6, wherein the mass ratio of the organic polymer to the polysilazane is 1:0.2-0.6.
  8. 根据权利要求2所述的石墨烯发热油墨，其特征在于，所述助剂至少包括含硅分散剂和增稠剂，以质量百分含量计，石墨烯发热油墨中，所述石墨烯占3-20％、有机聚合物占3-10％、聚硅氮烷占0.95-3.1％、交联剂占1-2.5％、含硅分散剂占0.1-0.6％、增稠剂占0.2-1.3％，溶剂占63-90％。The graphene heating ink according to claim 2, wherein the auxiliary agent comprises at least a silicon-containing dispersant and a thickening agent, and in terms of mass percentage, in the graphene heating ink, the graphene accounts for 3 -20%, organic polymer 3-10%, polysilazane 0.95-3.1%, crosslinking agent 1-2.5%, silicon-containing dispersant 0.1-0.6%, thickener 0.2-1.3% , the solvent accounts for 63-90%.
  9. 根据权利要求2或8所述的石墨烯发热油墨，其特征在于，所述有机聚合物为聚氨酯树脂和/或丙烯酸树脂，所述交联剂为选自含有胺基的交联剂中的一种或多种的组合，所述含有胺基的交联剂包括改性聚碳二亚胺交联剂、二亚乙基三胺、三亚乙基四胺、二甲胺基丙胺及二乙胺基丙胺。The graphene heating ink according to claim 2 or 8, wherein the organic polymer is a polyurethane resin and/or an acrylic resin, and the cross-linking agent is one selected from the cross-linking agents containing amine groups One or more combinations, the crosslinking agent containing amine group includes modified polycarbodiimide crosslinking agent, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine and diethylamine propylamine.
  10. 根据权利要求2或8所述的石墨烯发热油墨，其特征在于，所述含硅分散剂为选自聚醚改性硅油、硅树脂、硅橡胶和硅烷偶联剂中的一种或多种的组合；所述增稠剂为选自憎水改性纤维素增稠剂、聚丙烯酸酯中的一种或多种的组合；所述的助剂还选择性地包含有选自聚乙烯吡咯烷酮、十六烷基三甲基溴化铵中的一种或多种的组合。The graphene heating ink according to claim 2 or 8, wherein the silicon-containing dispersant is one or more selected from polyether-modified silicone oil, silicone resin, silicone rubber and silane coupling agent The thickener is a combination of one or more selected from hydrophobic modified cellulose thickener and polyacrylate; the auxiliary agent also optionally contains polyvinylpyrrolidone , a combination of one or more of cetyltrimethylammonium bromide.
  11. 根据权利要求2或8所述的石墨烯发热油墨，其特征在于，所述溶剂为选自N,N-二甲基甲酰胺、二氯甲烷、二甲基亚砜、氯仿和正己烷中的一种或多种的组合。The graphene heating ink according to claim 2 or 8, wherein the solvent is a solvent selected from N,N-dimethylformamide, dichloromethane, dimethyl sulfoxide, chloroform and n-hexane. a combination of one or more.
  12. 一种权利要求1-11中任一项所述的石墨烯发热油墨的制备方法，其特征在于，所述制备方法包括：石墨烯采用粉体形式的石墨烯粉体，聚硅氮烷采用溶液形式的聚硅氮烷溶液，首先将石墨烯粉体和聚硅氮烷溶液进行搅拌分散，使充分混合，待混合均匀后，在搅拌下加入剩余原料，制成所述石墨烯发热油墨。A method for preparing a graphene heating ink according to any one of claims 1-11, wherein the preparation method comprises: using graphene powder in the form of powder for graphene, and using a solution for polysilazane The polysilazane solution in the form of the graphene powder and the polysilazane solution are firstly stirred and dispersed to be fully mixed, and after the mixing is uniform, the remaining raw materials are added under stirring to prepare the graphene heating ink.
  13. 根据权利要求12所述的石墨烯发热油墨的制备方法，其特征在于，所述石墨烯粉体的D50为5-10μm。The method for preparing a graphene heating ink according to claim 12, wherein the D50 of the graphene powder is 5-10 μm.
  14. 一种电发热膜，包括基体以及覆设在所述基体上的电发热膜层，其特征在于，所述电发热膜层是通过将如权利要求1-11中任一项所述的石墨烯发热油墨涂布在所述基体上并加热至140～150℃交联固化形成的陶瓷化的高分子膜。An electric heating film, comprising a base body and an electric heating film layer covering the base body, wherein the electric heating film layer is made of graphene as claimed in any one of claims 1-11. The heat-generating ink is coated on the substrate and heated to 140-150° C. to form a ceramicized polymer film formed by cross-linking and curing.
  15. 根据权利要求14所述的电发热膜，其特征在于，所述基体为PET膜或PI膜。The electric heating film according to claim 14, wherein the substrate is a PET film or a PI film.
PCT/CN2020/134513 2020-12-08 2020-12-08 Graphene heating ink, preparation method therefor, and application thereof WO2022120565A1 (en)

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