阅读说明：本技术 一种水性石墨烯阻燃ptc导电浆料及其制备方法和柔性导电发热布 (Water-based graphene flame-retardant PTC conductive paste, preparation method thereof and flexible conductive heating cloth ) 是由 岳根基 高顺 岳天赐 曹卫华 张福志 于 2020-12-01 设计创作，主要内容包括：本发明提供了一种水性石墨烯阻燃PTC导电浆料及其制备方法和柔性导电发热布,涉及导电材料技术领域。本发明提供的水性石墨烯阻燃PTC导电浆料,以重量份数计,包括以下组分：PTC功能组分5～20份；所述PTC功能组分包括高分子PTC材料和石蜡中的一种或几种；水性柔性树脂10～20份；阻燃剂1～5份；导电填料5～20份；水20～60份；分散剂5～10份；助剂0.7～5份。本发明提供的水性石墨烯阻燃PTC导电浆料为具有PTC效应的阻燃发热体,能够控制温度,大大提高了安全性。以本发明提供的导电浆料制备的柔性导电发热布不仅提高了发热布的导电率以及发热布的导电均匀性,也使得发热布的耐揉搓性能大大提高。(The invention provides a water-based graphene flame-retardant PTC conductive paste, a preparation method thereof and flexible conductive heating cloth, and relates to the technical field of conductive materials. The invention provides a water-based graphene flame-retardant PTC conductive paste which comprises the following components in parts by weight: 5-20 parts of PTC functional components; the PTC functional component comprises one or more of a polymer PTC material and paraffin; 10-20 parts of water-based flexible resin; 1-5 parts of a flame retardant; 5-20 parts of conductive filler; 20-60 parts of water; 5-10 parts of a dispersing agent; 0.7-5 parts of an auxiliary agent. The water-based graphene flame-retardant PTC conductive paste provided by the invention is a flame-retardant heating body with PTC effect, can control the temperature and greatly improves the safety. The flexible conductive heating cloth prepared by the conductive slurry provided by the invention not only improves the conductivity of the heating cloth and the conductivity uniformity of the heating cloth, but also greatly improves the rubbing resistance of the heating cloth.)

1. The water-based graphene flame-retardant PTC conductive paste comprises the following components in parts by weight:

5-20 parts of PTC functional components; the PTC functional component comprises a high-molecular PTC material and/or paraffin;

10-20 parts of water-based flexible resin;

1-5 parts of a flame retardant;

5-20 parts of conductive filler;

20-60 parts of water;

5-10 parts of a dispersing agent;

0.7-5 parts of an auxiliary agent.

2. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the polymer PTC material comprises one or more of polycaprolactone, polyethylene, maleic anhydride grafted polyethylene and polypropylene.

3. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the aqueous flexible resin is a composite resin composed of flexible aqueous acrylic resin and flexible aqueous polyurethane.

4. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the flame retardant comprises one or more of dimethyl methyl phosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide.

5. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the conductive filler comprises one or more of graphene, conductive carbon black and nano graphite.

6. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the dispersant comprises one or more of acrylic block polymer, anionic polyacrylamide, BYK025 and BYK 9076.

7. The aqueous graphene flame-retardant PTC conductive paste according to claim 1, wherein the auxiliary agent comprises one or more of a leveling agent, a defoaming agent, a film forming auxiliary agent and a thickening agent.

8. A preparation method of the aqueous graphene flame-retardant PTC conductive paste according to any one of claims 1 to 7, comprising the following steps:

mixing water-based flexible resin with water to obtain a resin solution;

mixing the resin solution, the flame retardant and the PTC functional component to obtain a dispersion liquid;

and mixing the dispersion liquid, the dispersing agent, the auxiliary agent and the conductive filler, and grinding to obtain the water-based graphene flame-retardant PTC conductive slurry.

9. A flexible conductive heating cloth is characterized by comprising a cloth base body, an electric heating layer, an electrode plate and a protective layer which are sequentially stacked; the components of the electric heating layer are the aqueous graphene flame-retardant PTC conductive paste according to any one of claims 1-7 or the aqueous graphene flame-retardant PTC conductive paste prepared by the preparation method according to claim 8.

10. The flexible conductive heating cloth according to claim 9, wherein the thickness of the electrothermal layer is 50 to 150 μm.

Technical Field

The invention relates to the technical field of conductive materials, in particular to a water-based graphene flame-retardant PTC conductive paste, a preparation method thereof and flexible conductive heating cloth.

Background

Some small products sold in the market at present, such as electric heating thermal clothes, waist supports, knee pads and the like, are made of conductive heating cloth woven by mixing metal resistance wires and cotton wires, polyimide films and the like, have poor rubbing resistance and do not have the function of flame retardance and self temperature limitation, so that the danger of overheating caused by failure or extreme use exists. In addition, for large products such as electric mattresses, electric blankets, electric heating protective covers and the like, as the large products mostly use 220V alternating current as a power supply and do not have a flame-retardant self-temperature-limiting function, the products lack safety, the service life of the products is influenced, and the key for influencing the performance of the products lies in the selection and preparation of a heating element.

Disclosure of Invention

The invention aims to provide aqueous graphene flame-retardant PTC conductive paste, a preparation method thereof and flexible conductive heating cloth.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a water-based graphene flame-retardant PTC conductive paste which comprises the following components in parts by weight:

5-20 parts of PTC functional components; the PTC functional component comprises a high-molecular PTC material and/or paraffin;

10-20 parts of water-based flexible resin;

1-5 parts of a flame retardant;

5-20 parts of conductive filler;

20-60 parts of water;

5-10 parts of a dispersing agent;

0.7-5 parts of an auxiliary agent.

Preferably, the polymer PTC material comprises one or more of polycaprolactone, polyethylene, maleic anhydride grafted polyethylene and polypropylene.

Preferably, the aqueous flexible resin is a composite resin consisting of flexible aqueous acrylic resin and flexible aqueous polyurethane.

Preferably, the flame retardant comprises one or more of dimethyl methylphosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide.

Preferably, the conductive filler comprises one or more of graphene, conductive carbon black and nano graphite.

Preferably, the dispersing agent comprises one or more of acrylic block polymer, anionic polyacrylamide, BYK025 and BYK 9076.

Preferably, the auxiliary agent comprises one or more of a leveling agent, a defoaming agent, a film forming auxiliary agent and a thickening agent.

The invention provides a preparation method of the water-based graphene flame-retardant PTC conductive paste, which comprises the following steps:

mixing water-based flexible resin with water to obtain a resin solution;

mixing the resin solution, the flame retardant and the PTC functional component to obtain a dispersion liquid;

and mixing the dispersion liquid, the dispersing agent, the auxiliary agent and the conductive filler, and grinding to obtain the water-based graphene flame-retardant PTC conductive slurry.

The invention also provides flexible conductive heating cloth which comprises a cloth base body, an electric heating layer, an electrode plate and a protective layer which are sequentially laminated; the components of the electric heating layer are the aqueous graphene flame-retardant PTC conductive paste in the technical scheme or the aqueous graphene flame-retardant PTC conductive paste prepared by the preparation method in the technical scheme.

Preferably, the thickness of the electrothermal layer is 50-150 μm.

The invention provides a water-based graphene flame-retardant PTC conductive paste which comprises the following components in parts by weight: 5-20 parts of PTC functional components; the PTC functional component comprises a high-molecular PTC material and/or paraffin wax; 10-20 parts of water-based flexible resin; 1-5 parts of a flame retardant; 5-20 parts of conductive filler; 20-60 parts of water; 5-10 parts of a dispersing agent; 0.7-5 parts of an auxiliary agent. According to the invention, the water-based flexible resin is adopted, so that the adhesion force after film formation is better, and the heat-resistant aging performance is excellent; by adding the PTC functional component and the flame retardant, the flame retardant property of the product can be improved, and the electrical safety of the product is also improved. The water-based graphene flame-retardant PTC conductive paste provided by the invention is a flame-retardant heating body with PTC effect, and can control the temperature and greatly improve the safety.

The invention also provides a preparation method of the water-based graphene flame-retardant PTC conductive paste in the technical scheme, and the viscosity and the resistivity of the paste can be more easily controlled through a multiple-mixing process.

The invention also provides the flexible conductive heating cloth, which can greatly improve the flexibility and comfort performance of the product; the flexible conductive heating cloth prepared by the aqueous graphene flame-retardant PTC conductive paste provided by the invention not only improves the conductivity of the heating cloth and the conductive uniformity of the heating cloth, but also greatly improves the rubbing resistance and the flame retardance of the heating cloth.

Drawings

Fig. 1 is a schematic view of an internal structure of a flexible conductive heating fabric prepared in embodiment 1 of the present invention;

wherein, 1 is a cloth substrate, 2 is a silver paste-copper foil composite electrode, 3 is a soldering tin interface, 4 is a lead, and 5 is an electrothermal layer.

Detailed Description

The invention provides a water-based graphene flame-retardant PTC conductive paste which comprises the following components in parts by weight:

5-20 parts of PTC functional components; the PTC functional component comprises one or more of polymer PTC materials and/or paraffin;

10-20 parts of water-based flexible resin;

1-5 parts of a flame retardant;

5-20 parts of conductive filler;

20-60 parts of water;

5-10 parts of a dispersing agent;

0.7-5 parts of an auxiliary agent.

In the present invention, if not specifically required, the starting components used are all commercially available products well known to those skilled in the art.

The water-based graphene flame-retardant PTC conductive paste comprises, by weight, 5-20 parts of PTC functional components, and preferably 10-15 parts. In the present invention, the PTC functional component preferably comprises a polymeric PTC material and/or paraffin; the polymer PTC material preferably comprises one or more of polycaprolactone, polyethylene, maleic anhydride grafted polyethylene and polypropylene. In the specific embodiment of the invention, when the PTC functional component is polycaprolactone and polyethylene, the mass ratio of the polycaprolactone to the polyethylene is 1: 1; when the PTC functional component is polyethylene, maleic anhydride grafted polyethylene and polypropylene, the mass ratio of the polyethylene to the maleic anhydride grafted polyethylene to the polypropylene is preferably 1:1: 1; when the PTC functional components are polycaprolactone, maleic anhydride grafted polyethylene and polypropylene, the mass ratio of the polycaprolactone to the maleic anhydride grafted polyethylene to the polypropylene is preferably 4:8: 3; when the PTC functional components are paraffin and polycaprolactone, the mass ratio of the paraffin to the polycaprolactone is 2: 1.

Based on the weight parts of the PTC functional components, the water-based graphene flame-retardant PTC conductive paste provided by the invention comprises 10-20 parts of water-based flexible resin, and preferably 14-18 parts. In the invention, the aqueous flexible resin is preferably a composite resin consisting of flexible aqueous acrylic resin and flexible aqueous polyurethane. In the invention, the mass ratio of the flexible water-based acrylic resin to the flexible water-based polyurethane is preferably 2.9-8: 1, and more preferably 4-5: 1.

Based on the weight parts of the PTC functional components, the water-based graphene flame-retardant PTC conductive paste provided by the invention comprises 1-5 parts of a flame retardant, preferably 2-4 parts. In the invention, the flame retardant preferably comprises one or more of dimethyl methylphosphonate, a flame retardant PN-1, a flame retardant PN-2 and superfine antimony trioxide. In the specific embodiment of the invention, when the flame retardant is the flame retardant PN-1 and the flame retardant PN-2, the mass ratio of the flame retardant PN-1 to the flame retardant PN-2 is 2.5: 1; when the flame retardant is dimethyl methylphosphonate, a flame retardant PN-1 and a flame retardant PN-2, the mass ratio of the dimethyl methylphosphonate to the flame retardant PN-1 to the flame retardant PN-2 is preferably 1:9: 6; when the flame retardant is dimethyl methylphosphonate and superfine antimony trioxide, the mass ratio of the dimethyl methylphosphonate to the superfine antimony trioxide is 2: 1.

Based on the weight parts of the PTC functional components, the water-based graphene flame-retardant PTC conductive paste provided by the invention comprises 5-20 parts of conductive filler, preferably 10-15 parts. In the invention, the conductive filler preferably comprises one or more of graphene, conductive carbon black and nano graphite; the conductive filler preferably has an average particle diameter of 2 μm or less, more preferably 800 nm. In a specific embodiment of the present invention, when the conductive filler is graphene and conductive carbon black, the mass ratio of the graphene to the conductive carbon black is 1: 5; when the conductive filler is graphene, conductive carbon black and nano graphite, the mass ratio of the graphene to the conductive carbon black to the nano graphite is 3-10: 2; when the conductive filler is conductive carbon black and nano graphite, the mass ratio of the conductive carbon black to the nano graphite is 8.2: 3.8.

Based on the weight parts of the PTC functional components, the water-based graphene flame-retardant PTC conductive paste provided by the invention comprises 20-60 parts of water, preferably 30-50 parts of water. In the present invention, the water is preferably deionized water.

Based on the weight parts of the PTC functional components, the aqueous graphene flame-retardant PTC conductive paste provided by the invention comprises 5-10 parts of a dispersing agent, preferably 6-8 parts. In the present invention, the dispersant preferably includes one or more of acrylic block polymer, anionic polyacrylamide, BYK025 and BYK 9076. In a specific embodiment of the invention, when the dispersing agent is BYK9076 and anionic polyacrylamide, the mass ratio of the BYK9076 to the anionic polyacrylamide is 1.3-2.25: 1; when the dispersing agent is an acrylic acid block polymer, anionic polyacrylamide and BYK9076, the mass ratio of the acrylic acid block polymer to the anionic polyacrylamide to the BYK9076 is preferably 1:2: 5; when the dispersing agent is anionic polyacrylamide and BYK025, the mass ratio of the anionic polyacrylamide to the BYK025 is 12: 1.

Based on the weight parts of the PTC functional components, the water-based graphene flame-retardant PTC conductive paste provided by the invention comprises 0.7-5 parts of an auxiliary agent, preferably 1-4 parts. In the present invention, the auxiliary agent preferably includes one or more of a leveling agent, a defoaming agent, a film-forming auxiliary agent, and a thickener. In the present invention, the leveling agent is preferably an ionic polyacrylate; the defoaming agent preferably comprises a higher alcohol, a defoaming agent 901W or a defoaming agent BYK 025; the film-forming auxiliary agent is preferably an alcohol ester film-forming auxiliary agent, and particularly preferably a dodecanol ester film-forming auxiliary agent; the thickener is preferably a cellulose thickener, and more preferably hydroxyethyl cellulose.

The invention also provides a preparation method of the water-based graphene flame-retardant PTC conductive paste, which comprises the following steps:

mixing water-based flexible resin with water to obtain a resin solution;

mixing the resin solution, the flame retardant and the PTC functional component to obtain a dispersion liquid;

and mixing the dispersion liquid, the dispersing agent, the auxiliary agent and the conductive filler, and grinding to obtain the water-based graphene flame-retardant PTC conductive slurry.

The invention mixes the water-based flexible resin and water to obtain the resin solution. In the invention, the mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 1000-1500 rpm, more preferably 1200-1400 rpm; the stirring time is preferably 5-10 min, and more preferably 8-9 min.

After the resin solution is obtained, the resin solution, the flame retardant and the PTC functional component are mixed to obtain the dispersion liquid. In the invention, the mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 1500-2000 rpm, more preferably 1600-1800 rpm; the stirring time is preferably 5-10 min, and more preferably 6-8 min.

After the dispersion liquid is obtained, the dispersion liquid, the dispersing agent, the auxiliary agent and the conductive filler are mixed and ground to obtain the water-based graphene flame-retardant PTC conductive slurry. In the invention, the conductive filler is preferably added in 3-5 times in batches, so that the viscosity of the slurry is easier to control, and the dispersion is more uniform. In the present invention, the grinding is preferably carried out in a grinder; the rotation speed of the grinding is preferably 500-1500 rpm, more preferably 800-1000 rpm. The grinding time is not particularly limited, and the aqueous graphene flame-retardant PTC conductive paste with the average particle size of less than or equal to 2 mu m is preferably obtained. In the invention, the average particle size of the aqueous graphene flame-retardant PTC conductive paste is preferably 0.9-2 μm, and more preferably 1.2-1.5 μm.

The invention also provides flexible conductive heating cloth which comprises a cloth base body, an electric heating layer, an electrode plate and a protective layer which are sequentially laminated; the components of the electric heating layer are the aqueous graphene flame-retardant PTC conductive paste in the technical scheme or the aqueous graphene flame-retardant PTC conductive paste prepared by the preparation method in the technical scheme.

The invention provides a flexible conductive heating cloth which comprises a cloth base body. In the invention, the fabric substrate is preferably cotton cloth, polyester fabric or polyamide fabric, and the flexibility and comfort performance of the product are greatly improved by adopting the fabric substrate.

The flexible conductive heating cloth provided by the invention comprises an electric heating layer arranged on the surface of the cloth substrate. In the present invention, the electrothermal layer is disposed on a single-side surface or both-side surfaces of the cloth base. In the invention, the thickness of the electrothermal layer is preferably 50-150 μm, and more preferably 100-120 μm. The invention controls the thickness of the electric heating layer in the range, which is beneficial to controlling the stability of the compounding between the heating layer and the cloth substrate.

The flexible conductive heating cloth provided by the invention comprises an electrode plate arranged on the surface of the electric heating layer. As an embodiment of the present invention, when the electrothermal layers are disposed on both surfaces of the fabric substrate, including the first electrothermal layer and the second electrothermal layer, the electrode sheet is disposed on the surface of the first electrothermal layer and/or the surface of the second electrothermal layer. In the invention, the electrode plate is preferably a silver paste-copper foil composite electrode. The invention has no special requirements on the specific parameters of the silver paste-copper foil composite electrode, and the silver paste-copper foil composite electrode known by the technical personnel in the field can be adopted.

As an embodiment of the invention, the flexible conductive heating cloth provided by the invention further comprises a lead connected with the electrode plate and used for connecting a power supply. In the present invention, the lead wire is preferably connected to the electrode pad by soldering.

The flexible conductive heating cloth provided by the invention comprises a protective layer arranged on the surface of the electrode plate. In the present invention, the protective layer preferably includes a conventional cloth or a functional cloth; the conventional cloth is preferably cotton cloth, polyester cloth or polyamide cloth; the functional cloth is preferably waterproof cloth, anti-counterfeiting cloth or anti-static cloth. In the invention, the protective layer can protect the electrode plate on one hand, and can be used as a functional layer to produce flexible conductive heating cloth with multiple functions according to actual requirements on the other hand.

In the invention, the preparation method of the flexible conductive heating cloth preferably comprises the following steps:

coating the water-based graphene flame-retardant PTC conductive paste on the surface of a cloth substrate to form an electric heating layer on the surface of the cloth substrate;

and fixing the electrode plate on the outer surface of the electric heating layer, and coating a protective layer on the outer surface of the electrode plate to obtain the flexible conductive heating cloth.

According to the invention, the water-based graphene flame-retardant PTC conductive paste prepared by the technical scheme is preferably coated on the surface of a cloth substrate, and an electric heating layer is formed on the surface of the cloth substrate. In the present invention, the coating means preferably includes soaking or rolling; the soaking time is preferably 5-30 min, and more preferably 10-20 min; the linear speed of rolling is preferably 10-50 cm/s. According to the invention, preferably, after coating, the obtained material is dried to form an electrothermal layer; the drying temperature is preferably 70-90 ℃, and more preferably 80-85 ℃; the drying time is preferably 45-60 min, and more preferably 50-55 min.

In the specific embodiment of the invention, when the water-based graphene flame-retardant PTC conductive paste is coated on the surface of the cloth substrate in a soaking mode, heating layers are formed on the surfaces of two sides of the cloth substrate; when the water-based graphene flame-retardant PTC conductive paste is coated on the surface of the cloth substrate in a rolling mode, a heating layer is formed on the surface of one side of the cloth substrate.

After the electric heating layer is formed on the surface of the fabric substrate, the invention preferably fixes the electrode plate on the outer surface of the electric heating layer to obtain the flexible conductive heating fabric. In the present invention, when the electrode sheet is a silver paste-copper foil composite electrode, the fixing method of the electrode sheet preferably includes: and coating silver paste on the outer surface of the electric heating layer, and then fixing a copper foil on the surface of the silver paste, thereby forming a silver paste-copper foil composite electrode on the outer surface of the electric heating layer. In the present invention, the coating method of the silver paste is preferably printing, and the present invention has no special requirement on the specific process of the printing, and the printing method known to those skilled in the art can be adopted. In the invention, the coating amount of the silver paste is preferably controlled to be 30-100 μm, more preferably 60-80 μm of the corresponding wet film thickness. In the present invention, the thickness of the copper foil is preferably 5 to 20 μm.

According to the invention, preferably, after the electrode plate is fixed, the lead is fixed on the electrode plate in a tin soldering manner, and the outer surface of the electrode plate is coated with the protective layer to obtain the flexible conductive heating cloth. In the invention, the coating method of the protective layer is preferably hot pressing, and the temperature of the hot pressing is preferably 110-180 ℃, more preferably 130-150 ℃; the time for hot pressing is preferably 3-15 min, and more preferably 4-6 min. In the invention, the preparation process of the flexible conductive heating cloth adopts a mode of combining soaking dyeing and rolling, so that the conductivity of the heating cloth and the conductive uniformity of the heating cloth are greatly improved, and the rubbing resistance of the heating cloth is also greatly improved.

In the invention, the square resistance of the flexible conductive heating cloth is preferably 10.0-15.0 omega/□, more preferably 10.8-11.5 omega/□, can be as low as 10 omega/□, and has better conductivity.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Adding 11.2g of flexible waterborne acrylic resin, 3.8g of flexible waterborne polyurethane and 40g of deionized water into a high-speed stirrer, and stirring for 8min at the rotating speed of 1200rpm to obtain a uniform resin solution;

adding 2g of flame retardant PN-1, 0.8g of flame retardant PN-2, 5g of polycaprolactone and 5g of polyethylene into the resin solution, and stirring at the rotating speed of 1500rpm for 10min to obtain a dispersion liquid;

and transferring the dispersion liquid into a sand mill, respectively adding 4.5g of BYK9076, 2g of anionic polyacrylamide, 0.5g of a leveling agent and 0.5g of a film forming aid, adding 12g of a conductive filler for 3 times, grinding the conductive filler at the rotating speed of 850rpm until the average particle size is 1.5 mu m, and thus obtaining the water-based graphene flame-retardant PTC conductive slurry.

Placing 20cm × 15cm cotton cloth in the aqueous graphene flame-retardant PTC conductive paste, soaking for 30min, taking out, drying at 85 deg.C for 50min, and forming an electric heating layer on the surface of the cotton cloth;

coating silver paste on the surface of the electric heating layer in a printing mode to serve as a bottom layer; fixing a conductive copper foil with the thickness of 5 mu m and the width of 1cm on the upper layer of the conductive silver paste in a rolling way, thereby forming a silver paste-copper foil composite electrode;

fixing a lead on a tin welding port of the silver paste-copper foil composite electrode in a tin soldering mode, and compounding a layer of cotton cloth up and down in a hot pressing mode, wherein the hot pressing temperature is 110 ℃ and the hot pressing time is 15min, so that the graphene flame-retardant PTC flexible conductive heating cloth is obtained, and is shown in figure 1.

The square resistance of the flexible conductive heating cloth prepared by the embodiment is 11.5 omega/□; flame retardant rating (UL94) of V-1; the flexibility (GB/T1731 and 19932mm) is 2mm passing.

Example 2

Adding 13.3g of flexible waterborne acrylic resin, 2.7g of flexible waterborne polyurethane and 40g of deionized water into a high-speed stirrer, and stirring for 10min at the rotating speed of 1350rpm to obtain a uniform resin solution; adding 0.2g of dimethyl methyl phosphonate, 1.8g of flame retardant PN-1, 1.2g of flame retardant PN-2, 4g of polyethylene, 4g of maleic anhydride grafted polyethylene and 4g of polypropylene into the resin solution, and stirring at the rotating speed of 1650rpm for 8min to obtain a dispersion liquid;

transferring the dispersion liquid into a sand mill, respectively adding 3g of anionic polyacrylamide, 4g of BYK9076, 0.5g of defoaming agent 901W and 0.2g of thickening agent, adding 15g of conductive filler for 4 times, grinding the conductive filler at the rotating speed of 1500rpm until the average particle size is 0.9 mu m, and thus obtaining the water-based graphene flame-retardant PTC conductive slurry.

Placing 20cm × 15cm polyester fabric in the aqueous graphene flame-retardant PTC conductive paste, soaking for 20min, taking out, drying at 75 deg.C for 60min, and forming an electric heating layer on the surface of the polyester fabric;

coating silver paste on the surface of the electric heating layer in a printing mode to serve as a bottom layer; fixing a conductive copper foil with the thickness of 5 mu m and the width of 1cm on the upper layer of the conductive silver paste in a rolling way, thereby forming a silver paste-copper foil composite electrode;

and fixing the lead on a tin welding port of the silver paste-copper foil composite electrode in a tin soldering mode, and compounding a layer of polyester fabric up and down in a hot pressing mode, wherein the hot pressing temperature is 130 ℃, and the hot pressing time is 6min, so that the graphene flame-retardant PTC flexible conductive heating fabric is obtained.

The square resistance of the flexible conductive heating cloth prepared by the embodiment is 10.8 omega/□; flame retardant rating (UL94) of V-1; the flexibility (GB/T1731 and 19932mm) is 2mm passing.

Example 3

Adding 12.8g of flexible waterborne acrylic resin, 3.2g of flexible waterborne polyurethane and 50g of deionized water into a high-speed stirrer, and stirring at the rotating speed of 1500rpm for 5min to obtain a uniform resin solution;

adding 2.0g of dimethyl methyl phosphonate, 1.0g of superfine antimony trioxide, 4g of polycaprolactone, 8g of maleic anhydride grafted polyethylene and 3g of polypropylene into the resin solution, and stirring at the rotating speed of 1800rpm for 6min to obtain a dispersion liquid;

transferring the dispersion liquid into a sand mill, respectively adding 1g of acrylic block polymer, 2g of anionic polyacrylamide, 5g of BYK9076, 0.5g of leveling agent and 3g of thickening agent, adding 15g of conductive filler for 4 times, grinding the conductive filler by 10g of graphene, 3g of conductive carbon black and 2g of nano graphite at the rotating speed of 1350rpm until the average particle size is 1.2 mu m, and thus obtaining the water-based graphene flame-retardant PTC conductive slurry.

Coating the water-based graphene flame-retardant PTC conductive paste on 20cm × 15cm polyamide fabric in a rolling manner, drying at 90 ℃ for 40min, and forming an electric heating layer on the surface of the polyamide fabric;

coating silver paste on the surface of the electric heating layer in a printing mode to serve as a bottom layer; fixing a conductive copper foil with the thickness of 15 mu m and the width of 1cm on the upper layer of the conductive silver paste in a rolling way, thereby forming a silver paste-copper foil composite electrode; fixing a lead on a tin welding port of the silver paste-copper foil composite electrode in a tin soldering mode, compounding a layer of polyamide fabric on the surface of the silver paste-copper foil composite electrode in a hot pressing mode, and obtaining the graphene flame-retardant PTC flexible conductive heating fabric at the hot pressing temperature of 50 ℃ for 4 min.

The square resistance of the flexible conductive heating cloth prepared by the embodiment is 10.0 omega/□; flame retardant rating (UL94) of V-1; the flexibility (GB/T1731 and 19932mm) is 2mm passing.

Example 4

Adding 14.4g of flexible waterborne acrylic resin, 3.6g of flexible waterborne polyurethane and 50g of deionized water into a high-speed stirrer, and stirring for 8min at the rotating speed of 1200rpm to obtain a uniform resin solution;

adding 2.0g of dimethyl methyl phosphonate, 8.0g of paraffin and 4.0g of polycaprolactone into the resin solution, and stirring at the rotating speed of 1700rpm for 5min to obtain a dispersion liquid;

transferring the dispersion liquid into a sand mill, adding 6.0g of anionic polyacrylamide, 0.5g of BYK025, 0.5g of defoaming agent and 1.2g of film forming additive respectively, adding 12.0g of conductive filler in 3 times, grinding the conductive filler at the rotating speed of 1000rpm until the average particle size is 2 mu m, and obtaining the aqueous graphene flame-retardant PTC conductive slurry.

Coating the aqueous graphene flame-retardant PTC conductive paste on cotton cloth with the size of 20cm multiplied by 15cm in a rolling mode, drying for 45min at the temperature of 80 ℃, and forming an electric heating layer on the surface of the cotton cloth;

coating silver paste on the surface of the electric heating layer in a printing mode to serve as a bottom layer; fixing a conductive copper foil with the thickness of 5 mu m and the width of 1cm on the upper layer of the conductive silver paste in a rolling way, thereby forming a silver paste-copper foil composite electrode;

fixing a lead on a tin welding port of the silver paste-copper foil composite electrode in a tin soldering mode, and compounding a layer of cotton cloth on the surface of the silver paste-copper foil composite electrode in a hot pressing mode, wherein the hot pressing temperature is 180 ℃ and the time is 3min, so that the graphene flame-retardant PTC flexible conductive heating cloth is obtained.

The square resistance of the flexible conductive heating cloth prepared by the embodiment is 15.0 omega/□; flame retardant rating (UL94) of V-2; the flexibility (GB/T1731 and 19932mm) is 2mm passing.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.