A PTC effect electric heating film and a preparation method and application thereof

Abstract

The application discloses a PTC effect electrothermal film and a preparation method and application thereof. The composition of the PTC effect electrothermal film comprises a film base material, an electrothermal layer with a PTC effect, a conductive circuit and a circulating relay. The composition of the electrothermal layer with the PTC effect comprises nano-silicon hybrid resin, flaky graphene, a heat-sensitive material, a conductive agent and an additive. The electrothermal layer with the PTC effect is covered on one side or two sides of the film base material. The circulating relay is arranged in the conductive circuit. The preparation method of the PTC effect electrothermal film comprises the following steps: 1) preparing an electrothermal slurry; 2) coating the electrothermal slurry on the surface of the film base material to dry and form a film, and then arranging the conductive circuit, the circulating relay and a temperature sensor according to needs, so that the PTC effect electrothermal film is obtained. The PTC effect electrothermal film has the advantages of no overheating problem, low energy consumption, long service life and the like, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrothermal film, in particular to a PTC effect electrothermal film and a preparation method and application thereof. BACKGROUND

[0002] Electric heating is a heating method of converting electric energy into heat energy, which does not need to directly use fossil energy, and is different from traditional water-electric heating and low-heat floor heating, and has the advantages of fast heating speed, high comfort, self-control and the like, and has been widely applied. At present, among various electric floor heating, a planar heating body represented by an electrothermal film is pursued due to its safety and power saving. However, the electrothermal film cannot avoid being covered by a material with high thermal resistance in a long-term use process, which causes heat to be unable to be timely dissipated, and eventually leads to local overheating of the electrothermal film, and there is a great safety hazard. In addition, when a temperature controller, a temperature sensing probe and the like in the electrothermal film fail, the product temperature cannot be limited, and eventually the electrothermal film is overheated.

[0003] Therefore, it is of great significance to develop an electrothermal film without overheating problem, low energy consumption and long service life. SUMMARY

[0004] The present application aims to provide a PTC effect (positive temperature coefficient effect) electrothermal film and a preparation method and application thereof.

[0005] The technical scheme adopted by the present application is as follows:

[0006] A PTC effect electrothermal film comprises a film substrate, an electrothermal layer with PTC effect, a conductive circuit and a circulating relay; components of the electrothermal layer with PTC effect include nano-silicon hybrid resin, flaky graphene, a thermosensitive material, a conductive agent and an additive; the electrothermal layer with PTC effect is covered on one side or both sides of the film substrate; the circulating relay is arranged in the conductive circuit.

[0007] Preferably, the film substrate is one of polyethylene terephthalate (PET) film and polyimide (PI) film.

[0008] Preferably, the electrothermal layer with PTC effect comprises the following components by mass:

[0009] Nano-silicon hybrid resin: 40-50 parts;

[0010] Flaky graphene: 30-35 parts;

[0011] Thermosensitive material: 2-10 parts;

[0012] Conductive agent: 1-5 parts;

[0013] Additive: 0.5-3 parts.

[0014] Preferably, the flake graphite has a flake diameter of 2-10 microns and a thickness of 1-3 nanometers.

[0015] Preferably, the heat-sensitive material is at least one of polyethylene oxide, microcrystalline wax, and barium titanate.

[0016] Preferably, the conductive agent is at least one of conductive graphite, conductive carbon black, carbon nanotubes, carbon fibers, and conductive metal powder.

[0017] Preferably, the auxiliary agent is at least one of wetting dispersants, leveling agents, and thickening agents.

[0018] Preferably, the line connection time of the cycle relay is 20-40 seconds, and the line disconnection time is 3-7 seconds.

[0019] Preferably, the PTC-effect electrothermal film further comprises a temperature sensor.

[0020] A preparation method of the PTC-effect electrothermal film comprises the following steps:

[0021] 1) dispersing the aqueous organic-inorganic hybrid resin, flake graphite, heat-sensitive material, conductive agent, and auxiliary agent in water to obtain an electrothermal slurry;

[0022] 2) coating the electrothermal slurry on the surface of the film substrate to dry and form a film, and then arranging a conductive line, cycle relay, and temperature sensor as needed to obtain the PTC-effect electrothermal film.

[0023] An electric floor heating system comprises the PTC-effect electrothermal film.

[0024] The PTC-effect electrothermal film has the advantages of no overheating problem, low energy consumption, long service life, and wide application prospect.

[0025] Specifically:

[0026] 1) The PTC-effect electrothermal film uses a nano-silicon hybrid resin as a film-forming main body, has good temperature resistance, high-low temperature impact resistance, and long service life.

[0027] 2) The PTC-effect electrothermal film comprises a heat-sensitive material, which plays a role when the temperature rises to cause the resistance of the electrothermal film to rise and the power to drop, so that the heating temperature of the electrothermal film can be limited to avoid overheating problems.

[0028] 3) The PTC effect electric heating film of the present application introduces a cycle relay, which intermittently supplies power to the electric heating film by periodically opening and closing the power supply. Although the electric heating film will still have heat accumulation under the condition of being covered by a material with large thermal resistance, the line will automatically disconnect after a period of time, preventing the temperature of the electric heating film from rising further, thereby avoiding overheating problems. Moreover, the energy consumption of the intermittent power supply is significantly lower than that of traditional electric heating films. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Structure diagram of the PTC effect electric heating film in Examples 1-3.

[0030] Brief Description of the Drawings: 10, film substrate; 20, electric heating layer with PTC effect; 30, conductive circuit; 40, cycle relay. DETAILED DESCRIPTION

[0031] The present application will be further explained and described in conjunction with specific examples.

[0032] Example 1:

[0033] A PTC effect electric heating film (structure diagram as shown in Figure 1 ), which is composed of a film substrate 10, an electric heating layer with PTC effect 20, a conductive circuit 30, and a cycle relay 40. The electric heating layer with PTC effect 20 is covered on one side of the film substrate 10, and the cycle relay 40 is arranged in the conductive circuit 30.

[0034] The preparation method of the above-mentioned PTC effect electric heating film includes the following steps:

[0035] 1) Add 3g of polyethylene oxide (number average molecular weight 800000), 1g of wet dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.), and 0.2g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) into 180g of water, control the stirring speed of the mixer to 1200r / min and stir for 10min, then add 34g of sheet-shaped graphene (sheet diameter 2-10μm, thickness 1-3nm), 2g of carbon nanotubes, and 2g of conductive carbon black, adjust the stirring speed of the mixer to 2000r / min and stir for 30min, then add 42g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbin New Material Co., Ltd.), continue stirring for 10min, and then filter with a 500 mesh sieve to obtain an electric heating slurry;

[0036] 2) The electrothermal slurry is coated on one side of the PET film with a squeegee, dried at 60°C for 10 min to form a film, copper wires are attached to both ends of the film with a 70 cm spacing between the two ends, the copper wires are connected to a power source, and a circulating relay is connected in the conductive circuit, the line connection time of the circulating relay is set to 30 s and the line disconnection time is set to 5 s, to obtain a PTC effect electrothermal film.

[0037] Example 2

[0038] A PTC effect electrothermal film (structure same as Example 1) is prepared by the following method:

[0039] 1) 5 g of polyethylene oxide (number average molecular weight 800000), 1 g of wet dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3 g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.2 g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) are added to 180 g of water, the stirring speed of the stirrer is controlled at 1200 r / min and stirred for 10 min, then 32 g of flaky graphene (flake diameter 2 μm-10 μm, thickness 1 nm-3 nm), 3 g of carbon nanotubes and 1 g of conductive carbon black are added, the stirring speed of the stirrer is adjusted to 2000 r / min and stirred for 30 min, then 42 g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbin New Material Co., Ltd.) is added and stirred for another 10 min, and then filtered with a 500 mesh sieve to obtain an electrothermal slurry;

[0040] 2) The electrothermal slurry is coated on one side of the PET film with a squeegee, dried at 60°C for 10 min to form a film, copper wires are attached to both ends of the film with a 70 cm spacing between the two ends, the copper wires are connected to a power source, and a circulating relay is connected in the conductive circuit, the line connection time of the circulating relay is set to 30 s and the line disconnection time is set to 5 s, to obtain a PTC effect electrothermal film.

[0041] Example 3

[0042] A PTC effect electrothermal film (structure same as Example 1) is prepared by the following method:

[0043] 1) 3g of polyethylene oxide (number average molecular weight 800000), 1g of wetting dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.2g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) were added into 180g of water, the stirring speed of the stirrer was controlled at 1200r / min and stirred for 10min, then 30g of flaky graphene (flaky diameter 2-10μm, thickness 1-3nm), 2g of carbon nanotube and 2g of conductive carbon black were added, the stirring speed of the stirrer was adjusted to 2000r / min and stirred for 30min, then 48g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbien New Material Co., Ltd.) was added and stirred for another 10min, and then filtered through a 500-mesh sieve to obtain an electrothermal slurry;

[0044] 2) The electrothermal slurry was coated on one side of a PET film by a doctor blade, dried at 60℃ for 10min to form a film, then copper wires were attached to both ends of the film with a distance of 70cm between the two ends, the copper wires were connected to a power source, and a circulating relay was connected in the conductive circuit, the line connection time of the circulating relay was set to 30s and the line disconnection time was set to 5s, thus obtaining a PTC effect electrothermal film.

[0045] Example 4:

[0046] A PTC effect electrothermal film (structure same as Example 1), the preparation method comprising the following steps:

[0047] 1) 10g of polyethylene oxide (number average molecular weight 800000), 0.5g of wetting dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.4g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) were added into 180g of water, the stirring speed of the stirrer was controlled at 1200r / min and stirred for 10min, then 30g of flaky graphene (flaky diameter 2-10μm, thickness 1-3nm) and 1g of carbon nanotube were added, the stirring speed of the stirrer was adjusted to 2000r / min and stirred for 30min, then 50g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbien New Material Co., Ltd.) was added and stirred for another 10min, and then filtered through a 500-mesh sieve to obtain an electrothermal slurry;

[0048] 2) The electrothermal slurry was coated on one side of a PET film by a doctor blade, dried at 60℃ for 10min to form a film, then copper wires were attached to both ends of the film with a distance of 70cm between the two ends, the copper wires were connected to a power source, and a circulating relay was connected in the conductive circuit, the line connection time of the circulating relay was set to 30s and the line disconnection time was set to 5s, thus obtaining a PTC effect electrothermal film.

[0049] Comparative Example 1:

[0050] An electrothermal film (without circulating relay), the preparation method comprising the following steps:

[0051] 1) 3g of polyethylene oxide (number average molecular weight 800000), 1g of wet dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.2g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) were added to 180g of water, the stirring speed of the stirrer was controlled at 1200r / min for 10min, then 34g of flaky graphene (flaky diameter 2-10μm, thickness 1-3nm), 2g of carbon nanotube and 2g of conductive carbon black were added, the stirring speed of the stirrer was adjusted to 2000r / min for 30min, then 42g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbien New Material Co., Ltd.) was added, and the stirring was continued for 10min, then it was filtered with a 500 mesh screen to obtain an electrothermal slurry;

[0052] 2) The electrothermal slurry was coated on one side of a PET film with a squeegee, dried at 60℃ for 10min to form a film, then copper wires were attached to both ends of the film with a distance of 70cm between the two ends, and the copper wires were connected to a power source to obtain an electrothermal film.

[0053] Comparative Example 2:

[0054] An electrothermal film (without polyethylene oxide in the electrothermal slurry), the preparation method comprising the following steps:

[0055] 1) 1g of wet dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.2g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) were added to 180g of water, the stirring speed of the stirrer was controlled at 1200r / min for 10min, then 34g of flaky graphene (flaky diameter 2-10μm, thickness 1-3nm), 2g of carbon nanotube and 2g of conductive carbon black were added, the stirring speed of the stirrer was adjusted to 2000r / min for 30min, then 42g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbien New Material Co., Ltd.) was added, and the stirring was continued for 10min, then it was filtered with a 500 mesh screen to obtain an electrothermal slurry;

[0056] 2) The electrothermal paste is coated on one side of the PET film with a squeegee, dried at 60°C for 10 min to form a film, then copper wires are attached to both ends of the film with a 70 cm spacing between the two ends, the copper wires are then connected to a power source, and a circulating relay is connected in the conductive circuit, the on-time of the circulating relay is set to 30 s and the off-time is set to 5 s, thus obtaining the electrothermal film.

[0057] Comparative Example 3:

[0058] An electrothermal film (not containing a circulating relay and the electrothermal paste does not contain polyethylene oxide), the preparation method comprising the following steps:

[0059] 1) 1 g of wetting dispersant HS6066 (Anshan Huihong New Material Chemical Co., Ltd.), 0.3 g of leveling agent HL5007 (Anshan Huihong New Material Chemical Co., Ltd.) and 0.2 g of thickening agent HR7030 (Anshan Huihong New Material Chemical Co., Ltd.) are added to 180 g of water, the stirring speed of the stirrer is controlled at 1200 r / min and stirred for 10 min, then 34 g of flaky graphene (flake diameter of 2-10 μm, thickness of 1-3 nm), 2 g of carbon nanotubes and 2 g of conductive carbon black are added, the stirring speed of the stirrer is adjusted to 2000 r / min and stirred for 30 min, then 42 g of nano-silicon hybrid resin RS-9725 (Zhongshan Meilongbin New Material Co., Ltd.) is added and stirred for another 10 min, then filtered with a 500 mesh sieve to obtain an electrothermal paste;

[0060] 2) The electrothermal paste is coated on one side of the PET film with a squeegee, dried at 60°C for 10 min to form a film, then copper wires are attached to both ends of the film with a 70 cm spacing between the two ends, the copper wires are then connected to a power source, thus obtaining the electrothermal film.

[0061] Performance test:

[0062] The electrothermal films of Examples 1-4 and Comparative Examples 1-3 are laid on a heat insulation board (rigid polyurethane foam plastic board, size specification of 1000 mm x 1000 mm, thickness of 30 mm ± 1 mm, thermal conductivity of 0.022 W / mK ± 0.002 W / mK), and there is no gap between the heat insulation board and the electrothermal film, then the electrothermal film is powered on at 1.15 times the rated voltage (70 V) until it reaches a stable working state, then 4 points are measured on the surface of the heating part of the electrothermal film to obtain the average temperature before covering (the average of 4 points), then a polystyrene extruded board (size specification of 700 mm x 700 mm, thickness of 20 mm ± 1 mm, thermal conductivity of 0.03 W / mK ± 0.002 W / mK) is covered on the electrothermal film and the working time is 8 h, then 4 points are measured on the surface of the heating part of the electrothermal film to obtain the average temperature after covering, and the power change rate after the electrothermal film is covered for 360 h and the 3 kV voltage breakdown resistance are tested, and the test results are shown in the following table:

[0063] Table 1 Performance test results of the electrothermal films of Examples 1-4 and Comparative Examples 1-3

[0064]

[0065] From Table 1, it can be seen that:

[0066] 1) The temperature difference of the electrothermal films of Examples 1-4 before and after covering is very small, the power does not substantially attenuate after long-term covering aging test, and the basic performance of the electrothermal films is good;

[0067] 2) The temperature difference of the electrothermal films of Comparative Examples 1-3 before and after covering is large, the appearance of the films changes obviously, the power attenuates obviously after long-term covering aging test, and the films have the risk of electric leakage. In addition, because the time set by the cycle relay is 30s of connection, 5s of disconnection, and then connection, the energy consumption of the electrothermal films of Examples 1-4 can be reduced by about 1 / 7 compared with the electrothermal films without the cycle relay.

[0068] In summary, the PTC effect electrothermal film of the present application not only has no overheating problem, but also has higher safety, lower energy consumption, and longer service life.

[0069] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and are all included in the protection scope of the present application.

Claims

1. A PTC effect electrothermal film, characterized in that, The device includes a thin film substrate, a PTC-effect electrothermal layer, conductive circuitry, and a cyclic relay. The PTC-effect electrothermal layer comprises the following components in parts by weight: nano-silicon hybrid resin: 40-50 parts; sheet-like graphene: 30-35 parts; and thermosensitive material: 2-10 parts. Conductive agent: 1 to 5 parts; additives: 0.5 to 3 parts; the thermosensitive material is polyethylene oxide; the PTC-effect electrothermal layer covers one or both sides of the thin film substrate; the cyclic relay is disposed in the conductive circuit.

2. The PTC effect electrothermal film according to claim 1, characterized in that: The sheet-like graphene has a sheet diameter of 2μm to 10μm and a thickness of 1nm to 3nm.

3. The PTC effect electrothermal film according to claim 1, characterized in that: The conductive agent is at least one of conductive graphite, conductive carbon black, carbon nanotubes, carbon fibers, and conductive metal powder.

4. The PTC effect electrothermal film according to claim 1, characterized in that: The additive is at least one of wetting and dispersing agents, leveling agents, and thickeners.

5. The PTC effect electrothermal film according to claim 1, characterized in that: The circuit connection time of the cyclic relay is 20s to 40s, and the circuit disconnection time is 3s to 7s.

6. The PTC effect electrothermal film according to claim 1, characterized in that: The PTC effect electrothermal film is also equipped with a temperature sensor.

7. A method for preparing a PTC effect electrothermal film as described in any one of claims 1 to 6, characterized in that, Includes the following steps: 1) Disperse nano-silicon hybrid resin, sheet graphene, thermosensitive material, conductive agent and additives in water to obtain electrothermal paste; 2) The electrothermal paste is coated on the surface of the thin film substrate and dried to form a film. Then, conductive circuits and cyclic relays are set, and temperature sensors are set as needed to obtain the PTC effect electrothermal film.

8. An electric underfloor heating system, characterized in that, It includes the PTC effect electrothermal film as described in any one of claims 1 to 6.

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