TW200832453A - Composition for electric-heating film and electric-heating film and electric-heating device manufactured by the same - Google Patents

Abstract

A composition for an electric heating film comprises a fiber material and a conductive painting material, where the fiber material includes a plurality of fibers interconnected into a network and the painting material is absorbed onto the fiber material and includes an adhesive and a carbon conductive material with a weight ratio between 20:1 and 4:6. The carbon conductive material is a micron-carbon black, a nano-carbon black, a micron-graphite, a nano-graphite, a micron-carbon fiber, a nano-carbon fiber, a carbon nano-tube, or a combination of the above.

Description

200832453 IX. Description of the Invention: [Technical Field] The present invention relates to a composition for an electrothermal film, and more particularly to a composition for an electrothermal film having a fibrous material, and the fibrous material has a plurality of mutual A fiber connected to a network, and an electrothermal film formed by thermally curing or sintering the composition for the electrothermal film and an electric heating device containing the electrothermal film. ^, [Prior Art] It is known that the working principle of the electric heating device is mostly {conducting the electric energy into heat energy by the electric resistance effect generated by the electric electricity to achieve the purpose of heating. In general, there are two main types of direct and indirect heating, in which direct heating is to pass current directly through a heated body, and indirect heating is conducted to the heating element to conduct heat to the object to be heated. The method of direct teaching is because the inside of the heated body generates heat, and has the advantages of high heating speed and high efficiency, and can be used for requiring uniform heating inside, and the heating temperature is limited, but the heated body must have an appropriate resistance. value. The indirect heating method is to increase the heat to the object to be heated by radiation, conduction or convection. Therefore, the object to be heated is not limited, and the indirect heating device is simple and easy to use. Therefore, it is the most widely used in electroheating, but its heating temperature is limited by the allowable temperature of the heating element: due to: Limitation of use X to the heating element. The widely used indirect heating electric heating device is composed of a resistance wire, and the electric heating device surrounds the metal wire on the insulating material, and is covered with an insulating coating or resin after the absence. The test is filled with inertness. Gas of 5 200832453 in glass s. However, the use of a resistance wire as a heating element has the following disadvantages: (1) = the limit of the allowable temperature of the resistance wire; the resistance wire material is mostly a metal element, so if it is exposed to the air and after a period of time After use, it is easy to oxidize or become brittle and shorten the life of the product; (3) The electric enthalpy efficiency of the resistance wire is only about 50%, and it is impossible to reach the entire surface of the sentence, which causes the source to be wasted. Therefore, in order to overcome the shortcomings of the traditional resistance wire, in recent years, many studies have intensively explored how to improve the shortcomings caused by the t-resistance wire.

Various resistive materials such as graphite resistors, metal foil resistors and oxide film resistor materials were exhibited. /, medium, metal film resistor or oxide film resistance is by evaporation (CVD; PVD), _Sputter) or screen printing (s (10)n method and Lai new-generation electric heating material 'also known as electric heating film. The advantages of this electric heating film疋t heating is fast due to heat transfer, so the temperature rises faster; (2) the temperature of the heating element itself is not high, and no redness or hotness occurs, so the heat and light loss is small, and (3) can be made into a large area. The film increases the heat transfer area; (4) The electrical efficiency of the electrical appliance made of hot film is quite high; (5) The electric heating film is very thin 'nearly occupying volume, and it is very convenient to design, install and carry; (4) Electrothermal film The physicochemical properties are extremely stable and are not easily oxidized in the air. ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, When it is joined with the electric heating film, it often causes the phenomenon of unevenness in the second time: (3) the uneven distribution of the surface resistance is serious, and the surface temperature is uneven, and the heated body is broken. (4) The equipment is expensive and the manufacturing cost is high. Therefore, there are still = 6 200832453 exhibited - it is possible to obtain a low resistance value at a low cost, and at the same time, it can improve uneven distribution of resistance, uneven surface temperature, and problem of material breaking of the heated body. *The traditional resistance wire can not reach the whole surface of the whole sentence heating, twisting (about 5 〇), easy to produce oxidation, and its use voltage is higher. However, the existing new generation of metal film resistors or oxide film resistors 敎The amount of transfer is faster, the thermal efficiency is improved, and the thin film resistors are not easily oxidized in the air. However, when the thin film resistors are used, if the surface of the heated body is rough, the surface resistance is unevenly distributed, resulting in uneven surface temperature. Therefore, the object to be heated is broken by the action of thermal stress, and in addition, the cost of producing the resistor is high. ' Therefore, the applicant contemplates adsorbing a conductive coating on a fibrous material to obtain a thermoelectric film. The composition method is used to improve the uneven distribution of the surface resistance of the electrothermal film obtained, and the applicant speculates that the fibrous material includes a plurality of fibers interconnected into a network. Therefore, a plurality of conductive particles which are originally dispersed in the conductive paint can be concentrated on or near the fibers, and the conductive materials are electrically conducted through the guide materials to form a telephoto female to improve surface conductivity. In addition, the surface resistance distribution and the surface temperature are uneven and the object to be heated is broken. The first purpose of the present invention is to provide a second type of fiber-containing material and a conductive coating for the electrothermal film. And the fibrous material comprises a plurality of mutually-formed-networks, wherein the conductive coating comprises a weight ratio of m·/ to = 7 200832453

a binder and a carbon conductive material, and the binder comprises a first adhesive resin; wherein the first adhesive resin is selected from the group consisting of an epoxy resin, an acne resin, and a poly Polyester resin, Polyimide resin, Polyurethane resin, Polyacrylic resin, ABS resin (ACRYLONITRILE-BUTADIENE-STYRENE resin), Melamine resin (Polyester resin) Melamine resin, Silicone resin, Urea resin, Polycabonate resin, Polysulfone resin, Fluorocarbon resin, or a combination thereof. The carbon conductive material is selected from the group consisting of micro black carbon black, nano carbon black, micro graphite, nano graphite, micro carbon fiber, nano carbon fiber, Carbon nanotube, or a combination of these. A second object of the present invention is to provide a method for producing a composition for an electrothermal film as described above, comprising the steps of: (a) adsorbing the conductive coating material as described above to a fiber as described above And (b) applying a pressure-absorbing or pressure-scraping treatment to the fibrous material to which the conductive coating is adsorbed to obtain the composition for the electrothermal film. A third object of the present invention is to provide an electrothermal film obtained by subjecting the electrothermal film composition as described above to a heat treatment selected from thermal curing or sintering, and the electrothermal film has an A resistance value of 10 to 1200 ohms. A fourth object of the present invention is to provide an electrothermal device comprising a substrate, an electrothermal film as described above formed on the substrate, and two on the substrate of 20083232453 and correspondingly disposed on the electrothermal film The electrodes on the second side, and the electrodes are electrically connected to the electrothermal film, respectively. Therefore, the electrothermal film and the electrothermal coating of the present invention have a _resistance value because they contain the conductive paint, so that the use voltage is lower than that of a general heating element, and at the same time, the conductive particles can be concentrated by a small amount by the fibers. The particles can be energized to enhance the conductive effect, so 4 can increase the purity of the use, reduce the risk of contact, and can also have a faster heating rate.

The advantage of 'can also improve the uneven distribution of resistance, surface temperature unevenness, and the problem of cracking of the heated body. [Embodiment] The composition for an electrothermal film of the present invention comprises a fibrous material and a conductive coating J, and the fibrous material comprises a plurality of fibers interconnected into a network: the conductive coating is adsorbed on the fibers, and the electrical material is charged The coating includes a binder and a barrier conductive material having a weight ratio of between 20:1 and 4:6, and the drill. J 3 has a first adhesive resin; wherein the first adhesive resin is selected; the oxidizing tree knows that the resin, polyester resin, polyimine resin, polyurea, polyacrylonitrile resin, ABS resin, melamine Resin, eucalyptus, urea resin, polycarbonate resin, poly maple resin, fluorocarbon resin, or a combination thereof, the carbon conductive material is selected from the group consisting of micron-sized carbon black, nano-grade, and Card, and graphite, nanoscale graphite, micron carbon fiber, nano carbon fiber, carbon nanotube, or a combination of these. Preferably, the fibrous material suitable for use in the present invention is a mesh selected from a resistance value 疋η between 3 and 1 〇22 Ω. Preferably, the crucible suitable for use in the present invention is transported from a non-woven fabric, a woven fabric, a knitted fabric, a metal mesh or a window screen 9 200832453. The material of the mesh is selected from the group consisting of polypropylene and polyethylene. Polyester, polyamide, polyacrylonitrile, copper, nickel, aluminum or stainless steel. Preferably, the fibrous material suitable for use in the present invention is selected from a paper having a resistance value between 3 and 20 Ω. Preferably, the paper is selected from the group consisting of carbon fiber paper (CarbGn fiber paper), metal fiber paper, and metal fiber paper (Metal_plated fiw, or the like). Ground, the material of the paper is selected from the group consisting of carbon, graphite and gold.

Silver steel, nickel, chrome, Ming, Meng, Qin, no steel, or a combination of these. Further, the first adhesive resin is selected from the group consisting of epoxy resin, phenolic resin, polyester resin, polyimine resin, Shixi resin, polycarbonate resin, or a combination thereof. The electric resistance value of the adhesive is not particularly limited. When there is no progress in adding other conductive materials in the conductive paint, preferably, the electric resistance of the adhesive is between 1 G and 1 〇 8 Ω. Preferably, the binder further comprises a plurality of metal particles, and the metal particles are selected from the group consisting of silver, tin, copper, or the like. More preferably, the particle diameter of the metal particles is between 丨 and 5 〇 μΓΠ. In the specific case of the present invention, the adhesive is an electronic grade epoxy resin having a resistance value between 104 and ΙΟ6 Ω. In another embodiment of the present invention, the adhesive is an epoxy resin having a resistance value between 1 〇 ls and 1 〇 16 Ω 2 , and the overall resistance value of the conductive paint can be adjusted by adding other conductive materials. . For example, the user can adjust the resistance value of the adhesive by adding a plurality of metal particles to the first adhesive resin. Preferably, the conductive coating further comprises a conductive paste comprising 10 200832453 a plurality of first conductive particles having a particle diameter of between 1 and 50 μm, and a second adhesive resin, and the first conductive particles Is selected from the group consisting of silver, tin, copper, i, etc. The second adhesive resin is selected from the group consisting of epoxy resins, polyphenol ester resins, and polyacrylonitrile resins. More preferably, the conductive paste further contains a plurality of second conductive particles, and the second conductive particles are selected from the group consisting of gold, platinum, rhodium, ruthenium, moth, sulphate, or the like. The conductive coating may further include a plurality of semiconductor particles selected from the group consisting of Sn〇2, Zn〇, In2〇3, Ca2ln〇4, a blend of ruthenium and Sn〇2, and Fe and Sn〇2. Blend, 掺 and % blend, ΖηΟ and A1 blend, or a combination of these. Preferably, the semiconductor particles are a blend of Sb and SnO 2 . Preferably, the carbon conductive material has a resistance value of between 1 and 2 〇 Ω. Preferably, the carbon conductive material is selected from the group consisting of micron-sized carbon black, nano-carbon black, micro-grade graphite, nano-scale graphite or the like. More preferably, the average particle diameter of the micron-sized carbon conductive material is between j and 5 pm, and the average particle diameter of the nano-sized carbon conductive material is between 2 〇 and 1 〇〇 nm. . Preferably, the carbon conductive material is nano-carbon black, and the weight ratio of the adhesive to the nano-carbon black is between 90 ··10 and 85 ··15. The carbon conductor is nano-scale graphite, and the weight ratio of the binder to the nano-graphite is between 6:4 and 3:7. More specifically, the nanoscale graphite is selected from the group consisting of high purity graphite, flaky graphite powder, exfoliated graphite powder, or a combination thereof. Preferably, the carbon conductive material is a micron-sized carbon fiber having a length between 1 and mm, a diameter of between 1 and 7 μm, or a length of between 11 and 200832453 and greater than 0·1 to less than 1 mm. Nano-carbon fibers between 20 and 80 nm in diameter. Preferably, the conductive coating further comprises a solvent selected from the group consisting of toluene, xylene, acetone (Dimethylketone), methyl ethyl ketone (METHYL ETHYL KETONE), Methy Iso-butyl Ketone, two Diisobutyl Ketone, Methyl Amyl Ketone, Diacetone Alcohol, Tetrahydrofuran, Dioxane, N-Mercaptopyrrolidone (NMP), Dichloromethane, Ethylene Glycol Monobutyl ether, dimethylformide (DMF), N-methylethylpyrrolidone (NMP), Dimethy Sulfoxide (DMSO), or One of these combinations. The conductive coating can adjust its viscosity by the solvent described above, so that the conductive coating can be more uniformly bonded to the fibrous material. Preferably, the conductive coating has a viscosity of 30 to 40 cps, and more preferably, At 32 to 38 cps. Preferably, the solvent is toluene and the solvent weight is between 2 and 3 times the binder. Preferably, the composition for an electrothermal film of the present invention is obtained by immersing the fibrous material in the conductive coating, and then extracting and applying the impregnated fibrous material from the conductive coating. The pressure-sensitive or pressure-increasing treatment is performed, or the conductive coating is applied to at least one surface of the fibrous material, and is prepared by applying a pressure or pressure flattening treatment. The method for producing the electrothermal film composition of the present invention comprises the following steps: (a) adsorbing the conductive coating material as described above to a fibrous material as described above; and (b) adsorbing the fibrous material as described above; The fibrous material of the conductive coating is applied to 200832453 [sucking or adding a flattening treatment to obtain an electrothermal (four) composition. In the specific example of the wood, the step (4) is to adsorb the conductive coating to the fibrous material by using the fibrous material: in the conductive coating: another specificity of the water in the water In the example, the step (4) is performed by applying the conductive coating to at least one surface of the fibrous material to adsorb the conductive coating on the fibrous material. After the conductive particles in the conductive coating are subjected to the above-described pressure or pressure flattening treatment, the pressure of the pressurization treatment which is apparently formed toward the fibers is between . The pressure in the specific case of this case is 1.5 kg/cm2. The electrothermal film system of the present invention is obtained by subjecting a composition for electrothermal film as described above to a heat treatment selected from thermal curing or sintering, and the electrothermal film has a resistance value of 10 to 12 ohms. . When the substrate used is a woven fabric or glass, the heat treatment is heat curing, and the composition for the electrothermal film is first applied to the substrate and applied thereto; I at a temperature of 6 cm 50 C to make the substrate The electrothermal film is obtained by curing the composition. When the substrate to be used is ceramic, the heat treatment is sintering, and the electrothermal film composition is first attached to the substrate, and a temperature of 200-650 ° C is applied thereto to make the electric heating. The film is obtained by sintering a composition. The thermal film of the present invention can be further fabricated into an electric heating device. As shown in FIG. 1 , the electric heating device of the present invention comprises a substrate 1 , an electrothermal film 2 as described above formed on the substrate 1 , and two The electrodes 3 are disposed on the substrate 1 and correspondingly disposed on two sides of the electrothermal film 2, and the electrodes 3 are electrically connected to the 13200832453 electrothermal film 2, respectively. In view of the conduction mechanism of the electrothermal film, the conventional electrothermal film is mainly electrically conductive via a path formed by the aggregation effect of the conductive particles, and therefore, the aggregate formed by the conductive particles and the like The arrangement after firing is the resistance value exhibited by the resistor layer. When the content of the conductor particles is higher, the chance of the agglomerates forming a ring-shaped, network-like or chain-like structure after sintering is higher. The electric resistance of the obtained electrothermal film is also lower. The fibrous material of the present invention is used to guide the conductive particles to form a network aggregate and thereby reduce the addition of the conductive particles i. Further, when the conductive mechanism of the electrothermal film is invented, it can be divided into five knives to see (1) aggregation effect; (2) uniform (Unif〇rm) conductive type; (3) both staking grooves (Uniform Ch_el); (4) through the energy barrier "face (four) Bamer); (5) non-piercing energy barrier (N.t_ (four) b New Zealand (four) type. The so-called uniform conductivity refers to the uniform mixing of these conductive particles In the mixed strip", the impurity is provided by the miscellaneous type. The uniform channel type means that when the conductive and the sub-sinter are sintered to form a conducting groove, the electrons follow the path: electricity, but Uniform channel-type electrons can only form heterotropic conductivity along the conduction channel, but the invention can force electrons along the network by the fiber-optic material. The structural structure moves to overcome the shortcomings of the directionality. Retiring this money energy barrier means that when the conduction slot is separated by the energy barrier, if each energy barrier itself is not the same as the old one, the aggregate is between the aggregates. :, or some isolated conductive particles or small, due to the insulation layer ($1Onm), under the action of electric field,... The electrons that are excited and excited can move over the insulating layer and jump to the conductive particles on the adjacent layer of 200832453 to generate a flow phenomenon to provide conduction. And a = the conduction groove is blocked by the energy barrier and the electron cannot be used by the rhyme mode. In the case of a conductive mp hand containing a semiconductor or a poor insulator, it can be electrically conductive through the energy barrier by the casting body or the similar material particles present in the energy barrier, which is a so-called non-tunneling barrier type. In addition to the fibrous material, the fiber material can contribute to the aggregation effect and the hooking of the #-type conductive mode, and the binder and the carbon conductive material used are also ❿ (5) in the conductive mode of wearing the steep energy barrier, Since the micro/nano-grade conductive particles are more likely to jump over the energy barrier and transition to adjacent conductive particles, the present invention can achieve better conductive effects with less conductive materials and lower cost, and thus The present invention will be further described with respect to the following embodiments, but it should be understood that the embodiment is for illustrative purposes only and should not be construed as the invention. Implementation Limits • Days • Sources of Chemicals 1. Adhesives: (1) E-Epoxy Resin: purchased from Yusong Group Co., Ltd., with resistance values between 1 and 4 〇6Ω (2) Epoxy resin Β: purchased from Changchun Petrochemical Co., Ltd., model ΒΕ188, its resistance value is between 1〇ΐ5 and 1〇ΐ6Ω. 2. Nano, and Nano Conductive Carbon Black: purchased from Yusei Fei Enterprise Co., Ltd., with an average particle size of 3〇 to 35 nm and a resistance of 4 Ώ. 15 200832453 3·Nano-grade carbon black B ( Nano Conductive Carbon Black) · · purchased from Decusa Enterprise Co., Ltd., with an average particle size of 50 to 55 nm and a resistance of 4 Ω. 4. Highly Purified Graphite Powders: purchased from Sakamoto Black Lead Industrial Co., Ltd., having an average particle diameter of 15 μm and a resistance value of 1.5 Ω. 5. Laminate Graphite Powders: purchased from Japan Black Lead Industries Co., Ltd., having an average particle size of 15 μηη and a resistance value of 2.2 Ω 〇 6. Graphite Powders for General Use: It was purchased from Japan Black Lead Industrial Co., Ltd., and its average particle size was 40 μm, and the resistance value was 3 Ω. 7. Carbon fiber: purchased from Holley, having a cross-sectional diameter of 7 // m, a length of 3 mm and 6 mm, and a resistance value of 5 Ω. 8. Bismuth/tin dioxide blend: purchased from Nanjing Haitai Nano Materials Co., Ltd., model SN-1000. 9. Polypropylene breathable non-woven fabric (Polypropylene, PP): purchased from South Asia, model number 50401, base weight 14 m2 / g. 10. Polyester flame retardant suede cloth: purchased from Lili Company, cloth specifications: 30/12+80D/25f 361, size 8 cm X 8 cm. 11. Extrusion brick: Huagang Erding brick, purchased from Huatai Kiln Co., Ltd., model 5x23cm. 12·Silver gum: purchased from Zhijia Technology Co., Ltd., model G-7477, with a silver content of 66wt%. 16 200832453 13. Solder paste: purchased from Shengmao Technology Co., Ltd., model brain·p2〇 ’, its tin content is 65 wt%.

Ail L pressure dyeing test machine · Model is Rapid. 2. Torque quick agitator: Model G-750. 3. The oven · model number is D045. 4. Digital clamp meter · Model TES-3074.

As shown in Fig. 2, the surface resistance test is performed by using a digital clamp type meter-object test piece, and the four measurement points 91 are respectively taken from the center point 92 of the test piece 90 to the four vertex directions. At 5 cm, take it again

Q The temperature rising hedgehog is shown in Fig. 3. In this case, the copper foil tape 81 (resistance value 〇·7 Ω) which is respectively attached to the opposite sides of the rib of an object test piece is used as the electrode 81 of the test piece rib, and The electrodes 81 are connected to a transformer 82, and the voltage of the test piece at a certain time point is measured by changing the voltage, and the measurement point is the center point 83 of the test piece. _Electrothermal film with carbon black added to the group<Example 1> The operation steps of Example 1 are as follows: (1) One nanometer carbon black enamel is placed in an oven, and it is baked at 1 〇〇 After 'screening again with a mesh of 10 0 mesh; 17 200832453 (7) Adding the nano-scale carbon black A fraction to the epoxy resin a, the weight of the nano-carbon black A and the epoxy resin A Ratio of / two mixture; 0) Add appropriate amount of toluene to form a tree with a viscosity between 32 and a lipid solution; 38 cps (4)

Using a high-torque fast agitator, the rotation speed; the valley liquid for 15 minutes' makes the nano-grade carbon black to obtain a conductive coating; γ·ρ·πι stirs the resin and uniformly disperses therein, and (7)-polypropylene if gas The non-woven fabric is dipped in the electric paint, minute; (6) and then the non-woven fabric is taken out from the conductive paint and subjected to a dyeing test machine, wherein the pressure is M kg/em2, which can be obtained. Membrane composition. Μ <Examples 2 to 6>

Examples 2 to 6 were obtained in a similar manner to Example i. The difference was that the weight ratio of the nano-carbon black A to the epoxy resin A was 10/90, respectively. 15/85 ; 2〇/8〇·,以乃; 30/70. <Example 7 > Example 7 was obtained by the procedure of Example "the procedure of the electrothermal film, except that the nano-carbon black A was in a nanometer order Carbon black B is substituted. <Examples 8 to 12> The examples 8 to 12 were obtained in the same manner as in Example 7 to obtain the conductive 18 200832453 coating, except that the nano-carbon black B and the epoxy resin were eight. The weight ratio is 10/90; 15/85; 20/80; 25/75; 30/70. Paint scaly skin stone single <Examples 13 and 14> Examples 13 and 14 were obtained in the same manner as in Example 1 except that the nano-carbon black A was — #,,辞

The flake graphite was substituted, and the weight ratio of the flaky graphite to the epoxy resin A was 50/50; 70/30 〇遂1 plus flaky stone black&lt;Examples 15 to 17&gt; Examples 15 to 17 The composition for the electrothermal film was obtained in a similar manner to the example, except that the nano-carbon black A was replaced by a flake graphite and the flake graphite and the epoxy resin A were The ratio of weight ^ is 30/70; 50/50; 70/30. , 'Riga South Purity Stone Storm &lt;Example 18&gt; The procedure of Example 18 was as follows: (1) The high-purity graphite was placed in an oven at 卩1〇〇. . After drying for 1 hour, it is sieved with a 100 mesh screen; (2) the high-purity graphite is added to the epoxy resin B in portions to form a ratio of the high-purity graphite to the epoxy tree. /70 mixture^ (3) Add appropriate amount of benzene to form a fat solution between 1 and 38 (9); (4) Stir the tree with a high torque fast stirrer at 300 rpm. 200832453 Lipid solution, lasting 15 (5) adding a solder paste to the resin solution, the ratio of the high-purity graphite to the tin lean is 20/80, and the resin solution is also stirred at a rotation speed of 300 rpm for 15 minutes to obtain a conductive paint; (6) A polypropylene permeable non-woven fabric is dipped in the conductive paint for 1 minute; (7) The non-woven fabric is taken out from the conductive paint to be subjected to a pressure dyeing test machine, wherein the pressure is 1.5 kg/cm 2 A composition for the electrothermal film of the invention. <Examples 19 to 24> Examples 19 to 24 were obtained in the same manner as in Example 18 except that the weight ratio of the high-purity graphite to the solder paste was 30/ respectively. 70; 40/60; 50/50; 60/40; 70/30; 80/20 ° Addition/tin oxide exchange; &lt;Example 25&gt; Example 25 was obtained in a similar manner to Example 18. The electrothermal film composition is different in that the epoxy resin B in the step (2) is replaced by the epoxy resin A described in the embodiment 1, and the solder paste in the step (5) is The bismuth/tin dioxide admixture is substituted, and the weight ratio of the high purity graphite, the epoxy resin A' bismuth/tin dioxide admixture is 12::3, respectively. &lt;Example 26&gt; Example 26 is a composition similar to that of Example 18, which is similar to (4) the composition of the electrode of the electric heating film. The difference is that the step (5) is further added-recorded/dioxy 20 200832453 tin-supplemented body And the tin hex is replaced by one (three) 乂 silver 驭, the weight ratio of the high-purity graphite, the epoxy resin B, the silver paste, and the bismuth $ / - emulsified tin blend are respectively 3 : 14 : 2: 1 〇 Adding a carbon fiber cone <Example 27> The operation procedure of Example 27 is as follows: further placing a bake (1), immersing the fiber in an alcohol to disperse it, and baking it at 100 t for 1 hour; The carbon fan (2) adds the carbon fiber to the epoxy resin b in a ratio of 1:99 to the mixture 1: (7) by adding an appropriate amount of toluene to form a viscosity of 32 to 3_ lipid solution; (4) ^ High-torque quick-mixer, with the speed fan rpm (four) the tree cold liquid for 15 minutes 'to make the carbon fiber evenly dispersed in the conductive paint; - clothing line (5) future propylene breathable non-woven fabric dipped in the conductive paint minutes ; τ (6) Take the non-woven fabric out of the guide sputum and apply it evenly, On the surface, a composition for an electrothermal film of the present invention can be obtained. &lt;Example 28&gt; Example 28 was obtained by a similar procedure to that of Example 27, using a similar procedure to obtain the electric heating and the like, except that:疋 添加 在 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加 添加80: 19. 21 200832453 &lt;Example 29&gt; The polypropylene permeable nonwoven fabric for the electrothermal film was obtained in the same manner as in Example i except that the cloth was a carbon fiber in this step. Paper replaced. &lt;Example 30&gt;

The composition was used except that the woven fabric was replaced by a carbon fiber paper. <Example 31> Example 31 was obtained in the same manner as in Example 27 to obtain the electric (4) wire. It is: the poly (iv) in the (4) (7) is breathable; the woven fabric is replaced by a carbon fiber paper. In the table - the substance covered with the Benman film

Hereinafter, the composition for the electrothermal film obtained in the foregoing embodiment is actually applied to an object, for example, a polypropylene flame-retardant fabric or an extruded monument, i, and the composition of the electrothermal film is tested. Surface properties. &lt;Application Example 1&gt; The operation procedure of Application Example 1 is as follows: (1) The composition of the electrothermal film obtained in Example 1 (5) was applied to one surface of a polypropylene flame retardant fabric having a length of 8 cm and a width of 8 cm. (2) The polypropylene flame-retardant fabric to which the composition for the electrothermal film is attached is placed in a baking phase of a c for 1 hour to cure the electrothermal film composition into an electrothermal film, thereby obtaining a surface. Fabric 22 to which the electrothermal film of the present invention is applied 200832453 [Application Examples 2 to 14] Application Examples 2 to 14 are in the same manner as in Example 1 in which the coating is used to obtain the fabric of the electric film of the electric heating film. The electricity in the step (1): = was replaced by the composition for the electrothermal film obtained in Examples 2 to 14, respectively. <Application Example 15 &gt; The operation steps of Application Example 15 are as follows.

(1) The composition for an electrothermal film obtained by performing the method of 15-15 is applied to one surface of a glass substrate having a length of 1 cm, a width of 5 cm, and a thickness of 3 cm; (2) The glass substrate of the electrothermal film composition is heated in an oven for 1 hour to cure the electrothermal film composition into an electrothermal film, thereby obtaining a glass having the surface coated with the electrothermal film of the present invention. Substrate. &lt;Application Examples 16 and 17&gt; Application Examples 16 and 17 were obtained in the same manner as in Application Example 15 to obtain the glass substrate to which the electrothermal film of the present invention was applied, except that the electric heating film in the step 〇) The composition was replaced with the composition for the electrothermal film obtained in Examples 16 and 17 respectively. &lt;Application Example 18&gt; The operation procedure of Application Example 18 is as follows: (1) The composition for an electrothermal film obtained in Example 18 is applied to one surface of an extrusion tile 52 X 240 mm; (2) The extruded tile to which the composition for an electric heating film of the present invention is attached is placed on a high-temperature 23 200832453 warm-sintered towel, and the temperature is raised to 300 ° C at a heating rate of 1 Gt: per minute, and the temperature is raised at 30 CTC. The scorpion / / 凤凰 for 1 hour, in order to sinter the composition of the electrothermal film into an electric heating film, the other main body: r: pain | j to a surface of the extruded tile coated with the electrothermal film of the invention. <Application Examples 19 to 24> Application Examples 19 to 24 were obtained by the steps similar to those of Application Example 18, in which the extruded tile to which the electrothermal film of the present invention was applied was obtained, wherein: (1)

The composition for the electrothermal film in the above was replaced with the composition for the electrothermal film obtained in Examples 19 to 24, respectively. &lt;Application Example 25&gt; Application Example 25 is an extrusion tile to which the electrothermal film of the present invention is attached, in the same manner as in Application Example 18, except that the composition for the electrothermal film in the step (1) is carried out. The electrothermal film obtained in Example 25 was replaced with a composition, and the sintering temperature of the step (2) was 58 (rc. The surface resistance and the temperature rise of the cobalt were discussed in Examples 1 to 22 for surface resistance and different voltages, respectively. The temperature rise test 'further obtains the surface resistance value and the surface temperature of the application examples, ^ see Table 1 to Table 3. Here, the "damage" in Table 1 means that the substrate is damaged and not the composition of the electrothermal film. It is unusable, and the reason why the substrate is damaged is that the electric resistance film composition of the present invention can have a resistance value as low as 10 Ω, so that when the voltage is applied to a voltage, the composition for the electrothermal film can be heated rapidly, but there are two substrates. (for example, fabric) itself has a limited degree of heat, so the temperature is too high, the substrate is damaged by 3 $, but in actual application, the electrothermal film will match the substrate with 4 inches and will not be on the substrate. Can not withstand the temperature used. Because 24 200832453 Therefore, Table 1 is only used to show that the electrothermal film prepared by the invention in a low cost and simple method can indeed have a resistance value between 1 () and 1200 Ω and the temperature rises quickly. The data in Table 3 is The surface resistance value of the composition for an electrothermal film of the present invention measured when the extruded tile is a substrate, it is necessary to specifically indicate that when the silver gum content is as high as 80% by weight, the conductive paint is made The viscosity is greatly reduced, resulting in the punching of the fabric on the surface of the fabric during the pressing process of the fabric. The fiber is pulled up by the conductive coating due to the viscosity, resulting in some protrusion on the surface of the fabric after sintering. When the heating test is performed, the protrusions are crushed, and even sparks are generated to cause the composition of the electrothermal film to be destroyed. Therefore, when a metal such as silver glue is further added, attention should be paid to the conductive paint. The effect of overall viscosity.

25 200832453 Table 1 Surface temperature (°C) and power (W) of carbon conductors in the case of fabrics containing 3 conductive materials containing i 1 , different carbon t than surface resistance values after 30 minutes of voltage application Carbon Conductive Material/Epoxy Resin A Weight Ratio (wt%) Surface Resistance Value (kQ) Voltage 5V 10V 15V 20V 1 Carbon Black A 5/95 0.98 Temperature 42.4 79.9 Damage - Power 0.075 0.15 2 10/90 0.33 Temperature 85.3 Damage — — Power 0.275 3 15/85 0.31 Temperature 92.4 Damage — Power 0.325 4 20/80 0.37 Temperature 68.8 Damage 1 — Power 0.175 5 25/75 0.39 Temperature 63.6 Damage — — Power 0.125 6 30/70 0.39 Temperature 60.5 Damage — — Power 0.05 7 Carbon black B 5/95 1.01 Temperature 32.6 76.2 98.6 Damage power 0.05 0.25 0.9 8 10/90 0.36 Temperature 53.1 Damage - Power 0.2 9 15/85 0.32 Temperature 60.7 Damage - Power 0.225 10 20/80 0.42 Temperature 51.2 103.0 Damage - Power 0.2 1.35 11 25/75 0.43 Temperature 46.6 100.1 Damage - Power 0.1 0.8 12 30/70 0.43 Temperature 45.0 92.3 Damage - Power 0.1 0.7 13 Scale-like stone Ink 50/50 0.91 Temperature 49.5 Damage – Power 0.1 14 70/30 0.72 Temperature 52 Damage – Power 0.1 26 200832453

17 16 Application Example Carbon Conductor Γν时Ί Ί Λ, ο } Material ratio Ϊ曰; δ basis weight carbon material weight shift W5 ί Different carbon surface resistance values of different voltages after 10 minutes _ surface temperature (°c) Flaky stone 30/70 50/50 surface resistance (Ω) 810

10V

20V 450 Not tested Not tested 60 110 70/30

Table 3: Extrusion tile as application example Carbon conductive material type coffin ^ 'Different carbon conductive material content ratio - surface electric and dry carbon conductive material. / Epoxy B weight ^ ( wt % ) 18 Mutual 20ΎΓ 22ΎΓ South Purity Graphite 24 一丨·1_ Conclusion From the above surface between 10 and 1200 基材 substrate and different requirements, 30/70 carbon conductive material / solder paste weight ratio (wt%) surface resistance value (Ω) 20/80 919 __30/70 315 40/60 135.75 50/50 Γ 79.5 60/40 43.65 70/30 10.7 —80/20 12.175 % Resistance to surface temperature It can be seen that the electrothermal film of the present invention has a resistance value of The user can make electric heating films according to different resistance values. If you pay more attention to power saving 27 200832453:, 'You can choose the surface resistance value between 800Ω and 1200Ω, the right 疋 is too fast to increase the temperature, you can choose the surface resistance value between 10 Ω to _Ω The heating rate can be raised to 45 seconds to (4). c ° In addition, due to the fact that the electrothermal film of the present invention is directly attached to the substrate, the energy lost during the transfer process has been greatly reduced compared with the existing resistance wire, and the above-mentioned electrothermal film and electric heating of the present invention are integrated. Because the device contains the conductive paint, the lower resistance value makes the use voltage lower than that of the general heating element. It can increase the safety of use, reduce the risk of electric shock, and increase the heating rate. Advantages of the present invention, in addition, the electrothermal film and the electric heating device of the present invention, by the fibers of the pure material, cause the conductive particles which are originally randomly dispersed in the conductive paint to adhere to the fibrous material after being pressed. The position will be on or near the fibers, so that the conductive particles in the electrothermal film of the present invention can be simultaneously turned on by the network formed by the fibers, and the (four) less conductive particles can achieve better efficacy. Moreover, the coating and pressing equipment used is simple, and compared with the cost required for the conventional electrothermal film process, it is obvious that the case has a large economic benefit. Therefore, the electrothermal film and the electric heating device of the present invention can effectively solve the problem that the electric resistance is unevenness of the cloth, the surface temperature is uneven, and the object to be heated is broken, and the electric heating film having a low electric resistance value is obtained at a low cost. The above is only the preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the simple equivalent change and repair according to the scope of the patent and the description of the invention. Dance is still within the scope of the invention patent. [Simple description of the schema] 28 200832453

1 is a schematic view showing a preferred embodiment of the electric heating device of the present invention. FIG. 2 is a schematic view showing how the surface resistance value test of the electrothermal film of the present invention is performed; and FIG. 3 is a schematic view showing how the electrothermal film of the present invention is carried out. Surface temperature test. 29 200832453 [Explanation of main component symbols] 1...·.·Substrate 2······••...Electrothermal film 3........·Electrode 90 ·········· Sheet 91····Measurement point 92 ···················································· ···Transformer 83.........center point

30

Claims (1)

200832453 X. Patent application scope: 1. A composition for an electric heating film, comprising: a fiber-optic twin material comprising a plurality of fibers interconnected into a network; and a conductive coating adsorbed on the fibers, The conductive coating comprises a binder and a carbon conductive material having a reset ratio of between 20:1 and 4:6 and the binder comprises a -adhesive resin; wherein the first adhesive tree In the epoxy resin, phenolic resin, polyester resin, polyimide tree, polyurea resin, polyacrylonitrile resin, ABS resin, melamine resin, enamel resin, urea resin 'polycarbonate resin, poly maple resin, a fluorocarbon resin, or a combination thereof, which is selected from the group consisting of micron carbon black, nano carbon black, micron graphite, nano graphite, micron carbon fiber, nano carbon fiber, nano A carbon tube, or a combination of the same, wherein the fiber material is selected from a resistance value of between 3 and 1022 Ω. Mesh, or a resistance value is The composition for an electrothermal film according to claim 2, wherein the mesh is selected from the group consisting of a non-woven fabric, a woven fabric, a knitted fabric, and a metal. Net or screen. 4. The composition for an electrothermal film according to claim 2, wherein the material of the mesh is selected from the group consisting of polypropylene, polyethylene, polyester, polyamide, polyacrylonitrile, copper, and nickel. , aluminum or stainless steel. 31 200832453 5. The composition for an electrothermal film according to claim 2, wherein the paper is selected from the group consisting of carbon fiber paper, metal fiber paper, metallized fiber paper, or a combination thereof. . 6. The composition for an electrothermal film according to claim 2, wherein the material of the paper is selected from the group consisting of carbon, graphite, gold, silver, copper, iron, nickel, chromium, aluminum, and fissure. Titanium or stainless steel. 7. The composition for an electric heating film according to claim 1, wherein the resistance of the adhesive is between 1 〇 4 and 1 〇 8 Ω. 8. The composition for an electrothermal film according to claim 1, wherein the binder further comprises a plurality of metal particles, and the metal particles are selected from the group consisting of silver, tin, copper, or the like. combination. 9. The composition for an electrothermal film according to claim 8, wherein the particle diameter of the metal particles is between 〇·1 and 50 μηι. The electrothermal film composition according to claim 1, wherein the conductive coating further comprises a conductive paste containing a plurality of first conductive particles having a particle diameter of between 1 and 50 μm And a second adhesive resin' and the first conductive particles are selected from the group consisting of silver, tin, steel, or a combination thereof, the second adhesive resin is selected from the group consisting of epoxy resin and polyurea resin , polyacrylonitrile resin. The composition for an electrothermal film according to claim 10, wherein the conductive paste further contains a plurality of second conductive particles, and the second conductive particles are selected from the group consisting of gold, platinum, rhodium, and iridium. , 锇, 钌, or a combination of these. 12. The composition for an electrothermal film according to claim 1, wherein the conductive coating further comprises a plurality of semiconductor particles selected from the group consisting of Sn 〇 2, Zn 0 , (5) 仏, Ca2ln〇4, a blend of sb and Sn〇2, a blend of Fe and Sn〇2, a blend of In2〇3 and %, a blend of ZnO and A1, or a combination thereof. The composition for an electrothermal film according to claim 12, wherein the semiconductor particles are a blend of Sb and Sn02. 14. The composition for an electrothermal film according to the invention of claim 2, wherein the resistance of the carbon conductive material is between 1 and 2 〇 Ω. The composition for an electrothermal film according to the invention of claim 2, wherein the slavon conductive material is selected from the group consisting of micron carbon black, nano carbon black, micron graphite, nano graphite, or the like One of the combinations. The composition for an electrothermal film according to claim 15, wherein the micron-sized carbon conductive material has an average particle diameter of from 丄 to 5 〇pm. (4) The composition for an electrothermal film according to the fifteenth aspect of the invention, wherein the nano-carbon conductive material has an average particle diameter of between 2 Å and 1 〇〇 nm. According to the composition of the electrothermal film according to the scope of the Shenjing patent scope, wherein the carbon material is a carbon black material, and the weight ratio of the binder to the nano carbon black is 90:10. Between 85:15. 19. The composition for an electrothermal film according to claim 1, wherein the carbon material is a nano-scale graphite, and the weight ratio of the binder to the nano-graphite is between 6:4 and Between 3: 7. 2〇. According to the electric heating composition described in Item 19 of the patent application, 33 200832453 &quot;Heilite grade graphite is selected from high purity graphite, flaky graphite powder exfoliated graphite powder, or the like A combination. The composition for an electrothermal film according to the first aspect of the invention, wherein the stone-reacting conductive material is a glutinous carbon fiber having a length of between 1 and 10 mm. • The composition for an electrothermal film according to the first aspect of the patent application, wherein the nucleus material is a nano-carbon fiber having a length of not more than 〇1 to less than 1 mm. 3. The composition for an electrothermal film according to the above aspect of the invention, wherein the carbon conductive material is a micron-sized carbon fiber having a cross-sectional diameter of between 1 and 7 μm. The electrothermal film composition according to claim 1, wherein the nucleus conductive material is a nano-scale carbon fiber having a cross-sectional diameter of between 2 Å and 8 Å nm. 25. The material composition according to claim 1, wherein the v-electrocoat further comprises a solvent selected from the group consisting of methyl ketone, xylene x acetonate, methyl isobutyl ketone, Diisobutyl ketone, methyl ketone, diacetone alcohol, tetrahydro sigma sulphate, south, milk, ring, N-methyl pipirone, dichlorohydrazine, ethylene glycol monobutyl ether, Dimethylformamide, N-methylpyrrole S, dimethyl sulfoxide, or a combination of these. The composition for an electrothermal film according to the item i of the invention, wherein the conductive coating has a viscosity of 30 to 40 cps. The composition for an electrothermal film according to the first aspect of the patent application is obtained by the following steps: impregnating the fibrous material in the conductive paint 34 200832453, and then immersing the impregnated material The fibrous material is taken out from the conductive coating and subjected to a pressing or pressurization to form a composition for the electroconductive film. 28. According to the scope of patent application! The 4 w屯 hot pancreatic composition is obtained by the following steps: coating the conductive paint on at least the surface of the fibrous material, and applying pressure or pressure The composition for the electrothermal film can be obtained by flattening. A method for preparing a composition for an electrothermal film according to the above-mentioned claim, comprising the steps of: (4) absorbing the conductive coating as described in claim 1 of the patent application scope The fibrous material according to item 1; and (8) applying a pressure-absorbing or pressure-scraping treatment to the fibrous material to which the conductive paint is adsorbed, thereby obtaining the composition for the electric heating film. 30. The preparation method according to claim 29, wherein the step (4) is carried out by impregnating the fibrous material with the fibrous material by impregnating the fibrous material with the fibrous material. The preparation method according to claim 29, wherein the step (4) is applied to at least one surface of the fibrous material by (4) a conductive coating, and the conductive coating is adsorbed on the fibrous material. . The preparation method according to claim 29, wherein the pressure of the pressure suction treatment of the step (b) is between 1 main 3 kg/cm 2 . 3 3. The composition for an electric heating film according to claim 29, wherein the conductive coating has a viscosity of from 3{) to 4〇cp. 34. According to the patent application scope 29th jS %u, the electrothermal film composition described in Item 9, in 35 200832453, the fibrous material is selected from a resistance value of 3 to 1 〇·22 Ω. A mesh between them, or a paper having a resistance value between 3 and 20 Ω. The composition for an electric heating film according to claim 34, wherein the web is selected from the group consisting of a non-woven fabric, a woven fabric, a knitted fabric, a metal mesh or a window screen. The composition for an electrothermal film according to claim 34, wherein the paper is selected from the group consisting of carbon fiber paper, metal fiber paper, metal coated fiber paper, or a combination thereof. 3 7 . The private thermal film is obtained by heat-treating or sintering a composition for the electric heating film according to claim 1 of the patent application, and the electrothermal film has a dielectric film Resistance value from 1 〇 to 12 (10) ohms. The heat treatment 38. The electrothermal film according to claim 37 of the patent application is thermally cured, and the composition for the electrothermal film is first attached to a substrate and applied to a substrate of 6°°. From c to a temperature of 150 ° C, the electrothermal film is obtained by curing the composition. 40. An electric heating device comprising: a substrate; 36 200832453 electrothermal film; and two electrodes disposed on the substrate and correspondingly disposed on two sides of the electrothermal film, the electrodes being electrically connected to the electrothermal film, respectively. 41. The electric heating step w according to claim 40, and the substrate is made of woven fabric or glass, and the electric heating film is as claimed in claim 1 The composition for an electrothermal film is attached to the substrate first, and is applied thereto at a temperature of from 60 ° C to 150 ° C to cure the electrothermal film. The electric heating device according to claim 40, wherein the substrate is a ceramic, and the electrothermal film is first attached to the composition for an electric heating film according to claim 1 of the patent application. The substrate is obtained by applying a composition of 20 (TC to 650 ° C) to sinter the composition for the electrothermal film.