KR20170072594A - Planar heat element composition having high positive temperature coefficient characteristics and planar heat element using the same - Google Patents
Planar heat element composition having high positive temperature coefficient characteristics and planar heat element using the same Download PDFInfo
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- KR20170072594A KR20170072594A KR1020150180946A KR20150180946A KR20170072594A KR 20170072594 A KR20170072594 A KR 20170072594A KR 1020150180946 A KR1020150180946 A KR 1020150180946A KR 20150180946 A KR20150180946 A KR 20150180946A KR 20170072594 A KR20170072594 A KR 20170072594A
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- heating element
- carbon
- element composition
- binder
- weight
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Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/02—Heaters using heating elements having a positive temperature coefficient
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/022—Heaters specially adapted for heating gaseous material
- H05B2203/023—Heaters of the type used for electrically heating the air blown in a vehicle compartment by the vehicle heating system
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Resistance Heating (AREA)
- Surface Heating Bodies (AREA)
Abstract
The present invention relates to a planar heating element composition having high coefficient of constant temperature coefficient and a planar heating element using the same. More particularly, the present invention relates to a planar heating element composition comprising a carbon filler, a binder and a solvent, To a heating element composition.
The surface heating element composition can be improved in electrical and thermal stability by using carbon fiber as a carbon filler and having improved constant temperature coefficient characteristics.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a planar heating element composition having high constant temperature coefficient and a planar heating element using the same. More particularly, the present invention relates to a planar heating element composition containing carbon fibers and a planar heating element using the same.
As the development of electric vehicles is accelerated, there is a growing interest in heating systems that have not been a problem in conventional automobiles. Conventional automobiles use air-blowing heating elements. However, electric vehicles do not have separate heating means. Electric vehicles' batteries have a low fuel consumption rate when the outside temperature is drastically reduced in winter, There is a problem that the efficiency is reduced. To this end, a heater module using a planar heating element was developed. In particular, an electric vehicle using a lithium battery or a hydrogen fuel cell is vulnerable to a fire, so it is necessary to prevent a fire due to overheating of the heater module. In addition, in the case of an electric vehicle, energy efficiency must be considered due to the capacity limit of the battery mounted on the vehicle, so it is important that the resistance value changes rapidly only above the reference temperature.
A surface heating element having a positive temperature coefficient (PTC) characteristic in which electrical resistance increases sharply at a glass transition temperature of a polymer binder due to a rise in temperature due to a low resistance at a temperature of about room temperature, It is necessary to develop a technology capable
Generally, the planar heating element is formed by uniformly spraying or printing a metal heating element such as iron, nickel, chromium, or platinum having a high thermal conductivity in a film-like resin or the like, or by forming a non-metallic heating element such as carbon, graphite, or carbon black with a polymeric binder Coating. In recent years, many carbon-based surface heating elements having strong heat and durability, good thermal conductivity and light characteristics have been researched.
The surface heating element using a carbon-based material is made of a paste formed by mixing a conductive carbon-based powder such as carbon, graphite, carbon black or carbon nanotube with a polymeric binder, and the conductive material and the polymeric binder Conductivity, workability, adhesion, scratch resistance and the like are determined according to the amount used.
The conventional plane heating element composition is mainly produced by using graphite and carbon black. Graphite of the two-dimensional structure is in surface contact with thermal expansion of the thermoplastic resin, and the resistance change is insensitive. The spherical carbon black has a temperature rise The resistance increases steadily. Such a conventional technique is not only insensitive to the constant-temperature coefficient function, but also has a large energy loss because it constantly increases in resistance to temperature rise of the surface heating element. In addition, when carbon nanotubes are used, it is difficult to uniformly mix the carbon nanotubes with the binder, and carbon nanotubes aggregate in the drying process.
For example, Korean Patent Laid-Open Publication No. 2006-0004158 discloses an aqueous conductive polymer composition containing a surfactant and carbon black and exhibiting constant-temperature coefficient properties.
Korean Patent Publication No. 2006-0014491 discloses a conductive polymer composition comprising ozone-treated carbon nanotubes.
These patents raise the dispersibility of the carbon-based material and improve the performance of the constant temperature coefficient, but the reference temperature at which the above-mentioned constant temperature coefficient characteristic is exhibited is low and the obtained effect is not sufficient.
It is an object of the present invention to provide a planar heating element composition having improved stability and reliability through high constant temperature coefficient characteristics and a planar heating element using the same.
The inventors of the present invention have studied variously for effective control of the critical heat at a certain temperature. As a result, Applicant has confirmed that it can exhibit excellent constant temperature coefficient characteristics when a carbon fiber is contained as a carbon filler, thereby completing the present invention .
The present invention provides a planar heating element composition comprising a carbon filler, a binder and a solvent, wherein the carbon filler comprises carbon fibers.
The carbon fibers include PAN (polyacrylonitrile) type carbon fibers.
The carbon fibers have an average diameter of 3 to 10 mu m, an average length of 20 to 300 mu m, and an aspect ratio of 2 to 100.
The density of the carbon fibers is in the range of 0.1 to 3 g / ml.
The binder includes an acrylic resin, and the acrylic resin includes an alkyl (meth) acrylate repeating unit.
Further, the weight average molecular weight (M W) of the acrylic resin is 30,000 to 300,000 range and the glass transition temperature (T g) of the acrylic resin is 60 to 150 Range.
The solvent includes an acetate-based solvent.
The surface heating element composition comprises 5 to 40 parts by weight of a carbon filler, 5 to 30 parts by weight of a binder, and the solvent as the balance.
The planar heating element composition according to the present invention includes carbon fiber as a carbon filler, thereby exhibiting improved constant temperature coefficient characteristics as compared with a carbon filler conventionally used, thereby making it possible to produce a planar heating element composition having improved stability and reliability.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of evaluation of adhesive force of a planar heating element composition according to Examples and Comparative Examples of the present invention. FIG.
FIG. 2 is a graph showing the results of line resistance measurement by temperature of the planar heating element composition according to Examples and Comparative Examples of the present invention. FIG.
3 is a graph showing the line resistance recovery rates of the planar heating element compositions according to Examples and Comparative Examples of the present invention.
Hereinafter, the surface heating element composition of the present invention will be described in detail for each component.
In the present invention, the carbon filler plays a role in generating a resistance change depending on temperature together with a heat generation characteristic, and includes carbon fibers. The carbon fibers exhibit high thermal and electrical conductivity and form a conductive network through contact between the carbon fiber particles, thereby exhibiting excellent exothermic characteristics. In addition, the carbon fibers are composed of linear particles and form point contacts or line contacts in the binder. This is because, when using graphite or carbon black in the prior art, it is easy to separate from the surface contact or point contact which is formed when the graphite or carbon black is used, it is possible to maximize the resistance change according to the temperature change to improve the constant temperature coefficient characteristic and secure the electrical and thermal stability .
The carbon fibers have a carbon content of 90% or more, and may be PAN (polyacrylonitrile), pitch, or rayon carbon fiber depending on the starting material. Preferably, PAN (polyacrylonitrile) -based carbon fibers can be used. Generally, carbon fibers are produced by carbonizing fibers. PAN-based carbon fibers exhibit electrical conductivity of the order of 0.5 to 5 m? Cm, while pitch-based or rayon-based carbon fibers are typically several to several hundred times higher in electric conductivity than PAN-based carbon fibers even when carbonization is performed at high temperature. Due to such electrical characteristics, application to conductive materials may be limited.
The carbon fibers may have an average diameter of 3 to 10 mu m and an average length of 20 to 300 mu m, preferably an average diameter of 5 to 10 mu m and an average length of 30 to 150 mu m. The aspect ratio of the carbon fibers may be in the range of 2 to 100, preferably in the range of 3 to 30. [ When the average diameter, the average length and the aspect ratio of the carbon fibers are within the above ranges, they are suitable in terms of heat generation, durability and uniformity of heat generation, and at the same time, conductive network formation and destruction are easy.
The density of the carbon fibers used in the present invention may be in the range of 0.1 to 3 g / ml, preferably 1.3 to 2 g / ml. If the amount is less than or more than the above range, there is a problem that the conductivity is lowered or the mechanical properties are deteriorated at the time of coating.
The carbon filler may be included in an amount of 5 to 40 parts by weight, preferably 10 to 35 parts by weight, based on the total weight of the planar heating element composition. When the amount of the carbon filler is less than 5 parts by weight, there is a problem in forming a conductive network. When the amount of the carbon filler is more than 40 parts by weight, the dispersibility is lowered and the amount of heat generation is increased and destruction of the conductive network is difficult. , The viscosity of the composition is increased and the workability or the quality of the coating film may be deteriorated.
In the present invention, the binder changes the crystalline state in the binder at the reference temperature and thermally expands to increase the spacing between the carbon fillers, thereby inducing breakage of the conductive network formed between them. In addition, the carbon filler provides an adhesion force so that the carbon filler can be stably coated on the substrate, facilitates dispersion, and provides an appropriate viscosity for securing uniformity of the coating film.
The binder may be an acrylic resin, specifically, an alkyl (meth) acrylate-based repeating unit. The acrylic resin containing an alkyl (meth) acrylate repeating unit as the binder is a thermoplastic resin, and thermal behavior occurs at a temperature higher than a certain temperature, thereby increasing a distance between the carbon fillers and causing short-circuiting. As a result, the resistance can be increased and a constant temperature coefficient function in which heat generation is controlled can be developed. In the case of the above alkyl (meth) acrylate-based repeating units, it is possible to control the glass transition temperature (T g ) which causes crystal state change and increase the resistance of the composition due to temperature increase in a relatively narrow temperature range, Performance can be obtained. In addition, the acrylic resin containing the repeating unit has excellent applicability to substrates of various materials, has various types, and has an advantage of being easily commercially available.
The alkyl (meth) acrylate repeating unit may be a conventional acrylate or methacrylate repeating unit such as methyl acrylate (MA), methyl methacrylate (MMA), ethyl Acrylate (EA), ethyl methacrylate (EMA), n-butyl acrylate (BA), n-butyl methacrylate (BMA) And n-octyl acrylate (OA). Of these, only one kind of repeating unit derived from an acrylate-based or methacrylate-based monomer may be included, but two or more kinds of acrylate- Or a repeating unit in the form of a copolymer derived from a methacrylate monomer, that is, two or more repeating units.
The weight average molecular weight (M W) of the acrylic resin may be 30,000 to 300,000 may be, and preferably 40,000 to 200,000 range. If the weight average molecular weight is less than 30,000, the adhesiveness may be deteriorated and the thermal behavior may be changed. If the weight average molecular weight is more than 300,000, the heat distortion characteristics may be changed and the viscosity may be increased.
The glass transition temperature of the acrylic resin (T g) may be 60 to 150, preferably 70 to 110 range. When the above range is satisfied, good coefficient of constant temperature coefficient that can effectively control heat generation in an actual device is exhibited, and the stability and reliability enhancement effect can be obtained.
The binder may be included in an amount of 5 to 30 parts by weight, preferably 10 to 25 parts by weight, based on the total weight of the planar heating element composition. When the amount of the binder is less than 5 parts by weight, sufficient adhesion and durability can not be exhibited. When the amount of the binder is more than 30 parts by weight, the manufacturing cost increases and the viscosity increases excessively.
In the present invention, the solvent is used for viscosity control, ease of processing, and storage stability. The solvent is compatible with the above-described carbon filler and binder, and an acetate solvent can be used as a high boiling solvent having a boiling point ranging from 120 to 250 without reacting with the carbon filler and the binder.
Specifically, the acetate-based solvent is selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n- butyl acetate, iso-butyl acetate, sec-butyl acetate, pentyl acetate, iso-pentyl acetate, octyl acetate, benzyl Benzyl acetate, phenylacetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, Propylene glycol methyl ether acetate (PGMEA), ethyl 3-ethoxypropionate, and the like can be used. These solvents may be used alone or in combination of two or more.
The content of the solvent is not particularly limited, and may be used as the balance such that the sum of the components in the composition is 100 parts by weight. The content can be appropriately adjusted in consideration of coating property, stability, etc. of the composition.
The surface heating element composition of the present invention may further contain at least one additive selected from the group consisting of a defoaming agent and a leveling agent, in addition to the above-described components. The additive may be contained in an amount of up to 5 parts by weight based on the total weight of the composition. If the amount of the additive is more than 5 parts by weight, the adhesion and stability of the coating film may be deteriorated. In addition to the above additives, other additives such as a thickener, a dispersant, and a coupling agent may also be contained.
The surface heating element composition of the present invention can be produced by mixing and stirring or milling the above components. The stirring may be carried out using a conventional stirrer such as a flow type stirrer or a confronting type stirrer, and the milling may be carried out using a conventional milling apparatus such as a roll mill, a bead mill or a ball mill Lt; / RTI > It is preferable to prepare the composition by milling in order to uniformly disperse the components in the surface heating element composition.
The present invention can be effectively used as a material for a surface heat emission element that generates heat by applying power to a base material of the above-described surface heating element composition. The surface heating element composition according to the present invention can be produced as a sheet-like heating element of a sheet or a molded article having a three-dimensional shape.
The substrate may be formed of a material such as polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyimide, cellulose ester, nylon, polypropylene, polyacrylonitrile, polysulfone, polyester sulfone, polyvinylidene fluoride, glass, , Ceramic, SUS, copper or aluminum, and the like. The substrate is not limited to those listed above, and may be appropriately selected depending on the application field of the surface heating element or the temperature of use.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples.
Examples and Comparative Examples
Examples 1 to 3 and Comparative Examples 1 to 2: Preparation of a surface heating element composition
[Example 1]
A binder of methyl methacrylate and n- butyl-meta-polymerized acrylic resin and a copolymer of repeating units of the acrylate (glass transition temperature (
[Example 2]
Except that the binder was changed to an acrylic resin (glass transition temperature (T g ) 100, weight average molecular weight (M w ) 125,000) polymerized with methyl methacrylate as a repeating unit, A heating element composition was prepared. The content of each component is shown in Table 1 below.
[Example 3]
A methylmethacrylate polymerized by a methacrylate as a repeating unit an acrylic resin binder (a transition temperature (T g glass) 105, a weight average molecular weight (M w) 150,000) except that a change in, the surface in the same manner as in Example 1 A heating element composition was prepared. The content of each component is shown in Table 1 below.
[Comparative Example 1]
A surface heating element composition was prepared in the same manner as in Example 2, except that the carbon filler was changed to graphite (xGnP 占 Grade M15 (particle diameter 15 占 퐉), manufactured by XG Sciences). The content of each component is shown in Table 1 below.
[Comparative Example 2]
A surface heating element composition was prepared in the same manner as in Example 2, except that the carbon filler was changed to carbon black (# 3050B (particle diameter: 55 nm), manufactured by Mitsubishi Chemical). The content of each component is shown in Table 1 below.
Filler
Unit: parts by weight
Experimental Example
(1) Evaluation of adhesion
The compositions of the above Examples and Comparative Examples were applied to polyethylene terephthalate with a thickness of 100 mu m and heat-treated at 140 for 20 minutes to prepare a planar heating element. The adhesive force of the obtained surface heating element was measured by the method of ASTM D3359. The results obtained at this time are shown in Table 2 and FIG.
(2) Line resistance measurement
The compositions of the above Examples and Comparative Examples were applied to polyethylene terephthalate with a thickness of 100 mu m and heat-treated at 140 for 20 minutes to prepare a planar heating element. Subsequently, electrodes were closely contacted to the surface heating element using a screen printing method on both sides to prepare a sample for a heating test. The line resistance was measured by the temperature and the line resistance after cooling to room temperature while the electrode voltage was applied to the prepared sample. The results obtained at this time are shown in the following Table 2 and Figs.
(100/100)
(Ω)
(Ω)
(%)
As shown in Table 2, it was confirmed that the surface heating element compositions of Examples 1 to 3 of the present invention exhibited sufficient adhesive strength and selective resistance value change with respect to a specific temperature.
In particular, as shown in Fig. 2, in Examples 1 to 3 including linear carbon fibers as compared with the conventional comparative examples using graphite or carbon black, while maintaining a low resistance value below the glass transition temperature of the binder, It was confirmed that the resistance value greatly changes at around the temperature and has a high constant temperature coefficient characteristic. It was also confirmed that the resistance change temperature increased as the glass transition temperature of the binder used was higher.
In addition, as shown in FIG. 3, it can be confirmed that the sheet resistance heating element composition according to the present invention recovered to the original resistance level when the resistance value returned to a low temperature state after the change of the resistance value at a high temperature, .
Claims (11)
Wherein the carbon filler comprises carbon fibers.
Wherein the carbon fiber comprises a PAN (polyacrylonitrile) -based carbon fiber.
Wherein the carbon fibers have an average diameter of 3 to 10 mu m and an average length of 20 to 300 mu m.
Wherein the aspect ratio of the carbon fibers is in the range of 2 to 100. [
And the density of the carbon fibers is in the range of 0.1 to 3 g / ml.
Wherein the binder comprises an acrylic resin.
Wherein the acrylic resin comprises an alkyl (meth) acrylate-based repeating unit.
The weight average molecular weight of the acrylic resin (M W) of 30,000 to 300,000 is the range of the planar heating element composition.
The glass transition temperature of the acrylic resin (T g) from 60 to 150 range of the planar heating element composition.
Wherein the solvent comprises an acetate-based solvent.
5 to 40 parts by weight of a carbon filler,
5 to 30 parts by weight of a binder, and
And a solvent remaining portion.
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