WO2012148126A2 - Plane heating element composition having specific temperature coefficient of resistance and plane heating element using same - Google Patents

Plane heating element composition having specific temperature coefficient of resistance and plane heating element using same Download PDF

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Publication number
WO2012148126A2
WO2012148126A2 PCT/KR2012/002988 KR2012002988W WO2012148126A2 WO 2012148126 A2 WO2012148126 A2 WO 2012148126A2 KR 2012002988 W KR2012002988 W KR 2012002988W WO 2012148126 A2 WO2012148126 A2 WO 2012148126A2
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Prior art keywords
heating element
planar heating
element composition
temperature
resistance
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PCT/KR2012/002988
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French (fr)
Korean (ko)
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WO2012148126A3 (en
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김병철
이고르 유리예비치쉘레호프
니콜라이 아카디예비치이바노프
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(주)피엔유에코에너지
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Publication of WO2012148126A2 publication Critical patent/WO2012148126A2/en
Publication of WO2012148126A3 publication Critical patent/WO2012148126A3/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater

Definitions

  • the present invention relates to a planar heating element composition and a method of manufacturing the planar heating element using the same, and more particularly, having a heat generating function due to the supply of power, a temperature planar heating element composition having a specific resistance temperature coefficient of the temperature control component and a planar shape using the same It relates to a method for producing a heating element.
  • planar heating element which is recently emerging, is a product which reduces power by 20 to 40% than the electric heating element that is generally used, and is expected to have a large electric energy saving and economic ripple effect.
  • the planar heating element is easy to control the temperature by using the radiant heat generated by the electric current, it does not pollute the air has advantages in terms of hygiene and noise has been used for bedding, such as heating mats and pads.
  • it is widely used for heating of floors of houses, industrial heating of offices and workplaces, heating devices in various industrial fields such as painting and drying, vinyl houses, barns, agricultural equipment, automobile back mirrors, freezing prevention devices for parking lots, cold protection equipment for leisure, home appliances, etc. It is used.
  • the planar heating element is mainly composed of a metal heating element etched a thin metal plate such as iron, nickel, chromium, platinum, and non-metal heating element such as silicon carbide, zirconium, carbon.
  • a metal heating element etched a thin metal plate such as iron, nickel, chromium, platinum, and non-metal heating element such as silicon carbide, zirconium, carbon.
  • Multilayer heating elements in the form of layered products with conductive layers on both sides insulated with insulating layers are well known. It also has a heat reflecting layer of metal or metal polymer film on one side of the surface of the heating element.
  • the conductive layer is made based on coal-fiber paper, and the insulating layers are known to be made of thermoplastic polymer film material.
  • a conductive layer of element carbon, graphite, and modified phenolformaldehyde resin is formed to form a resistance element in a manner that is infiltrated with the insulation in the insulating substrate. It is coated with an absorbent layer of epoxy or epoxyphenol or phenolformaldehyde binder to form an insulating coating and all layers are pressurized at the appropriate temperature, time and pressure.
  • the resistive element is separated together with similar resistive elements before application of a resistive coating thereon and in a separate form at 130-140 ° C. Heat-cure (cure) for 10-12 minutes per millimeter of lamination thickness.
  • planar heating element was not easy to control the temperature accurately, and even after rising to a constant boiling point temperature, the same power supply was continuously maintained at the boiling temperature, resulting in excessive energy loss. Therefore, there is a need for a technology that enables easy control of a specific temperature range while not only applying a specific electric power among the planar heating elements, but also using power efficiency.
  • the present invention is to solve the problems of the prior art, it is possible to precisely control the temperature in a specific temperature range according to the composition ratio of the material and the heat loss is less power consumption and the surface heating element having a specific resistance temperature coefficient of the temperature control component It is an object to provide a composition.
  • the resistance temperature coefficient is 560 ⁇ 10. -6 To 40 ⁇ 10 -4 It provides a planar heating element composition that is / °C.
  • planar heating element comprising a; electrode formed on the heating layer.
  • planar heating element composition according to the present invention can provide a planar heating element capable of precise temperature control in a specific temperature range according to the composition ratio of the material, and self-control of power and temperature over time to ensure stability.
  • planar heating element of the present invention can be manufactured in a form that is applied to the substrate, the structure is very simple and excellent heat generation compared to the existing heating element products, the efficiency of the heat dissipated to the surroundings is excellent.
  • Example 1 is a view showing the temperature control effect according to Example 1 and Comparative Example 1 of the present invention.
  • Figure 2 shows the results of the power test according to an embodiment of the present invention.
  • Figure 4 shows the results of the temperature change experiment according to an embodiment of the present invention.
  • the present invention is composed of (A) insulation binder component, (B) resistance component and (C) temperature control component, and the resistance temperature coefficient is 560 ⁇ 10. -6 To 40 ⁇ 10 -4 It provides a planar heating element composition that is / °C.
  • This resistance temperature coefficient represents the resistance change in the resistor material as a function of temperature. While not necessarily a linear relationship, positive values refer to materials whose resistance properties increase or decrease in proportion to rising or falling temperatures, whereas negative values refer to materials whose resistance properties change in inverse proportion to temperature changes. Point to.
  • the distance between the resistive particles will also increase, so the resistance will generally decrease.
  • the conductivity will generally increase because the distance between each particle will generally be smaller.
  • the resistance temperature coefficient is generally directly related to the coefficient of thermal expansion ('CTE') of the insulating binder.
  • 'CTE' coefficient of thermal expansion
  • Certain insulating binders not only have relatively high CTE, but can also provide other physical properties (eg, thermal, mechanical and / or chemical stability) useful for any use of the present invention.
  • the (A) insulating binder component can be used for a conventional planar heating element, for example, phenol-based, amide-based, polyester-based, epoxy-based, polyvinyl alcohol-based, polyvinyl butyral-based, polyimide And polyetherimide, polycarbonate, polysulfone, polyether, polyether ketone, urethane, rubber chloride, acrylic, vinyl chloride, nitrocellulose, and acetylcellulose.
  • fluoropolymers examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene hexafluoropropylene copolymer (FEP), tetrafluoroethylene perfluoroalkylvinylether copolymer (PFA, non-limiting examples): Tetrafluoroethylene perfluoromethylvinylether copolymer, tetrafluoroethylene perfluoroethylvinylether copolymer), tetrafluoroethyleneperfluoropropylvinylether copolymer), ethylene tetrafluoroethylene copolymer (ETFE) , Ethylene chlorotrifluoroethylene copolymer (ECTFE) and polyvinylidene fluoride (PVDF) and the like can be optionally used.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene hexafluoropropylene copolymer
  • PFA
  • the content of the insulating binder component is preferably 5 to 28% by weight, and the content of the insulating binder component is less than 5% by weight, which is not preferable because the bonding strength of the composition is lowered. It is not preferable because the composition content of the composition is small and the exothermic performance is lowered.
  • the resistive composition is preferably a mixture of nickel and aluminum.
  • one or more calibration components selected from molybdenum (Mo), boron (B), and silicon (Si) may be further included.
  • the calibration component can be said to be a stabilizer in the form of a nanostructured powder to stabilize the parameters. It is preferable that the specific surface area of such a stabilizer is 200 m ⁇ 2> / g or less. At this time, the formation time of the structure is shortened, and the content used may be 0.4 to 0.6% by weight of the composition content. At this time, stability of resistance temperature coefficient change does not change even after long-term use.
  • the content of the (B) resistance component is preferably 46 to 75% by weight.
  • the content of the resistive component is less than 46% by weight, it is not preferable to realize the exothermic performance of the heating element, and when it exceeds 75% by weight is not preferable because the stability of temperature control is lowered.
  • the content of the component for correcting this in the resistive component is preferably 1/10 to 1/100 at%.
  • Calibration here can be understood as an additive which is added in order to further improve the effect of the resistive component.
  • the resistance component determines the base level of the relative resistance and the resistance temperature coefficient, while the calibration components of the molybdenum and boron additives change the relative resistance value.
  • the change in the resistance temperature coefficient is controlled by changing the dispersion value of the particle component from 0.5 to 5.0 mu m, which is determined by the preparation time in the ball mill. It is controlled by PSK-12, an instrument that measures relative surfaces by air permeation.
  • (C) plays a role in controlling the planar heating element up to 30 ⁇ 450 °C in the state energized through the temperature control component.
  • a specific substance should be included in an appropriate amount to prevent overheating of the heating element and to contribute to proper power consumption.
  • the temperature control component is preferably at least one oxide selected from the group consisting of silicon oxide, aluminum oxide, boron oxide, barium oxide.
  • the temperature controlling component (C) may use a lead-free glass powder mixture, and may include, for example, SiO 2 -BaO-B 2 O 3 -Al 2 O 3 .
  • the content of the regulative composition is preferably 10 to 40% by weight. If the content of the temperature control component is less than 10% by weight, it is not sufficient to realize the function of adjusting to a specific temperature, and if it exceeds 40% by weight, the content of other components such as the resistance component is too small. Can not do it.
  • Temperature control components are produced in a closed space of planetary ball mills for 6 to 10 hours without the ingress of oxygen.
  • the particle diameter of the particles is preferably determined within the range of 0.1 to 1.0 ⁇ m.
  • heating elements having various resistance temperature coefficients can be obtained in a wide range of resistivity.
  • the content of lead-free glass added to the control component determines the level at which it begins to affect the general properties of the heating element, the amount of which is determined empirically for each resistive component.
  • the planar heating element composition according to the present invention is an alcoholic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, benzene, xylene, texanol, ethylene glycol, butyl carbitol, ethyl cellosolve, glycerol, dimethyl sulfoxide , N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), N, N'-dimethyl-formamide (DMF), dimethyl sulfoxide (DMSO), tetramethylurea (TMU), diethylene glycol diethyl Ether, 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), 1,2-bis- (2-methoxyethoxy) ethane (triglyme), bis [2- (2 -Methoxyethoxy) ethyl)] ether (tetraglyme), gamma-butyrol
  • planar heating element composition according to the present invention may be used by further adding a dispersant, a thickener, an accelerator, an antifoaming agent, a leveling agent, an antioxidant, and the like.
  • the dispersant may use at least one selected from the group consisting of urethane, acrylic, phosphorus, organic acid salts and inorganic acid salts.
  • the thickener is to increase the viscosity on the paste for the processability, such as coating properties in the manufacturing of the planar heating element, which is selected from the group consisting of cellulose-based, polyacrylamide-based, polyurethane-based, polysaccharide-based and copolymers thereof
  • the cellulose-based may include methyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, and the like
  • the polyacrylamide-based polyacrylamide and copolymers thereof may be exemplified.
  • the polyurethane-based may include polyurethane, polyurethane-acryl, and a combination thereof.
  • the polysaccharide-based may include biopolymers such as wellan gum and curdlan.
  • Accelerators are tributyl tin acetate (TBTA), tributyl tin oxide (TBTO), triethanol amine (TEA), triisopropanol amine (TIA), 2-amino-1-propanol (APP), 2-amino-1-propanol (APT), 2-amino-2-methyl-1-propanol (AMP), dimethyl amino pyridine (DMAP), triphenyl phosphite (TPPI), pyridine, t-butyl aminoethyl methacrylate (BM-615), Isoquinolinecarbonitrile, 1-isoquinolinecarboxylic acid, isoquinoline, 5-isoquinoline sulfonic acid, 2,4-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-hydroxyphenylacetic acid, and 2-hydroxyisoquinoline It may be selected from the group consisting of.
  • a hot plate, a heating film, a heating cable, a cooking heater, and the like can be manufactured, and in addition, various types of applications can be manufactured.
  • the planar heating element generates heat when a voltage is applied to the electrode.
  • a uniform heating temperature is distributed over the entire surface of the heating element, and resistance is constant, thereby generating a constant heating temperature. It is applicable to all industrial fields where heating element is used. In addition, it is more durable than conventional copper heating wire and carbon planar heating element.
  • planar heating element composition according to the present invention can be usefully used as a material of the heating element that generates heat by applying power.
  • the planar heating element composition according to the present invention may be prepared as a heating element of a plate-like sheet or a molded body having a three-dimensional shape, and preferably may be applied as a heating layer of the planar heating element according to the present invention described below.
  • Planar heating element according to the present invention is a substrate; An exothermic layer formed on the substrate using the planar heating element composition; And an electrode formed in the heating layer.
  • Planar heating element formed using the composition according to the invention is characterized in that the temperature is controlled to a maximum 30 ⁇ 450 °C in the energized state.
  • the heat capacity of the water supplies power similarly to the nonlinear curve. This can reduce the loss of the amount of power supplied by about 40% energy can be reduced by significantly reducing the heat loss compared to supplying the same amount of power until the water boils the conventional planar heating element products.
  • the method of manufacturing the planar heating element will be described in more detail.
  • the method of preparing a base material and the method of manufacturing the planar heating element may include: forming a paste by mixing a binder including an insulating binder, a resistance component, and a control component;
  • the paste may be applied to a substrate, and may be manufactured through a process including an electrode forming step of forming an electrode after the applying step.
  • the substrate is flexible, and may be selected from a synthetic resin film, a fiber sheet, or paper.
  • the synthetic resin film is PE (polyethylene), PP (polypropylene), PS (polystyrene), PC (polycarbonate), PA (polyamide), PET (polyethylene terephthalate), PU (polyurethane) or fluorine resin And a foamed sheet thereof (foamed PS sheet or the like).
  • the fiber sheet includes a woven fabric and a nonwoven fabric made from natural fibers or synthetic fibers.
  • various methods such as screen printing, roll, gravure, knife, spraying, and immersion coating may be used, and it is preferable to apply the paste using screen printing.
  • the electrode may be made of a single metal or alloy selected from the group consisting of aluminum, silver, gold, iron, platinum, copper, and the like, and the electrode may be attached after being cut into a strip or by being cut to a predetermined width. Can be.
  • the electrode may be laminated on the heating layer (or deposited) or included in the heating layer.
  • the composite paste After the composite paste has been applied, it is heat-treated in a conveyor furnace that emits infrared rays for 8 to 12 minutes at 130 to 160 ° C, and then for 10 to 30 minutes at 170 to 200 ° C. Then conductive paths are fabricated, which may be any of known methods, including screen printing.
  • the heating elements are then coated with a polyethylene terephthalate film and bonded to each other by thermal compression.
  • the power supply to the heating element can be made in a mechanical manner, by peeling off the protective film at the location of the conductive passage.
  • the low temperature paste composition prepared in Examples 1 to 10 was applied to polyethylene terephthalate and heat treated at 140 ° C. for 10 minutes in a conveyor furnace with infrared rays, and then heat treated at 180 ° C. for 20 minutes. Next, after the heat treatment, the electrode was brought into close contact with the screen printing method to prepare a planar heating element.
  • the AC was applied for 1 minute and the exothermic temperature was measured using the non-contact temperature.
  • Table 1 shows the temperature, specific resistance, and resistance temperature coefficient of the planar heating element using Examples 1 to 10.
  • Example 1 Heating element temperature (°C) Resistivity ( ⁇ / Square) Resistance temperature coefficient (/ °C)
  • Example 1 67 0.1 74 ⁇ 10 -5
  • Example 2 63 0.3 69 ⁇ 10 -5
  • Example 3 56 0.4 95 ⁇ 10 -5
  • Example 4 59 0.2 80 ⁇ 10 -5
  • Example 5 54 0.1 86 ⁇ 10 -5
  • Example 6 52 0.8 98 ⁇ 10 -5
  • Example 7 60 0.2 78 ⁇ 10 -5
  • Example 8 61 0.3 65 ⁇ 10 -5
  • Example 9 54 0.1 68 ⁇ 10 -5
  • Example 10 63 0.7 75 ⁇ 10 -5 Comparative Example 1 65 1.3 90 ⁇ 10 -7
  • the temperature range was changed in the range of 52 to 67 ° C., and the specific resistance was 0.09 to It was measured as 0.9 ⁇ / square and the resistance temperature coefficient was measured to be 65 ⁇ 10 ⁇ 5 to 95 ⁇ 10 ⁇ 5 .
  • Example 1 and Comparative Example 1 was carried out a self-regulation effect, power experiment, impedance, temperature control experiment, the results are shown in Figures 1 to 4.
  • 1 is a view showing the temperature control effect according to Example 1 and Comparative Example 1 of the present invention.
  • the member number 1 shows a temperature rise curve according to Comparative Example 1 without the control component added
  • the member number 2 shows a temperature rise curve according to Example 1 with the control component added. 1 shows that the planar heating element composition according to the present invention exhibits a self-regulation effect.
  • the temperature is similarly increased in Example 1 and Comparative Example 1.
  • the resistance value (impedance) increases with time, and thus the power usage decreases.
  • Comparative Example 1 the impedance is almost constant and the power consumption is almost constant. Therefore, the planar heating element according to the present invention can increase the resistance value with time to reduce the power consumption, and the power and temperature self-regulation with time is possible due to the increase of the resistance value (material characteristics). You can see that.

Abstract

Disclosed is a plane heating element composition comprising: (A) an insulating binder component; (B) a resistant component; and (C) a temperature adjusting component, the plane heating element composition having a temperature coefficient of resistance of 560×10-6-40×10-4℃. The plane heating element composition of the present invention enables an accurate temperature adjustment in a specific temperature zone according to the composition ratio of a substance, and enables an autogenous regulation of the electric power and the temperature according to the time, thus, providing a stable plane heating element. Also, the plane heating element of the present invention can be manufactured in the form of being coated on a basic material, thus being very simple in structure, and has an excellent exothermic feature and radiates less heat to the surroundings compared to a conventional heating element, thus enabling an excellent efficiency.

Description

특정한 저항온도계수를 갖는 면상발열체 조성물 및 이를 이용한 면상발열체Planar heating element composition having a specific resistance temperature coefficient and planar heating element using the same
본 발명은 면상발열체 조성물 및 이를 이용한 면상발열체의 제조방법에 관한 것으로서, 더욱 상세하게는 전원의 공급으로 인하여 발열기능을 가지며, 온도조절성분이 특정한 저항온도계수를 갖는 온도면상발열체 조성물 및 이를 이용한 면상발열체의 제조방법에 관한 것이다. The present invention relates to a planar heating element composition and a method of manufacturing the planar heating element using the same, and more particularly, having a heat generating function due to the supply of power, a temperature planar heating element composition having a specific resistance temperature coefficient of the temperature control component and a planar shape using the same It relates to a method for producing a heating element.
에너지 자원의 고갈에 따라 세계 각국은 에너지 절약 부분에 많은 투자를 하고 있다. 이러한 흐름에 맞춰 최근 부각되고 있는 면상발열체는 일반적으로 사용하고 있는 전기발열체보다 20 ~ 40%의 전력을 감소하는 제품으로 전기 에너지 절약 및 경제적 파급효과가 클 것으로 예상된다.With the depletion of energy resources, countries around the world are investing heavily in energy conservation. According to this trend, the planar heating element, which is recently emerging, is a product which reduces power by 20 to 40% than the electric heating element that is generally used, and is expected to have a large electric energy saving and economic ripple effect.
일반적으로 면상발열체는 전기통전에 의해 발생하는 복사열을 이용하고 있어 온도조절이 용이하고, 공기를 오염시키지 않아 위생과 소음 면에서 장점이 있어 히팅 매트나 패드 등의 침구류에 이용되고 왔다. 또한 주택의 바닥 난방, 사무실 및 작업장 등의 산업용 난방, 도장 건조 등 각종 산업장의 가열장치, 비닐하우스나 축사, 농업용 설비, 자동차용 백밀러, 주차장의 동결방지장치, 레저용 방한용 장비, 가전제품 등 폭넓게 이용되고 있다.In general, the planar heating element is easy to control the temperature by using the radiant heat generated by the electric current, it does not pollute the air has advantages in terms of hygiene and noise has been used for bedding, such as heating mats and pads. In addition, it is widely used for heating of floors of houses, industrial heating of offices and workplaces, heating devices in various industrial fields such as painting and drying, vinyl houses, barns, agricultural equipment, automobile back mirrors, freezing prevention devices for parking lots, cold protection equipment for leisure, home appliances, etc. It is used.
면상발열체는 특히, 최근에 그 이용이 활발하여 유럽의 주택난방의 많은 부분을 대체하고 있으며 주택분야 외에 산업용 건조기, 농산물 건조기, 건장의료 보조제품 및 건축부자재 등으로 응용이 가능한 신소재로 국내뿐만 아니라 수출주력이 가능한 제품으로 평가받고 있다.Planar heating elements have been widely used in recent years, replacing many parts of heating in Europe. In addition to the housing sector, cotton heating elements are new materials that can be applied to industrial dryers, agricultural product dryers, health care auxiliary products, and construction subsidiary materials. It is evaluated as a flagship product.
통상적으로 면상발열체는 철, 니켈, 크롬, 백금 등의 금속 박판을 에칭한 금속 발열체와 탄화규소, 지르코늄, 탄소 등의 비금속 발열체 등이 주류를 이루고 있었다. 그러나 이들은 열과 내구성이 약하고 제작이 어려운 문제점이 지적되어 왔다. In general, the planar heating element is mainly composed of a metal heating element etched a thin metal plate such as iron, nickel, chromium, platinum, and non-metal heating element such as silicon carbide, zirconium, carbon. However, they have been pointed out that the heat and durability is weak and difficult to manufacture.
양쪽이 절연층으로 절연되어 있는 전도층을 갖는 층상 제품 형태의 다층 가열요소는 잘 알려져 있다. 이것은 가열요소의 표면 중 한 면에 금속이나 금속 폴리머 필름 재질의 열반사층도 지니고 있다. 전도층은 석탄 섬유(coal-fiber) 종이에 기반하여 제작되고, 절연층들은 열가소성 폴리머 필름 재질로 된다고 알려져 있다.Multilayer heating elements in the form of layered products with conductive layers on both sides insulated with insulating layers are well known. It also has a heat reflecting layer of metal or metal polymer film on one side of the surface of the heating element. The conductive layer is made based on coal-fiber paper, and the insulating layers are known to be made of thermoplastic polymer film material.
또한 폴리머 전기가열기 제조 방법도 잘 알려져 있다. 제조 시에 절연 기판에 단열재와 함께 스며들게 하는 방식으로 저항요소(resistance element)를 형성하는 탄소(element carbon), 흑연, 변형된 페놀포름알데히드 수지로 된 전도층을 입힌다. 그 위에 에폭시 또는 에폭시페놀 또는 페놀포름알데히드 바인더를 흡수한 층을 입혀 절연 코팅을 형성하고 적합한 온도와 시간, 압력에서 모든 층들이 압력을 받도록 한다. 저항요소는 그 위에 저항 코팅을 하기 전에 유사한 저항요소들과 함께 분리하고 분리된 형태로 130 - 140℃에서 적층 두께 1 밀리미터 당 10-12분간 열처리(경화)한다. Also known are methods of making polymer electric heaters. During fabrication, a conductive layer of element carbon, graphite, and modified phenolformaldehyde resin is formed to form a resistance element in a manner that is infiltrated with the insulation in the insulating substrate. It is coated with an absorbent layer of epoxy or epoxyphenol or phenolformaldehyde binder to form an insulating coating and all layers are pressurized at the appropriate temperature, time and pressure. The resistive element is separated together with similar resistive elements before application of a resistive coating thereon and in a separate form at 130-140 ° C. Heat-cure (cure) for 10-12 minutes per millimeter of lamination thickness.
그러나 기존 면상발열체는 정확한 온도조절이 용이하지 않았고, 일정한 비등점 온도까지 상승한 이후에도 지속적으로 비등 온도에 동일한 전력공급 유지하고 있어서 에너지 손실이 과다하였다. 따라서 면상발열체 중에서도 특정한 전력을 단순히 인가하는 것이 아니라 전력사용의 효율성을 기하면서 특정한 온도범위의 조절이 용이한 기술을 필요로 하고 있다. However, the existing planar heating element was not easy to control the temperature accurately, and even after rising to a constant boiling point temperature, the same power supply was continuously maintained at the boiling temperature, resulting in excessive energy loss. Therefore, there is a need for a technology that enables easy control of a specific temperature range while not only applying a specific electric power among the planar heating elements, but also using power efficiency.
본 발명은 상기 종래 기술의 문제점을 해결하기 위한 것으로서, 물질의 조성비에 따라 특정한 온도 영역에서 정확한 온도조절이 가능하고 열손실이 적어서 전력사용량이 절감되고 온도조절 성분이 특정한 저항온도계수를 갖는 면상발열체 조성물을 제공하는 것을 목적으로 한다. The present invention is to solve the problems of the prior art, it is possible to precisely control the temperature in a specific temperature range according to the composition ratio of the material and the heat loss is less power consumption and the surface heating element having a specific resistance temperature coefficient of the temperature control component It is an object to provide a composition.
또한 상기 조성물을 이용하여 물의 비선형 곡선과 유사하게 전력을 공급하여 소모전력을 자기 제어할 수 있어 안정성이 확보된 면상발열체를 제공하는 것을 목적으로 한다. In addition, it is an object of the present invention to provide a planar heating element having a stable stability by supplying power similar to the non-linear curve of water to self-control the power consumption.
상기 목적을 달성하기 위하여 본 발명은,The present invention to achieve the above object,
(A)절연바인더 성분, (B)저항 성분, (C)온도조절 성분을 포함하는 면상발열체 조성물에서, 저항온도계수가 560×10-6 내지 40×10-4/℃ 인 면상발열체 조성물을 제공한다.In the planar heating element composition comprising (A) an insulation binder component, (B) resistance component, and (C) temperature control component, the resistance temperature coefficient is 560 × 10.-6To 40 × 10-4It provides a planar heating element composition that is / ℃.
또한 상기 다른 목적을 달성하기 위하여 본 발명은,In addition, the present invention to achieve the above other object,
기재;materials;
상기 기재 상에 상기 발열체 조성물을 이용하여 형성된 발열층; 및An exothermic layer formed on the substrate by using the exothermic composition; And
상기 발열층에 형성된 전극;을 포함하는 것을 특징으로 하는 면상발열체를 제공한다.It provides a planar heating element comprising a; electrode formed on the heating layer.
본 발명에 따른 면상발열체 조성물은, 물질의 조성비에 따라 특정한 온도 영역에서 정확한 온도조절이 가능하고, 시간에 따른 전력 및 온도의 자기제어가 가능하여 안정성이 확보된 면상발열체를 제공할 수 있다.The planar heating element composition according to the present invention can provide a planar heating element capable of precise temperature control in a specific temperature range according to the composition ratio of the material, and self-control of power and temperature over time to ensure stability.
또한 본 발명의 면상발열체는 기재에 도포하는 형태로 제조가 가능하므로 구조가 매우 간단하고 기존의 발열체 제품에 비하여 발열이 우수하고 주위로 발산되는 열의 적어 효율이 우수하다.In addition, the planar heating element of the present invention can be manufactured in a form that is applied to the substrate, the structure is very simple and excellent heat generation compared to the existing heating element products, the efficiency of the heat dissipated to the surroundings is excellent.
도 1은 본 발명의 실시예 1 및 비교예 1에 따른 온도조절효과를 나타내는 그림이다. 1 is a view showing the temperature control effect according to Example 1 and Comparative Example 1 of the present invention.
도 2는 본 발명의 일 실시예에 따른 전력실험 결과를 도시한 것이다. Figure 2 shows the results of the power test according to an embodiment of the present invention.
도 3은 본 발명의 일 실시예에 따른 임피던스 실험 결과를 도시한 것이다. 3 shows impedance test results according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 온도변화 실험 결과를 도시한 것이다. Figure 4 shows the results of the temperature change experiment according to an embodiment of the present invention.
본 발명은 (A)절연바인더 성분, (B)저항 성분, (C)온도조절 성분으로 구성되고, 저항온도계수가 560×10-6 내지 40×10-4/℃ 인 면상발열체 조성물을 제공한다. 이러한 저항온도계수는 저항기 물질에 있어서 저항 변화를 온도의 함수로서 나타낸다. 반드시 선형 관계는 아니지만, 정(+) 값은 저항 특성이 온도가 올라가거나 떨어지는 것에 정비례하여 증가하거나 감소하는 물질을 가리키고, 반대로, 부(-) 값은 저항 특성이 온도 변화에 반비례하여 변화하는 물질을 가리킨다.The present invention is composed of (A) insulation binder component, (B) resistance component and (C) temperature control component, and the resistance temperature coefficient is 560 × 10.-6To 40 × 10-4It provides a planar heating element composition that is / ℃. This resistance temperature coefficient represents the resistance change in the resistor material as a function of temperature. While not necessarily a linear relationship, positive values refer to materials whose resistance properties increase or decrease in proportion to rising or falling temperatures, whereas negative values refer to materials whose resistance properties change in inverse proportion to temperature changes. Point to.
온도조절 성분이 팽창하면(전형적으로 온도 상승으로 인해), 저항성분 입자 사이의 거리도 또한 증가할 것이므로, 저항은 일반적으로 감소할 것이다. 온도조절 성분이 수축하면, 각 입자 사이의 거리가 일반적으로 작아지게 되기 때문에 전도성은 일반적으로 증가할 것이다. As the temperature control component expands (typically due to temperature rise), the distance between the resistive particles will also increase, so the resistance will generally decrease. As the thermostatic component shrinks, the conductivity will generally increase because the distance between each particle will generally be smaller.
본 발명의 온도조절 성분에 있어서, 저항온도계수는 일반적으로 절연바인더의 열팽창계수('CTE')와 직접적인 관계가 있다. 특정 절연바인더는 비교적 높은 CTE를 가질 뿐만 아니라, 본 발명의 임의의 용도에 유용한 다른 물성(예컨대, 열적, 기계적 및(또는) 약품 안정성)을 제공할 수 있다.In the temperature control component of the present invention, the resistance temperature coefficient is generally directly related to the coefficient of thermal expansion ('CTE') of the insulating binder. Certain insulating binders not only have relatively high CTE, but can also provide other physical properties (eg, thermal, mechanical and / or chemical stability) useful for any use of the present invention.
본 발명에서 (A)절연바인더 성분은 통상의 면상 발열체에 사용되는 것을 사용할 수 있으며, 예를 들어 페놀계, 아미드계, 폴리에스테르계, 에폭시계, 폴리비닐알콜계, 폴리비닐부티랄계, 폴리이미드계, 폴리에테르이미드, 폴리카르보네이트, 폴리술폰, 폴리에테르, 폴리에테르케톤, 우레탄계, 염화고무계, 아크릴계, 염화비닐계, 니트로셀룰로스, 및 아세틸셀룰로스 등이 있다. 적합한 플루오로중합체의 예로는 폴리테트라플루오로에틸렌(PTFE), 테트라플루오로에틸렌 헥사플루오로프로필렌 공중합체(FEP), 테트라플루오로에틸렌 퍼플루오로알킬비닐에테르 공중합체(PFA, 비제한적인 예: 테트라플루오로에틸렌 퍼플루오로메틸비닐에테르 공중합체, 테트라플루오로에틸렌 퍼플루오로에틸비닐에테르 공중합체, 테트라플루오로에틸렌퍼플루오로프로필비닐에테르 공중합체), 에틸렌 테트라플루오로에틸렌 공중합체(ETFE), 에틸렌 클로로트리플루오로에틸렌 공중합체(ECTFE) 및 폴리비닐리덴 플루오라이드(PVDF) 등에서 임의로 선택되어 사용될 수 있다. 그 중에서도 폴리에스테르계 또는 에폭시계 고분자가 바람직하다. 또한, 사용되는 고분자 수지에 맞는 경화제를 선택하여 통상의 사용범위 내에서 추가로 투입하여 사용할 수 있다.In the present invention, the (A) insulating binder component can be used for a conventional planar heating element, for example, phenol-based, amide-based, polyester-based, epoxy-based, polyvinyl alcohol-based, polyvinyl butyral-based, polyimide And polyetherimide, polycarbonate, polysulfone, polyether, polyether ketone, urethane, rubber chloride, acrylic, vinyl chloride, nitrocellulose, and acetylcellulose. Examples of suitable fluoropolymers include polytetrafluoroethylene (PTFE), tetrafluoroethylene hexafluoropropylene copolymer (FEP), tetrafluoroethylene perfluoroalkylvinylether copolymer (PFA, non-limiting examples): Tetrafluoroethylene perfluoromethylvinylether copolymer, tetrafluoroethylene perfluoroethylvinylether copolymer), tetrafluoroethyleneperfluoropropylvinylether copolymer), ethylene tetrafluoroethylene copolymer (ETFE) , Ethylene chlorotrifluoroethylene copolymer (ECTFE) and polyvinylidene fluoride (PVDF) and the like can be optionally used. Especially, polyester type or an epoxy type polymer is preferable. In addition, by selecting a curing agent suitable for the polymer resin to be used can be added to use within the usual use range.
(A)절연바인더 성분의 함량은 5 내지 28 중량%인 것이 바람직하고, 함량이 5 중량% 미만인 경우에는 조성물의 결합력이 저하되기 때문에 바람직하지 못하고, 28 중량%를 초과하는 경우에는 저항 성분 등 기타 조성물의 성분 함량이 적어서 발열성능이 저하되기 때문에 바람직하지 못하다.(A) The content of the insulating binder component is preferably 5 to 28% by weight, and the content of the insulating binder component is less than 5% by weight, which is not preferable because the bonding strength of the composition is lowered. It is not preferable because the composition content of the composition is small and the exothermic performance is lowered.
(B)저항 성분(resistive composition)은 니켈과 알루미늄의 혼합물인 것이 바람직하다. 저항 성분에 상대저항값을 변화시키기 위하여 몰리브덴(Mo), 보론(B), 규소(Si) 중에서 선택된 하나 이상의 교정 성분들이 추가로 포함되는 것이 바람직하다. 교정 성분은 파라메터를 안정화시키기 위하여 나노 구조의 분말 형태의 안정화물이라고 할 수 있다. 이러한 안정화물의 비표면적은 200 m2/g 이하인 것이 바람직하다. 이때 구조(structure)의 형성 시간이 단축되며, 사용되는 함량은 조성물 함량의 0.4 ~ 0.6 중량%가 첨가될 수 있다. 이때 저항온도계수 변화의 안정성은 장기간 사용하여도 변화하지 않는다.(B) The resistive composition is preferably a mixture of nickel and aluminum. In order to change the relative resistance value in the resistance component, one or more calibration components selected from molybdenum (Mo), boron (B), and silicon (Si) may be further included. The calibration component can be said to be a stabilizer in the form of a nanostructured powder to stabilize the parameters. It is preferable that the specific surface area of such a stabilizer is 200 m <2> / g or less. At this time, the formation time of the structure is shortened, and the content used may be 0.4 to 0.6% by weight of the composition content. At this time, stability of resistance temperature coefficient change does not change even after long-term use.
(B)저항 성분의 함량은 46 내지 75 중량%인 것이 바람직하다. 저항 성분의 함량이 46 중량% 미만인 경우에는 발열체의 발열 성능을 구현하기에 미흡하기에 바람직하지 못하고, 75 중량%를 초과하는 경우에는 온도조절의 안정성이 저하되기 때문에 바람직하지 못하다.The content of the (B) resistance component is preferably 46 to 75% by weight. When the content of the resistive component is less than 46% by weight, it is not preferable to realize the exothermic performance of the heating element, and when it exceeds 75% by weight is not preferable because the stability of temperature control is lowered.
저항 성분에서 이를 교정하기 위한 성분의 함량은 1/10 ~ 1/100 at%인 것이 바람직하다. 여기서 교정이라는 것은 저항 성분의 효과를 더욱 개선하기 위하여 추가로 첨가되는 첨가제로 이해되어질 수 있다.The content of the component for correcting this in the resistive component is preferably 1/10 to 1/100 at%. Calibration here can be understood as an additive which is added in order to further improve the effect of the resistive component.
저항 성분은 상대 저항의 기본 수준과 저항온도계수를 결정하고 몰리브덴과 보론 첨가물의 교정 성분들은 상대 저항값을 변경시킨다. 저항온도계수의 변화는 입자 성분의 분산값이 0.5 ~ 5.0㎛로 변화함으로써 조절되는데, 그러한 변화는 보올밀(ball mill)에서의 준비 시간에 의해 결정된다. 공기투과법으로 상대표면을 측정하는 기기인 PSK-12에 의해 제어된다. The resistance component determines the base level of the relative resistance and the resistance temperature coefficient, while the calibration components of the molybdenum and boron additives change the relative resistance value. The change in the resistance temperature coefficient is controlled by changing the dispersion value of the particle component from 0.5 to 5.0 mu m, which is determined by the preparation time in the ball mill. It is controlled by PSK-12, an instrument that measures relative surfaces by air permeation.
본 발명에서는 (C)온도조절 성분을 통하여 통전된 상태에서 면상발열체가 최대 30 ~ 450℃로 조절되는 데에 역할을 담당한다. 온도조절 성분으로서 특정한 물질이 적절한 함량으로 포함되어야 발열체의 과열을 방지하고, 적절한 전력을 소모하는데 기여하는 것이다. 구체적으로 (C)온도조절 성분은 산화규소, 산화알루미늄, 산화붕소, 산화바륨으로 이루어진 군으로부터 선택된 하나 이상의 산화물인 것이 바람직하다. (C)온도조절 성분은 무연 유리 분말 혼합물을 사용할 수 있고, 예를 들어, SiO2-BaO-B2O3-Al2O3를 포함할 수 있다. In the present invention (C) plays a role in controlling the planar heating element up to 30 ~ 450 ℃ in the state energized through the temperature control component. As a temperature control component, a specific substance should be included in an appropriate amount to prevent overheating of the heating element and to contribute to proper power consumption. Specifically, (C) the temperature control component is preferably at least one oxide selected from the group consisting of silicon oxide, aluminum oxide, boron oxide, barium oxide. The temperature controlling component (C) may use a lead-free glass powder mixture, and may include, for example, SiO 2 -BaO-B 2 O 3 -Al 2 O 3 .
(C)온도조절(regulative composition) 성분의 함량은 10 내지 40 중량%인 것이 바람직하다. 온도조절 성분의 함량이 10 중량% 미만인 경우에는 특정 온도로 조절하는 기능을 실현하기에 부족하기에 바람직하지 못하고, 40 중량%를 초과하는 경우에는 저항 성분 등 기타 성분들의 함량이 너무 적게 되어 바람직하지 못하다.(C) The content of the regulative composition is preferably 10 to 40% by weight. If the content of the temperature control component is less than 10% by weight, it is not sufficient to realize the function of adjusting to a specific temperature, and if it exceeds 40% by weight, the content of other components such as the resistance component is too small. Can not do it.
(C)온도조절 성분은 산소의 유입없이 6 ~ 10 시간 동안 유성형 볼 밀의 폐쇄공간에서 제작된다. 입자의 입경은 0.1 ~ 1.0㎛ 범위 내에서 정해지는 것이 바람직하다. (C) Temperature control components are produced in a closed space of planetary ball mills for 6 to 10 hours without the ingress of oxygen. The particle diameter of the particles is preferably determined within the range of 0.1 to 1.0 μm.
나머지 각 성분들의 비율 대비 전체 조성물의 중량%를 변경하는 방식으로 광범위한 비저항 범위에서 다양한 저항온도계수를 갖는 가열요소들을 얻을 수 있다. By varying the weight percent of the total composition relative to the proportions of the remaining components, heating elements having various resistance temperature coefficients can be obtained in a wide range of resistivity.
조절성분에 첨가되는 납성분이 없는 유리(lead-free glass)의 함량은 가열 요소의 일반적인 특성에 영향을 미치기 시작하는 수준을 결정하는데, 그 양은 각각의 저항성분에 대하여 경험적인 방법으로 결정된다. The content of lead-free glass added to the control component determines the level at which it begins to affect the general properties of the heating element, the amount of which is determined empirically for each resistive component.
본 발명에 따른 면상발열체 조성물은 유기용제로서 메틸알콜, 에틸알콜, 이소프로필알콜, 부탄올 등의 알콜류, 벤젠, 크실렌, 텍사놀, 에틸렌글리콜, 부틸카비톨, 에틸셀로솔브, 글리세롤, 디메틸술폭시드, N-메틸피롤리돈(NMP), 디메틸아세트아미드(DMAc), N,N'-디메틸-포름아미드(DMF), 디메틸 술폭사이드(DMSO), 테트라메틸우레아(TMU), 디에틸렌글리콜 디에틸 에테르, 1,2-디메톡시에탄(모노글림), 디에틸렌 글리콜 디메틸 에테르(디글림), 1,2-비스-(2-메톡시에톡시) 에탄(트리글림), 비스[2-(2-메톡시에톡시)에틸)]에테르(테트라글림), 감마-부티로락톤, 및 비스-(2-메톡시에틸) 에테르, 테트라히드로푸란 등으로부터 선택된 단독 또는 2종 이상을 혼합하여 사용할 수 있다. 또한, 이러한 유기용제 대신에 수성(물)을 용제로 사용할 수 있다.The planar heating element composition according to the present invention is an alcoholic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, benzene, xylene, texanol, ethylene glycol, butyl carbitol, ethyl cellosolve, glycerol, dimethyl sulfoxide , N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), N, N'-dimethyl-formamide (DMF), dimethyl sulfoxide (DMSO), tetramethylurea (TMU), diethylene glycol diethyl Ether, 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), 1,2-bis- (2-methoxyethoxy) ethane (triglyme), bis [2- (2 -Methoxyethoxy) ethyl)] ether (tetraglyme), gamma-butyrolactone, bis- (2-methoxyethyl) ether, tetrahydrofuran, or the like, or a mixture of two or more thereof can be used. . In addition, aqueous (water) may be used as the solvent instead of the organic solvent.
본 발명에 따른 면상발열체 조성물은 분산제, 증점제, 가속제, 소포제, 레벨링제, 산화방지제 등을 더 첨가하여 사용할 수 있다.The planar heating element composition according to the present invention may be used by further adding a dispersant, a thickener, an accelerator, an antifoaming agent, a leveling agent, an antioxidant, and the like.
분산제는 우레탄계, 아크릴계, 인계, 유기산염계 및 무기산염계로 이루어진 군 중에서 선택된 하나 이상을 사용할 수 있다.The dispersant may use at least one selected from the group consisting of urethane, acrylic, phosphorus, organic acid salts and inorganic acid salts.
증점제는 페이스트 상에서의 점도를 증가시켜 면상발열체의 제조 시 코팅성 등의 가공성을 위한 것으로, 이는 셀룰로즈계, 폴리아크릴아미드계, 폴리우레탄계, 폴리사카라이드계 및 이들의 공중합체로 이루어진 군중에서 선택된 하나 이상을 사용할 수 있다. 이때, 상기 셀룰로즈계로는 메틸 셀룰로즈, 하이드록시 에틸셀룰로즈, 하이드록시 프로필셀룰로즈 등을 예로 들 수 있으며, 상기 폴리아크릴아미드계로는 폴리아크릴아미드 및 이의 공중합체 등을 예로 들 수 있다. 또한 상기 폴리우레탄계로는 폴리우레탄, 폴리우레탄-아크릴 및 이들의 공합체 등을 예로 들 수 있으며, 상기 폴리사카라이드계는 웰란검, 커들란 등의 바이오 고분자 등을 예로 들 수 있다.The thickener is to increase the viscosity on the paste for the processability, such as coating properties in the manufacturing of the planar heating element, which is selected from the group consisting of cellulose-based, polyacrylamide-based, polyurethane-based, polysaccharide-based and copolymers thereof The above can be used. In this case, the cellulose-based may include methyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, and the like, and the polyacrylamide-based polyacrylamide and copolymers thereof may be exemplified. In addition, the polyurethane-based may include polyurethane, polyurethane-acryl, and a combination thereof. Examples of the polysaccharide-based may include biopolymers such as wellan gum and curdlan.
가속제는 트리부틸 주석 아세테이트(TBTA), 트리부틸 주석 옥사이드(TBTO), 트리에탄올 아민(TEA), 트리이소프로판올 아민(TIA), 2-아미노-1-프로판올(APP), 2-아미노-1-프로판올(APT), 2-아미노-2-메틸-1-프로판올(AMP), 디메틸 아미노 피리딘(DMAP), 트리페닐 포스파이트(TPPI), 피리딘, t-부틸 아미노에틸 메타크릴레이트(BM-615), 이소퀴놀린카르보니트릴, 1-이소퀴놀린카르복실산, 이소퀴놀린, 5-이소퀴놀린술폰산, 2,4-히드록시벤조산, 4-히드록시벤조산, 4-히드록시페닐아세트산, 및 2-히드록시이소퀴놀린로 이루어진 군에서 선택될 수 있다. Accelerators are tributyl tin acetate (TBTA), tributyl tin oxide (TBTO), triethanol amine (TEA), triisopropanol amine (TIA), 2-amino-1-propanol (APP), 2-amino-1-propanol (APT), 2-amino-2-methyl-1-propanol (AMP), dimethyl amino pyridine (DMAP), triphenyl phosphite (TPPI), pyridine, t-butyl aminoethyl methacrylate (BM-615), Isoquinolinecarbonitrile, 1-isoquinolinecarboxylic acid, isoquinoline, 5-isoquinoline sulfonic acid, 2,4-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-hydroxyphenylacetic acid, and 2-hydroxyisoquinoline It may be selected from the group consisting of.
본 발명의 고온용 발열체 조성물로는 핫 플레이트, 난방 필름, 히팅 케이블, 취사용 가열기구 등을 제조할 수 있으며, 그 이외에도 다양한 형태의 응용품을 제조할 수 있다.As the high temperature heating element composition of the present invention, a hot plate, a heating film, a heating cable, a cooking heater, and the like can be manufactured, and in addition, various types of applications can be manufactured.
면상발열체는 전극에 전압을 걸어주게 되면 열이 발생하게 되는데, 본 발명에서는 발열체 전면에 걸쳐 균일한 발열온도 분포를 보임과 동시에 저항이 일정하여 발열온도가 일정하게 된다. 발열체가 사용되는 전 산업분야에 적용이 가능하다. 또한 기존의 구리 열선 및 탄소 면상발열체 대비 내구성이 뛰어나다. The planar heating element generates heat when a voltage is applied to the electrode. In the present invention, a uniform heating temperature is distributed over the entire surface of the heating element, and resistance is constant, thereby generating a constant heating temperature. It is applicable to all industrial fields where heating element is used. In addition, it is more durable than conventional copper heating wire and carbon planar heating element.
본 발명에 따른 면상발열체 조성물은 전원 인가에 의해 열을 발생시키는 발열체의 재료로 유용하게 사용될 수 있다. 본 발명에 따른 면상발열체 조성물은 판상의 시트나 입체적 형상을 가지는 성형체의 발열체로 제조될 수 있으며, 바람직하게는 이하에서 설명되는 본 발명에 따른 면상발열체의 발열층으로 적용될 수 있다.The planar heating element composition according to the present invention can be usefully used as a material of the heating element that generates heat by applying power. The planar heating element composition according to the present invention may be prepared as a heating element of a plate-like sheet or a molded body having a three-dimensional shape, and preferably may be applied as a heating layer of the planar heating element according to the present invention described below.
본 발명에 따른 면상발열체는 기재; 상기 기재 상에 상기 면상발열체 조성물을 이용하여 형성된 발열층; 및 상기 발열층에 형성된 전극;을 포함한다. 본 발명에 따른 상기 조성물을 이용하여 형성된 면상발열체는 통전된 상태에서 최대 30 ~ 450℃로 온도조절되는 것이 특징이다. 상기 면상발열체에 전압을 인가하는 경우 물의 Heat Capacity가 비선형 곡선과 유사하게 전력을 공급한다. 이는 종래의 면상발열체 제품이 물이 끓을 때까지 동일한 전력량을 공급하는 것에 비하여 열손실을 상당 부분 줄임으로써 공급되는 전력량의 손실을 감소시킬 수 약 40% 정도의 에너지를 절약할 수 있다.Planar heating element according to the present invention is a substrate; An exothermic layer formed on the substrate using the planar heating element composition; And an electrode formed in the heating layer. Planar heating element formed using the composition according to the invention is characterized in that the temperature is controlled to a maximum 30 ~ 450 ℃ in the energized state. When a voltage is applied to the planar heating element, the heat capacity of the water supplies power similarly to the nonlinear curve. This can reduce the loss of the amount of power supplied by about 40% energy can be reduced by significantly reducing the heat loss compared to supplying the same amount of power until the water boils the conventional planar heating element products.
면상발열체의 제조방법을 보다 상세하게 설명하면, 기재를 준비하는 단계와, 면상발열체를 제조하는 방법은 용제에 절연성바인더, 저항 성분, 조절성분을 포함하는 바인더를 혼합하여 페이스트를 형성하는 단계와, 상기 페이스트를 기재에 도포하는 단계와, 도포단계 이후에 전극을 형성시키는 전극형성단계를 포함하는 공정을 통하여 제조될 수 있다.The method of manufacturing the planar heating element will be described in more detail. The method of preparing a base material and the method of manufacturing the planar heating element may include: forming a paste by mixing a binder including an insulating binder, a resistance component, and a control component; The paste may be applied to a substrate, and may be manufactured through a process including an electrode forming step of forming an electrode after the applying step.
상기 기재는 유연성을 갖는 것으로서, 합성수지 필름, 섬유시트 또는 종이로부터 선택될 수 있다. 이때, 상기 합성수지 필름은 PE(폴리에틸렌), PP(폴리프로필렌), PS(폴리스티렌), PC(폴리카보네이트), PA(폴리아미드), PET(폴리에틸렌테레프탈레이트), PU(폴리우레탄) 또는 불소 수지 등으로의 구성된 필름 및 이들의 발포 시트 (발포 PS 시트 등)를 예로 들 수 있다. 또한, 상기 섬유시트는 천연섬유나 합성섬유로부터 제조된 직포 및 부직포를 포함한다.The substrate is flexible, and may be selected from a synthetic resin film, a fiber sheet, or paper. In this case, the synthetic resin film is PE (polyethylene), PP (polypropylene), PS (polystyrene), PC (polycarbonate), PA (polyamide), PET (polyethylene terephthalate), PU (polyurethane) or fluorine resin And a foamed sheet thereof (foamed PS sheet or the like). In addition, the fiber sheet includes a woven fabric and a nonwoven fabric made from natural fibers or synthetic fibers.
상기 페이스트를 기재 상에 도포함에 있어서, 스크린 프린팅, 롤, 그라비아, 나이프, 분사, 침지코팅방식 등 다양한 방법을 이용할 수 있고 스크린 프린팅 방식을 이용하여 도포하는 것이 바람직하다.In applying the paste onto the substrate, various methods such as screen printing, roll, gravure, knife, spraying, and immersion coating may be used, and it is preferable to apply the paste using screen printing.
또한, 상기 전극은 알루미늄, 은, 금, 철, 백금, 및 구리 등으로 이루어진 군중에서 선택된 단일 금속 또는 합금을 이루어질 수 있으며, 이러한 전극은 띠 형상으로 증착에 의하거나 소정의 폭으로 절단된 후 부착될 수 있다. 또한, 상기 전극은 발열층 상에 적층 부착(또는 증착)되거나, 발열층에 포함될 수 있다. In addition, the electrode may be made of a single metal or alloy selected from the group consisting of aluminum, silver, gold, iron, platinum, copper, and the like, and the electrode may be attached after being cut into a strip or by being cut to a predetermined width. Can be. In addition, the electrode may be laminated on the heating layer (or deposited) or included in the heating layer.
복합 페이스트는 발려진 후 130 ~ 160 ℃에서 8 ~ 12분 동안 적외선 광선이 나오는 컨베이서 용광로(conveyer furnace)에서 열처리되고, 그 후 170 ~ 200 ℃에서 10-30분간 열처리된다. 그 다음 전도 통로(pathes)가 제작되는데, 스크린 프린팅을 비롯하여 알려져 있는 방법 중 어떠한 것을 사용하여도 된다. 그 후 가열요소는 폴리에틸렌테레프탈레이트(polyethylene terephthalate) 필름으로 코팅되고 열 압축법으로 서로 결합된다. 가열요소에 대한 전원공급은 기계적인 방식, 전도 통로가 있는 위치에서 보호 필름을 박리하는 방식으로 이루어질 수 있다. After the composite paste has been applied, it is heat-treated in a conveyor furnace that emits infrared rays for 8 to 12 minutes at 130 to 160 ° C, and then for 10 to 30 minutes at 170 to 200 ° C. Then conductive paths are fabricated, which may be any of known methods, including screen printing. The heating elements are then coated with a polyethylene terephthalate film and bonded to each other by thermal compression. The power supply to the heating element can be made in a mechanical manner, by peeling off the protective film at the location of the conductive passage.
이하 본 발명을 하기 실시예를 통하여 보다 상세하게 설명하기로 하나, 이는 본 발명의 이해를 돕기 위하여 제시된 것일 뿐, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention, but the present invention is not limited thereto.
실시예Example
<면상발열체 조성물의 제조><Production of Planar Heating Element Composition>
실시예 1Example 1
에폭시 페놀 래커 수지 18g, 니켈-알루미늄(Ni-53%, Al-47%) 62g, SiO2-BaO-B2O3-Al2O3 20g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18 g of epoxy phenolic lacquer resin, 62 g of nickel-aluminum (Ni-53%, Al-47%), and 20 g of SiO 2 -BaO-B 2 O 3 -Al 2 O 3 were dispersed in 200 g of ethanol, premixed and stirred at high speed. To prepare a low-temperature planar heating element paste composition.
실시예 2Example 2
에폭시 페놀 래커 수지 14g, 니켈-알루미늄(Ni-53%, Al-47%) 62g, SiO2-BaO-B2O3-Al2O3 24g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.14 g of epoxy phenolic lacquer resin, 62 g of nickel-aluminum (Ni-53%, Al-47%), and 24 g of SiO 2 -BaO-B 2 O 3 -Al 2 O 3 were dispersed in 200 g of ethanol, premixed and stirred at high speed. To prepare a low temperature planar heating element paste composition.
실시예 3Example 3
에폭시 페놀 래커 수지 28g, 니켈-알루미늄(Ni-53%, Al-47%) 52g, SiO2-BaO-B2O3-Al2O3 20g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.28 g of epoxy phenolic lacquer resin, 52 g of nickel-aluminum (Ni-53%, Al-47%), and 20 g of SiO 2 -BaO-B 2 O 3 -Al 2 O 3 were dispersed in 200 g of ethanol, followed by premixing and stirring at high speed. To prepare a low temperature planar heating element paste composition.
실시예 4Example 4
에폭시 페놀 래커 수지 22g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 60g, SiO2-BaO-B2O3-Al2O3 18g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.Epoxy phenolic lacquer resin 22g, NiAl [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%) 60g, SiO 2 -BaO-B 18 g of 2 O 3 -Al 2 O 3 was dispersed in 200 g of ethanol, premixed, and stirred at a high speed to prepare a low-temperature planar heating paste composition.
실시예 5Example 5
에폭시 페놀 래커 수지 28g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 46g, SiO2-BaO-B2O3-Al2O3 26g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.Epoxy phenolic lacquer resin 28g, NiAl [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%) 46g, SiO 2 -BaO-B 26 g of 2 O 3 -Al 2 O 3 was dispersed in 200 g of ethanol, premixed, and stirred at a high speed to prepare a low-temperature planar heating paste composition.
실시예 6Example 6
에폭시 페놀 래커 수지 18g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 46g, SiO2-BaO-B2O3-Al2O3 36g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18g epoxy phenolic lacquer resin, 46g NiNi [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%), SiO 2 -BaO-B 36 g of 2 O 3 -Al 2 O 3 was dispersed in 200 g of ethanol, premixed, and stirred at a high speed to prepare a low-temperature planar heating paste composition.
실시예 7Example 7
에폭시 페놀 래커 수지 18g, 니켈-알루미늄(Ni-53%, Al-47%) 52g, SiO2-BaO-B2O3-Al2O3 20g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18 g of epoxy phenolic lacquer resin, 52 g of nickel-aluminum (Ni-53%, Al-47%), and 20 g of SiO 2 -BaO-B 2 O 3 -Al 2 O 3 were dispersed in 200 g of ethanol, premixed and stirred at high speed. To prepare a low-temperature planar heating element paste composition.
실시예 8Example 8
에폭시 페놀 래커 수지 18g, 니켈-알루미늄(Ni-53%, Al-47%) 62g, SiO2-BaO-B2O3-Al2O3 20g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18 g of epoxy phenolic lacquer resin, 62 g of nickel-aluminum (Ni-53%, Al-47%), and 20 g of SiO 2 -BaO-B 2 O 3 -Al 2 O 3 were dispersed in 200 g of ethanol, premixed and stirred at high speed. To prepare a low-temperature planar heating element paste composition.
실시예 9Example 9
에폭시 페놀 래커 수지 18g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 46g, SiO2-BaO-B2O3-Al2O3 36g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18g epoxy phenolic lacquer resin, 46g NiNi [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%), SiO 2 -BaO-B 36 g of 2 O 3 -Al 2 O 3 was dispersed in 200 g of ethanol, premixed, and stirred at a high speed to prepare a low-temperature planar heating paste composition.
실시예 10Example 10
에폭시 페놀 래커 수지 18g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 62g, SiO2-BaO-B2O3-Al2O3 20g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 저온용 면상발열체 페이스트 조성물을 제조하였다.18g epoxy phenolic lacquer resin, NiAl [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%) 62g, SiO 2 -BaO-B 20 g of 2 O 3 -Al 2 O 3 was dispersed in 200 g of ethanol, premixed, and stirred at a high speed to prepare a planar heating element paste composition for low temperature.
비교예 1Comparative Example 1
에폭시 페놀 래커 수지 27g, NiAl[(Ni-53%, Al-47%)(45wt%)]-B(5wt%)-Mo(30wt%)-Si(20wt%) 73 g를 에탄올 200g에 분산하고 프리 믹싱한 후 고속으로 교반하여 면상발열체 페이스트 조성물을 제조하였다.27 g of epoxy phenolic lacquer resin and 73 g of NiAl [(Ni-53%, Al-47%) (45wt%)]-B (5wt%)-Mo (30wt%)-Si (20wt%) were dispersed in 200g of ethanol After premixing, the mixture was stirred at a high speed to prepare a planar heating element paste composition.
<면상발열체의 제조><Production of Planar Heating Element>
실시예 1 내지 10에서 제조된 저온용 페이스트 조성물을 폴리에틸렌테레프탈레이트에 도포하고 적외선 광선이 나오는 컨베이어 용광로에서 140℃에서 10 분 동안 열처리하고 그 후 180℃에서 20분간 열처리하였다. 다음으로 열처리 이후 스크린 프린팅 방법을 이용하여 전극을 밀착시키고 면상발열체를 제조하였다. The low temperature paste composition prepared in Examples 1 to 10 was applied to polyethylene terephthalate and heat treated at 140 ° C. for 10 minutes in a conveyor furnace with infrared rays, and then heat treated at 180 ° C. for 20 minutes. Next, after the heat treatment, the electrode was brought into close contact with the screen printing method to prepare a planar heating element.
<평가 및 결과><Evaluation and result>
제조된 면상발열체에 대하여 양 전극간 저항을 측정한 후 AC를 1분간 인가하여 발열온도를 비접촉시 온도를 이용하여 측정하였다.After measuring the resistance between the two electrodes for the planar heating element, the AC was applied for 1 minute and the exothermic temperature was measured using the non-contact temperature.
경화된 실시예 1 내지 10의 시료를 손더스 앤 어쏘시에이션 인코포레이티드(Saunders amp; Assoc. Inc.)의 저항온도계수 시험 챔버 모델 4210A에 넣었다. 다중주파수 LCR 미터, HP 모델-4274를 저항온도계수 챔버에 연결하였다. 4-프로브 키이쓸리(Keithley) 미터 모델-2400을 사용하여 저항을 측정하였다. Cured samples of Examples 1-10 were placed in a resistance temperature coefficient test chamber model 4210A from Saunders &amp; Assoc. Inc. A multi-frequency LCR meter, HP Model-4274, was connected to the resistance temperature coefficient chamber. Resistance was measured using a four-probe Keithley meter model-2400.
실시예 1 내지 10을 이용한 면상발열체의 온도, 비저항 및 저항온도계수를 표 1에 나타내었다. Table 1 shows the temperature, specific resistance, and resistance temperature coefficient of the planar heating element using Examples 1 to 10.
표 1
발열체 온도(℃) 비저항(Ω/스퀘어) 저항온도계수(/℃)
실시예 1 67 0.1 74×10-5
실시예 2 63 0.3 69×10-5
실시예 3 56 0.4 95×10-5
실시예 4 59 0.2 80×10-5
실시예 5 54 0.1 86×10-5
실시예 6 52 0.8 98×10-5
실시예 7 60 0.2 78×10-5
실시예 8 61 0.3 65×10-5
실시예 9 54 0.1 68×10-5
실시예 10 63 0.7 75×10-5
비교예 1 65 1.3 90×10-7
Table 1
Heating element temperature (℃) Resistivity (Ω / Square) Resistance temperature coefficient (/ ℃)
Example 1 67 0.1 74 × 10 -5
Example 2 63 0.3 69 × 10 -5
Example 3 56 0.4 95 × 10 -5
Example 4 59 0.2 80 × 10 -5
Example 5 54 0.1 86 × 10 -5
Example 6 52 0.8 98 × 10 -5
Example 7 60 0.2 78 × 10 -5
Example 8 61 0.3 65 × 10 -5
Example 9 54 0.1 68 × 10 -5
Example 10 63 0.7 75 × 10 -5
Comparative Example 1 65 1.3 90 × 10 -7
표 1을 참조하면, 본 발명의 실시예 1 내지 10에 따른 저온용 면상발열체 조성물로 제조한 면상발열체의 경우 전압을 인가한 경우 온도범위가 52 ~ 67℃의 범위에서 변경되었으며, 비저항은 0.09 ~ 0.9 Ω/스퀘어로 측정되었으며, 저항온도계수는 65×10-5 내지 95×10-5인 것으로 측정되었다.Referring to Table 1, in the case of the planar heating element manufactured from the planar heating element composition for low temperature according to Examples 1 to 10 of the present invention, when the voltage was applied, the temperature range was changed in the range of 52 to 67 ° C., and the specific resistance was 0.09 to It was measured as 0.9 Ω / square and the resistance temperature coefficient was measured to be 65 × 10 −5 to 95 × 10 −5 .
또한 실시예 1 및 비교예 1에 대하여 자가조절 효과, 전력실험, 임피던스, 온도제어 실험을 실시하였고, 결과를 도 1 내지 4에 도시하였다. 도 1은 본 발명의 실시예 1 및 비교예 1에 따른 온도조절효과를 나타내는 그림이다. 도 1을 참고하면 부재번호 1은 조절성분을 첨가하지 않은 비교예 1에 따른 온도상승 곡선을 나타내고, 부재번호 2는 조절성분을 첨가한 실시예 1에 따른 온도상승 곡선을 나타낸다. 도 1은 본 발명에 따른 면상발열체 조성물이 자가제어(Self-Regulation) 효과를 나타낸다는 것을 표시하고 있다. In addition, Example 1 and Comparative Example 1 was carried out a self-regulation effect, power experiment, impedance, temperature control experiment, the results are shown in Figures 1 to 4. 1 is a view showing the temperature control effect according to Example 1 and Comparative Example 1 of the present invention. Referring to Figure 1, the member number 1 shows a temperature rise curve according to Comparative Example 1 without the control component added, the member number 2 shows a temperature rise curve according to Example 1 with the control component added. 1 shows that the planar heating element composition according to the present invention exhibits a self-regulation effect.
도 2 내지 도 4를 참조하면, 온도는 실시예 1과 비교예 1이 유사하게 증가하고 있다. 그러나 실시예 1은 시간에 따라 저항값(임피던스)이 증가하여 전력사용량이 감소하는 것을 확인할 수 있고, 비교예 1은 임피던스도 거의 일정하게 나타나고 전력사용량도 거의 일정하게 나타난다. 따라서 본 발명에 따른 면상발열체는 시간에 따라 저항값이 증가하여 전력사용량을 감소시킬 수 있고, 저항값의 증가(물질 특성)로 인하여 시간에 따른 전력 및 온도 자기제어(Self-Regulation)이 가능하다는 것을 확인할 수 있다. 2 to 4, the temperature is similarly increased in Example 1 and Comparative Example 1. However, in Example 1, the resistance value (impedance) increases with time, and thus the power usage decreases. In Comparative Example 1, the impedance is almost constant and the power consumption is almost constant. Therefore, the planar heating element according to the present invention can increase the resistance value with time to reduce the power consumption, and the power and temperature self-regulation with time is possible due to the increase of the resistance value (material characteristics). You can see that.

Claims (12)

  1. (A)절연바인더 성분, (B)저항 성분, (C)온도조절 성분를 포함하는 면상발열체 조성물에서, In the planar heating element composition comprising (A) an insulating binder component, (B) a resistance component and (C) a temperature control component,
    저항온도계수가 560×10-6 내지 40×10-4/℃ 인 것을 특징으로 하는 면상발열체 조성물.Resistance temperature coefficient 560 × 10-6To 40 × 10-4Planar heating element composition, characterized in that / / ℃.
  2. 제1항에 있어서,The method of claim 1,
    상기 (A)절연바인더 성분은 폴리에스테르계 또는 에폭시 페놀 래커 수지계 재료인 것을 특징으로 하는 면상발열체 조성물.The planar heating element composition (A) wherein the insulating binder component is a polyester or epoxy phenol lacquer resin material.
  3. 제1항에 있어서,The method of claim 1,
    상기 (B)저항 성분은 니켈과 알루미늄의 혼합물인 것을 특징으로 하는 면상발열체 조성물.The (B) resistance component is a planar heating element composition, characterized in that the mixture of nickel and aluminum.
  4. 제3항에 있어서,The method of claim 3,
    상기 (B)저항 성분에 상대저항값을 변화시키기 위하여 몰리브덴(Mo), 보론(B), 규소(Si) 중에서 선택된 하나 이상의 교정 성분들이 추가로 포함되는 것을 특징으로 하는 면상발열체 조성물. The planar heating element composition further comprises one or more calibration components selected from molybdenum (Mo), boron (B), silicon (Si) to change the relative resistance value to the (B) resistance component.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 교정 성분의 함량은 1/10 ~ 1/100 at%인 것을 특징으로 하는 면상발열체 조성물.The content of the calibration component is a planar heating element, characterized in that 1/10 ~ 1/100 at%.
  6. 제3항에 있어서,The method of claim 3,
    상기 혼합물의 평균 분산값이 0.5 ~ 5.0㎛인 것을 특징으로 하는 면상발열체 조성물.Planar heating element composition, characterized in that the average dispersion value of the mixture is 0.5 ~ 5.0㎛.
  7. 제4항에 있어서,The method of claim 4, wherein
    상기 규소의 비표면적이 200 m2/g 이하인 것을 특징으로 하는 면상발열체 조성물.The planar heating element composition, characterized in that the specific surface area of the silicon is 200 m 2 / g or less.
  8. 제1항에 있어서,The method of claim 1,
    상기 (C)온도조절 성분은 산화규소, 산화알루미늄, 산화붕소, 산화바륨으로 이루어진 군으로부터 선택된 하나 이상의 산화물인 것을 특징으로 하는 면상발열체 조성물.The (C) temperature control component is a planar heating element, characterized in that at least one oxide selected from the group consisting of silicon oxide, aluminum oxide, boron oxide, barium oxide.
  9. 기재;materials;
    상기 기재 상에 제1항 내지 제8항 중 어느 하나의 항에 따른 고온용 발열체 조성물을 이용하여 형성된 발열층; 및A heat generating layer formed on the substrate using the high temperature heating element composition according to any one of claims 1 to 8; And
    상기 발열층에 형성된 전극;을 포함하는 것을 특징으로 하는 면상발열체.Planar heating element comprising a; electrode formed on the heating layer.
  10. 제1항 내지 제8항 중 어느 한 항에 따른 면상발열체 조성물을 적용한 핫 플레이트.A hot plate to which the planar heating element composition according to any one of claims 1 to 8 is applied.
  11. 제1항 내지 제8항 중 어느 한 항에 따른 면상발열체 조성물을 적용한 난방 필름.A heating film to which the planar heating element composition according to any one of claims 1 to 8 is applied.
  12. 제1항 내지 제8항 중 어느 한 항에 따른 면상발열체 조성물을 적용한 히팅 케이블.A heating cable to which the planar heating element composition according to any one of claims 1 to 8 is applied.
PCT/KR2012/002988 2011-04-26 2012-04-19 Plane heating element composition having specific temperature coefficient of resistance and plane heating element using same WO2012148126A2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000077167A (en) * 1998-08-31 2000-03-14 Kyocera Corp Planar heating element
KR20010022476A (en) * 1999-06-09 2001-03-15 엔도 마사루 Ceramic heater and method of producing the same and electrically conductive paste for heating body
KR20010061925A (en) * 1999-12-17 2001-07-07 임무현 Resistive paste composition for the formation of electrically heat-generating layer
KR20100133407A (en) * 2008-04-07 2010-12-21 토요 보세키 가부시기가이샤 Conductive paste for planar heating element, and printed circuit and planar heating element using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000077167A (en) * 1998-08-31 2000-03-14 Kyocera Corp Planar heating element
KR20010022476A (en) * 1999-06-09 2001-03-15 엔도 마사루 Ceramic heater and method of producing the same and electrically conductive paste for heating body
KR20010061925A (en) * 1999-12-17 2001-07-07 임무현 Resistive paste composition for the formation of electrically heat-generating layer
KR20100133407A (en) * 2008-04-07 2010-12-21 토요 보세키 가부시기가이샤 Conductive paste for planar heating element, and printed circuit and planar heating element using same

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