TW457497B - Organic positive temperature coefficient thermistor and manufacturing method thereof - Google Patents

Abstract

An organic positive temperature coefficient thermistor comprising a thermoplastic polymer matrix, a low-molecular organic compound having a melting point that is equal to or greater than 40 DEG C and less than 100 DEG C and conductive particles, each having spiky protuberances, is obtained by crosslinking a milled mixture of these components with a silane coupling agent comprising a vinyl group or a (meth)acryloyl group and an alkoxy group. This organic positive temperature coefficient thermistor has sufficiently low resistance at room temperature and a large rate of resistance change between an operating state and a non-operating state, and can be operated at less than 100 DEG C with a reduced temperature vs. resistance curve hysteresis, ease of control of operating temperature, and high performance stability.

Description

A7 B7 Secret 7497 V. Description of the invention (1) Background of the invention The prior art The present invention relates to an organic positive temperature coefficient thermal resistor, which is used as a temperature sensor or an overcurrent protection element, and has a PTC (resistivity) (Positive temperature coefficient), its resistance 値 increases with temperature. Technical background An organic positive temperature coefficient thermal resistor, which has conductive particles dispersed in a crystalline polymer, is known in this type of technology and is typically disclosed in United States Patent Nos. 3, 2 4 3, 7 5 3 and 3, 3 5 1, 8 8 2. This increase in electrical resistance is due to the expansion of the crystalline polymer during melting, which causes the current transport path formed by fine conductive particles to be cut off. An organic type PTC thermistor can be used as a self-controlling heater, an excessive current protection element, and a temperature sensor. The requirements of these components are a sufficiently low resistance 値 in a non-operating state at room temperature, a sufficiently large rate of change between the room temperature resistance 値 and the operating resistance 、, and a reduced resistance 値 change under repeated operation. To meet this demand, it is proposed to add low-molecular organic compounds such as paraffin to the polymer matrix. The organic type PTC thermistor 'includes, for example, a polyisobutylene / ballast / carbon black system (F. Bueche, J. Appl. Phys. '44, 532, 1973)' styrene-butadiene rubber / stone躐 / Carbon black system (F. Bueche, J. Pomber Sci. 11 '1319' This paper size is applicable to China National Standard (CNS) A4 (210x297 mm) ---------:- --- Equipment ----AS ~ (Please read the precautions on the back before printing this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 57497 A7 _ B7 (2) 1973), and low density polyethylene / paraffin / carbon black system (K. Ohe et al., Jpn. J_Appl. Phys_10, 99, 1971). Self-controlled heaters, current-limiting elements, etc., including organic type PTC thermistors, which use low-molecular organic compounds are also disclosed in JP-B's 62-16523, 7-109786 and 7-48396, and JP -A's 62-51184, 62-51185, 62-51186, 62-51187, 1-231284, 3-132001 '9-27383 and 9-69410. In these cases, the increase in resistance is due to the melting of low-molecular organic compounds. One of the advantages of using low-molecular organic compounds is that the resistance increases sharply with increasing temperature, because low-molecular organic compounds generally have higher crystallinity than polymers. And because the polymer can be easily placed in a supercooled state, it can exhibit hysteresis. The temperature at which the resistance decreases with decreasing temperature is usually lower than the temperature at which the resistance increases with increasing temperature. Hysteresis can be kept small when low-molecular organic compounds are added. By using low-molecular organic compounds with different melting points, this temperature (operating temperature) can be easily controlled to increase resistance. Polymers that are prone to change in melting point depend on the following differences: molecular weight and crystallinity, and their copolymerization with comonomers, resulting in changes in crystalline state. In this case it is often not possible to obtain sufficient p T C characteristics. This is particularly true in cases where the operating temperature is set below 100 ° C. One of the above-mentioned documents, I p η. 〖. Ap p 1. p h y s ·, 10, 9 9, 1 9 7 1 Exhibit-Example where the increase factor of resistivity 値 (Ω cm) is 108. However, the resistivity is as high as 104 Ω cm at room temperature, and it is so particularly insensitive. <Please read the precautions on the back first, then this page.) Binding ) A4 size (210x297 mm) -5-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) It is actually used as an overcurrent protection element or temperature sensor. Other literatures show an increase in resistance 値 (Ω) or resistivity (Qcm) in the range between 1 ◦ times (or lower) and 104 times, while the room temperature resistance has not completely decreased. In many cases, carbon Black and graphite have been used as conductive particles. In the prior art organic type PTC thermistors, including the foregoing. However, the problem with carbon black is that when the amount of carbon black used to reduce the initial resistance is increased, a sufficient resistance change rate cannot be obtained; a reasonable balance cannot be obtained between a low initial resistance and a large resistance change rate. Sometimes * particles of generally available metals are used as conductive particles. In this case, it is also difficult to achieve a clear balance between a low initial resistance and a large resistance change rate. An investigation to solve this problem is disclosed in J P-A 5-47 5 0 3, which mentions the use of conductive particles having sharp protrusions. More specifically, it discloses a poly (vinylidene fluoride) as a crystalline polymer and a sharp nickel powder as conductive particles having sharp protrusions. United States Patent No. 5 '3 7 8, 4 0 7 also discloses a thermistor comprising a filamentous nickel having pointed protrusions, and a polyolefin, an olefin copolymer or a fluoropolymer. However, these thermal rheostats are still insufficient in hysteresis and are therefore unsuitable for applications such as temperature sensors, although they have improved the balance between low initial resistance and large resistance changes. In addition, these thermal resistors have an operating temperature of 10 o ° c or higher. Although some thermal resistors have an operating temperature range of 60 to 90 ° C, it is impractical because in the reverse --------- ^ --- :! equipment --- ( Please read the precautions on the back of the page before ordering this page) Order. Ί Line 1 The meaning of this paper applies to China National Standard (CNS) A4 (210 X 297 public love) -6- 4 5 7 4 9 7 a? B7 5. Description of the invention (4) Its performance becomes unstable during the overlay operation. When thermistors are used as protection elements for secondary batteries, electric blankets, toilet seats and heaters for vehicle seats, an operating temperature of 100 ° C or higher will cause a high degree of danger to the human body. For the sake of human safety, the operating temperature must be below 10 o ° c. In recent years, there has been an increasing demand for organic type PTC thermistors as excess current protection components for portable meter phones, personal computers, and the like. At the same time, at the commonly used temperature of 40 to 90 ° C, it is necessary to have a thermal resistor with an operating temperature from 40 ° c to less than 100 ° c. In this way, there have never been completed organic type PTC thermal resistors, which can exhibit good performance and have high performance stability at operating temperatures below 100 t. _ In Japanese Patent Application No. 9-350108, the present inventors have published an organic positive temperature coefficient thermal resistor which includes a thermoplastic polymer matrix, a low-molecular organic compound, and conductive particles having pointed protrusions. This thermal resistor has a sufficiently low room temperature resistivity of 8 X 1 0 · 2 Ω cm, an amount of resistance change rate of ten between the operating state and the non-operating state, and a reduced temperature pair. The resistance curve is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Magnetic Economics {Please read the precautions on the back before ^ k · this page). In addition, the operating temperature is equal to or higher than 40 ° C and lower than 100 ° C. However, it is found that the thermal resistor is not sufficiently stable in performance, especially at high temperatures and temperatures. The resistance. This is due to the action or separation of active materials, that is, the low-molecular organic compounds undergo repeated melting / solidification cycles during operation. The separation can be attributed to the low-melting point and low-melt viscosity of the low-molecular organic compounds. This in turn caused the low-molecular-weight organic compounds and the paper size to be in compliance with the Chinese National Standard (CNS) A4 (210 X 297 mm) -7 ~ ^ 4 5 ^ 49 7 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (5) The change in the dispersion state of the electrical particles causes the performance to decrease. This problem of performance stability is important for low molecular organic compounds as active substances. The present invention requires that the object of the present invention is to provide an organic positive temperature coefficient thermal change resistor which has sufficiently low resistance at room temperature, and has a large resistance change rate between an operating state and a non-operating state, and can be lower than 1 0 0 ° C operation, and with reduced temperature versus resistance curve hysteresis, the operating temperature is easy to control 'and has high performance stability. This object is achieved by the present invention described below. (1) Organic type positive temperature coefficient thermal resistor, comprising a thermoplastic polymer matrix, a low-molecular organic compound having a melting point equal to or higher than 40 ° C and lower than 100 ° C, and each having a pointed protrusion Conductive particles, wherein: a mixture of the thermoplastic polymer matrix, the low-molecular organic compound, and the conductive particles is crosslinked with a silane coupling agent, wherein the silane coupling agent contains a vinyl group or (methyl) Acrylic fluorenyl and alkoxy groups. (2) The organic type positive temperature coefficient thermal resistor according to (1), wherein the low-molecular organic compound has a weight average molecular weight of 1,000 or less. (3) The organic positive temperature coefficient thermal variable resistor according to (1), wherein the low-molecular organic compound is petroleum wax. (4) Organic positive temperature coefficient thermal resistor according to (1), (CNS) Al (2) 〇χ 297) 7〇. &Quot; --------]-i --- install ----. 、-(Please read the precautions on the back before rL? This page) Order —-Line 11 45 7 4 9 7 a? _ B7 Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs (6) The conductive particles each having a pointed protrusion are connected in a chain shape. (5) The organic positive temperature coefficient thermal resistor according to (1), wherein the thermoplastic polymer matrix is polyolefin. (6) The organic positive temperature coefficient thermal resistor according to (5), wherein the polyolefin is a high-density polyethylene. (7) The organic-type positive temperature coefficient thermal variable resistor according to (6), wherein the high-density polyethylene has a melt flow rate of 3.0 g / 1 0 m i η · or lower. (8) The organic positive temperature coefficient thermal resistor according to (1), wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane. (9) The organic positive temperature coefficient thermal resistor according to (1), whose operating temperature is lower than 100 ° C. (10) A method of preparing an organic type positive temperature coefficient thermal resistor as described in (1), wherein a thermoplastic polymer matrix, a melting point equal to or higher than 40 ° C and lower than 100 ° C The low-molecular organic compound and the conductive particles each having a pointed protrusion are ground together into a ground mixture, and the ground mixture is then crosslinked with a silane coupling agent, which contains a vinyl group or (Meth) acrylfluorenyl and alkoxy groups. The organic positive temperature coefficient thermal resistor of the present invention comprises a thermoplastic polymer matrix, a low-molecular organic compound having a melting point equal to or higher than 40 ° C and lower than 100 ° C, and a conductive body each having a pointed protrusion. Sex particles. The mixture of these ingredients is crosslinked with a silane coupling agent, which contains B (please read the precautions on the back before widening this page). _ Packing · Λ / ·. _ Line_ This paper size applies to China Standard (CNS) A4 specification (210 X 297 metric tons). 9. A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Agricultural Printing 5. Description of the invention (7) Alkenyl group or (meth) acrylfluorenyl group And alkoxy hydrazone. In the present invention, the shape of the protruding tips on the conductive particles allows the tunnel current to immediately pass through the thermal resistor, so that it is possible to obtain an initial 'resistance lower than that which can be achieved with spherical conductive particles. resistance. When the thermistor is in operation, a large resistance change is obtained because the space between the conductive particles between the tips is larger than the space between the spherical conductive particles. In the present invention, the low-molecular-weight organic compound added with a thermoplastic polymer matrix is preferably a polyolefin matrix, so that by melting the low-molecular-weight organic compound, the characteristic of ρ τ c which increases in resistance with increasing temperature is achieved. As a result, the temperature versus resistance curve hysteresis can be further reduced to less than that obtained from using the polymer matrix alone. It is easier to control the operating temperature by using a low-molecular organic compound having a changed melting point, etc., than to change the melting point of a polymer to control the operating temperature. According to the present invention, the use of a low-molecular organic compound having a melting point equal to or higher than 40 ° C and lower than 100 ° C as an active substance can further reduce the operating temperature to below 100 ° C. In the present invention, a mixture of a thermoplastic polymer matrix, a low-molecular organic compound, and conductive particles having pointed protrusions is crosslinked with a silane coupling agent, and the silane coupling agent contains a vinyl group or (meth) propylene The fluorenyl group and the alkoxy group are used to achieve a considerable improvement in the performance stability of the thermal resistor during storage and repeated operation. The improvement of the stability of the performance of the organic type PTC thermistor is due to the crosslinked structure of the polymer matrix and the low-molecular organic compound, which allows the polymer matrix to maintain the shape, so that the thermal resistor is inversely affected during operation. --------------- Packing --- (Please read the precautions on the back before this page)

'• PPV This paper size is in accordance with Chinese National Standard (CNS) A 彳 specification (210 X 297 mm) -10- 457497 A7 V. Description of the invention) The agglomeration and curing of low-molecular-weight organic compounds can be suppressed under the cladding / curing cycle Separation ° This coupling agent not only cross-links the above-mentioned organic matrix, but also forms a chemical bond between organic and inorganic materials, which has some great effects on the improvement of the interface between them. Treatment of a mixture of a thermoplastic polymer matrix, low-molecular organic compounds, and conductive particles with a silane coupling agent can result in additional performance stability improvements. This is due to the increased interface strength of the following: polymer matrix-conductive particle interface, low-molecular organic compound-conductive particle interface, polymer matrix-metal electrode interface, and low-molecular organic compound-metal electrode interface. In the present invention, a coupling agent is first grafted to a thermoplastic polymer matrix and a low-molecular organic compound via a group having a carbon-carbon double bond (c = c). The alcohol is removed in the presence of water, dehydrated and condensed, and then a crosslinking reaction occurs according to the figure below. {Please read the precautions on the back before widening this page) The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is again applicable to the Chinese National Standard (CNS) A4 Specification (2) 〇X 297. Meals) -11- 4 5 7 4 9 7 a? _B7 V. Description of the invention (9)

This paper size applies to Chinese National Standard (CN: S) A4 (210 X 297 mm) ---------- I]-* II '.' · ^ (Please read the precautions on the back before (This page) Order ·-丨 Line-A7 B7 457497 V. Description of the invention (10) Other cross-linking methods can also be used, including chemical cross-linking methods using organic peroxides, and irradiation cross-linking methods using electron beam irradiation . However, it should be noted that the chemical cross-linking method makes it difficult to maintain the shape. This is because the polymer matrix needs to be heat-treated at a temperature much higher than its melting point after molding, which may cause thermal degradation of the device. It should also be noted that this irradiation crosslinking method uses expensive equipment, and it is difficult to provide sufficient cross-linking of internal devices, especially when the thickness is thick, it is difficult to achieve uniform cross-linking. In this regard, a person performing a silane crosslinking treatment has been proposed. For example, for a system containing no low-molecular-weight organic compounds, JP-A 5 9-6 0 9 0 4 discloses that semiconducting compositions in which 15 to 50% by weight of the conductive carbon are unevenly dispersed in water are crosslinked. Silane-modified polyolefins, which have a gel fraction of 60% or higher. JP-A 4-68501 discloses that the resistor has p T C characteristics, in which a conductive powder is dispersed in a water-crosslinked polymer, such as an organic silane-modified polymer. JP-A 4-15 7701 reveals a resistor with PTC characteristics, which is a mixture prepared by mixing a polymer (polyolefin resin) that is not crosslinked with water with a conductive powder (carbon black), and mixed in the mixture Water-crosslinked polymer (polyethylene with reactive silane groups), followed by water cross-linking. However, in these cases, any low-molecular organic compound is not contained, polyolefin is used as an active material 'and has an operating temperature of 100 ° C or higher. Because the use of carbon black or the like as conductive particles will have a performance lower than that of satisfactory 値 'at room temperature, the resistivity is as high as 101 Qcm or higher, and the resistance change rate is 十 2 to 5 times. The above literature makes no recommendations at all about performance stability. The paper wattage is in accordance with Chinese National Standard (CNS) A4 (2W X 297 mm) _ 13. ------------------ Packing --- (Please read the back first (Note on r'x this page) Order-Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs 457497 A7 ____ B7 Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs 5. Description of Invention () JP-B 3- 7 4 4 8 1 shows a heater element resin composition containing a polyolefin crystalline polymer resin, a silane compound, an organic peroxide, a stabilizer, and a conductive powder such as carbon. This document claims that the high performance stability is achieved because the silane compound is chemically bonded to the crystalline polymer. This bonding is based on the use of organic peroxides in the presence of stabilizers to form functional groups chemically bonded to the carbon surface. Group, or improve the affinity of carbon, so any resistance change caused by the local presence of carbon can be avoided, and the chemical combination of the silane compound can improve the adhesion of the resin composition to the electrode material. J PA 4-3 4 5 7 8 5 reveals that the resistor has a positive temperature coefficient of resistance, which is obtained by dispersing a conductive powder in a crystalline polymer composition to prepare a conductive composition, and crosslinking the conductive composition The powder was surface-treated with a silane coupling agent, and the surface-treated powder was mixed and dispersed in a crystalline polymer composition. This document claims that the increase in resistance in heater elements has been reduced, resulting in an increase in its service life, because the silane coupling agent is coated on the particulate conductive composition, thereby interposing between the binder polymer and the metal electrode. A strong chemical bond is formed. When a current is passed, a current transport path is formed, and the thermal expansion caused by the heat generated by the current can be suppressed to cause cracks in the conductive powder. However, the performance stability improved by the surface treatment alone is limited. Clearly, long-term stable performance can be obtained according to the present invention. The above two documents do not show the initial performance in the examples; the degree to which the component is degraded under the test is still unclear = because carbon is used as the conductive powder, it is not possible to achieve a range between that expected in the present invention. Low initial resistance and large resistance change -at n K. ^ 1 ty I n ^ i ^ -n I ^ &lt; n I •-.) (Please read the precautions on the back first before r'A page) • Line. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 g) -14-457497 A7 B7 V. Description of the invention (12) Proper balance between the two. In addition, these elements do not contain any low-molecular organic compound 'using a crystalline polymer resin as an active material, and have an operating temperature of 100 t or higher. For systems using low-molecular organic compounds, it has also been proposed to perform a silane crosslinking treatment. Consumption cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed JP-A 1-2 3 1 2 3 4 reveals that its temperature-controlled heater elements contain water-crosslinkable polyolefins, such as organic silane-modified polyolefins with electrical conductivity And low-molecular-weight polyolefin paraffin is added to it. J PA 9-6 9 4 1 0 reveals that the current-limiting element contains a water-crosslinkable polyolefin, such as an organosilane-modified polyolefin with a conductive binder. And low molecular weight polyolefin paraffin is added to it. However, these documents mention a mixture of a water-crosslinkable polyolefin and a low-molecular-weight polyolefin wax, but do not mention a crosslinked structure comprising a polymer matrix and a low-molecular-weight organic compound as expected in the present invention. The performance stability improvements achieved thus will be very limited. In other words, the long-term high performance as achieved in the present invention cannot be maintained. In addition, this document does not make any recommendations regarding performance stability. J P-A 9-6 9 4 1 0 shows the use of carbon black, graphite, carbon fiber, and metal powder (such as Ni powder) as conductive filler, but does not mention conductive particles with sharp protrusions. For this reason, the element disclosed therein has a low-resistance rate of about ten to the third power, although its room-temperature resistivity is as low as 10'1 to 10ΰΩcm. In other words, this element does not have sufficient performance to be used as an overcurrent protection element or a temperature sensor. Revealed in] p-A 1-2312 8 4 element also does not have sufficient performance 'because the room temperature resistivity is as high as 101 to 10 2 Ω cm and the rate of change in resistance is as low as the third power of about ten. -15- This paper size is in accordance with China National Standard (CNTS) A4 (210 X 297 mm) 4 5 7 4 3 7 a? B7 V. Description of the invention (13) This is because carbon black is used as a conductive material. Among these components', both organic paraffin-modified polyolefins and low-molecular-weight polyolefin paraffins are used as active materials, and the operating temperature thereof is higher than that of the components of the present invention because the melting point of the paraffin waxes is in the range of 100 to 1601. In other words 'these prior art components cannot be operated below 100 ° C ° however' according to the invention, the operating temperature can reach below 100 ° C, because only its melting point is equal to or higher than 40 ° C and low Low molecular weight organic substances at I ◦ 0 ° C are used as active substances. Brief description of the drawings Fig. 1 is a sectional view of a system of an organic positive coefficient thermal variable resistor according to the present invention. Fig. 2 is a temperature-resistance curve of the thermal resistor element in the first embodiment. Fig. 3 is a diagram illustrating the room temperature resistance and resistance change rate of the thermal resistor element in Example 1 when the acceleration test time was changed at 80 ° C and 80% RH. FIG. 4 is a diagram illustrating the room temperature resistance and resistance change rate of the thermal resistor element in Comparative Example 1 at 80 ° C and 80% RH when the acceleration test time is changed. Component comparison table II Electrode 12 Thermal resistor element sheet The paper size is applicable to the Chinese National Standard (CNS) Al specification (210 X 297 male) --------- ϊ--I --- pack- -(Please read the precautions on the back first, and then t this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * 'Λ -16- 457497 at B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (14) Description of the preferred system The present invention will now be described in more detail. The organic positive temperature coefficient thermal resistor of the present invention comprises a thermoplastic polymer matrix, a low-molecular organic compound having a melting point equal to or higher than 40 ° C and lower than 100 ° C, and conductive particles having pointed protrusions. And obtained by cross-linking the mixture of these components with a silane coupling agent. The silane coupling agent contains a vinyl group or a (meth) acryl group and an alkoxy group. The melting point should have a higher melting point than low-molecular organic compounds, preferably at least 30 ° C, and more preferably 30 ° C to 110 ° C (inclusive) to prevent melting due to low-molecular organic compounds. Melt and fluidize during operation, deformation of components, etc. In other words, the melting point of the thermoplastic polymer matrix is usually preferably in the range of 70 to 200 ° C. The thermoplastic polymer matrix used herein may be crystalline or amorphous. Exemplary thermoplastic polymers are those polyolefins such as polyethylene, ethylene-vinyl acetate copolymers, polyalkyl acrylates such as polyethylene acrylate, poly (meth) acrylates such as poly (meth) acrylate, Fluoropolymers such as polyvinylidene fluoride, and polytetrafluoroethylene, polyhexafluoropropyl 'or copolymers thereof, halogen polymers such as chloropolymers, such as polyvinyl chloride, polyethylene chloride, and chlorinated Polyvinyl chloride, chlorinated polyethylene and chlorinated polypropylene or their copolymers, polystyrene, and thermoplastic elastomers. The polyolefin may be a copolymer. The cases mentioned are high-density polyethylene (such as Hizex 2100JP made by Mitsui Petrochemical Industries, Ltd. and Marlex 6003 by Phillips Petroleum Co.), low-density polyethylene (such as LC500 ----- ----------------/} (谙 Please read the precautions on the back and then this page) Order .. --line · 2 · This paper size applies to China National Standard (CNS) A4 Specifications (2i0 X 297 male niches) -17- ftg7497 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (15) · Produced by Nippon Polychem. Co., Ltd., and DYNH-I by Union Carbide Corp.), medium density polyethylene (such as 2604M by Gulf Oil Corp.), ethylene-ethyl acrylate copolymers (such as DPD6169 by Union Carbide Corp.), and ethylene-acetic acid copolymers (such as Novatec EVALV241 By Nippon Polychem Co., Ltd.), polyvinyl fluoride (eg Kynar 711 by Elf. Atchem Co., Lid.), And vinylidene fluoride-tetrafluoroethylene_hexafluoropropyl copolymers (eg Kynar ADS is produced by Elf, Atchem Co., Ltd.). The thermoplastic polymer should preferably have a weight-average molecular weight Mw of about 10,000 to 5,000,000. For this thermoplastic polymer matrix, polyolefins are preferred, and especially high density polyethylene. The term "polyethylene" refers herein to polyethylene having a density of at least 0.942 g / cm3. This linear chain polyethylene is made by using transition metal catalysts at a moderate or low pressure of tens of atmospheric pressure to coordinate anionic polymerization. The high-density polyethylene should preferably have a melt flow rate (MFR) of up to 3.0 g / 10 mi η., And in particular up to 1.5 g / lO min., As measured in accordance with the provisions of ASTM D1238. At higher M F R, the tendency of performance stability becomes worse due to too low melt viscosity. The lower limit of the MFR is usually about 0.1 g / 10 min., Although this does not matter in carrying out the present invention. In the present invention, the thermoplastic polymer matrix may be used alone or in combination of two or more kinds. -Instead, only high-density polyethylenes with MFR up to 3.0 g / 10m in. Should be used. f Qi first read the precautions on the back, then X, this page) &*; * This paper is suitable for Chinese National Standard (CNS) A4 (210 X 297 mm) -18- 4 5 7 4 9 7 Α7 Β7 5 Explanation of the invention (16) Preferably, but not exclusively, the low-molecular organic compound used herein is a crystalline solid (at normal temperature or about 25 ° C) substance, which has a molecular weight as high as about 1 '00, And it is preferably 200 to 800, and the melting point is equal to or higher than 40 ° C and lower than 100 ° C. The low-molecular organic compounds include, for example, waxes (such as petroleum waxes such as paraffin and microcrystalline waxes, and natural waxes such as vegetable waxes, animal waxes, and mineral waxes), and fats and oils (such as fats, and those called solid fat ). The actual composition of this wax and fats and oils may be hydrocarbons (for example, alkane-type linear hydrocarbons having 2 or more carbon atoms), and fatty acids (for example, alkane-type linear hydrocarbon fatty acids having 12 or more carbon atoms) ), Fatty esters (such as methyl esters of saturated fatty acids, which are derived from saturated fatty acids with 20 or more carbon atoms and lower alcohols such as methanol), fatty ammonium (such as ammonium of unsaturated fatty ammonium Such as ammonium oleate and erucamide), aliphatic amines (such as aliphatic primary amines having 16 or more carbon atoms), and higher alcohols (such as n-amines having 16 or more carbon atoms) Alkanol). However, these ingredients can be used as low-molecular organic compounds per se. For low-molecular organic compounds, petroleum waxes are preferred. These low-molecular-weight organic compounds are commercially available from employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economics, and the commercial products are ready for immediate use = one of the goals of the present invention is to provide thermal resistors that can The operation is preferably 0 ° C, and the low-molecular organic compound used has a better melting point, mp, which is equal to or higher than 40 ° C and lower than 100 ° C. The low-molecular-weight organic compound includes, for example, paraffin (for example, tetratetracane C 2 4 Η 5 〇m ρ 49-5 2 ° (:; hexacosane 〇36 only 74 -19- • I1III1IJII —- — — * 11- V). {Please read the precautions on the back before this page) 丨 Line · The meaning of this paper applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) A7 B7 457497 V. Description of the invention (17) mp 7 3 ° C Η NP-10 mp 75 ° C, Nippon Seiro Co., Ltd .; and HNP-3 mp 66 ° C, Νίρροη Seiro Co., Ltd.), microcrystalline wax (such as Hi-Mic- 1 080 mp 83 ° C 'Nippon Seiro Co_, Ltd .: Hi-Mic-1045 mp 70 ° C, Nippon Seiro Co., Ltd .; Hi-Mic-2045 mp 64 ° C, Nippon Seiro Co., Ltd .; Hi-

Mic-3090 mp 89 ° C. Nippon Seiro Co., Ltd .; Seratta 104 mp 96 ° C, Nippon SekLyu Seisei Co., Ltd .; and 155 Microwax mp 70 ° C, Nippon Seklyu Seisei Co., Ltd.), Fatty acids (eg n-dodecanoic acid mp 81 ° C, Nippon Seika Co., Ltd .; stearic acid mp 72 ° C, Nippon Seika Co., Ltd .; and hexadecanoic acid mp 64 ° C, Nippon Seika Co. , Ltd.), fatty vinegar (arachidonic acid methyl ester mp 48 ° C, Tokyo Kasei Co., Ltd.), and fatty ammonium (such as ammonium oleate mp 76 ° C, N.ippon Se) ka Co., Ltd.). It is also possible to use paraffin mixtures which contain paraffin and resin, and which may additionally contain microcrystalline waxes, whose melting point is equal to or higher than 40 ° C and lower than 100 ° C. The low-molecular organic compound may be used alone or in a combination of two or more, but it depends on the operating temperature and the like. The conductive particles (each having a sharp protrusion) used here are made of free primary particles, and the first-order particles have sharp protrusions. More specifically, many (usually 10 to 500) conical and pointed protrusions, each having a height of 1/3 to 1/50 of the particle diameter, exist on a single particle. The conductive particles are preferably made of Ni or the like. Although the conductive particles can be used in the form of separated powders, it is preferable to use the conductive particles in the form of secondary particles having a chain type of about 10 to 1,000, and to form secondary particles. The chain-connected first-order particles may partially include first-order particles. The former paper is also applicable to the Chinese National Standard (CNS) A4 specification (2) 0 × 297 public copy. --------------- Install i I--.) (Please read the back first Note for re-^ "-this page). --Line. Printed by the Consumers 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers’ Cooperatives of the Ministry of Economics and Intellectual Property Bureau *' 1 ^ 457497 A7 ---- B7 V. Description of the invention ( 18) The examples include nickel powder in a spherical form with pointed protrusions, one of which is commercially available from the market under the trade name I NCO type 1 2 3 nickel powder (INCO Co., Ltd.). These powders have average particles The diameter is about 3 to 7, the apparent density is about 1.8 to 2, 7 g / cm3, and the specific surface area is about 0.34 to 0.44 m2 / g. The preferred embodiment of the latter is a wire-like nickel powder, some of which may be In the shopping mall, it is obtained from the following trade names: INC 0 type 2 5 5 nickel powder, INC 0 type 270 nickel powder, 11 ^ 0 0 type 287 nickel powder, and INCO type 2 1 0 nickel powder, all from INC 0 Co., Ltd. made 'the previous three items is better. Primary particles have an average particle diameter of preferably at least 0.1 # m' and more preferably about 0.5 to about 4.0 μm (inclusive). First-order particles with a sub-diameter of 1.0 to 4 Ogm (inclusive) are optimal and can be mixed with first-order particles with an average particle diameter of 0.1 # m to less than 1.0 μm in a weight ratio of 50% or less Its apparent density is about 0.3 to 1.0 Og / cm3 and the specific surface area is about 0.4 to 2 5 m 2 / g. In this regard, it should be noted that the average particle diameter is determined by Fischer (Fischer ) Measured by the secondary sieve method, the conductive particles first appeared in JF-A 5-4 7 5 0 3 and United States Patent No. 5, 3 7 8, 4 0 7 ° In addition to the conductive particles with sharp protrusions, conductive The carbon particles, such as carbon black, graphite, carbon fiber, metallized carbon black, graphitized carbon black and metallized carbon fiber, spherical, exfoliated or fibrous metal particles can also be used. Nickel particles), ceramic conductive particles ------------- Ϊ I -----Ί- (please read the precautions on the back before going to this page) Order _: Wire · Book Paper significance applies to China National Standard (CNS) A4 specification (210 X 297 male i) -21-45749 7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Explanation (19) such as those of tungsten carbide, zinc nitride, titanium nitride, hafnium carbide, titanium boride and molybdenum sand, and conductive potassium titanate whiskers, which are disclosed in JP — A's 8-3 1 5 5 4 and 9-2 7 3 8 3. The content of the conductive particles, which should preferably be up to 25% by weight, is conductive particles having pointed protrusions. With reference to the mixing ratio between the thermoplastic polymer matrix and the low-molecular-weight organic compound, the use ratio of the low-molecular-weight organic compound should be 0.2 to 4 (weight ratio) per thermoplastic polymer molecule. When this ratio becomes lower or the low-molecular organic compound content becomes smaller, it will be difficult to obtain any satisfactory resistance change rate. When this ratio becomes higher or the content of the low-molecular organic compound becomes larger, on the contrary, the thermal resistor element will not only be unacceptably deformed when the low-molecular compound is melted, but it is also difficult to mix the low-molecular compound with the conductive particles. The content of the conductive particles should preferably be 2 to 5 times the total weight of the polymer matrix and the low-molecular organic compound. When this mixing ratio becomes low or the content of conductive particles becomes small, it will be impossible to make room temperature resistance in a sufficiently low non-operating state. When the content of conductive particles becomes larger, on the contrary, it is not only difficult to obtain any large resistance change rate, but it is also difficult to achieve any uniform mixing, which makes it impossible to obtain any reproducible resistance. In carrying out the invention, the temperature at which the milling is performed should preferably be higher than the melting point of the thermoplastic polymer matrix (especially the melting point + 5 to 40 ° C). Milling may be performed in a known manner, for example, about 5 to 90 minutes during a milling. Alternatively, the thermoplastic polymer and the low-molecular organic compound may have been previously mixed together in a molten state or dissolved in a solvent before being mixed. Then add the silane coupling agent to the ground mixture to make them cross-linked together -------------.-- pack ----、 / (Please read the precautions on the back before ^ -¾ This page) Order · Line-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) -22- &lt; 45749 7 A7 B7 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumption Du printed V. Description of the invention (20) □ Silane coupling agent can be condensed by alcohol removal and dehydration, and each molecule has an alkoxy group which can be chemically bonded to inorganic oxide and vinyl group, or (meth) acrylic acid. The radical has an affinity for the organic material or can be chemically bonded to the organic material. In the case of silane coupling agents, trialkoxysilanes having a C = C bond are preferred. It is preferred to use alkoxy groups which usually have a small number of carbon atoms, and especially methoxy or ethoxy groups a. This group containing a c = C bond is a vinyl group or (meth) propylene A fluorenyl group is preferred, with a vinyl group being preferred. These groups may have been directly bonded or bonded to S i via a &lt;: 1 to 03 carbon chain. The preferred silane coupling agent is liquid at normal temperatures. Demonstrated silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane'vinyl-tri (/ 5-methoxyethoxy) silane'r- (meth) propenylpropylpropyl Trimethoxysilane, r- (meth) acrylfluorenylpropyltriethoxysilane, r- (meth) acrylfluorenylpropylmethyldimethoxysilane, and r- (meth) acrylfluorenyl Propylmethyldiethoxysilane, with vinyltrimethoxysilane and vinyltriethoxysilane being the best = for the coupling treatment, the content will be the total weight of the thermoplastic polymer and the low molecular weight organic compound A silane coupling agent of 0.1 to 5% by weight is added dropwise with a mixture of the ground thermoplastic polymer matrix, the low-molecular organic compound and the conductive particles, followed by thorough stirring and water crosslinking. When the content of the coupling agent is less than this, the crosslinking treatment effect becomes insufficient. However, using larger amounts of coupling agents does not increase any effect. When using vinyl-based (please read the precautions on the back before ti, this page) -_ installed._. \) · Line · 1 This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 Gong) -23- 457497 hi B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (21) Silane coupling agent for the group. Organic peroxides with a coupling agent content of 5 to 20% by weight Such as 2,2-di- (tertiary monobutylperoxy) butane, dianisyl peroxide, and 1,1-di-tertiary monobutylperoxy-3,3,5-tris Methyl-cyclohexane to graft onto organic materials (ie, thermoplastic polymers and low-molecular organic compounds) via vinyl groups. The thermoplastic polymer, low-molecular organic compounds and conductive particles are milled together After a sufficiently uniform state, a silane coupling agent was added. The ground mixture is pressed into flakes having a predetermined thickness and then crosslinked in the presence of water. For example, this pressurized sheet is immersed in warm water for 6 to 8 hours using a metal carboxylic acid catalyst such as dibutyltin dilaurate, dioctyltin dilaurate 'tin acetate, tin octoate, and zinc octoate. Either way, when the catalyst and thermistor element are ground, this cross-linking can be performed under high temperature and high humidity. As the catalyst, dibutyltin dilaurate is particularly preferably used. Preferably, the cross-linking temperature should be equal to or lower than the melting point of the low-molecular-weight organic compound to improve the performance stability of repeated operations. After the cross-linking process is completed, 1 the sheet is dried, and the metal made of Cu and Ni The electrode was hot-pressed to prepare a thermistor element. The organic type positive temperature coefficient thermal variable resistor according to the present invention has a low initial resistance or room temperature resistivity in a non-operating state of about 10 to 2 to 100 Ω cm, and has a rapid resistance rise in operation. , And when changing from the non-operating state to the operating state, the resistance change rate is higher than ten to the sixth power. After 80 ° C and 80% R Η after 5000 hours, the performance of the thermal resistor is minimal or no deterioration (humidity-related operating life is 20 years or longer in Tokyo and 1 in Naha 〇 or longer). ---— — — — — — II (Please read the notes on the back before #. \ This page) -Embroidery. This paper size applies to China National Standard (CNS) A4 (210 X 297 male stem) -24- 457497 A7 B7 V. Description of the invention (22 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to prevent the thermal degradation of low molecular organic compounds, antioxidants can also be added to the organic positive temperature coefficient thermal resistors of the present invention. Organic sulfur, phosphite (based on organic phosphorus), etc. can be used as antioxidants. In addition, the thermal resistor of the present invention may include, for example, silicon nitride, silicon dioxide, alumina, and clay (mica) with good thermal and electrical conductivity , Talc, etc.) which are described in JP-A 57-12061; silicon 'silicon carbide, silicon nitride, beryllium oxide, and selenium are described in JP-B 777161; inorganic nitrides and magnesium oxide are described in JP-A 5 -2 1 7 7 1 1 and the like. As a solid improvement, the thermal resistor of the present invention may include titanium oxide, iron oxide, zinc oxide, silicon dioxide, magnesium oxide, aluminum oxide, chromium oxide, barium sulfate, Calcium carbonate, calcium hydroxide and lead oxide Described in; rp-a 5-2 2 6 1 1 2, inorganic solids with high relative dielectric constants described in JP-A 6-6 8 9 6 3, such as barium titanate, hafnium titanate and potassium niobate For the improvement of voltage resistance, the thermal resistor of the present invention may include the boron carbide described in JP-A 474383, etc. For the improvement of strength, the thermal resistor of the present invention may include the JP described in JP. -A 5-7 4 6 0 3 Hydrated basic titanate, described in JP-A 8-1 7 5 6 3 Titanium oxide, iron oxide, zinc oxide, silicon dioxide, etc. As the crystal nuclei, The thermal resistor of the present invention may include a basic halide and a melamine resin described in JP-B 5 9-1 0 5 5 3, a benzoic acid described in J PA 6-76 5 1 1 and a dibenzylidene sorbide Please read the precautions on the back of the alcohol and gold first, and then the reverse of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 Gongchu) -25- 457497 A7 B7 V. Description of the invention (23) belongs to benzoate Talc, zeolite and dibenzylidene sorbitol described in J PA 7-686 4 and sorbitol derivatives (gelatinized) described in J PA 7-2 6 3 1 2 7 Agent) 'asphalt and di (4-tertiary-butylphenyl) sodium phosphonate, etc. As an arc control agent' The thermal resistor of the present invention may contain alumina described in JP-B 4-2 8 7 4 4 And magnesium oxide hydrate, and metal hydrate and silicon carbide described in JP-A 61-250058. As a precautionary measure against the harmful effects of metals, the thermal resistor of the present invention may include Irganox MD1024 (Ciba-Geigy), which is described in J P · A 7-6 8 6 4 〇 As a flame retarder, the thermal resistor of the present invention may include a description Antimony trioxide and aluminum hydroxide in JP-A 6 1 · 2 3 9 5 8 1: Magnesium hydroxide described in JP-A 5.7 4 6 0 3; organic compounds (including polymers) containing halogens Such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and poly (vinylidene fluoride) (PVDF): phosphorus compounds such as ammonium phosphate. In addition to these additives, the thermal resistor of the present invention may include zinc sulfide, alkaline magnesium carbonate, aluminum oxide, calcium silicate 'magnesium silicate, aluminosilicate clay (mica, talc, kaolinite, montmorillonite, etc.), Glass powder, glass flakes, glass fibers, calcium sulfate, etc. The amount of the above-mentioned additives should be up to 25% by weight based on the total weight of the polymer matrix, the low-molecular organic compound and the conductive particles. Example ---------- I ---- install i 1--/) (Please read the precautions on the back before saving this page); line · _

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperatives -M This paper is suitable for 0 Chinese standards (Cls: S) A4 specifications &lt; 210 * 297 mm) -26- 457497 A7 B7 Printing 5. Description of the Invention (24) The present invention will now be described more specifically with reference to Examples and Comparative Examples. Example 1 A local density polyethylene resin (HY 5 40 manufactured by Nippon Polychem Co., Ltd., whose MFR is 1.0 g / l0 mi η, and the melting point is 1 35 ° C) is used as a polymerization. Substrate with microcrystalline wax (<: 1-M ic-1 0 8 0 manufactured by Nippon Seiro Co., Ltd., with melting point of 8 3 ° C) as low molecular organic compounds, and filamentous Nickel powder (type 255 nickel powder, manufactured by INCO Co., Ltd.) was used as conductive particles. This conductive particle has an average particle diameter of 2.2 to 2.8, an apparent density of 0.5 to 0.65 g / cm3, and a specific surface area of 〇f 〇.68m2 / g. This high-density polyethylene and nickel powder four times the weight of the polyethylene were milled in a mill at 150 ° C for 5 minutes. To this mixture were added 1.5 times the weight of polyethylene wax and 4 times the weight of wax nickel powder. After grinding for another 60 minutes, while milling the mixture, a silane coupling agent or vinyl ethoxysilane (KBE1003 by The Shin-Etsu Chemical) containing 1.0% by weight of the total weight of polyethylene and wax was added dropwise while the mixture was being milled. Co., Ltd.), and an organic peroxide or 2 '2-di' (tertiary-butylperoxy) butyl compound containing 20% by weight of vinyl triethoxysilane D -T 5 0 by Kayaku Akuzo KK). This ground mixture was pressed into a 1 · 1-mm thick sheet at 15 by a hot press. After that, the sheet was dipped in an aqueous emulsion containing 20% by weight of dibutyltin dilaurate (Tokyo Kasei κ * κ ·) 'Applicable to the Chinese National Standard (CNS) A4 specification (210 χ 297 公 Chu_ ) ~ ^ 7-(Please read the precautions on the back before fc this page) Installation · -I line · 457497 a7 B7 V. Description of the invention (25) 6.5 ° C Cross-linking treatment for 8 hours. (Please read the precautions on the back before coming to this page.) After drying, press the two sides of this cross-linked sheet to a temperature of 3 0-# m thick ί foil electrode at 150 ° C using a hot press. A tablet having a total thickness of 1 mm was obtained. Thereafter, the thin-film mallet was formed into a disc shape with a diameter of 10 mm to obtain a thermistor element, and a cross section thereof is shown in FIG. 1. As shown in FIG. 1, the thermal resistor element sheet 12 is a ground molded sheet, which contains a low-molecular organic compound, a polymer matrix, and conductive particles, and is sandwiched between electrodes 1 1 formed by Ni foil. . The element is heated and cooled in a thermostat, and the resistance 値 (measured by the four-terminal method) is measured at a predetermined temperature to obtain a temperature versus resistance curve. This result is plotted in Figure 2. The resistance 値 is 2 · 0 × 10 · 3Ω (1 _ 6 X 1 〇—2Ω cm) at room temperature (25 ° C). There is a rapid resistance increase around 7 5 ° C, and the maximum resistance 値 is 1 · 6 × 1〇 5Ω (1, 3X106 Ω cm) The rate of change of resistance is ten to the power of 7.9. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This component can be placed in a hybrid thermostat and humidity regulator. It is preset at 80 ° C and 80% RH to perform accelerated testing. Figure 3 illustrates the room temperature resistance and resistance change rate at certain test times. After 500 hours, the room temperature (25 ° C) resistance 値 is 5.3 × 10 · 3Ω (4 2X 1 0_2 Ω cm) and the resistance change rate is ten to the power of 7.2. In this way, both the room temperature resistance 値 and the rate of change in resistance remain substantially unchanged; sufficient P T C performance is well maintained. This 80 ° C and 50% R Η 50 ◦ hour accelerated test is equivalent to a humidity-related operating life of 20 years or more in Tokyo, and the Zhongguan Family Standard (CNS) A applies to Naha paper standards. "Specifications (210 x 297 male Chu) ΓΤ 一 &quot; &quot; 45 7 4 9 7 A7 B7 Printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by a cooperative Fifth, the description of the invention (26) 1 ◦ humidity or related operations for years or longer Life is calculated on the basis of absolute humidity. The calculation based on the absolute humidity is based on the operating life under the conditions of 80 ° C and 80% R Η, corresponding to the operating life under the conditions of 25 ° C and 60% RH. The absolute humidity at 80 ° C and 80% RH is 232.5 g / m3, and the absolute humidity at 25 ° C and 60% RH is 13 · 8g / m3. It is assumed here that the acceleration constant is two. And (232.5 / 13.8) 2 is almost equal to 283.85. In this case, if the operating life is 500 hours at 80 ° C and 80% RH, the operating life is 500 hours at 25 ° C and 60% R Η × 283 · 85 With 141,925 hours, blue, 5,914 days and 16.2 years, the annual humidity in Tokyo and Naha is noted here. It is calculated based on the monthly average relative humidity and is based on the absolute humidity standard. Example 2 The thermal resistor element obtained from Example 1 except that paraffin (Η NP-1 0 manufactured by Nippon Seiro Co ,, Ltd., with a melting point of 7 5 ° C) was used as the low-molecular, water-insoluble Organic compounds. An acceleration test was performed as in Example 1 and a temperature versus resistance curve was obtained. This device has a resistance of 値 2. 0 X 1 0 · 3 0 (1.6X10 2 Ocm) at room temperature (2 5 ° C), a rapid resistance rise around 75 ° C, and the maximum resistance 7 is 7.7 × 106Ω (6. 0x 10 7 Ω cm), and the resistance change rate is ten to the power of 9.6. In the accelerated test at 80 ° C and 80% RH, in 500 hours (please read the notice on the back of this page and then this page). --Line- 1) This paper standard applies the national solid standard (CNS) ) A4 specification (210 297 Gong Chu) -29-A7 B7 4574 9? V. Description of the invention (27) * Room temperature (2 5 ° C) resistance 値 is 6.2 X 1 0 3 Ω (4.9- --------------- ΐ 衣 --- 〆J \ — ·. (Please read the precautions on the back before rking this page) X 1 0 2 Ω cm), and the resistance changes The rate is 8.7 to the power of ten. In this way, both the 'room temperature resistance' and the rate of change in resistance remain substantially unchanged; sufficient P T C performance is well maintained. Example 3 The thermal resistor element obtained from Example 1, except that the high-density polyethylene (Η Y 4 2 0 was produced by Nippon Polychem Co., Ltd. and its MFR was 4 g / l0 mi η. And The melting point is 134 nm) as a polymer matrix. An accelerated test was performed as in Example 1 and a temperature versus resistance curve was obtained. Wire_ This device has a resistance of 値 4. 〇xl〇 · 3 Ω (3 · 1χ1〇 · 2Ωοπί) at room temperature (25 ° C) 'There is a rapid resistance rise around 75 ° C, and the maximum resistance 値 is 6 〇χ104Ω (4.7x 105 Ω cm), and the resistance change rate is ten to the 7.2 power. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy printed the accelerated test at 8 Ot and 80% RH. After 500 hours, the room temperature (25 ° C) resistance 値 was 7.5 X 1 0.3 Ω (5. 9 X 1 〇 2 Ω cm), and the resistance change rate is ten to the power of 6.5. In this way, both the room temperature resistance 値 and the resistance change rate remain substantially unchanged; a sufficient P T C performance is maintained well. Comparative Example 1 The thermal rheostat element obtained from Example 1, except that a silane coupling agent and an organic peroxide were not added, and no crosslinking treatment was performed. This paper size applies Chinese National Standard (CNS) / Vi specifications (210 X 297 mm) -30- 457497 A7 ----- B7_ V. Description of the invention (28) The temperature vs. resistance curve of this sample is obtained as in Example 1. . This device has a resistance at room temperature (25 ° C) of 3, 0x0-3Ω (2.4x 1 0 2 0 C m) 'There is a rapid resistance rise around 7 5 ° C, and the maximum resistance is 8.2 &gt; &lt; 1〇4ω (6.4xlOsncm), and the resistance change rate is 7.4 to the power of 7.4 * &gt; Using this element, as in Example 1, at 80 ° C and 80% R Η Perform accelerated testing. Room temperature resistance and resistance change rate are shown in Figure 4 at certain test times. After 500 hours, the room temperature resistance 値 is 3.4 χΐ〇 · 2Ω C2 · ΪΧί〇-'Ωοπι), which is 10 times the initial value, and the resistance change rate drops to 5.4 power of ten. . Comparative Example 2 The thermal rheostat element obtained from Example 2 was used without the addition of a silicon coupling agent and an organic peroxide, and without a cross-linking treatment. An accelerated test was performed as in Example 1 and a temperature versus resistance curve for this sample was obtained. This device has a resistance 値 2.0 0 × 10 · 3Ω (1 · 6x 1 Ο 'Ξ Ω C ΙΏ) at room temperature (25 ° C), a rapid resistance rise near 7 5 ° C, and the maximum resistance 8 is 8 _ 0 × 107Ω (6.3xl08Dcm), and the resistance change rate is 10 to the power of 10. In the accelerated test at 80 ° C and 80% RH, the room temperature resistance 値 is 7.7Ω (60.5ficm) and the resistance change rate is ten to the power of 7.1. As such, some considerable degradation was observed at both room temperature resistance 値 and resistance change rate. (Please read the precautions on the back before f this page) Install i _-, line _ € Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy This paper is compliant with Chinese National Standard (CNS) A4 (210 χ 297 mm) ) -31-457497 A7 B7 Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by a consumer cooperative V. Description of Invention (29) Comparative Example 3 The thermal resistor element obtained from Example 1 except for a low-density polyacetylene (LC 5 0 0 was produced by Nippon Polychem Co., Ltd. with an MFR of 4.0 g / lOmin. And a melting point of 106 t) as a polymer matrix. An accelerated test was performed as in Example 1 and a temperature versus resistance curve was obtained. This device has a resistance of 値 3 * 〇xl03 Ω (2 · 4χ1〇 · 2Ωοηι) at room temperature (25 ° C), a rapid resistance rise near 80 ° C, and the maximum resistance 値 is 1.0 × 109Ω ( 7.8X 1 0 9 Ω-cm), and the resistance change rate is ten to the eleventh power. "At 80 ° C and 80% R Η accelerated test, after 1000 hours, the maximum resistance 値 is 1. 0.x 1 09Ω or higher. However, the room temperature resistance 値 greatly increased to 7. 〇χΙΟ ^ Ω (5, 5Qcm) ° Comparative Example 4 The thermally variable resistor element obtained from Example 1 except for high density polyethylene (HJ 3 6 0 The polymer matrix was produced by Nippon Polychem Co., Ltd. with an MFR of 6 Og / lOmin and a melting point of 131.0). An accelerated test was performed as in Example 1 and a temperature versus resistance curve was obtained. This device has a resistance of 値 3.8 X 1 〇-3 Ω (3.0 × 10_2 Ω) at room temperature (2 5 ° C.), A rapid resistance rise near 7 5 ° C, and the maximum resistance 8 is 8 0 × 106Ω (6.3xl〇7 ----— — — — 4 ------ ·! 』4 SX) (Please read the precautions on the back before ^ 'too much on this page)-Line · One Γ This paper size applies the Chinese National Standard (CNS) AJ specification (210 &gt;: 297mm) -32-A7 457497 ------- B7____ V. Description of the invention (30) &quot; ~ 'Ω cm), and resistance The rate of change is ten to the power of 9.3. In 80 ° C and 80% R Η accelerated tests, after the tree says, &amp; after 5000 hours, the room temperature resistance 値 is 6. 4χ10_3Ώ &amp; ν 0 0 χ 1 ◦ _2 Ω cm), which The system is substantially similar to the starting point. However, no clear transition point of resistance was observed, although the resistance 增加 increased with increasing temperature ^ the resistance at 75 ° C is 1.3 χ 1 〇.ιΩ: the rate of change in resistance calculated from room temperature For the power of ten. Table 1 lists the room temperature resistances 电阻 and resistance change rates 各 of the components of Examples 1 to 3 and Comparative Examples 1 to 4, which were measured before and after the acceleration test. Melt flow rate (MFR) and the melting point (m ρ) of low molecular weight organic compounds. -------- 14 .----! Outfit --- • Λ / (Please read the precautions on the back before ^ ί this page)-Line. 1. Consumers' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The printed paper is applicable to the national standard (CNS) A4 specification (210 X 297 mm) -33- 4 5 7 4 9 7 A7 _B7 V. Description of the invention (31) Table 1 Employee Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Print

Polymer matrix low-molecular organic chopping cross-linking room temperature resistance (Ω) resistance 値 rate compound (mp) after starting the test Example 1 HD polyethylene microcrystalline marrow cross-linking 2.0x10-5.3xl. · 3 7.9 7.2 (MFR = 1.0) 83 ° C Example 2 HD polyethylene paraffin 75 t: Crosslinked 2.0x10- 6.2x10 &quot; 9.6 8.7 (MFR = 1.0) Example 3 HD polyethylene. Microcrystalline wax cross 40xl0 · 3 7.5x10 · 3 7.2 6,5 (MFR = 0.4) 83 r Comparative HD polyethylene microcrystalline wax uncrosslinked 3xχ10- 14x20 ° 7,4 5,4 Example I (MER = L0 ) 83 ° c Comparative HD polyethylene paraffin 75 ° C Uncrosslinked 2.0x10 '7.7 10.6 7.1 Example 2 (MFR = 1.0) Comparative LD polyethylene microcrystalline circle crosslinked 3.0x10-7.0x10, £ 11 Example 3 (MFR = 4.0) 83 ° C Comparative HD polyethylene microcrystalline wax cross-linked 3.8x10 &quot; 6,4xlO &quot; 3 9.3-Example 4 (MFR = 6.0) 83 ° C HD is the abbreviation for high density and LD Abbreviation for low density. * After 100 hours have passed * * Power of ten ---------: --- Γ! Equipment ---. J} (Please read the precautions on the back before re-production '-this page ) · -Line · This paper size is in accordance with China National Standard (C1 \ TS) A4 (210 x 297 mm) -34- A7 B7 457Λ9 7 V. Description of the invention (32) Ethylene is also used in Examples 1 to 3. Trimethoxysilicon was used as a silane coupling agent, and the results were the same as those obtained in Examples i to _3. Similar results were obtained when using 7-methacrylmethylpropyltrimethoxysilane and r-methacrylmethylpropyltriethoxysilane. The effect of the present invention is based on the present invention, so it is possible to provide an organic positive temperature coefficient thermal resistance resistor which has a sufficiently low resistance at room temperature and a large resistance change rate between an operating state and a non-operating state, and Can operate below 10 Q ° C with reduced hysteresis of temperature versus resistance curve, easy to control operating temperature, and high performance stability. --------.----- =-1-install --- *., (Please read the precautions on the back before following this page) Order .Γ. 线 _ Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to China National Standard (CNS) A4 (210 X 297 mm) -35-

Claims (1)

m 4 7 9 4 7 8888 Printed by ABCD Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application scope of patents * 1. An organic positive temperature coefficient thermal resistor, which contains a thermoplastic polymer matrix and has a melting point equal to or higher Low-molecular organic compounds at 40 ° C and lower than 100 ° C, and conductive particles each having pointed protrusions, wherein: the thermoplastic polymer matrix, the low-molecular organic compound, and the conductive particles The mixture is crosslinked with a silane coupling agent, which contains a vinyl group or a (meth) acrylfluorenyl group and an alkoxy group. 2. The organic type positive temperature coefficient thermal resistance resistor according to item 1 of the patent application range, wherein the low-molecular organic compound has a weight average molecular weight of 1,000,000 or less. 3. The organic type positive temperature coefficient thermal variable resistor according to item 1 of the patent application range, wherein the low-molecular organic compound is petroleum wax. 4. The organic positive temperature coefficient thermal resistance resistor according to item 1 of the scope of the patent application, wherein the conductive particles each having a sharp protrusion are connected in a chain shape. 5. The organic positive temperature coefficient thermal resistance resistor according to item 1 of the application, wherein the thermoplastic polymer matrix is polyolefin. 6. The organic positive temperature coefficient thermal variable resistor according to item 5 of the patent application, wherein the polyolefin is high-density polyethylene. 7. The organic positive temperature coefficient thermal resistance resistor according to item 6 of the patent application scope, wherein the melt flow rate of the high-density polyethylene is 3.0 g / 1 ◦ m i η. Or lower. 8. The organic type positive temperature coefficient thermal variable resistor according to item 1 of the application, wherein the silane coupling agent is vinyltrimethoxysilane or ethylene ---: --- ΓΙ-„I 康- (Please read the precautions on the back before filling this page) Order f. The size of the thread paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public envy) -36- A8 B8 C8 D8 45749 7 Ethoxysilane. 9. If the organic type positive temperature coefficient thermal variable resistor of item 1 of the scope of patent application, its operating temperature is lower than 100. 10 · —preparation of the organic type of positive type coefficient of scope of patent application Method for temperature coefficient thermal resistance resistor device, in which a thermoplastic polymer matrix, a low molecular organic compound having a melting point equal to or higher than 40 ° C and lower than 100 ° C, and The conductive particles are milled together into a ground mixture, and then the ground mixture is crosslinked with a silane coupling agent, which contains a vinyl group or a (meth) acrylfluorene group. Groups and alkoxy groups. (锖 Read the note on the back first Please fill in this tile for the matters needing attention.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is in accordance with China National Wax Standard (CNS) Λ4 specification (210X297 cm) -37-