CN100437840C - Macromolecular thermosensitive resistor and method for making same - Google Patents
Macromolecular thermosensitive resistor and method for making same Download PDFInfo
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- CN100437840C CN100437840C CNB2005100333301A CN200510033330A CN100437840C CN 100437840 C CN100437840 C CN 100437840C CN B2005100333301 A CNB2005100333301 A CN B2005100333301A CN 200510033330 A CN200510033330 A CN 200510033330A CN 100437840 C CN100437840 C CN 100437840C
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Abstract
The present invention discloses a macromolecule thermistor and a manufacturing method thereof. A substrate comprises the following components: 30 to 65 parts by weight of polymer, 30 to 60 parts by weight of conductive filler, 10 to 40 parts by weight of inorganic filler and 0.2 to 5 parts by weight of processing aid, wherein the conductive filler is nickel powder, copper powder or carbon black; the inorganic filler is metal oxide, silicon dioxide or pottery clay; the processing aid comprises the mixture of an antioxidant and a coupling agent; the weight ratio of the antioxidant to the coupling agent is 1:1.5 to 2.5; the antioxidant is an acrylic acid alcohol ester compound; the coupling agent is a titanate compound or a silane compound. The macromolecule thermistor is composed of the substrate, chip electrodes, wire electrodes and an insulation layer, wherein the chip electrodes are compounded on both surfaces of the substrate; the wire electrodes are welded on the surfaces of the electrodes; the insulation layer is coated on the outer surface of the macromolecule thermistor. The macromolecule thermistor solves the problems of voltage resistance, etc. of a thermistor. Besides, the present invention has the advantages of simple manufacturing technology, good technical effect, wide application, etc., and is suitable for various fields of telecommunication equipment, industrial control, household electric appliances, etc.
Description
Technical field
The present invention relates to a kind of resistance and manufacture method thereof, relate in particular to a kind of macromolecular thermosensitive resistor and manufacture method thereof.
Background technology
As everyone knows, add conducting particles in crystallinity or hemicrystalline high molecular polymer, can show positive temperature coefficient (PTC) characteristic: resistivity can increase fast with the rising of temperature in a relatively shorter temperature range.Because high molecular PTC thermistor has lower initial resistance, and increase sharply 5 more than the order of magnitude at time internal resistance value faster, can prevent effectively that circuit from breaking down, as short circuit, overlap joint, when situations such as induction took place, the big electric current that produces in the circuit was to the destruction of other critical elements in the circuit.After fault was got rid of, the temperature of thermistor descended, and its resistance value returns to low resistive state again.Need manually not change, so macromolecular PTC thermistor is called self-healing fuse again.
Macromolecular PTC thermistor has been widely used in numerous areas such as telecommunication apparatus, Industry Control, household electrical appliance now.In the macromolecular thermosensitive resistor practical application, it is inconsistent to appear in the use resistance change rate through regular meeting, will directly have influence on the operate as normal of electric equipment.
Summary of the invention
The present invention aims to provide a kind of macromolecular PTC thermistor and manufacture method thereof, makes more homogeneous such as resistance change rate behind its various electrical properties such as withstanding current capability or proof voltage ability, anti-electric current or the proof voltage, thereby guarantees the operate as normal of electric equipment.
In order to achieve the above object, the invention provides following technical scheme: develop a kind of macromolecular thermosensitive resistor, by substrate and be compound in the pellet electrode on substrate two sides, the insulating barrier that is welded in electrode surface lead-in wire shape electrode and is encapsulated in outer surface constitutes, the component of described substrate and parts by weight are: polymer 30～65, conductive filler 30～60, inorganic filler 10～40, processing aid 0.2～5.Described polymer is homopolymers or copolymer, comprise polyethylene, polypropylene, the ethylene/propylene copolymer, the blend of one or more arbitrary proportions of ethylene/acrylic acid copolymer and acrylate, described conductive filler is a nickel powder, copper powder, the mixture of one or more arbitrary proportions of carbon black, described inorganic filler is a calcium oxide, zinc oxide, magnesium oxide, aluminium oxide, antimonous oxide, silicon dioxide, magnesium hydroxide, the above particle diameter of one or more arbitrary proportions of aluminium hydroxide or potter's clay is the mixture of 1～170 μ m, described processing aid is to comprise antioxidant and coupling agent mixture, antioxidant: the weight ratio of coupling agent is 1: (1.5～2.5), wherein, antioxidant is acrylic acid alkoxide compound, and coupling agent is titanate esters or silane compound.In the above-mentioned raw materials proportioning, the ratio of conductive filler and inorganic filler is important, adds in described ratio, and the substrate resistance rate can be controlled in the scope of 2-7 Ω .cm.Wherein the antioxidant of Jia Ruing can prevent polymer processing generation oxidation, and coupling agent can guarantee compatibility good between polymer and the filler.Described promoter addition should be controlled, if processing aid is too much, auxiliary agent easily produces residual in polymeric system, has influence on the electrical property of final products.
In the inorganic filler of 10～40 parts by weight of the present invention, particle diameter is that 1-30 μ m contains 5～20 parts, and particle diameter is that 70-170 μ m contains 5～20 parts.Owing to adopt the inert filler of two kinds of big small particle diameter of difference, the inert filler of the broad particle size range that therefore distributed in the substrate microstructure, the motion of conducting particles when effectively having suppressed high temperature, system is through behind the cross-linking radiation, cross-linked structure is also more stable, improve the heat-resistant stability of product, thereby improved the anti-electric current of product, withstand voltage properties.
The manufacture method of thermistor of the present invention comprises following process: (1) with polymer, conductive filler, inorganic filler and processing aid, uses double screw extruder mixing by metering under 140 ℃～240 ℃ temperature, extrudes, and pulling-on piece is hot pressed into area 50-500cm
2The sheet material of thickness 0.1～1.8mm, then (2) by hot pressing metal electrode be compound to step (1) resulting sheet two surfaces, obtain composite sheet, be the electron beam or the Co60 cross-linking radiation of 10-60 Megarad again with composite sheet dosage, perhaps (3) are the electron beam or the Co60 cross-linking radiation of 10～60 Megarads with step (1) resulting sheet dosage earlier, by hot pressing metal electrode is compound on the sheet material again, get composite sheet, (4) are washed into the composite sheet of step (2) or (3) gained the small pieces of required size at last, lead-in wire shape electrode in the welding, and seal insulating barrier at lead-in wire shape electrode outer surface, the thermistor product.In concrete manufacture process, should be mixing with double screw extruder under 140 ℃～240 ℃ temperature, temperature is crossed low sizing and can not fully be distributed in the polymeric system, and temperature is crossed high polymer and is easily produced degraded; In addition, irradiation dose should be low at the electron beam or the Co60 cross-linking radiation irradiation dose of 10～60 Megarads, and polymer can not be full cross-linked, and irradiation dose height, polymer easily produce degraded.
The present invention's the mixing temperature of usefulness double screw extruder is to be to outlet temperature by the double screw extruder import to increase progressively, and inlet temperature is 140 ℃～170 ℃, and outlet temperature is 190 ℃～240 ℃.In the practical operation, control inlet temperature and outlet temperature are convenient to operation.
Compared with prior art, the present invention has following tangible advantage: 1, manufacturing process is simple, is easy to control; 2, technique effect is good: owing to use the inert filler of two kinds of big small particle diameter of difference, the inert filler of the broad particle size range that therefore distributed in the substrate microstructure, the motion of conducting particles when effectively having suppressed high temperature, system is through behind the cross-linking radiation, cross-linked structure also stablizes 3 more, good product quality: the substrate resistance rate can be controlled in the scope of 2-7 Ω .cm, because substrate microcosmic cross-linked structure is stable homogeneous more, improved the heat-resistant stability of product, thereby improve the anti-electric current of product, withstand voltage properties, product is through anti-electric current, and resistance varying-ratio is less than 30% after the withstand voltage test; 4, be widely used: can be used for numerous areas such as telecommunication apparatus, Industry Control, household electrical appliance.
Embodiment
Below by specific embodiment the present invention is carried out more detailed description:
Embodiment 1 takes by weighing polymer-high density polyethylene (HDPE) 380 grams, electric conducting material-carbon black 350 grams, inorganic filler-magnesium hydroxide granularity is each 70 gram of 10 μ m, 104 μ m, antioxidant-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 18 carbonic acid alcohol ester Irganox1076 are that 12 grams, coupling agent-titanate esters 201 are 20 grams, each component places double screw extruder mixing evenly, each section of extruder temperature is set at 160 ℃ 170 ℃ 180 ℃ 190 ℃ respectively, extrude, pulling-on piece, at pressure 6Mpa, under 185 ℃ of conditions of temperature, be hot pressed into area 130cm
2The sheet material of thickness 0.8mm, with dosage is 42 Megarads (Mrad) electron beam irradiations, at pressure 6Mpa, following single face roughening of 185 ℃ of conditions of temperature crossed nickel foil and is hot-pressed onto on the sheet material, use electron beam irradiation, dosage is 12Mrad, strikes out the small pieces of Φ 10.7, and welding the zero power resistance that the tinned wird of Φ 0.8mm can make then respectively on the two sides is the thermistor of 0.35～0.9 Ω.Product carries out anti-power current and the ability test of anti-the power-frequency voltage according to YD/T 741-2002.The test of anti-power current: at 90V, 20A switched on 6 seconds, cut off the power supply 60 seconds, and resistance change rate is 19% behind the rush of current 100 times.The ability test of anti-power-frequency voltage the: 90V, 20A energising 240 minutes, resistance change rate is 23%.
Embodiment 2 takes by weighing polymer-high density polyethylene (HDPE) 280 grams, ethylene/propylene acid copolymer 110 grams, electric conducting material-copper powder 150 grams, carbon black 450 grams, inorganic filler-hydroxide particle-size is 10 μ m, each 50 gram of 104 μ m, antioxidant-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 18 carbonic acid alcohol ester Irganox1076 are 2 grams, coupling agent-titanate esters 201 is 4 grams, each component is mixing even in double screw extruder, each section of extruder temperature is set at 160 ℃ respectively, 170 ℃, 180 ℃, 190 ℃, extrude, pulling-on piece, at pressure 6Mpa, under 185 ℃ of conditions of temperature, be hot pressed into area 130cm
2The sheet material of thickness 0.4mm, with dosage is the 15Mrad electron beam irradiation, at pressure 6Mpa, following single face roughening of 185 ℃ of conditions of temperature crossed nickel foil and is hot-pressed onto on the sheet material, with dosage is the 40Mrad electron beam irradiation, strike out the small pieces of Φ 6.7, weld the tinned wird of Φ 0.6mm then on the two sides respectively, seal with epoxy and can make the thermistor that zero power resistance is 0.41～0.77 Ω.Product carries out anti-power current and the ability test of anti-the power-frequency voltage according to YD/T 741-2002.The test of anti-power current: at 60V, 40A switched on 6 seconds, cut off the power supply 60 seconds, and resistance change rate is 18% behind the rush of current 100 times.The ability test of anti-power-frequency voltage the: 60V, 40A switched on 240 minutes, and resistance change rate is 26%.
Embodiment 3 takes by weighing polymer-low density polyethylene (LDPE) 300 grams, electric conducting material-copper powder 100 grams, nickel powder 20 grams, carbon black 420 grams, inorganic filler-potter's clay granularity is 10 μ m, antimonous oxide 104 μ m are respectively 40 grams and 60 grams, antioxidant-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 18 carbonic acid alcohol ester Irganox1076 are 1 gram, coupling agent-titanate esters 201 is 2 grams, mixing mode changes banbury processing into, temperature is 170 ℃, open the refining pulling-on piece, other conditions obtain the similar products like with embodiment 1-2 respectively respectively with embodiment 1, detect anti-power current test with quadrat method: resistance change rate is 19% behind the rush of current 100 times.The ability test of anti-the power-frequency voltage: switched on 240 minutes, resistance change rate is 24%.
Embodiment 4 takes by weighing polymer-low density polyethylene (LDPE) 100 grams, acrylate 270 grams, electric conducting material-nickel powder 100 grams, carbon black 200 grams, inorganic filler-hydroxide particle-size is 10 μ m, each 200 gram of 104 μ m, antioxidant-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 18 carbonic acid alcohol ester Irganox1076 are 3 grams, coupling agent-vinyltrimethoxy silane, titanate esters 201 each 7 gram, mixing mode changes banbury processing into, temperature is 170 ℃, open the refining pulling-on piece, use the Co60 cobalt-60 radiosterilize instead, irradiation dose is identical with embodiment 3 with other conditions, other conditions are respectively with embodiment 1, obtain 1～2 similar products like with embodiment respectively, detect with quadrat method, anti-power current test: resistance change rate is 20% behind the rush of current 100 times.The ability test of anti-the power-frequency voltage: switched on 240 minutes, back resistance change rate is 24%.
Embodiment 5 takes by weighing polymer-high density polyethylene (HDPE) 500 grams, electric conducting material-copper powder 300 grams, inorganic filler-zinc oxide granularity is 10 μ m, the silicon dioxide granularity is that 104 μ m are respectively 50 grams, 300 grams, antioxidant-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 18 carbonic acid alcohol ester Irganox1076 are 15 grams, coupling agent-vinyltrimethoxy silane is 35 grams, mixing mode changes banbury processing into, temperature is 190 ℃, open the refining pulling-on piece, use the Co60 cobalt-60 radiosterilize instead, irradiation dose is identical with embodiment 4 with other conditions, other conditions are respectively with embodiment 1, detect anti-power current test with quadrat method: resistance change rate is 18% behind the rush of current 100 times.The ability test of anti-the power-frequency voltage: switched on 240 minutes, back resistance change rate is 22%.
Claims (1)
1, a kind of macromolecular thermosensitive resistor, by substrate and be compound in the pellet electrode on substrate two sides, the insulating barrier that is welded in electrode surface lead-in wire shape electrode and is encapsulated in outer surface constitutes, it is characterized in that: the component of substrate and parts by weight are:
Polymer 30～65
Conductive filler 30～60
Inorganic filler 10～40
Processing aid 0.2～5
Described polymer is homopolymers or copolymer, comprise polyethylene, polypropylene, the ethylene/propylene copolymer, the blend of one or more arbitrary proportions of ethylene/acrylic acid copolymer and acrylate, described conductive filler is a nickel powder, copper powder, the mixture of one or more arbitrary proportions of carbon black, described inorganic filler is a calcium oxide, zinc oxide, magnesium oxide, aluminium oxide, antimonous oxide, silicon dioxide, magnesium hydroxide, the particle diameter of one or more arbitrary proportions of aluminium hydroxide or potter's clay is the mixture of 1～170 μ m, in the inorganic filler of described 10～40 parts by weight, particle diameter is that 1-30 μ m contains 5～20 parts, particle diameter is that 70-170 μ m contains 5～20 parts, described processing aid is the mixture that comprises antioxidant and coupling agent, antioxidant: the weight ratio of coupling agent is 1: (1.5～2.5), wherein, antioxidant is acrylic acid alkoxide compound, and coupling agent is titanate esters or silane compound.
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| CNB2005100333301A CN100437840C (en) | 2005-02-24 | 2005-02-24 | Macromolecular thermosensitive resistor and method for making same |
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| CNB2005100333301A CN100437840C (en) | 2005-02-24 | 2005-02-24 | Macromolecular thermosensitive resistor and method for making same |
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| CN1655291A CN1655291A (en) | 2005-08-17 |
| CN100437840C true CN100437840C (en) | 2008-11-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509884C (en) * | 2007-08-16 | 2009-07-08 | 聊城大学 | Copolymerization type intrinsic conductive polymer and method for preparing same |
| CN101930819A (en) * | 2010-01-15 | 2010-12-29 | 上海长园维安电子线路保护股份有限公司 | Positive temperature coefficient thermosensitive resistor for overtemperature and overcurrent protection of secondary battery |
| CN102260385B (en) * | 2010-05-31 | 2013-07-24 | 比亚迪股份有限公司 | Positive temperature coefficient material and thermistor containing same |
| WO2019077811A1 (en) * | 2017-10-17 | 2019-04-25 | 信越化学工業株式会社 | Millable silicone rubber composition and electric-field relaxation layer |
| CN108822492A (en) * | 2018-05-23 | 2018-11-16 | 江苏时瑞电子科技有限公司 | A kind of macromolecular PTC thermistor material and preparation method thereof |
| CN110911075B (en) * | 2019-12-17 | 2021-11-30 | 深圳市慧瑞电子材料有限公司 | Preparation method of high-molecular thermistor and high-molecular thermistor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254932A (en) * | 1998-11-19 | 2000-05-31 | 上海维安热电材料有限公司 | Low-resistance thermosensitive resistor and its making method |
| CN1581371A (en) * | 2003-08-15 | 2005-02-16 | 比亚迪股份有限公司 | Thermistor material and method for manufacturing thermistor containing same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254932A (en) * | 1998-11-19 | 2000-05-31 | 上海维安热电材料有限公司 | Low-resistance thermosensitive resistor and its making method |
| CN1581371A (en) * | 2003-08-15 | 2005-02-16 | 比亚迪股份有限公司 | Thermistor material and method for manufacturing thermistor containing same |
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Granted publication date: 20081126 Termination date: 20130224 |