CN1254932A - Low-resistance thermosensitive resistor and its making method - Google Patents
Low-resistance thermosensitive resistor and its making method Download PDFInfo
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- CN1254932A CN1254932A CN 98122016 CN98122016A CN1254932A CN 1254932 A CN1254932 A CN 1254932A CN 98122016 CN98122016 CN 98122016 CN 98122016 A CN98122016 A CN 98122016A CN 1254932 A CN1254932 A CN 1254932A
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Abstract
A low-resistance thermosensitive resistor is made up of high-molecular polymer, electrically conducting filler, inorganic filler and assistance, and features that the specially treated electrically conducting filler is used to increase surficial active radicals, the bind nature with high-molecular substrate, and in turn the thermal stability. After shocked by high current several times, it can still restore its low-resistance state.
Description
The present invention relates to a kind of is the electronic devices and components of primary raw material with the conducting high polymers thing, especially a kind of low-resistance thermosensitive resistor and manufacture method thereof.
The resistivity of a lot of electric conducting materials varies with temperature, and has the conductor of positive temperature coefficient (PTC) characteristic, and in certain temperature range, the resistivity of self can increase with the rising of temperature.After the high molecular polymer of mass part crystallization and the conducting particles blend, has the obvious PTC characteristic.These partially crystalline polymers comprise polyethylene, polypropylene, polyformaldehyde etc., and their copolymer.Conducting particles comprises carbon black, metal dust etc.When lower temperature, this class blend presents lower resistivity, and is elevated near its high molecular polymer fusing point when temperature, during just so-called " shutoff " temperature, and the hurried rising of resistivity.This class conductor with ptc characteristics can be made into thermistor, is applied to the overcurrent protection of circuit.In the normal state; electric current in the circuit is less relatively; the thermistor actuator temperature is lower; and when the big electric current that is caused by fault passes through; its temperature can be elevated to " shutoff " temperature suddenly; cause its resistance value to become very big, so just make circuit be in a kind of approximate " open circuit " state, thereby protected other element in the circuit.And after fault was got rid of, the temperature of thermistor descended, and its resistance value can return to the low resistance state again.
Thermistor has been widely used in the various fields such as communication, computer, automobile, Industry Control, electronics, but, the thermal stability of the high molecular polymer thermistor that occurs is relatively poor at present, that is to say through heavy current impact repeatedly or under certain voltage, be in " shutoff " state for a long time, after making its " recovery ", its zero-power resistance can raise a lot, and really " recovery " is to original initial resistance.
Purpose of the present invention exactly overcome the defective that above-mentioned prior art exists and a kind of good heat stability be provided, behind heavy current impact, still can keep the low-resistance thermosensitive resistor of low zero power resistance.
Purpose of the present invention can realize in the following manner:
This low-resistance thermosensitive resistor, it by core and be covered on above-mentioned core two sides tinsel, be welded on the above-mentioned tinsel outer surface sheet or the lead-in wire shape extraction electrode and be coated on the outside insulating barrier constitute, it is characterized in that above-mentioned core is mixed by high molecular polymer, conductive filler, inorganic filler and processing aid, its prescription following (percetage by weight):
High molecular polymer 34～60%
Conductive filler 34～60%
Inorganic filler 5～20%
Processing aid 1～5%
The core component high molecular polymer of above-mentioned resistor can be the copolymer of a kind of polymer or two or more polymer, mainly contains: polyethylene, polypropylene, poly-1-butylene, Kynoar, polytrifluorochloroethylene, nylon, poly terephthalic acid diethylester, polybutyl terapthalate.
The core component conductive filler of above-mentioned resistor is made up of two parts, one, the carbon black of special processing, they are two years old, one or more mixtures of following material: the glass microballoon of carbon black, graphite, carbon fiber, metal dust, plating metal on surface, wherein the filler of first accounts for 20%～80% (volume) of conductive filler total amount.
The core component inorganic filler of above-mentioned resistor mainly is the inorganic matter of particle diameter＜50 μ m, as magnesium oxide, aluminium oxide, silicon dioxide, potter's clay, talcum powder, calcium carbonate, magnesium hydroxide, aluminium hydroxide.
The core component processing aid of above-mentioned resistor is meant antioxidant, crosslinking accelerator, coupling agent, wherein antioxidant can be phenols or aminated compounds, crosslinking accelerator can be the polyfunctional group unsaturated compound, and coupling agent can be silane or titanate ester organic compound.
The manufacture method of low-resistance thermosensitive resistor, it is characterized in that under 190～200 ℃ of temperature, in banbury or double screw extruder, carrying out core component high molecular polymer, conductive filler, inorganic filler and processing aid mixing, wherein conductive filler comprises the carbon black of special processing, and making area with mold pressing or the method extruded then is 100～1000cm
2, thick 0.1～1.0mm sheet material, be the core of polymer thermistor, on hot press, tinsel is compound in two surfaces of above-mentioned core, make composite sheet, and then with this composite sheet with ν ray (Co
60) or electron beam to irradiate crosslinked, dosage is 5～100Mrad, also can be earlier core be pasted tinsel after with the said method cross-linking radiation again, and then composite sheet is cut into the small pieces of certain size, sheet or lead-in wire shape metal electrode in the welding, the outside behind the coated insulation layer, promptly obtains the polymer thermistor device again.
The described carbon black of above-mentioned manufacture method can carry out special processing in order to following method: at first, with chemical method or heat treatment method carbon black is carried out oxidation processes, such as: in air, heated under the high temperature 4～8 hours, make its PH＜7, best PH＜4, then, behind organic solvent dissolutions such as titanate coupling agent benzinum, cyclohexane, toluene, dimethylbenzene, under stirring, be added drop-wise in the carbon black that above-mentioned surface oxidation treatment crosses, at last dry for standby in vacuum drying oven.
Compared with prior art, advantage of the present invention is to have adopted two or more conductive fillers, and wherein a kind of is carbon black through special processing, has increased the quantity of its surface active groups, has improved the associativity of it and macromolecule matrix, thereby has improved thermal stability; Another kind of conductive filler is the better conductivity conducting particles, has reduced the resistance value of whole polymer thermistor, can obtain lower zero power resistance.
Below in conjunction with embodiment, the present invention is described in further detail: embodiment 1～5
Table 1 unit: g
Annotate: carbon black A CTAB adsorption specific surface area 36m
2/ g is through surface treatment
| The numbering project | ????1 | ????2 | ????3 | ????4 | ????5 |
| High density polyethylene (HDPE) | ??400 | ??350 | ??380 | ??400 | ??400 |
| EVA | ????- | ???50 | ????- | ????- | ???30 |
| Carbon black A | ??150 | ??150 | ??170 | ??150 | ??150 |
| Carbon black B | ??200 | ??200 | ??200 | ??150 | ??150 |
| Nickel powder | ????- | ????- | ????- | ???50 | ???50 |
| Magnesium hydroxide | ???80 | ???80 | ????- | ???80 | ????- |
| Aluminium hydroxide | ????- | ????- | ???60 | ????- | ???80 |
| Antioxidant | ????2 | ????2 | ????2 | ????2 | ????2 |
| Crosslinking accelerator | ????5 | ????5 | ????5 | ????5 | ????5 |
| Coupling agent | ????1 | ????1 | ????1 | ????1 | ????1 |
Carbon black B CTAB adsorption specific surface area 110m
2/ g is without surface treatment
The coupling agent titanate coupling agent
Each component in the table 1 is mixing even in banbury under 195 ℃ of temperature, after cooling, pulverizing, place it in the pressing mold, pressure 4MPa is pressed into area 100cm under 170 ℃ of conditions of temperature
2, thick 0.2mm core.To at pressure 5Mpa, be hot-pressed onto the two-sided of core under 200 ℃ of conditions of temperature through the nickel sheet behind the surface coarsening after leveling, 85 ℃ of heat treatments are after 8 hours, with gamma-rays (Co in vacuum drying oven
60) irradiation, dosage is 20Mrad, strike out the small pieces of 5 * 12mm then, and then the thick 0.10mm that burn-ons respectively on the two sides, the sheet metal electrode of 4 * 10mm size can make the polymer thermistor device of zero power resistance 0.05～0.09 Ω, through 15V, behind the 100A rush of current 300 times, resistance change amount＜5%.Embodiment 6
Table 2 unit: g
Annotate: carbon black A CTAB adsorption specific surface area 36m
2/ g is through surface treatment
| High density polyethylene (HDPE) | Carbon black A | Carbon black B | Magnesium hydroxide | Antioxidant | Crosslinking accelerator | Coupling agent |
| ????460 | ?200 | ?140 | ????100 | ????2 | ?????5 | ????2 |
Carbon black B CTAB adsorption specific surface area 110m
2/ g is without surface treatment
The coupling agent titanate coupling agent
Each component of table 2 is mixing even in banbury under 190 ℃ of temperature, after cooling, pulverizing, place it in the pressing mold, pressure 4Mpa is pressed into area 100cm under 170 ℃ of conditions of temperature
2, the core of thick 0.2mm.To at pressure 5Mpa, under 200 ℃ of conditions of temperature, be pressed onto the two-sided of core through the nickel sheet of surface coarsening after leveling, 85 ℃ of heat treatments are after 8 hours, with gamma-rays (Co in vacuum drying oven
60) irradiation, dosage is 25Mrad, on punch press, strike out φ 6.7mm sequin again, burn-on respectively on the two sides again tin-coated copper lead-in wire of φ 0.6mm, and then seal material package with epoxy and seal, promptly obtain the polymer thermistor device of zero power resistance 0.15～0.9 Ω, through 60V, behind the 40A rush of current 300 times, resistance change amount＜100%.Embodiment 7～12
Radiation mode changes electron beam irradiation into, and irradiation dose is identical with embodiment 1～6 respectively with other conditions, can obtain the product similar with embodiment 1～6.Embodiment 13～18
The preparation of core is used extruder instead and is extruded.Each section of extruder temperature is controlled at 150 ℃, and 160 ℃, 170 ℃, carry out under 180 ℃ the condition, the melt of extruding is finalized the design with calender, after the cooling, cut into the core of certain size again, other conditions are identical with embodiment 1～6 respectively, can obtain the product similar with embodiment 1～6.Embodiment 19～24
Radiation mode changes electron beam irradiation into, and irradiation dose is identical with embodiment 13～18 respectively with other conditions, can obtain the product similar with embodiment 13～18.Embodiment 25
Table 3 unit: g
Annotate: carbon black A CTAB adsorption specific surface area 36m
2/ g is through surface treatment
| High density polyethylene (HDPE) | Carbon black A | Carbon black B | Magnesium hydroxide | Antioxidant | Crosslinking accelerator | Coupling agent |
| ????460 | ?200 | ?140 | ????100 | ????2 | ?????5 | ????2 |
Carbon black B CTAB adsorption specific surface area 110m
2/ g is without surface treatment
The coupling agent titanate coupling agent
It is even that each component of above-mentioned table 3 is mixed in banbury under 200 ℃ of temperature, after cooling, pulverizing, puts it into pressing mold voltage power 4Mpa, is pressed into area 100cm under 170 ℃ of conditions of temperature
2, the core of thick 0.2mm is with gamma-rays (Co
60) irradiation, dosage is 25Mrad.Will be after leveling through the nickel sheet of surface coarsening, at pressure 5Mpa, under 200 ℃ of conditions of temperature, be pressed onto the two-sided of core, 85 ℃ of heat treatments strike out the sequin of φ 6.7mm after 8 hours again on punch press in vacuum drying oven, the tin-coated copper lead-in wire of the φ 0.6mm that burn-ons respectively on the two sides again, and then seal material package envelope with epoxy, promptly obtain the product similar with embodiment 6.
Claims (7)
1. low-resistance thermosensitive resistor, it by core and be covered on above-mentioned core two sides tinsel, be welded on the above-mentioned tinsel outer surface sheet or the lead-in wire shape extraction electrode and be coated on the outside insulating barrier constitute, it is characterized in that above-mentioned core is mixed by high molecular polymer, conductive filler, inorganic filler and processing aid, its prescription following (percetage by weight):
High molecular polymer 34～60%
Conductive filler 34～60%
Inorganic filler 5～20%
Processing aid 1～5%
2. low-resistance thermosensitive resistor according to claim 1, it is characterized in that core component high molecular polymer can be the copolymer of a kind of polymer or two or more polymer, mainly contain: polyethylene, polypropylene, poly-1-butylene, Kynoar, polytrifluorochloroethylene, nylon, poly terephthalic acid diethylester, polybutyl terapthalate.
3. low-resistance thermosensitive resistor according to claim 1, it is characterized in that core component conductive filler is made up of two parts, one, the carbon black of special processing, they are two years old, one or more mixtures of following material: the glass microballoon of carbon black, graphite, carbon fiber, metal dust, plating metal on surface, wherein the filler of first accounts for 20%～80% (volume) of conductive filler total amount.
4. low-resistance thermosensitive resistor according to claim 1, it is characterized in that the inorganic filler of core component mainly is the inorganic matter of particle diameter＜50 μ m, as magnesium oxide, aluminium oxide, silicon dioxide, potter's clay, talcum powder, calcium carbonate, magnesium hydroxide, aluminium hydroxide.
5. low-resistance thermosensitive resistor according to claim 1, it is characterized in that core component processing aid is meant antioxidant, crosslinking accelerator, coupling agent, wherein antioxidant can be acids or aminated compounds, crosslinking agent can be the polyfunctional group unsaturated compound, and coupling agent can be silane or titanate ester organic compound.
6. the manufacture method of low-resistance thermosensitive resistor, it is characterized in that under 190～200 ℃ of temperature, in banbury or double screw extruder, carrying out core component high molecular polymer, conductive filler, inorganic filler and processing aid mixing, wherein conductive filler comprises the carbon black of special processing, and making area with mold pressing or the method extruded then is 100～1000cm
2, thick 0.1～1.0mm sheet material, be the core of polymer thermistor, on hot press, tinsel is compound in two surfaces of above-mentioned core, make composite sheet, and then with this composite sheet with gamma-rays (Co
60) or electron beam to irradiate crosslinked, dosage is 5～100Mrad, also can be earlier core be pasted tinsel after with the said method cross-linking radiation again, and then composite sheet is cut into the small pieces of certain size, sheet or lead-in wire shape metal electrode in the welding, the outside behind the coated insulation layer, promptly obtains the polymer thermistor device again.
7. the manufacture method of low-resistance thermosensitive resistor according to claim 6, it is characterized in that carbon black can carry out special processing in order to following method: at first, with chemical method or heat treatment method carbon black is carried out oxidation processes, such as: in air, heated under the high temperature 4～8 hours, make its PH＜7, best PH＜4, then, behind organic solvent dissolutions such as titanate coupling agent benzinum, cyclohexane, toluene, dimethylbenzene, under stirring, be added drop-wise in the carbon black that above-mentioned surface oxidation treatment crosses, at last dry for standby in vacuum drying oven.
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| CN98122016A CN1091931C (en) | 1998-11-19 | 1998-11-19 | Low-resistance thermosensitive resistor and its making method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122016A CN1091931C (en) | 1998-11-19 | 1998-11-19 | Low-resistance thermosensitive resistor and its making method |
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| CN1091931C CN1091931C (en) | 2002-10-02 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312705C (en) * | 2001-11-15 | 2007-04-25 | Tdk株式会社 | On-machine posistor and its mfg. method |
| CN1331165C (en) * | 2003-04-08 | 2007-08-08 | 上海维安热电材料股份有限公司 | Chip type macromolecule PTC thermistor |
| CN100426424C (en) * | 2004-12-21 | 2008-10-15 | 上海长园维安电子线路保护股份有限公司 | Method for manufacturing high-temp PTC thermosensitive resistor |
| CN100437840C (en) * | 2005-02-24 | 2008-11-26 | 深圳市固派电子有限公司 | Macromolecular thermosensitive resistor and method for making same |
| CN101477859B (en) * | 2009-01-16 | 2011-11-30 | 上海科特高分子材料有限公司 | Novel surface mounting type thermistor and manufacturing method thereof |
| CN103113695A (en) * | 2013-01-29 | 2013-05-22 | 上海科特高分子材料有限公司 | High-temperature and high-voltage resistant high-molecular conductive composite material and thermistor |
| CN103345993A (en) * | 2013-06-21 | 2013-10-09 | 兴勤（常州）电子有限公司 | Ultralow-resistance thermistor and forming processing method thereof |
| CN103762052A (en) * | 2013-12-30 | 2014-04-30 | 深圳市慧瑞电子材料有限公司 | PPTC (polymer positive temperature coefficient) overcurrent protector with low holding current and preparation method thereof |
| CN104558869A (en) * | 2014-12-27 | 2015-04-29 | 北京化工大学 | Polybutylene-1 material filled with calcium carbonate after surface treatment with coupling agent, and preparation method of polybutylene-1 material |
| CN106024230A (en) * | 2016-08-10 | 2016-10-12 | 安徽省宁国天成电工有限公司 | Modified graphene/PVDF composite PTC thermistor |
| CN107625633A (en) * | 2017-09-11 | 2018-01-26 | 华南理工大学 | A kind of micromolecular water is atomized moisturizing beauty mask |
| CN108528955A (en) * | 2018-03-26 | 2018-09-14 | 广东恒联食品机械有限公司 | A kind of controllable temperature kitchen insulation barrel |
| CN108553243A (en) * | 2017-12-29 | 2018-09-21 | 珠海富伊特科技有限公司 | A kind of medical child-bearing thermostatic protectiving incubator |
| 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 |
| CN109417834A (en) * | 2016-07-22 | 2019-03-01 | E.I.内穆尔杜邦公司 | Thin film heating device |
| CN112094449A (en) * | 2020-09-16 | 2020-12-18 | 东莞市竞沃电子科技有限公司 | Curie point adjustable PTC polymer conductive composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378407A (en) * | 1992-06-05 | 1995-01-03 | Raychem Corporation | Conductive polymer composition |
| CN1027666C (en) * | 1993-02-20 | 1995-02-15 | 袁晓辉 | High molecular polymer thermistor material with positive temperature coefficient |
-
1998
- 1998-11-19 CN CN98122016A patent/CN1091931C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312705C (en) * | 2001-11-15 | 2007-04-25 | Tdk株式会社 | On-machine posistor and its mfg. method |
| CN1331165C (en) * | 2003-04-08 | 2007-08-08 | 上海维安热电材料股份有限公司 | Chip type macromolecule PTC thermistor |
| CN100426424C (en) * | 2004-12-21 | 2008-10-15 | 上海长园维安电子线路保护股份有限公司 | Method for manufacturing high-temp PTC thermosensitive resistor |
| CN100437840C (en) * | 2005-02-24 | 2008-11-26 | 深圳市固派电子有限公司 | Macromolecular thermosensitive resistor and method for making same |
| CN101477859B (en) * | 2009-01-16 | 2011-11-30 | 上海科特高分子材料有限公司 | Novel surface mounting type thermistor and manufacturing method thereof |
| CN103113695B (en) * | 2013-01-29 | 2015-10-28 | 上海科特新材料股份有限公司 | A kind of high temperature resistant high-tension conductive polymer composites and thermistor |
| CN103113695A (en) * | 2013-01-29 | 2013-05-22 | 上海科特高分子材料有限公司 | High-temperature and high-voltage resistant high-molecular conductive composite material and thermistor |
| CN103345993A (en) * | 2013-06-21 | 2013-10-09 | 兴勤（常州）电子有限公司 | Ultralow-resistance thermistor and forming processing method thereof |
| CN103762052A (en) * | 2013-12-30 | 2014-04-30 | 深圳市慧瑞电子材料有限公司 | PPTC (polymer positive temperature coefficient) overcurrent protector with low holding current and preparation method thereof |
| CN104558869A (en) * | 2014-12-27 | 2015-04-29 | 北京化工大学 | Polybutylene-1 material filled with calcium carbonate after surface treatment with coupling agent, and preparation method of polybutylene-1 material |
| CN109417834A (en) * | 2016-07-22 | 2019-03-01 | E.I.内穆尔杜邦公司 | Thin film heating device |
| US11259368B2 (en) | 2016-07-22 | 2022-02-22 | Dupont Electronics, Inc. | Thin-film heating device |
| CN109417834B (en) * | 2016-07-22 | 2022-04-12 | E.I.内穆尔杜邦公司 | Film heating device |
| CN106024230A (en) * | 2016-08-10 | 2016-10-12 | 安徽省宁国天成电工有限公司 | Modified graphene/PVDF composite PTC thermistor |
| CN107625633A (en) * | 2017-09-11 | 2018-01-26 | 华南理工大学 | A kind of micromolecular water is atomized moisturizing beauty mask |
| CN108553243A (en) * | 2017-12-29 | 2018-09-21 | 珠海富伊特科技有限公司 | A kind of medical child-bearing thermostatic protectiving incubator |
| CN108528955A (en) * | 2018-03-26 | 2018-09-14 | 广东恒联食品机械有限公司 | A kind of controllable temperature kitchen insulation barrel |
| 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 |
| CN112094449A (en) * | 2020-09-16 | 2020-12-18 | 东莞市竞沃电子科技有限公司 | Curie point adjustable PTC polymer conductive composite material and preparation method thereof |
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