CN102176342A - Conductive polymer composition and overcurrent protection element made from same - Google Patents
Conductive polymer composition and overcurrent protection element made from same Download PDFInfo
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- CN102176342A CN102176342A CN2011100277754A CN201110027775A CN102176342A CN 102176342 A CN102176342 A CN 102176342A CN 2011100277754 A CN2011100277754 A CN 2011100277754A CN 201110027775 A CN201110027775 A CN 201110027775A CN 102176342 A CN102176342 A CN 102176342A
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Abstract
The invention relates to a conductive polymer composition and an overcurrent protection element prepared from the same. The polymer composition comprises the following components in percentage by weight: 5 to 30 percent of crystalline high molecular polymer, 50 to 95 percent of conductive metal filling material and 1 to 20 percent of polyethylene wax, wherein the conductive filling material may be one or compositions of more than one of nickel powder, silver powder and gold powder. A method for preparing the overcurrent protection element from the conductive polymer composition comprises the following steps of: firstly, mixing the composition, and drawing the mixed composition to form a sheet; secondly, laminating metal foils onto the upper and lower surfaces of the sheet; thirdly, performing irradiation and stamping to mold a chip meeting size requirements; and fourthly, welding a nickel sheet onto the chip as an extraction electrode to obtain the required overcurrent protection element. The overcurrent protection element prepared from the conductive polymer composition has the advantages of low room temperature resistance and high environmental resistance.
Description
Technical field
The present invention relates to a kind of electric conductive polymer and over-current protecting element, specifically, the present invention relates to a kind of the have conductive polymer composition of positive temperature coefficient (PTC) characteristic and the over-current protecting element of preparation thereof.
Background technology
Polymer has been a called optical imaging with the over-current protecting element technology with positive temperature coefficient (PTC) characteristic of electric conductive polymer that is dispersed in the conductive filling material composition in the polymer and electric conductive polymer preparation thus.Usually, the PTC electric conductive polymer is made up of one or more a crystalline polymer and a conductive filling material, and this conductive filling material is dispersed in this polymer.Conductive filling material can be a kind of or wherein several mixture in polyethylene, ethene copolymer, the fluoropolymer; Conductive filling material can be carbon black, metallic particles or inorganic ceramic powder.The ptc characteristics of this type of electric conductive polymer (resistance value with temperature rise increase) is considered to because the expansion of crystalline polymer causes the formed conductive channel of conducting particles to disconnect causing during fusion.
In existing disclosed technology; the most generally with carbon black as conductive filling material; but carbon black is difficult to obtain very low room temperature resistivity as the electric conductive polymer that conductive filling material prepares; when particularly this polymer being used for preparing the over-current protecting element of battery (group), can not device miniaturization, the requirement of low room temperature resistance.Though; metallic particles (as nickel powder) can be made electric conductive polymer than low room temperature resistivity as conductive filling material; but over-current protecting element with this type of electric conductive polymer preparation; its environmental resistance is relatively poor; specifically, be exactly that element is in the high temperature put procedure, along with the prolongation of time; the room temperature resistance of element can progressively rise, until inefficacy.We infer that its reason may be owing to the metal powder oxidation as conductive filler, forms due to the low metal oxide of conductivity.
For this reason, the present invention discloses a kind of conductive polymer material with ptc characteristics, not only has very low room temperature resistivity, and when as over-current protecting element, has good environmental resistance.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of conductive polymer composition with ptc characteristics.
Another technical problem to be solved by this invention is to provide the over-current protecting element that utilizes above-mentioned conductive polymer composition preparation, and this element not only has very low room temperature resistance, and has good environmental resistance.
The present invention solves the problems of the technologies described above the technical scheme of taking: a kind of conductive polymer composition, and wherein, the weight percent content of each component comprises in the described polymer composition:
Crystalline polymer polymer 5～30%
Conducting metal packing material 50～95%
Macromolecule wax 1～20%, wherein,
Described conducting metal filler is one kind of multiple the composition in nickel powder, silver powder, the bronze.
Concrete, the consumption of crystalline polymer polymer can be 5,8,10,12,15,18,20,22,25,28 or 30%;
The consumption of conducting metal packing material can be 50,55,60,65,70,75,80,85,90 or 95%;
The consumption of macromolecule wax can be 1,1.05,1.1,1.2,1.5,1.8,2,5,8,10,12,15,18 or 20%.
On the such scheme basis, described crystalline polymer polymer is one or more the mixture in polyethylene, ethene copolymer, the fluoropolymer (as PVDF), wherein, described ethene copolymer comprises one or more the composition in ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), the ethylene-vinyl acetate copolymer (EVA).
The shared percentage by weight of crystalline polymer polymer is preferably 5～20%.
On the such scheme basis, described conducting metal filler is a nickel powder, as T210, the T240 of INCO company, T255, T287, CNP525 etc., and conducting metal filler shared ratio preferred 70～90% in polymer composition.
On the such scheme basis, described conducting metal filler is preferably nickel powder, more preferably a kind of nickel powder with chain pearlitic texture.
On the such scheme basis, in order to prevent the oxidation of conducting metal packing material, improve the environmental resistance of element, the anti-oxidation inorganic agent that needs to add an amount of conducting metal packing material carries out anti-oxidation processing to described conductive metal powder.Described conduction nickel powder is the nickel powder after carrying out anti-oxidation processing through anti-oxidation inorganic agent.
On the such scheme basis, described anti-oxidation inorganic agent is a silane coupler, the silane coupler of preferred primary amine groups, and consumption is 0.5～10% of a nickel powder weight.
On the such scheme basis, described anti-oxidation inorganic agent consumption is 1～5% of a nickel powder weight.
On the such scheme basis, the described method that nickel powder is carried out anti-oxidation processing is: nickel powder is immersed in the solution of silane coupler, stir with the dry type mixer, after waiting to stir, place dry the removing of vacuum drying oven to desolvate, obtain the nickel powder of anti-oxidation processing.
On the such scheme basis, for improving the dispersing uniformity of conductive filler in polymeric matrix, described macromolecule is cured to be ethylene-vinyl acetate copolymer (EVA) wax.
The shared percentage by weight of described macromolecule wax is preferably 1～2%.
Utilize the preparation over-current protecting element method of above-mentioned conductive polymer composition, comprise the steps:
The first step: in regular turn each component of polymer is passed through mixing, pulling-on piece;
Second step: tinsel in the upper and lower faces pressing of sheet material;
The 3rd step: irradiation, punching moulding meet the chip of dimensional requirement;
The 4th step: the nickel sheet of burn-oning on chip is as extraction electrode, and obtains over-current protecting element.
Moreover for promoting other performance that this has the ptc characteristics conducing composite material, conducing composite material of the present invention also can further comprise crosslinking agent, antioxidant, non-conducting filler etc.
Superiority of the present invention is:
A kind of conducing composite material with ptc characteristics that is provided, the over-current protecting element that reaches by this Composite Preparation not only has very low room temperature resistance, and has good environmental resistance.
Description of drawings
Fig. 1 is the side-looking structural representation of over-current protecting element of the present invention.
Fig. 2 is 85 ℃ an environmental resistance testing experiment comparison diagram.
Fig. 3 is the schematic diagram that silane coupler and nickel powder surface chemistry bond are closed.
Fig. 4 is the schematic diagram of the nickel powder of anti-oxidation processing.
Label declaration in the accompanying drawing
1-core 2,2 '-tinsel 3,3 '-extraction electrode.
Embodiment
A kind of conductive polymer composition with ptc characteristics, the weight percent content of each component comprises in the described polymer composition:
Crystalline polymer polymer 5～30%
Conducting metal packing material 50～95%
Macromolecule wax 1～20%, wherein,
Described conducting metal filler is one kind of multiple the composition in nickel powder, silver powder, the bronze.
Embodiment
Each component is pressed table 1 proportioning:
Nickel powder CNP525 in the table 1 is immersed in the ethanolic solution of silane coupler KBE903, stirred 30 minutes, place vacuum drying oven (vacuum degree: 10 with the dry type mixer
-1Mpa, 25 ℃ of temperature) removed ethanol in dry 24 hours, obtain the nickel powder of anti-oxidation processing.
The nickel powder handled and high density polyethylene (HDPE) and EVA wax are put into banbury successively, mixing down even at 190 ℃, in mill, pull out the sheet material of 0.65mm left and right thickness, be cut into the core 1 of 200mm * 200mm, upper and lower faces is respectively put a tinsel 2,2 ', on 180 ℃ press, be pressed into the compound chip of 0.6mm left and right thickness.This compound chip is carried out electron beam irradiation, and irradiation dose is 10Mrad to 100Mrad.Die-cut or cutting-up becomes the chip of 3mm * 4mm with this chip then; respectively burn-on at the chip tow sides and one to be of a size of the nickel sheet of 2.3mm * 5.8mm as extraction electrode 3; 3 ', just can obtain the over-current protecting element shown in Fig. 1 over-current protecting element schematic diagram of the present invention with ptc characteristics.Made over-current protecting element is placed in 85 ℃ the baking oven and carries out 1000 hours environmental resistance test.
After nickel powder carried out anti-oxidation processing, form chemical bond between antioxidant and nickel powder and combine, shown in the schematic diagram of the schematic diagram that closes as Fig. 3 silane coupler and nickel powder surface chemistry bond and the nickel powder of the anti-oxidation processing of Fig. 4.
Comparative example 1
With embodiment compare the batching identical, it is the technology difference, that is: nickel powder is not carried out preliminary treatment with silane coupler, but nickel powder CNP525, silane coupler KBE903 and other component in the table 1 are directly put into banbury, 190 ℃ down mixing evenly, in mill, pull out the core 1 of 0.65mm left and right thickness, be cut into the core of 200mm * 200mm, respectively put a tinsel 2,2 ' up and down, on 180 ℃ press, be pressed into the compound chip of 0.6mm left and right thickness.This compound chip is carried out electron beam irradiation, and irradiation dose is 10Mrad to 100Mrad.Die-cut or cutting-up becomes the blockage chip of 3mm * 4mm with this chip then; respectively burn-on at these chip tow sides and one to be of a size of the nickel sheet of 2.3mm * 5.8mm as extraction electrode 3; 3 ', just can obtain required over-current protecting element with ptc characteristics.Made over-current protecting element is placed in 85 ℃ the baking oven and carries out 1000 hours environmental resistance test.
Comparative example 2
Each component is pressed table 2 proportioning:
Compare with embodiment, do not add silane coupler, other is identical with embodiment.Made over-current protecting element is placed in 85 ℃ the baking oven and carries out 1000 hours environmental resistance test.
The environmental resistance test result is shown in the environmental resistance testing experiment comparison diagram of 5 ℃ of Figure 28.
As can be seen from Figure 2; the over-current protecting element that is made by the nickel powder without anti-oxidation processing is under 85 ℃ condition; prolongation along with the time; its room temperature resistance progressively rises; its room temperature resistance has reached hundreds of ohm after 1000 hours, has lost the practical value as over-current protecting element.And by carrying out the over-current protecting element that pretreated nickel powder makes through silane coupler, under 85 ℃ condition, though the prolongation of time, it is stable that its room temperature resistance keeps, and has good environmental resistance.
We infer that its reason may carry out chemical reaction for some chemical bonds on silane coupler and nickel powder surface, in conjunction with the network structure that has formed HMW (as shown in Figure 3), in the middle of this layer coupling agent film on nickel powder surface wraps in nickel powder just (as shown in Figure 4), stoped the infiltration of oxygen, prevent the oxidation of nickel powder, kept good electrical conductivity.
It can also be seen that from Fig. 2; nickel powder is not carried out preliminary treatment; but silane coupler directly joined the over-current protecting element that makes in the compound; under 85 ℃ condition; prolongation along with the time; though comparatively speaking the ascensional range of its room temperature resistance and the made device of unprocessed nickel powder have certain improvement; but certain rising is arranged; illustrate that nickel powder still has oxidation to a certain degree; we infer that its reason may be that silane coupler is directly joined in the compound, owing to disperse inequality, part nickel powder surface does not form the coupling agent film; under 85 ℃ condition, place for a long time, gradually due to the oxidation.
According to the present invention; by metal powder is carried out anti-oxidation preliminary treatment; thereby can provide a kind of like this conducing composite material with ptc characteristics; reach over-current protecting element by this Composite Preparation; this element not only has very low room temperature resistance, and has good environmental resistance.
Claims (10)
1. conductive polymer composition, it is characterized in that: the weight percent content of each component comprises in the described polymer composition:
Crystalline polymer polymer 5～30%
Conducting metal packing material 50～95%
Macromolecule wax 1～20%, wherein,
Described conducting metal filler is one kind of multiple the composition in nickel powder, silver powder, the bronze.
2. conductive polymer composition according to claim 1, it is characterized in that: described crystalline polymer polymer is one or more the mixture in polyethylene, ethene copolymer, the fluoropolymer, wherein, described ethene copolymer comprises one or more the composition in ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, the ethylene-vinyl acetate copolymer.
3. conductive polymer composition according to claim 1 and 2 is characterized in that: described conducting metal filler is a nickel powder, shared ratio 70～90% in polymer composition.
4. conductive polymer composition according to claim 3 is characterized in that: described nickel powder has the chain pearlitic texture.
5. conductive polymer composition according to claim 3 is characterized in that: described conduction nickel powder is the nickel powder after carrying out anti-oxidation processing through anti-oxidation inorganic agent.
6. conductive polymer composition according to claim 5 is characterized in that: described anti-oxidation inorganic agent is a silane coupler, and consumption is 0.5～10% of a nickel powder weight.
7. conductive polymer composition according to claim 6 is characterized in that: described anti-oxidation inorganic agent consumption is 1～5% of a nickel powder weight.
8. conductive polymer composition according to claim 5, it is characterized in that: the described method that nickel powder is carried out anti-oxidation processing is: nickel powder is immersed in the solution of silane coupler, stir with the dry type mixer, after waiting to stir, place dry the removing of vacuum drying oven to desolvate, obtain the nickel powder of anti-oxidation processing.
9. conductive polymer composition according to claim 1 is characterized in that: described macromolecule is cured to be ethylene-vinyl acetate copolymer wax.
10. utilize the preparation over-current protecting element method of the described conductive polymer composition of claim 1, it is characterized in that comprising the steps:
The first step: in regular turn each component of polymer is passed through mixing, pulling-on piece;
Second step: tinsel in the upper and lower faces pressing of sheet material;
The 3rd step: irradiation, punching moulding meet the chip of dimensional requirement;
The 4th step: the nickel sheet of burn-oning on chip is as extraction electrode, and obtains over-current protecting element.
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| CN103258607A (en) * | 2012-02-16 | 2013-08-21 | 聚鼎科技股份有限公司 | Overcurrent protection element |
| CN103772782A (en) * | 2013-12-03 | 2014-05-07 | 上海神沃电子有限公司 | Self-limited flexible PTC (positive temperature coefficient) exothermic material and PTC core material prepared from same and preparation method of PTC core material |
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| CN101281811A (en) * | 2007-04-06 | 2008-10-08 | 浙江工业大学 | Method for preparing NdFeB/PPS injection moulding particle material |
| CN101528829A (en) * | 2006-08-08 | 2009-09-09 | 沙伯基础创新塑料知识产权有限公司 | Improved thermal conductive polymeric ptc compositions |
| CN101560325A (en) * | 2009-05-26 | 2009-10-21 | 上海科特高分子材料有限公司 | High-temperature resistant PTC electroconductive composition, high-temperature resistant PTC device containing composition and manufacturing method thereof |
| CN101728039A (en) * | 2009-12-31 | 2010-06-09 | 上海长园维安电子线路保护股份有限公司 | Over-current protection element |
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| CN101281811A (en) * | 2007-04-06 | 2008-10-08 | 浙江工业大学 | Method for preparing NdFeB/PPS injection moulding particle material |
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| CN103772782A (en) * | 2013-12-03 | 2014-05-07 | 上海神沃电子有限公司 | Self-limited flexible PTC (positive temperature coefficient) exothermic material and PTC core material prepared from same and preparation method of PTC core material |
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Address after: Seven road 201202 Shanghai Pudong New Area Shiwan No. 1001 Applicant after: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. Address before: Seven road 201202 Shanghai Pudong New Area Shiwan No. 1001 Applicant before: Shanghai Changyuan Wayon Circuit Protection Co., Ltd. |
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Application publication date: 20110907 |