CN102831997B - Overcurrent protection element with positive temperature coefficient - Google Patents
Overcurrent protection element with positive temperature coefficient Download PDFInfo
- Publication number
- CN102831997B CN102831997B CN201110156860.0A CN201110156860A CN102831997B CN 102831997 B CN102831997 B CN 102831997B CN 201110156860 A CN201110156860 A CN 201110156860A CN 102831997 B CN102831997 B CN 102831997B
- Authority
- CN
- China
- Prior art keywords
- polyolefin
- weight
- reinforcing
- temperature coefficient
- material layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000098 polyolefin Polymers 0.000 claims abstract description 78
- 229920000642 polymer Polymers 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 230000003014 reinforcing effect Effects 0.000 claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000007943 implant Substances 0.000 claims description 19
- 229920002521 macromolecule Polymers 0.000 claims description 19
- 239000006104 solid solution Substances 0.000 claims description 19
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 claims description 16
- 229910021352 titanium disilicide Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- ZTJWUVMPZRLXAB-UHFFFAOYSA-N [Ta].[Ti].[W] Chemical compound [Ta].[Ti].[W] ZTJWUVMPZRLXAB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910039444 MoC Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910026551 ZrC Inorganic materials 0.000 claims description 3
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 3
- DZZDTRZOOBJSSG-UHFFFAOYSA-N [Ta].[W] Chemical compound [Ta].[W] DZZDTRZOOBJSSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 claims description 3
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 3
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- AAKSBDQCDUIGHH-UHFFFAOYSA-N chromium tantalum titanium tungsten Chemical compound [Cr][Ti][W][Ta] AAKSBDQCDUIGHH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 3
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 claims description 3
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 3
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021334 nickel silicide Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- GJIKIPCNQLUSQC-UHFFFAOYSA-N bis($l^{2}-silanylidene)zirconium Chemical compound [Si]=[Zr]=[Si] GJIKIPCNQLUSQC-UHFFFAOYSA-N 0.000 claims 1
- 229910021353 zirconium disilicide Inorganic materials 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 4
- 229920001112 grafted polyolefin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000843 powder Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATCDNCMWCPJXNQ-UHFFFAOYSA-N [Nb].[Ta].[Ti].[W] Chemical compound [Nb].[Ta].[Ti].[W] ATCDNCMWCPJXNQ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 description 1
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000285023 Formosa Species 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 206010020741 Hyperpyrexia Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DSSYKIVIOFKYAU-UHFFFAOYSA-N camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 208000015994 miscarriage Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 208000000995 spontaneous abortion Diseases 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910021355 zirconium silicide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Thermistors And Varistors (AREA)
Abstract
The invention relates to an overcurrent protection element with positive temperature coefficient. The overcurrent protection element comprises an positive temperature coefficient material layer and two electrodes disposed on the temperature coefficient material layer, wherein the temperature coefficient material layer comprises a polymer matrix and conductive particle fillers distributed in the polymer matrix uniformly; and the polymer matrix has a polymer composition, wherein the polymer composition comprises at least one main polymer unit and a reinforced polyolefin; the main polymer unit comprises a basic polyolefin and optionally a grafted polyolefin; the polymer matrix is formed by co-fusing, mixing and curing the main polymer unit and the reinforced polyolefin; the basic polyolefin has a fusing flow rate between 10 g/10 min an 100 g/10 min; the reinforced polyolefin has a fusing flow rate between 0.01g/10 min an 1.0 g/10 min; the weight of the main polymer unit is 50-95 wt% that of the polymer composition; and the weight of the reinforced polyolefin is 5-50 wt% that of the polymer composition.
Description
Technical field
The present invention relates to a kind of overcurrent protection element with positive temperature coefficient, more particularly to a kind of to have different molecular weight model
The basic polyolefin for enclosing and the polyolefinic overcurrent protection element with positive temperature coefficient of a reinforcing.
Background technology
PTC conductive macromolecule element due to positive temperature coefficient effect, so can be used as overcurrent protection
Element purposes.PTC conductive macromolecule element includes a PTC conductive macromolecular material and is formed in this
Positive and negative electrode on two corresponding surfaces of PTC conductive macromolecular material.The PTC conductive high score
Sub- material include one tool crystalline phase area and amorphous phase region macromolecule matrix and one be scattered in the macromolecule matrix amorphous phase region and
Form the conductive particle implant in a continuous conduction path.Positive temperature coefficient effect refers to the temperature liter when the macromolecule matrix
During to its fusing point, the crystalline phase area starts melting and produces new amorphous phase region.Deposit with original when amorphous phase region increases to a degree
Amorphous phase region when combining, the conductive path that can cause the conductive particle implant forms discontinuous shape, and causes this just
The resistance of Temperature Coefficient conductive macromolecular material rapidly increases, and thus formation power-off.
PTC conductive macromolecule element importantly requires that there is high positive temperature coefficient effect, height to lead simultaneously
Electric degree, high electric stability, high environmental stability.
Traditional PTC conductive macromolecular material generally includes a macromolecule matrix and a carbon dust electric conductivity is filled out
Fill thing.The macromolecule matrix is constituted with a macromolecule.The macromolecule composition generally comprises weight average molecular weight scope Jie
(there is the melt flow rate between 0.01g/10min to 10g/10min in the polyolefin of 50,000g/mol to 300,000g/mol
(at 190 DEG C, under conditions of 2.16kg)) with a selectively weight average molecular weight scope between 50,000g/mol to 200,
000g/mol graft type polyolefin (have between 0.5g/10min to 10g/10min melt flow rate (at 190 DEG C, 2.16kg
Under conditions of)).The polyolefinic major function of the graft type be increase PTC conductive macromolecular material and electrode it
Between adherence.
Due to the electric conductivity of carbon dust conductive filling it is low, therefore be not suitable for some need compared with high connductivity degree (low resistance)
Overcurrent protection element.On electric conductivity is lifted, although can fill out by the non-carbons conductive particle with high conductivity is increased
Fill the kenel (such as metallic particles, conductive ceramic granule and surface metalation granule etc.) of thing to increase PTC conductive
The electric conductivity of property macromolecular material (deteriorates to less than 0.05ohm- from the specific insulation of the about 1.0ohm-cm or higher of script
The specific insulation of cm), but its electric stability, because of the high conductivity conductive filler that there is high-load, and cannot avoid leading
Between electric filler particle, the caused arc phenomenon under electrical condition.The hyperpyrexia of electric arc, destroys and is wrapped in conductive fill
Polyolefin blend around thing so that polyolefin blend structure produces irreversible destruction, is causing electroconductive polymer just
Therefore the electric stability of temperature coefficient materials reduces with service life.
The content of the invention
It is an object of the invention to provide a kind of can improve the electrically stable of electroconductive polymer PTC material
Property with the overcurrent protection element with positive temperature coefficient of service life.
A kind of overcurrent protection element with positive temperature coefficient of the present invention, comprising：One PTC material layer；And two electricity
Pole, is located on the PTC material layer.The PTC material layer is dispersed in including a macromolecule matrix and one
The polymer-based internal conductive particle implant, electric conductivity the leading higher than carbon black of the material of the conductive particle implant
Electric degree.The macromolecule matrix is constituted with a polymer, and the polymer composition includes an at least host polymer unit and a reinforcing
Polyolefin, the host polymer unit includes a basic polyolefin and optionally a graft type polyolefin, the reinforcing polyolefin
Weight average molecular weight higher than the basic polyolefin weight average molecular weight, the host polymer unit and the reinforcing polyolefin
It is total to melting mixing solidify afterwards and forms the macromolecule matrix.The basic polyolefin have one according to ASTM D-1238 230 DEG C with
Between the melt flow rate of 10g/10min to 100g/10min under 12.6kg pressure.The reinforcing polyolefin has one according to ASTM D-
1238 under 230 DEG C with 12.6kg pressure between the melt flow rate of 0.01g/10min to 1.0g/10min.The host polymer unit
The 50-95wt% that the polymer constitutes weight is accounted for, the reinforcing polyolefin accounts for the 5-50wt% that the polymer constitutes weight.
It is preferred that the host polymer unit accounts for the 75-95wt% that the polymer constitutes weight, and the reinforcing polyolefin accounts for this
Polymer constitutes the 5-25wt% of weight.
It is preferred that the reinforcing polyolefin have one between 600,000g/mol to 1, weight between 500,000g/mol is put down
Average molecular weight.
It is preferred that the basic polyolefin have one between 50,000g/mol to the weight average between 300,000g/mol
Molecular weight.
It is preferred that the conductive particle implant is selected from titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, carbon
Change chromium, molybdenum carbide, tungsten carbide, titanium nitride, zirconium nitride, vanadium nitride, niobium nitride, tantalum nitride, chromium nitride, titanium disilicide, two silication
Zirconium, niobium disilicide, tungsten silicide, gold, silver, copper, aluminum, nickel, plating nickel on surface glass bead, plating nickel on surface graphite, titanium tantalum solid solution, tungsten
Titanium tantalum chromium solid solution, tungsten tantalum solid solution, tungsten titanium tantalum niobium solid solution, tungsten titanium tantalum solid solution, tungsten titanium solid solution, tantalum niobium solid solution or front
State the combination of material.
It is preferred that the conductive particle implant is nickel or titanium disilicide.
It is preferred that the basic polyolefin is polyethylene with the reinforcing polyolefin.
It is preferred that the PTC material layer has more than zero and the specific insulation less than 0.05ohm-cm.
It is preferred that the reinforcing polyolefin accounts for the 0.5-10wt% of the PTC material layer weight, the host polymer list
Unit accounts for the 5-20wt% of the PTC material layer weight, and the conductive particle implant accounts for the PTC material layer weight
The 70-90wt% of amount.
The beneficial effects of the present invention is：Using addition with higher molecular weight reinforcing polyolefin (have one between
Weight average molecular weight or one between 600,000g/mol to 1,500,000g/mol is between 0.01g/10min to 1.0g/
The melt flow rate of 10min) (have one between 50,000g/mol to 300,000g/mol weight averages point in traditional polyolefin
Son amount or one between 10g/10min to 100g/10min melt flow rate) in, both Jing altogether melting mixing solidify afterwards and form one
With high structural strength and high temperature-resistant polymer matrix, the electric steady of electroconductive polymer PTC material is improved whereby
Qualitative and service life.
Description of the drawings
Fig. 1 is a schematic diagram, illustrates a kind of overcurrent protection element with positive temperature coefficient of a preferred embodiment of the present invention
Structure；
Fig. 2 is an experimental data figure, illustrates the embodiment of an overcurrent protection element with positive temperature coefficient containing titanium disilicide
With the relation between the resistance change rate of comparative example and the polyolefinic molecular weight of reinforcing；
Fig. 3 is an experimental data figure, illustrate one containing nikel powder overcurrent protection element with positive temperature coefficient embodiment with than
Compared with the relation between the resistance change rate and the polyolefinic molecular weight of reinforcing of example；
Fig. 4 is an experimental data figure, illustrates the embodiment of an overcurrent protection element with positive temperature coefficient containing titanium disilicide
It is the relation between the polyolefinic weight of reinforcing of 1.5M with the resistance change rate of comparative example and molecular weight；
Fig. 5 is an experimental data figure, illustrate one containing nikel powder overcurrent protection element with positive temperature coefficient embodiment with than
It is the relation between the polyolefinic weight of reinforcing of 1.5M compared with the resistance change rate and molecular weight of example；
Fig. 6 is an experimental data figure, illustrates the embodiment of an overcurrent protection element with positive temperature coefficient containing titanium disilicide
It is the relation between the polyolefinic weight of reinforcing of 0.6M with the resistance change rate of comparative example and molecular weight；
Fig. 7 is an experimental data figure, illustrate one containing nikel powder overcurrent protection element with positive temperature coefficient embodiment with than
It is the relation between the polyolefinic weight of reinforcing of 0.6M compared with the resistance change rate and molecular weight of example；
Fig. 8 is an experimental data figure, illustrates the positive temperature coefficient overcurrent protection unit of embodiment 2 and 18 and comparative example 7 and 8
The resistance change rate of part.
Specific embodiment
For the present invention aforementioned and other technology contents, feature and effect, in the following preferable reality coordinated with reference to schema
In applying the detailed description of example, can clearly present.
Refering to Fig. 1, an a kind of preferred embodiment of overcurrent protection element with positive temperature coefficient of the present invention is included：One positive temperature
Degree index material 2, the PTC material layer 2 has more than zero and the specific insulation less than 0.05ohm-cm；And two
Individual electrode 3, is located on the PTC material layer 2.The PTC material layer 2 includes that a macromolecule matrix 21 and is equal
The even conductive particle implant 22 being scattered in the macromolecule matrix 21, the conduction of the material of the conductive particle implant 22
Electric conductivity of the degree higher than carbon black.The macromolecule matrix 21 is constituted with a polymer, and the polymer composition is fusible comprising at least one
Stream (melt-extrudable) host polymer unit and one can melt flow reinforcing polyolefin.The host polymer unit is basic comprising one
Polyolefin and optionally a graft type polyolefin.The polyolefinic weight average molecular weight of the reinforcing is higher than the basic polyolefin
Weight average molecular weight.The host polymer unit and the reinforcing polyolefin altogether melting mixing solidify afterwards and to form this polymer-based
Body 21.The basic polyolefin have one according to ASTM D-1238 230 DEG C with 12.6kg pressure under between 10g/10min extremely
The melt flow rate (M.F.R.) of 100g/10min.The reinforcing polyolefin have one according to ASTM D-1238 at 230 DEG C and 12.6kg
Between the melt flow rate of 0.01g/10min to 1.0g/10min under pressure.The host polymer unit accounts for the polymer composition weight
50-95wt%, and the reinforcing polyolefin accounts for the 5-50wt% that the polymer constitutes weight.More preferably, the host polymer unit
The 75-95wt% that the polymer constitutes weight is accounted for, and the reinforcing polyolefin accounts for the 5-25wt% that the polymer constitutes weight.
It is preferred that the reinforcing polyolefin accounts for the weight of PTC material layer 2 (the polymer composition and the electric conductivity
The gross weight of grain implant 22) 0.5-10wt%, the host polymer unit accounts for the 5- of the weight of PTC material layer 2
20wt%, and the conductive particle implant 22 accounts for the 70-90wt% of the weight of PTC material layer 2.More preferably, this is strong
Change the 0.5-6wt% that polyolefin accounts for the weight of PTC material layer 2, the host polymer unit accounts for the PTC material
The 9-18wt% of 2 weight of layer, and the conductive particle implant 22 accounts for the 76-90wt% of the weight of PTC material layer 2.
It is preferred that the basic polyolefin is high density polyethylene (HDPE) with the reinforcing polyolefin, and the graft type polyolefin is not for
Saturated carboxylic acid grafted high density polyethylene.The polyolefinic major function of the graft type is to increase the PTC material layer 2
With the adherence of electrode 3.
It is preferred that the basic polyolefin have one between 50,000g/mol to the weight average between 300,000g/mol
Molecular weight, and the reinforcing polyolefin is with a weight averaged molecular between 600,000g/mol to 1, between 500,000g/mol
Amount.
It is preferred that the conductive particle implant 22 is selected from titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, carbonization
Tantalum, chromium carbide, molybdenum carbide, tungsten carbide, titanium nitride, zirconium nitride, vanadium nitride, niobium nitride, tantalum nitride, chromium nitride, titanium disilicide, two
Zirconium silicide, niobium disilicide, tungsten silicide, gold, silver, copper, aluminum, nickel, plating nickel on surface glass bead, plating nickel on surface graphite, titanium tantalum melt admittedly
Body, tungsten titanium tantalum chromium solid solution, tungsten tantalum solid solution, tungsten titanium tantalum niobium solid solution, tungsten titanium tantalum solid solution, tungsten titanium solid solution, tantalum niobium melt admittedly
The combination of body or aforementioned substances.More preferably, the conductive particle implant 22 is nikel powder or titanium disilicide.
The embodiment and effect of each purpose of the invention will be illustrated with embodiment and comparative example below.It is noted that
The embodiment is only the purposes for illustrating, and is not necessarily to be construed as the restriction implemented to the present invention.
<Embodiment 1 (E1)>
Using 2g as the polyolefinic polyethylene (marque of the reinforcing：GHR8110, purchased from Ticona, weight averaged molecular
Amount 600,000g/mol, at 230 DEG C, the M.F.R. under 12.6kg is about 0.96g/10min), 19g is used as the basic polyolefin
Polyethylene (marque：HDPE9002, purchased from Formosa plastic Corp., weight average molecular weight 150,000g/
Mol, at 230 DEG C, the M.F.R. under 12.6kg is about 45g/10min), 19g is used as the polyolefinic unsaturated carboxylic acid of the graft type
Graft type polyethylene (marque：MB 100D, purchased from Dupont, weight average molecular weight 80,000g/mol, at 230 DEG C,
M.F.R. under 12.6kg is about 75g/10min) and 160g as the conductive particle implant nikel powder (marque：
N525, purchased from Novamet Specialty Products) add mixing in a Brabender kneading machines.Melting temperature is 200
℃；Mixing speed is 50rpm；Pressurization weight is 5kg；Mixing time is 10 minutes.The mixture of gained after mixing is placed in into one
In mould, afterwards, hot pressing is carried out to blend sample with hot press, hot pressing temperature is 200 DEG C, hot pressing time is 4 minutes, hot pressing
Pressure is 80kg/cm2, the sample after mixing is hot pressed into into thickness after 0.12mm thin slices, in thin slice both sides a piece of plating respectively to be pasted
Ambrose alloy paper tinsel, then according to same hot pressing condition hot pressing, a sandwich structure is formed, this sandwich structure is punched into into 4.5mm X
The chip of 3.2mm, measures the resistance value (being shown in Table 1) of sample obtained by embodiment 1.PE/m-PE in table 1 represents the host polymer
The basic polyolefin (PE) of unit and the graft type polyolefin (m-PE), V-R represents volume resistance (ohm-cm).The institute of embodiment 1
Obtained PTC material layer 2 comprising 1wt% reinforcing polyolefin, 19wt% host polymer units (basic polyolefin with
The polyolefinic weight ratio of the graft type is 1: 1) with the percentage by weight of 80wt% conductive particle implants, and polymerization therein
Thing composition includes that 95wt% host polymers unit strengthens polyolefin with 5wt%.
Table 1
<Embodiment 2-10 (E2-E10)>
The preparation procedure of the sample of embodiment 2-10 and condition difference from Example 1 are the host polymer unit
(basic polyolefin is 1: 1 from the polyolefinic weight ratio of the graft type) is different (being shown in Table 1) with the polyolefinic consumption of the reinforcing.Survey
The resistance value of sample is as shown in table 1 obtained by amount embodiment 2-10.
<Embodiment 11-16 (E11-E16)>
The preparation procedure of the sample of embodiment 11-16 is that the reinforcing polyolefin is with condition difference from Example 1
Commodity in use model GUR4012 replaces the GHR8110 of embodiment 1.Marque GUR4012 is available from Ticona, molecular weight 1,
500,000g/mol, at 230 DEG C, the M.F.R. under 12.6kg is about 0.03g/10min.The reinforcing that embodiment 11-16 is used
Polyolefinic concentration is to correspond to embodiment 1-6 (being shown in Table 1) respectively.The resistance value of sample obtained by measurement embodiment 11-16 is such as
Shown in table 1.
<Embodiment 17-26 (E17-E26)>
The preparation procedure of the sample of embodiment 17-26 is the conductive particle filling with condition difference from Example 1
Thing is with titanium disilicide (TiSi2) replace nikel powder.The polyolefinic concentration of reinforcing that embodiment 17-26 is used is to correspond to respectively
Embodiment 1-10 (is shown in Table 1).The resistance value of sample is as shown in table 1 obtained by measurement embodiment 17-26.
<Embodiment 27-32 (E27-E32)>
The preparation procedure of the sample of embodiment 27-32 is that the reinforcing polyolefin is with condition difference from Example 1
Commodity in use model GUR4012 replaces the GHR8110 of embodiment 1 and replaces nikel powder using titanium disilicide.Embodiment 27-32 is made
The polyolefinic concentration of reinforcing is to correspond to embodiment 11-16 (being shown in Table 1) respectively.Sample obtained by measurement embodiment 27-32
Resistance value it is as shown in table 1.
<Comparative example 1-2 (CE1-CE2)>
The preparation procedure of the sample of comparative example 1-2 and condition difference from Example 1 be comparative example 1-2 be without
The reinforcing polyolefin.In addition, the conducting particle fillers that comparative example 1-2 is used are respectively nikel powder and titanium disilicide.Measurement
The resistance value of sample is as shown in table 1 obtained by comparative example 1-2.
<Comparative example 3-4 (CE3-CE4)>
It is that addition is super that the preparation procedure and condition difference from Example 2 of the sample of comparative example 3-4 is comparative example 3-4
High molecular reinforcing polyolefin (marque GUR4120, purchased from Ticona, molecular weight 5,000,000g/mol, M.F.R. without
Method is measured, that is, is insoluble under 12.6kg at 230 DEG C).In addition, the conducting particle fillers that comparative example 3-4 is used
Respectively nikel powder and titanium disilicide.The resistance value of sample is as shown in table 1 obtained by measurement comparative example 3-4.
<Comparative example 5-6 (CE5-CE6)>
It is that addition is super that the preparation procedure and condition difference from Example 2 of the sample of comparative example 5-6 is comparative example 5-6
Reinforcing polyolefin (the marque GUR4170, purchased from Ticona, molecular weight 10,000,000g/mol, M.F.R. of high molecular
Cannot measure, that is, be insoluble under 12.6kg at 230 DEG C).In addition, the conductive particle filling that comparative example 5-6 is used
Thing is respectively nikel powder and titanium disilicide.The resistance value of sample is as shown in table 1 obtained by measurement comparative example 5-6.
Respectively periodicity test (cycle test) is carried out to embodiment 1-32 and comparative example 1-6.Periodically test be with
6V (volt) dc (direct current) and 50A (ampere) and energization power-off in 60 seconds carries out 7200 loop cycles tests under conditions of 60 seconds.
Test sample is shown in Fig. 2 to Fig. 7 after 7200 period measurings are completed with the resistance variations degree result before test.
Fig. 2 (using titanium disilicide) and Fig. 3 (using nikel powder) shows the polyolefinic molecular weight of reinforcing for electric stability
Impact.Can learn from the result of Fig. 2 and Fig. 3, addition strengthens polyolefinic molecular weight ranges from 600,000g/mol to 1,
When 500,000g/mol (namely M.F.R. is in about 0.01g/10min to 1.0g/10min), its period measuring has minimum
Resistance change rate.Under this molecular weight ranges, reinforcing polyolefin produces melt flow phenomenon under melting temperature (200 DEG C), and with
Strand between host polymer unit is mutually molten and formation is a kind of stable homogeneous, can so lift the structure of high molecular polymer
Intensity, and then lift electric stability.But strengthen polyene when super high molecular weight (such as comparative example 3-6 is used) conduct is used
During hydrocarbon, because the reinforcing polyolefin for having super high molecular weight cannot be melted in mixing, and phase separation is produced with the host polymer unit,
Prevent strengthening polyolefinic addition from lifting the structural strength of high molecular polymer with super high molecular weight.Comparative example 3-6
The chip sample of formation, Jing after the test of many second periodicities, its electric stability is substantially poor than embodiment person.
Fig. 4 and Fig. 5 shows the reinforcing polyolefin (molecular weight is 1,500,000g/mol) of different amounts for electrically stable
The impact of property.From Fig. 4 and Fig. 5 results, add 1wt% to the 4wt% (weight percents based on PTC material layer 2
Than) scope 1, during 500,000g/mol High molecular weight polyethylene, can obtain with minimum resistance change rate, and with adding
Dosage continues to improve, and rate of change is also with rising.
Fig. 6 and Fig. 7 shows the reinforcing polyolefin (molecular weight is 600,000g/mol) of different amounts for electric stability
Impact.From Fig. 6 and Fig. 7 results, add 1wt% to 6wt% (percentage by weight based on PTC material layer 2)
During 600, the 000g/mol High molecular weight polyethylenes of scope, can obtain with minimum resistance change rate, and with addition
Continue to improve, rate of change is also with rising.
<Comparative example 7-8 (CE7-CE8)>
The preparation procedure of the sample of comparative example 7-8 is identical with 18 with embodiment 2 with condition, but the mixing temperature of comparative example 7-8
Degree pressurization protocols when original 200 DEG C are reduced to 150 DEG C of mixings are cancelled, thus, in mixing, only host polymer unit has molten
Miscarriage life, and the reinforcing polyolefin is produced without melt flow, thus the reinforcing polyolefin main is polymerized with this after the completion of mixing and solidification
Thing unit produces split-phase.The same chip sample to comparative example 7-8 carries out periodicity test (cycletest).
From the result of Fig. 8, the electric stability of comparative example 7-8 is substantially than embodiment 2 and 18 (having homogeneous phase person)
It is poor.
In sum, the reinforcing polyolefin of higher molecular weight is added by the polymer composition, and makes the reinforcing polyene
Hydrocarbon is total to melting mixing solidify afterwards and can form one and have high structural strength and high temperature-resistant polymer with host polymer unit Jing
Matrix, improves whereby the electric stability and service life of electroconductive polymer PTC material.
But the above, only presently preferred embodiments of the present invention, when the scope of present invention enforcement can not be limited with this,
Namely all simple equivalence changes made according to claims of the present invention and description and modification, all still belong to the present invention
The scope for covering.
Claims (6)
1. a kind of overcurrent protection element with positive temperature coefficient, it is characterised in that include：
One PTC material layer；And
Two electrodes, are located on the PTC material layer；
The PTC material layer is dispersed in the polymer-based internal electric conductivity including a macromolecule matrix and one
Grain implant, the electric conductivity of the material of the conductive particle implant is higher than the electric conductivity of carbon black；
The macromolecule matrix is constituted with a polymer, and the polymer composition is poly- comprising an at least host polymer unit and a reinforcing
Alkene, the host polymer unit includes a basic polyolefin and optionally a graft type polyolefin, and the reinforcing is polyolefinic
Weight average molecular weight is higher than the weight average molecular weight of the basic polyolefin, and the host polymer unit is total to the reinforcing polyolefin
Melting mixing solidify afterwards and form the macromolecule matrix；
The basic polyolefin have one according to ASTM D-1238 230 DEG C with 12.6kg pressure under between 10g/10min extremely
The melt flow rate of 100g/10min；
The reinforcing polyolefin have one according to ASTM D-1238 230 DEG C with 12.6kg pressure under between 0.01g/10min extremely
The melt flow rate of 1.0g/10min；
The host polymer unit accounts for the 50-95wt% that the polymer constitutes weight；
The reinforcing polyolefin accounts for the 5-50wt% that the polymer constitutes weight；
The reinforcing polyolefin has a weight average molecular weight between 600,000g/mol to 1,500,000g/mol；
The basic polyolefin has a weight average molecular weight between 50,000g/mol to 300,000g/mol；And
The basic polyolefin is polyethylene with the reinforcing polyolefin.
2. overcurrent protection element with positive temperature coefficient according to claim 1, it is characterised in that：The host polymer unit is accounted for
The polymer constitutes the 75-95wt% of weight, and the reinforcing polyolefin accounts for the 5-25wt% that the polymer constitutes weight.
3. overcurrent protection element with positive temperature coefficient according to claim 1, it is characterised in that：The conductive particle filling
Thing is selected from titanium carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, molybdenum carbide, tungsten carbide, titanium nitride, nitridation
Zirconium, vanadium nitride, niobium nitride, tantalum nitride, chromium nitride, titanium disilicide, zirconium disilicide, niobium disilicide, tungsten silicide, gold, silver, copper,
Aluminum, nickel, plating nickel on surface glass bead, plating nickel on surface graphite, titanium tantalum solid solution, tungsten titanium tantalum chromium solid solution, tungsten tantalum solid solution, tungsten titanium tantalum
The combination of niobium solid solution, tungsten titanium tantalum solid solution, tungsten titanium solid solution, tantalum niobium solid solution or aforementioned substances.
4. overcurrent protection element with positive temperature coefficient according to claim 3, it is characterised in that：The conductive particle filling
Thing is nickel or titanium disilicide.
5. overcurrent protection element with positive temperature coefficient according to claim 1, it is characterised in that：The PTC material
Layer has more than zero and the specific insulation less than 0.05ohm-cm.
6. overcurrent protection element with positive temperature coefficient according to claim 5, it is characterised in that：The reinforcing polyolefin accounts for this
The 0.5-10wt% of PTC material layer weight, the host polymer unit accounts for the 5- of the PTC material layer weight
20wt%, the conductive particle implant accounts for the 70-90wt% of the PTC material layer weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110156860.0A CN102831997B (en) | 2011-06-13 | 2011-06-13 | Overcurrent protection element with positive temperature coefficient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110156860.0A CN102831997B (en) | 2011-06-13 | 2011-06-13 | Overcurrent protection element with positive temperature coefficient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102831997A CN102831997A (en) | 2012-12-19 |
| CN102831997B true CN102831997B (en) | 2017-04-12 |
Family
ID=47335086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110156860.0A Expired - Fee Related CN102831997B (en) | 2011-06-13 | 2011-06-13 | Overcurrent protection element with positive temperature coefficient |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102831997B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425088A (en) * | 2013-08-19 | 2015-03-18 | 富致科技股份有限公司 | Over-current protection apparatus and battery assembly using same |
| CN105590710B (en) * | 2014-10-22 | 2020-01-03 | 富致科技股份有限公司 | Positive temperature coefficient overcurrent protection element |
| CN106298119B (en) * | 2015-05-13 | 2019-02-15 | 富致科技股份有限公司 | PTC circuit protection element |
| CN107591228B (en) * | 2016-07-07 | 2019-02-15 | 富致科技股份有限公司 | Overcurrent protection element with positive temperature coefficient |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259745A (en) * | 1998-11-02 | 2000-07-12 | Tdk株式会社 | Positive temp. coefficient thermal resistance |
| CN1844232A (en) * | 2005-04-06 | 2006-10-11 | 富致科技股份有限公司 | Positive temperature coefficient polymer composition and circuit protection device made therefrom |
| CN1993778A (en) * | 2004-06-08 | 2007-07-04 | 泰科电子雷伊化学株式会社 | Polymer ptc device |
| CN101707104A (en) * | 2009-11-20 | 2010-05-12 | 上海长园维安电子线路保护股份有限公司 | High voltage-resistant high polymer PTC thermosensitive resistor and manufacturing method thereof |
-
2011
- 2011-06-13 CN CN201110156860.0A patent/CN102831997B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259745A (en) * | 1998-11-02 | 2000-07-12 | Tdk株式会社 | Positive temp. coefficient thermal resistance |
| CN1993778A (en) * | 2004-06-08 | 2007-07-04 | 泰科电子雷伊化学株式会社 | Polymer ptc device |
| CN1844232A (en) * | 2005-04-06 | 2006-10-11 | 富致科技股份有限公司 | Positive temperature coefficient polymer composition and circuit protection device made therefrom |
| CN101707104A (en) * | 2009-11-20 | 2010-05-12 | 上海长园维安电子线路保护股份有限公司 | High voltage-resistant high polymer PTC thermosensitive resistor and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102831997A (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102831997B (en) | Overcurrent protection element with positive temperature coefficient | |
| JP5711365B2 (en) | Conductive composite material having positive temperature coefficient resistance and overcurrent protection element | |
| CN105321639B (en) | overcurrent protection element | |
| TW201305351A (en) | A positive temperature coefficient material composition for making a positive temperature coefficient circuit protection device includes a positive temperature coefficient polymer unit and a conductive filler | |
| Yang et al. | Electrical properties and morphology of carbon black‐filled HDPE/EVA composites | |
| CN1970612A (en) | Preparation method of electrically conductive composite material with positive temperature coefficient effect | |
| Yuan et al. | Low percolation threshold and high conductivity in carbon black filled polyethylene and polypropylene composites | |
| CN110283392A (en) | Thermoplastic elastomer with high conductivity and mechanical property and preparation method thereof | |
| CN102280233B (en) | High-temperature macromolecule PTC (positive temperature coefficient) thermal resistor and manufacturing method thereof | |
| CN102924776B (en) | PTC material composition and the overcurrent protection assembly be made up of it | |
| CN101026029B (en) | Overcurrent protection element | |
| CN101192461A (en) | High polymer PTC chip electrical heating composite process | |
| CN106146984B (en) | A kind of thermistor composite material and preparation method | |
| US6479575B1 (en) | Electrical devices comprising conductive polymer blend compositions | |
| CN105590710B (en) | Positive temperature coefficient overcurrent protection element | |
| CN106548839A (en) | Overcurrent protection | |
| TWI407458B (en) | Positive temperature coefficient Conductive polymer composition and its material | |
| TWI460746B (en) | A positive temperature coefficient circuit protection device | |
| CN107591228B (en) | Overcurrent protection element with positive temperature coefficient | |
| TWI598893B (en) | Positive temperature coefficient overcurrent protection device | |
| CN106601393B (en) | Positive temperature coefficient current protection chip apparatus and its preparation method | |
| CN106189219A (en) | A kind of polymer base conductive composite material and circuit protecting element | |
| CN1379415A (en) | Composite structural material for thermosensitive resistor with positive temp coefficient and its preparing process | |
| CN102134345A (en) | Conductive composite material for improving switching temperature of PTC (positive temperature coefficient) thermal element and manufacturing method thereof | |
| TWI434300B (en) | Over-current protection device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170412 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |