CN103108906A - 利用炭纳米管的ntc特性减少的ptc元件用导电性聚合物组合物 - Google Patents
利用炭纳米管的ntc特性减少的ptc元件用导电性聚合物组合物 Download PDFInfo
- Publication number
- CN103108906A CN103108906A CN2011800447503A CN201180044750A CN103108906A CN 103108906 A CN103108906 A CN 103108906A CN 2011800447503 A CN2011800447503 A CN 2011800447503A CN 201180044750 A CN201180044750 A CN 201180044750A CN 103108906 A CN103108906 A CN 103108906A
- Authority
- CN
- China
- Prior art keywords
- resin
- ptc element
- mentioned
- conductive polymer
- polymer composition
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 23
- 230000003247 decreasing effect Effects 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 93
- 229920001225 polyester resin Polymers 0.000 claims abstract description 9
- 229920002678 cellulose Polymers 0.000 claims abstract description 8
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 229920001038 ethylene copolymer Polymers 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 5
- 239000004702 low-density polyethylene Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229920005678 polyethylene based resin Polymers 0.000 claims description 2
- 229920005673 polypropylene based resin Polymers 0.000 claims description 2
- 150000003376 silicon Chemical class 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
- C08L1/18—Cellulose nitrate, i.e. nitrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/008—Thermistors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/75—Single-walled
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
- Y10S977/752—Multi-walled
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49085—Thermally variable
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Resistance Heating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Thermistors And Varistors (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及一种NTC特性减少的PTC元件用导电性聚合物组合物及利用该PTC元件用导电性聚合物组合物的PTC元件、电路、面状发热体,所述PTC元件用导电性聚合物组合物利用了碳纳米管、作为PTC粘合剂的树脂以及用于固定碳纳米管和PTC粘合剂的纤维素系或者聚酯系树脂。
Description
技术领域
本发明涉及一种利用碳纳米管的热敏电阻(NTC)特性减少的正温度系数(PTC,positive temperature coefficient)元件用导电性聚合物组合物及利用该PTC元件用导电性聚合物组合物的PTC元件、电路、面状发热体。
背景技术
PTC特性是指,虽然在常温程度的低温下,电阻低而具有导电性,但随着温度的上升,在比较窄的温度区域内电阻急剧上升的特性。因此,具有这种特性的PTC导电性聚合物组合物适合用作随着周围温度以及电流条件而变化的电路保护元件等的电气元件。
通常的PTC元件的结构包括:由导电性聚合物组合物组成的电阻体、附着于电阻体并与电力供给源相连接的2个电极、以及电极上的电解质金属箔。
电路保护元件通常在电路中与负荷串联连接,维持低温、低电阻状态。但是,暴露于过电流或者过温度条件时,元件的电阻会增加,有效地阻断电路内的向负荷流动的电流。这种元件虽然只要重新回到常温低电流以及低温状态就能恢复低电阻状态,但是存在着如下问题:当温度持续维持在熔融点或者上升到更高的温度时,由于因导电性填充剂的布朗运动以及凡得瓦力而引起的再凝聚,产生减少树脂的电阻的NTC现象。
另一方面,以往作为使用于PTC组合物的导电性高分子,通常使用碳黑、石墨等。它们是短径和长径的比为80%以上的球形粒子,易于随着树脂的膨胀而短路,因此能容易地表现出PTC特性,但在由于外部的冲击而产生弯曲的情况下,存在短路的粒子不再接触的问题(图1)。
因此,本发明人在研究对外部冲击也能够维持导电性的PTC元件的过程中确认了,在使用具有如发丝般细长的形状的碳纳米管作为导电性高分子的情况下,即使发生了弯曲等情况,因碳纳米管的恢复性良好,所以对外部冲击也能够继续维持导电性。
并且,寻求了如下方法:与在通常溶剂中的分散性以及可溶性相对好的碳黑或者石墨相比,为了分散因分子间的结合更强而容易凝聚的碳纳米管,而使用体积变化大的结晶性聚合物作为PTC粘合剂(即,第一树脂)。
但是,即使制造了利用碳纳米管(CNT)的PTC元件,在反复施加电压时还是出现了NTC现象。本发明人继续研究的结果,确认了在进一步包含热固性树脂或者Tm或软化点比第一树脂高或者分子量比第一树脂大的第二树脂的情况下,通过固定CNT和第一树脂,可以防止在温度反复变化时CNT移动的同时,也可以防止在温度持续上升时电阻下降的NTC现象。
发明内容
技术问题
本发明的目的在于,提供一种减少NTC现象的PTC元件用导电性聚合物组合物。
并且,本发明的目的在于,提供一种NTC现象减少的PTC元件及其制造方法。
此外,本发明的目的在于,提供一种NTC现象减少、并具有PTC特性的面状发热体。
另外,本发明的目的在于,提供一种NTC现象减少、并具有PTC特性的电路。
解决问题的手段
为达成上述目的,本发明提供一种包含碳纳米管、包含以下第一树脂以及第二树脂的PTC元件用导电性聚合物组合物。上述第一树脂以及第二树脂如下:
1)第一树脂,其为选自由聚烯烃系树脂以及硅系树脂组成的组中的任一种树脂;
2)第二树脂,其为选自由纤维素系树脂以及聚酯系树脂组成的组中的任一种树脂。
并且,本发明提供一种包含上述PTC元件用导电性聚合物组合物的PTC元件、包含上述组合物的面状发热体以及电路。
并且,本发明提供一种包括在包含上述组合物的电阻体薄膜层压电极以及电解质金属箔的步骤的PTC元件的制造方法。
有益效果
本发明的PTC元件用导电性聚合物组合物使利用该PTC元件用导电性聚合物组合物的电路、发热体(加热器)、PTC元件等即使应对外部冲击或者弯曲也不容易致使接触电阻发生变化,即使在温度上升后再下降的情况下,其恢复力也很优秀。
附图说明
图1是在150mm×300mm的BOPET上分别印刷碳黑和CNT并干燥后,在实施180度弯曲试验(Bending test)的过程中将数字万用表(Digital Multimeter,YOKOGAWA 733)连接到电极后测定电阻变化,表示对碳黑和CNT的弯曲的电阻变化以及对反复冲击的耐久性变化。
图2表示对本发明的PTC-CNT加热器的NTC特性被防止的PTC功能的评价。
具体实施方式
本发明提供一种包含碳纳米管、以下第一树脂以及第二树脂的PTC元件用导电性聚合物组合物。上述第一树脂以及第二树脂如下:
1)第一树脂,其为选自由聚烯烃系树脂以及硅系树脂组成的组中的任一种树脂;
2)第二树脂,其为选自由纤维素系树脂以及聚酯系树脂组成的组中的任一种树脂。
并且,本发明提供一种包含上述PTC元件用导电性聚合物组合物的PTC元件、包含上述组合物的面状发热体以及电路。
并且,本发明提供一种包括在包含上述组合物的电阻体薄膜层压电极以及电解质金属箔的步骤的PTC元件的制造方法。
以下,将对本发明进行详细说明。
本发明的碳纳米管为通常的碳纳米管,可以是单壁纳米管(SWNT)或者多壁纳米管(MWNT)。并且,上述碳纳米管的直径为10nm~60nm,高宽比(aspectratio)优选为1000以上,并具有用少量也能够在12V下每分钟加热10℃以上的高效发热特性,但并不局限于此。
上述碳纳米管和第一树脂以及第二树脂的质量比优选为1∶4~1∶16,这在使得碳纳米管的量并不过多以至于引起因流动性差而使得印刷性下降、树脂分散性降低、附着力低下的程度的同时,作为能够使面电阻值具有适当大小进而能够高效发热的程度,是充分包含CNT的含量。优选上述碳纳米管和第一树脂的质量比为1∶2~1∶9(即,相对于碳纳米管100重量份,第一树脂为200重量份~900重量份),上述碳纳米管和第二树脂的质量比为1∶2~1∶7(即,相对于碳纳米管100重量份,第二树脂为200重量份~700重量份),但并不局限于此。
上述第一树脂起到起PTC功能的PTC粘合剂(binder)的作用。
上述聚烯烃系树脂均属于在本领域公知的一般聚烯烃系树脂。并且,上述聚烯烃系树脂可以是聚乙烯系树脂或者聚丙烯系树脂,可以是改性聚乙烯树脂、改性聚丙烯系树脂、乙烯共聚物或者丙烯共聚物。
上述聚乙烯包含高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)以及它们的混合物,还可利用接枝有马来酸酐的聚乙烯,具体为接枝有马来酸酐的高密度聚乙烯(m-HDPE)、接枝有马来酸酐的低密度聚乙烯(m-LDPE)等。上述乙烯共聚物以及上述丙烯共聚物可以是具有乙烯和极性基团的单体的共聚物、具有丙烯和极性基团的单体的共聚物或者是这些的混合物,但并不局限于此。
作为乙烯共聚物或者丙烯共聚物的例,可以举出乙烯/丙烯酸共聚物、乙烯/甲基丙烯酸共聚物、乙烯/丙烯酸乙酯、乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯/衣康酸共聚物、乙烯/马来酸单甲酯共聚物、乙烯/马来酸共聚物、乙烯/丙烯酸/甲基丙烯酸甲酯共聚物、乙烯/甲基丙烯酸/丙烯酸乙酯共聚物、乙烯/马来酸单甲酯/丙烯酸乙酯共聚物、乙烯/甲基丙烯酸/乙酸乙烯酯共聚物、乙烯/丙烯酸/乙烯醇共聚物、乙烯/丙烯/丙烯酸共聚物、乙烯/苯乙烯/丙烯酸共聚物、乙烯/甲基丙烯酸/丙烯腈共聚物、乙烯/富马酸/乙烯基甲醚共聚物、乙烯/氯乙烯/丙烯酸共聚物、乙烯/偏二氯乙烯/丙烯酸共聚物、乙烯/三氟氯乙烯/甲基丙烯酸共聚物以及相对应的丙烯共聚物,优选为乙烯-乙烯-醋酸乙烯(EVA)共聚物、乙烯-甲基丙烯酸甲酯(MMA)共聚物。
上述硅系树脂,只要是通常的硅系树脂,就均可使用,并包含改性硅系树脂。上述硅系树脂可以是硅蜡。例如,作为上述硅系树脂,可以使用硅橡胶,例如道康宁公司的Silastic、作为硅蜡(Wax)的瓦克(WACKER)公司的E32等。
上述第二树脂起到如下作用:在通过固定CNT和第一树脂来防止在温度反复变化时CNT流动的同时,防止在温度持续上升时电阻变低的NTC现象。因此,上述第二树脂应使用热固化性树脂、或者其Tm或软化点要比第一树脂高,优选第二树脂的软化点为130℃以上、或者上述Tm或软化点比第一树脂高1.5倍以上,但并不局限于此。
并且,为了在上述第二树脂在涂敷干燥后、减少碳纳米管的流动性,优选上述第二树脂的分子量要比第一树脂高,更优选第二树脂的分子量为10000~50000,考虑到成本效率,分子量进一步优选为10000~30000。
只要是通常的纤维素系树脂,都可以用作上述纤维素系树脂,可以是硝酸纤维素以及乙酰纤维素。并且,作为本发明的纤维素系树脂,还可以使用纯正化学(Junsei)公司的乙基纤维素、丁基纤维素或者Dow公司的STD-10等。
只要是通常的聚酯系树脂,都可以用作上述聚酯系树脂。例如,作为本发明的聚酯,可以使用聚酯粘合剂(Polyester Binder)KSA公司的SP-1、K150等。
优选上述第一树脂的分子量为3000以上,软化点为45℃-150℃。更优选软化点为120℃-150℃,但并不局限于此。
优选上述第二树脂的分子量为10000以上,软化点为130℃,但并不局限于此。
上述组合物进一步可以包含任意的作为通常的导电性填充剂的镍粉末、金粉末、铜粉末、金属合金粉末、碳粉末及石墨粉末等。
并且,上述组合物进一步可以包含聚氯乙烯及聚偏二氯乙烯、聚氟乙烯及聚偏氟乙烯等聚乙烯系高分子;和聚砜、聚酰胺等热塑性高分子。
并且,上述组合物进一步可以包含抗氧化剂、防劣化剂或者消泡剂。
上述组合物可通过印刷或者涂敷于器材上来制成PTC元件、面状发热体及电路。
为了起到发热油墨或者浆的作用,本发明的组合物优选在涂敷后所形成的干燥膜的厚度薄,这是因为,能够快速干燥而批量生产性高,并且因能够实现从表面到内部的完全干燥而使得电阻下降。更优选为10微米以下,进一步优选为5微米以下。
并且,在将本发明的组合物用作PTC元件、面状发热体、电路等时,以5微米涂敷的原材料的面电阻优选为50-1000Ω/sq,更优选为50-800Ω/sq。在面电阻过低的情况下,流动性变差,从而印刷性下降、粘度过度上升,进而制造过程的效率下降。当面电阻达到1000Ω/sq以上时,在12V下表现出10℃/分钟以下的发热性能,当面电阻达到50Ω/sq以下时,因急剧的发热现象,在三分钟内温度将达到200℃以上,因此有烧伤危险,即使添加PTC粘合剂,电子的移动仍然非常快,因而借助于PTC的电阻的控制变得困难。但是,这种面电阻范围是为了最佳、最高效地实施本发明的范围,虽然在脱离该范围的情况下,效率或稳定性会有所降低,但即便如此也并不是用该范围来限定本发明的权利范围。
以下,通过如下实施例及实验例来更详细地说明本发明。但,以下实施例及实验例仅仅是例示本发明的内容,本发明的范围并不限定于实施例及实验例。
<实施例1至6以及比较例1至7>
按照下表1的组成来制备导电性聚合物组合物,利用上述组合物来制造PTC元件用导电性薄膜试片。为了测定电阻值,将电极粘结于上述所制造的PTC元件用导电性薄膜试片,从而制作PTC元件。具体察看该过程如下。
利用金属催化剂来合成CNT,通过酸处理来在所合成的碳纳米管的表面形成羧基(-COOH),经酰氯化(acyl chlorination)和氨基功能化(aminofunctionalization)将得到带有胺基的CNT。在如此被功能化的CNT中,混合作为PTC粘合剂的乙烯-乙烯醋酸乙烯共聚物(Ethylene-EVA copolymer:ASTOR 538、ASTOR 635)、乙烯-甲基丙烯酸甲酯共聚物(Ethylene-MMAcopolymer:WK-402、WK-307)、聚乙烯蜡(PE Wax:802C、503NC、106N)、Dow(STD-10)和分散剂(BYK 9076、BYK 9077)以及乙基纤维素粘合剂(Ethyl Cellulose Binder:JUNSEI EC50,Dow STD-10)或者聚酯粘合剂(Polyester Binder:KSA SP-1),并且通过利用调糊机(Paste Mixer:DAE WHATECH DDM-300)的工序去除气泡后,通过利用三辊压机(EXAKT 80S)的工序来制备浆。用凹版(Gravure)印刷机,将所制造的浆以5微米的厚度涂敷(Coating)于BOPET,然后在130℃下干燥10分钟,随后,通过丝印法(Silk Screen)以7微米~10微米的厚度来印刷经图案(Pttn)化的银浆(AgPaste,大洲电子材料,DHC-7075或者7045),在130℃下干燥10分钟,来制造低电压用PTC用发热体。
表1
实验例1
对上述PTC元件测定了面电阻(Ω/sq)、附着力(Cross Cut)、PTC特性、面电阻增加比(=130℃/25℃测定)以及是否产生NTC。
面电阻用Loresta-GP(MCP-T610)来测定。附着力通过将10个格子以1mm的间隔横切(Cross Cut),粘贴并揭开3M SEIL TAPE来测定。将用上述配方制造的PTC浆印刷在150mm×300mm的、厚度为100微米的BOPET上并进行干燥后,将连续隔开4mm间隔的Ag电极涂敷于PTC-CNT干燥面上并进行干燥,将数字万用表(Digital Multimeter,YOKOGAWA 733)与电极可拆式连接后,附着到热板(Hot Plate),以10℃/分钟(min)调高温度来测定了电阻变化。当温度持续上升时,如果数字万用表的电阻持续增加或所增加的电阻处于静止状态,则视为未产生NTC现象,如果在热板的温度上升时,出现电阻减少的现象,则视为出现NTC现象。
结果
在没有第二树脂,而使用作为第一树脂的硅蜡和CNT的情况下,表现出明显的PTC特性,因与CNT的分散力的问题,在降低面电阻方面存在着问题(比较例1)。另一方面,在没有第二树脂,而使用LDPE和CNT的情况下,如果通过凹版印刷,在BOPET上进行印刷、干燥,就会从BOPET脱落,因此在附着力上存在问题,由此难以分析PTC特性以及NTC特性(比较例2)。
并且,因第一树脂起到PTC粘合剂的作用,所以在仅使用作为第二树脂的聚酯树脂和CNT的情况下,无法分析PTC特性以及NTC特性(比较例3),并且在所包含的第一树脂的含量少的情况下,难以分析PTC特性(比较例6)。
并且,可知,即使在同时包含第一树脂以及第二树脂的情况下,当相对于碳纳米管100重量份,第一树脂为200重量份至900重量份、且第二树脂脱离200重量份至700重量份的范围时,如同实施例1至6,在面电阻、附着力、PTC特性以及NTC特性方面均没有表现出优秀的效果(比较例4至7)。
但是,在将乙烯-EVA共聚物、聚酯系树脂与CNT一同使用的情况下,根据使用比例,PTC温度发生了变化(实施例3及4),因此可判断,通过改变上述第一树脂及第二树脂的种类以及比例,可精密改变PTC特性。并且,在将乙烯-乙烯醋酸乙烯共聚物、聚酯系树脂混合使用时,在面电阻、附着力方面没有问题,并且也没有表现出NTC特性(表2)。
因此,将本实验结果综合来看,在使用纤维素树脂以及聚酯系树脂作为第二树脂的情况下,可将NTC特性最小化(实施例1至6),可通过调节第一树脂和第二树脂的含量来制造面电阻约为200Ω/sq的PTC元件。特别是在实施例1、实施例2以及实施例5、实施例6的情况下,可见,未产生NTC特性,而且其他测定结果优异,可知,最优选相对于CNT100重量份,包含200重量份至900重量份的第一树脂及200重量份至700重量份的第二树脂。
表2
面电阻(Ω/sq) | 附着力 | PTC特性 | 面电阻增加比 | 是否产生NTC | |
实施例1 | 195 | O | 57 | 308 | X |
实施例2 | 200 | O | 63 | 211 | X |
实施例3 | 160 | O | 67 | 305 | X |
实施例4 | 240 | O | 78 | 302 | X |
实施例5 | 210 | O | 59 | 207 | X |
实施例6 | 190 | O | 60 | 301 | X |
比较例1 | 6000 | O | 60 | 100 | X |
比较例2 | 140000 | X | - | - | - |
比较例3 | 200 | O | - | - | - |
比较例4 | 5150 | X | 75 | 120 | O |
比较例5 | 3800 | X | 79 | 150 | X |
比较例6 | 7000 | X | - | - | - |
比较例7 | 90000 | X | - | - | - |
实验例2
利用在上述实验例1中防止NTC特性的同时PTC特性显著优秀的实施例1以及实施例2中的实施例1,制作400mm(L)×300mm(D)的形成了图案的薄膜加热器(Film Heater)后,将其放入与加热器使用条件相类似的马蒂兹烘箱,通过使温度以10℃/分钟(min)从25℃上升至180℃,用数字万用表观察了电阻变化。并且用相同的方法观察了根据上述实验例1的比较例的温度增加的电阻变化。
试验条件如同下述,用万用表测定了加热器的电阻变化。
-设定温度:180℃
-升温条件:10℃/min
-周边温度:25℃
其结果,确认了本发明的PTC-CNT加热器的电阻随着温度从30℃上升到130℃而增加,并且不产生NTC现象。相反,比较例的CNT加热器到110℃为止没有电阻的变化,当温度持续上升时电阻有所下降(图2)。
实验例3
将上述实验例2的PTC-CNT加热器反复开启-关闭(On-off),用初始电阻对加热器的电阻的变化率来反复评价了耐久性。试验条件如下。
-使用电压:12V
-耗电量:42W
-周边温度:25℃
-开启2分钟/关闭3分钟(评价基准:将一个循环(1-cycle)的产生时间定为5分钟以内)
-在完全关闭后,过30分钟之后用万用表测定电阻。
其结果,可以确认本发明的PTC-CNT加热器虽根据电冲击产生电阻增加,但在5%以内,具有优秀的耐久性(表3)。
表3
开启/关闭次数 | 电阻(Ω) | 变化率(%) |
0次 | 3.5 | 0 |
500次 | 3.5 | 0 |
1000次 | 3.53 | 0.9 |
2000次 | 3.56 | 1.7 |
3000次 | 3.60 | 2.8 |
5000次 | 3.64 | 4.0 |
8000次 | 3.66 | 4.5 |
10000次 | 3.66 | 4.5 |
15000次 | 3.66 | 4.7 |
20000次 | 3.67 | 4.9 |
Claims (12)
1.一种正温度系数即PTC元件用导电性聚合物组合物,其特征在于,包含:
碳纳米管;
第一树脂,其为选自由聚烯烃系树脂以及硅系树脂组成的组中的任一种树脂;以及
第二树脂,其为选自由纤维素系树脂以及聚酯系树脂组成的组中的任一种树脂。
2.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,上述第一树脂为聚乙烯系树脂或者聚丙烯系树脂。
3.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,上述第一树脂为改性聚乙烯树脂、改性聚丙烯系树脂、乙烯共聚物、丙烯共聚物或者改性硅系树脂。
4.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,上述第一树脂为LDPE、乙烯-EVA共聚物、乙烯-MMA共聚物或者硅蜡。
5.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,上述第二树脂为硝酸纤维素或者乙酰纤维素。
6.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,上述碳纳米管为单壁纳米管SWNT或者多壁纳米管MWNT。
7.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,相对于上述碳纳米管100重量份,上述第一树脂为200重量份至900重量份。
8.根据权利要求1所述的PTC元件用导电性聚合物组合物,其特征在于,相对于上述碳纳米管100重量份,上述第二树脂为200重量份至700重量份。
9.一种PTC元件,其特征在于,包含权利要求1至8中任一项所述的组合物。
10.一种面状发热体,其特征在于,包含权利要求1至8中任一项所述的组合物。
11.一种电路,其特征在于,包含权利要求1至8中任一项所述的组合物。
12.一种PTC元件的制造方法,其特征在于,包括在包含权利要求1至8中任一项所述的组合物的电阻体薄膜层压电极以及电解质金属箔的步骤。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2010-0092126 | 2010-09-17 | ||
KR20100092126 | 2010-09-17 | ||
PCT/KR2011/006919 WO2012036538A2 (ko) | 2010-09-17 | 2011-09-19 | 탄소나노튜브를 이용한, ntc 특성이 감소된 ptc 소자용 전도성 중합체조성물 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103108906A true CN103108906A (zh) | 2013-05-15 |
CN103108906B CN103108906B (zh) | 2015-08-05 |
Family
ID=45832146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180044750.3A Expired - Fee Related CN103108906B (zh) | 2010-09-17 | 2011-09-19 | 利用炭纳米管的ntc特性减少的ptc元件用导电性聚合物组合物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8968605B2 (zh) |
JP (1) | JP5674947B2 (zh) |
KR (1) | KR101344584B1 (zh) |
CN (1) | CN103108906B (zh) |
DE (1) | DE112011103114T5 (zh) |
WO (1) | WO2012036538A2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106084800A (zh) * | 2016-08-11 | 2016-11-09 | 安徽省宁国天成电工有限公司 | 一种基于活性炭纳米管的ptc热敏电阻器材料及其制备方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101225759B1 (ko) * | 2012-06-29 | 2013-01-23 | 엔디티엔지니어링(주) | 고분자 ptc 정온발열잉크 제조 방법 |
BR112015001272A2 (pt) * | 2012-07-23 | 2017-07-04 | Hewlett Packard Indigo Bv | composição de tinta eletrostática, substrato e método para imprimir eletrofotograficamente uma composição de tinta |
WO2014024977A1 (ja) * | 2012-08-08 | 2014-02-13 | 株式会社ダイセル | 導電性セルロース系樹脂組成物 |
CN106317544B (zh) * | 2015-06-30 | 2018-12-21 | 上海利韬电子有限公司 | 导电聚合物组合物、导电聚合物片材、电气器件以及它们的制备方法 |
WO2017147480A1 (en) | 2016-02-24 | 2017-08-31 | LMS Consulting Group | An electrically conductive ptc ink with double switching temperatures and applications thereof in flexible double-switching heaters |
US11332632B2 (en) | 2016-02-24 | 2022-05-17 | Lms Consulting Group, Llc | Thermal substrate with high-resistance magnification and positive temperature coefficient ink |
US10276286B2 (en) | 2016-03-09 | 2019-04-30 | Lawrence Livermore National Security, Llc | Polymer-carbon composites for temperature-dependent electrical switching applications |
KR102320339B1 (ko) * | 2016-06-22 | 2021-11-03 | 튀링기셰스 인슈티투트 퓌르 텍스틸-운트 쿤스트슈토프-포르슝 이.브이. | 정 온도 계수를 갖는 전기 전도성 성형체 |
IT201700038877A1 (it) * | 2017-04-07 | 2018-10-07 | Eltek Spa | Materiale composito ad effetto ptc, relativo procedimento di ottenimento e dispositivo riscaldatore includente tale materiale |
KR102624065B1 (ko) * | 2021-11-25 | 2024-01-12 | 전북대학교산학협력단 | 이종 전도성 고분자를 이용한 적층구조의 ptc 소자 및 그 제조방법 |
CN114316734A (zh) * | 2021-12-20 | 2022-04-12 | 华碳创新(广东)材料技术有限公司 | 一种发热涂料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101003418A (zh) * | 2006-07-14 | 2007-07-25 | 上海兰度科技有限公司 | 一种定向排列碳纳米管复合纳米纤维、高速制备设备及其制备方法 |
CN101098921A (zh) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | 碳纳米管在制备导电有机组合物中的用途及这种组合物的应用 |
CN101333338A (zh) * | 2007-06-25 | 2008-12-31 | 帝人化成株式会社 | 导电性稳定的热塑性树脂组合物 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4357684B2 (ja) | 2000-01-25 | 2009-11-04 | 株式会社フジクラ | 導電性インキ組成物およびそれを用いた面状発熱体 |
JP2003086403A (ja) | 2001-09-07 | 2003-03-20 | Nec Tokin Corp | 高分子ptc素子 |
JP2003163104A (ja) * | 2001-11-28 | 2003-06-06 | Mitsubishi Electric Corp | 有機ptc組成物 |
JP5025079B2 (ja) | 2003-12-05 | 2012-09-12 | 昭和電工株式会社 | 導電性樹脂組成物及びその成形体 |
US20060043343A1 (en) * | 2004-08-24 | 2006-03-02 | Chacko Antony P | Polymer composition and film having positive temperature coefficient |
EP2082405B1 (en) * | 2006-11-20 | 2018-10-31 | SABIC Global Technologies B.V. | Thermally regulated electrically conducting compositions |
US8003016B2 (en) * | 2007-09-28 | 2011-08-23 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition with improved positive temperature coefficient behavior and method for making thereof |
JP5512983B2 (ja) | 2009-02-17 | 2014-06-04 | 国立大学法人北海道大学 | 面状発熱体 |
EP2333795A1 (en) | 2009-12-08 | 2011-06-15 | Nanocyl S.A. | PTC resistor |
-
2011
- 2011-09-19 WO PCT/KR2011/006919 patent/WO2012036538A2/ko active Application Filing
- 2011-09-19 KR KR1020110094241A patent/KR101344584B1/ko active IP Right Grant
- 2011-09-19 CN CN201180044750.3A patent/CN103108906B/zh not_active Expired - Fee Related
- 2011-09-19 US US13/814,013 patent/US8968605B2/en not_active Expired - Fee Related
- 2011-09-19 DE DE112011103114T patent/DE112011103114T5/de not_active Withdrawn
- 2011-09-19 JP JP2013529081A patent/JP5674947B2/ja not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101098921A (zh) * | 2005-01-05 | 2008-01-02 | 阿克马法国公司 | 碳纳米管在制备导电有机组合物中的用途及这种组合物的应用 |
CN101003418A (zh) * | 2006-07-14 | 2007-07-25 | 上海兰度科技有限公司 | 一种定向排列碳纳米管复合纳米纤维、高速制备设备及其制备方法 |
CN101333338A (zh) * | 2007-06-25 | 2008-12-31 | 帝人化成株式会社 | 导电性稳定的热塑性树脂组合物 |
Non-Patent Citations (3)
Title |
---|
B LI ET AL: "Easy Fabrication and Resistivity-Temperature Behavior of an Anisotropically Conductive Carbon Nanotube-Polymer Composite", 《J.PHYS.CHEM.B》, vol. 114, no. 2, 23 December 2009 (2009-12-23), pages 689 - 696 * |
JIE-FENG GAO ET AL: "Large-scale fabrication and electrical properties of an anisotropic conductive polymer composite utilizing preferable location of carbon nanotubes in a polymer blend", 《COMPOSITES SCIENCE AND TECHNOLOGY》, vol. 70, no. 13, 1 August 2010 (2010-08-01), pages 1973 - 1979 * |
SERTAN YESIL ET AL: "Effect of Microfiber Reinforcement on the Morphology, Electrical, and Mechanical Properties of the Polyethylene/Poly(ethylene terephthalate)/Carbon Nanotube Composites", 《POLYMER ENGINEERING AND SCIENCE》, vol. 5, no. 11, 25 June 2010 (2010-06-25), pages 2093 - 2105 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106084800A (zh) * | 2016-08-11 | 2016-11-09 | 安徽省宁国天成电工有限公司 | 一种基于活性炭纳米管的ptc热敏电阻器材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20120030030A (ko) | 2012-03-27 |
CN103108906B (zh) | 2015-08-05 |
WO2012036538A3 (ko) | 2012-06-21 |
JP5674947B2 (ja) | 2015-02-25 |
US8968605B2 (en) | 2015-03-03 |
US20130140499A1 (en) | 2013-06-06 |
JP2013539800A (ja) | 2013-10-28 |
KR101344584B1 (ko) | 2013-12-26 |
WO2012036538A2 (ko) | 2012-03-22 |
DE112011103114T5 (de) | 2013-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103108906B (zh) | 利用炭纳米管的ntc特性减少的ptc元件用导电性聚合物组合物 | |
JP4936142B2 (ja) | 導電性ペースト組成物及び電子回路並びに電子部品 | |
JP2000208302A (ja) | 正の温度係数抵抗組成物を含む電気装置及びその製法 | |
JP6598692B2 (ja) | 銀ナノワイヤを含む組成物 | |
JP2010047716A (ja) | スクリーン印刷用導電性インキ組成物及び導電性塗膜 | |
KR20090119260A (ko) | 고전도성 페이스트 조성물 | |
JP6412106B2 (ja) | ポリマー厚膜正温度係数カーボン組成物 | |
CN102827513A (zh) | 一种可光聚合的催化油墨及其应用 | |
JP3882622B2 (ja) | Ptc抵抗体 | |
JPH11310739A (ja) | 導電性インキ組成物およびそれを用いた面状発熱体 | |
JP5353163B2 (ja) | 導電性インク組成物及び該組成物を用いて集電極が形成された太陽電池セル | |
KR101434565B1 (ko) | 전도성 페이스트 조성물을 포함하는 후막형 ptc 발열체 | |
JP2018135422A (ja) | ホットメルト接着剤組成物、および積層体 | |
JP5522390B2 (ja) | 導電性ペースト組成物および導電接着方法 | |
JP2014183222A (ja) | Ptc組成物 | |
KR20170072594A (ko) | 높은 정온도 계수 특성을 갖는 면상 발열체 조성물 및 이를 이용한 면상 발열체 | |
JPH11310738A (ja) | 導電性インキ組成物およびそれを用いた面状発熱体 | |
JP2001076850A (ja) | 導電性インキ組成物およびそれを用いた面状発熱体 | |
TW202037687A (zh) | 可拉伸導電墨水組合物 | |
JP3684867B2 (ja) | Ptc組成物および面状発熱体 | |
JP2008184599A (ja) | 導電性インキ、導電回路および非接触型メディア | |
JP2001202821A (ja) | 導電性インキ組成物およびそれを用いた面状発熱体 | |
RU2612717C2 (ru) | Токопроводящая клеевая композиция | |
JP2019033172A (ja) | 有機ptc素子およびその製造方法 | |
Ismail et al. | Resistivity of Graphene/Silver Hybridization Conductive Ink on Bending Test |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150805 Termination date: 20180919 |
|
CF01 | Termination of patent right due to non-payment of annual fee |