WO2011065229A1 - 防食剤、端子付き被覆電線およびワイヤーハーネス - Google Patents
防食剤、端子付き被覆電線およびワイヤーハーネス Download PDFInfo
- Publication number
- WO2011065229A1 WO2011065229A1 PCT/JP2010/070051 JP2010070051W WO2011065229A1 WO 2011065229 A1 WO2011065229 A1 WO 2011065229A1 JP 2010070051 W JP2010070051 W JP 2010070051W WO 2011065229 A1 WO2011065229 A1 WO 2011065229A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- terminal
- wire
- electric wire
- ethylene
- conductor
- Prior art date
Links
- 239000003518 caustics Substances 0.000 title abstract 6
- 239000004020 conductor Substances 0.000 claims abstract description 55
- 239000004711 α-olefin Substances 0.000 claims abstract description 41
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 12
- 239000012212 insulator Substances 0.000 description 10
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003298 Nucrel® Polymers 0.000 description 2
- -1 Polyethylene Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/10—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation
- H01R4/18—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping
- H01R4/183—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping for cylindrical elongated bodies, e.g. cables having circular cross-section
- H01R4/184—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation effected solely by twisting, wrapping, bending, crimping, or other permanent deformation by crimping for cylindrical elongated bodies, e.g. cables having circular cross-section comprising a U-shaped wire-receiving portion
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
- H01R13/52—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases
- H01R13/5216—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases characterised by the sealing material, e.g. gels or resins
Definitions
- the present invention relates to an anticorrosive, a coated electric wire with a terminal, and a wire harness, and more specifically, an anticorrosive suitable for anticorrosion of a connection portion between a conductor and a terminal in a coated electric wire with a terminal, It relates to a wire harness.
- a covered electric wire in which an outer periphery of a conductor made of a soft material such as tough pitch copper is coated with an insulator is often used.
- the insulator is peeled off to expose the conductor, and the terminal is connected to the exposed conductor.
- the terminal connected to the end of the covered wire is inserted and locked to the connector.
- a plurality of such covered wires are bundled to form a wire harness.
- the covered electric wire is usually routed to a vehicle such as an automobile in the form of a wire harness.
- Patent Document 1 discloses that grease is injected into the connector in which the terminal connected to the conductor of the wire terminal is inserted and locked. Yes.
- An object of the present invention is to provide an anticorrosive, a covered electric wire with a terminal and a wire harness using the same.
- the anticorrosive agent according to the present invention has a melt flow rate of 200 g / 10 min. At 190 ° C. and 21.18 N measured according to JIS K6922-1. It contains the above ethylene- ⁇ olefin copolymer, and the gist is that the copolymerization ratio of the ⁇ olefin in the ethylene- ⁇ olefin copolymer is 10% by mass or more.
- ⁇ olefin one or more selected from vinyl esters, ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters, and carboxyl group-containing monomers can be suitably used.
- the gist of the covered electric wire with terminal according to the present invention is that the connecting portion between the electric wire conductor and the terminal is covered with the anticorrosive agent.
- the electric wire conductor contains a strand made of aluminum or an aluminum alloy, and the terminal is made of copper or a copper alloy.
- the anticorrosive agent according to the present invention since it contains a specific ethylene- ⁇ olefin copolymer, the anticorrosive treatment is not applied to the connection portion between the conductor of the electric wire and the terminal, and the handleability is excellent. Thus, the connecting portion can be reliably covered to prevent corrosion of the connecting portion.
- the anticorrosive has excellent affinity with the electric wire conductor and the terminal due to the polar functional group of the ⁇ -olefin. Therefore, it is especially excellent in corrosion resistance.
- the connection portion between the conductor and the terminal is covered with the anticorrosive agent, corrosion hardly occurs. Therefore, it is suitably routed in the engine room or indoor environment of the flooded area. Also, in the case of dissimilar metal connection consisting of a wire conductor containing a strand made of aluminum or an aluminum alloy and a terminal made of copper or a copper alloy, the connection portion between the conductor and the terminal is covered by the anticorrosive agent. Therefore, it has excellent corrosion resistance.
- FIG. 2 is a cross-sectional view taken along the line AA in FIG. It is a schematic diagram explaining a corrosion test method.
- the anticorrosive agent according to the present invention mainly comprises an ethylene- ⁇ olefin copolymer.
- the anticorrosive agent according to the present invention may be composed of an ethylene- ⁇ -olefin copolymer alone, and may contain additives and other polymers as long as they do not impair physical properties. .
- the ethylene- ⁇ olefin copolymer has a melt flow rate (MFR) at 190 ° C. of 21.18 N measured according to JIS K6922-1 of 200 g / 10 min. That's it.
- MFR melt flow rate
- the MFR of the ethylene- ⁇ -olefin copolymer is 200 g / 10 min. If it is less than 1, the fluidity is low, and the portion to be subjected to the anticorrosion treatment cannot be sufficiently covered.
- the MFR of the ethylene- ⁇ -olefin copolymer is more preferably 500 g / 10 min. Or more, more preferably 1000 g / 10 min. That's it.
- the ethylene- ⁇ olefin copolymer has a copolymerization ratio of ⁇ olefin of 10% by mass or more.
- the copolymerization ratio of the ⁇ -olefin is less than 10% by mass, the affinity (wetting property) with the wire conductor and the terminal is not sufficient, and the anticorrosion effect cannot be sufficiently exhibited.
- the copolymerization ratio of ⁇ -olefin is preferably 15% by mass or more, and more preferably 20% by mass or more.
- Preferred examples of the ⁇ -olefin in the ethylene- ⁇ -olefin copolymer include vinyl esters, ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters, and carboxyl group-containing monomers. These ⁇ -olefins are particularly excellent in the effect of increasing the affinity (wetting properties) with the wire conductor and the terminal.
- the ethylene- ⁇ olefin copolymer may be a copolymer of ethylene and one kind of ⁇ olefin, or may be a copolymer of ethylene and two or more kinds of ⁇ olefins.
- vinyl ester examples include vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, and the like.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester include methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.
- Examples of the carboxyl group-containing monomer include maleic anhydride.
- ethylene- ⁇ olefin copolymers include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl acrylate copolymer.
- EVA ethylene-vinyl acetate copolymer
- EAA ethylene-ethyl acrylate copolymer
- EMA ethylene-methyl acrylate copolymer
- EMMA ethylene-methyl methacrylate copolymer
- maleic anhydride modified EMA maleic anhydride modified EMA
- the additive that can be added as needed is not particularly limited as long as it is an additive generally used for resin molding materials.
- inorganic fillers, antioxidants, metal deactivators (copper damage inhibitors), UV absorbers, UV masking agents, flame retardant aids, processing aids (lubricants, waxes, etc.) examples thereof include carbon and other coloring pigments.
- a polymer component other than the ethylene- ⁇ -olefin copolymer may be blended as necessary.
- the ethylene- ⁇ -olefin copolymer and the polymer component blended as necessary may be cross-linked as necessary for the purpose of increasing heat resistance and mechanical strength.
- crosslinking there are no particular limitations on the means of crosslinking, such as thermal crosslinking, chemical crosslinking, silane crosslinking, electron beam crosslinking, and ultraviolet crosslinking.
- thermal crosslinking chemical crosslinking
- silane crosslinking silane crosslinking
- electron beam crosslinking and ultraviolet crosslinking.
- what is necessary is just to perform the bridge
- the anticorrosive agent according to the present invention can be suitably used, for example, for preventing corrosion of a connection portion between a conductor and a terminal of a covered electric wire arranged in a vehicle such as an automobile.
- a coated electric wire 10 with a terminal includes a covered electric wire 12 in which an outer periphery of an electric wire conductor 18 is covered with an insulator 20, and an electric wire conductor of the covered electric wire 12. And a terminal 14 connected to 18 terminals.
- the insulator 20 is peeled off at the end to expose the electric wire conductor 18, and the terminal 14 is connected to the end of the exposed electric wire conductor 18.
- the electric wire conductor 18 is formed of a stranded wire formed by twisting a plurality of strands 18a.
- the stranded wire may be composed of one type of metal strand, or may be composed of two or more types of metal strand.
- the twisted wire may contain the strand etc. which consist of organic fibers other than a metal strand.
- the stranded wire may include a reinforcing wire (tension member) that reinforces the covered electric wire.
- Examples of the material of the metal wire include copper, copper alloy, aluminum, aluminum alloy, and materials obtained by performing various platings on these materials.
- Examples of the material of the metal strand as the reinforcing wire include copper alloy, titanium, tungsten, and stainless steel.
- Examples of the organic fiber as the reinforcing wire include aramid fibers such as Kevlar (registered trademark of DuPont).
- Examples of the material of the insulator 20 include rubber, polyolefin, PVC, and thermoplastic elastomer. These may be used alone or in combination of two or more.
- Various additives may be appropriately added to the material of the insulator 20. Examples of the additive include a flame retardant, a filler, a colorant and the like.
- the terminal 14 includes a tab-like connection portion 14c connected to the counterpart terminal, a wire barrel 14a that extends from the proximal end of the connection portion 14c, and that crimps the end of the wire conductor 18 of the covered wire 12, and a wire barrel
- the insulation barrel 14b is further extended from 14a and crimps the insulator 20 at the end of the covered electric wire 12.
- the material of the terminal 14 material of the base material
- various copper alloys, copper, etc. can be used in addition to commonly used brass.
- a part (for example, a contact) or the entire surface of the terminal 14 may be plated with various metals such as tin, nickel, and gold.
- a part of the wire conductor 18 is exposed at the connection portion between the wire conductor 18 and the terminal 14 at the wire terminal.
- the exposed portion of the covered electric wire with terminal 10 according to the present invention is covered with the anticorrosive agent.
- the anticorrosive coating film 16 covers the boundary between the base end of the connection portion 14c of the terminal 14 and the tip end of the electric wire conductor 18 to the base end of the connection portion 14c, and the insulation barrel of the terminal 14 14b and the insulator 20 are covered up to the insulator 20 across the boundary.
- the anticorrosive may be appropriately selected according to the combination of the material of the wire conductor 18 and the material of the terminal 14.
- the thickness of the anticorrosive coating film 16 may be adjusted as appropriate, but is preferably in the range of 0.01 mm to 0.1 mm. If the coating film 16 is too thick, it is difficult to insert the terminal 14 into the connector. Moreover, when the thickness of the coating film 16 is too thin, an anticorrosion effect will fall easily.
- the anticorrosive is formed by crimping the terminal 14 at the wire end to connect the wire conductor 18 and the terminal 14, and then the surface of the connection portion between the wire conductor 18 and the terminal 14, that is, the surface of the insulator 20 at the end, and the insulation. It is applied to the surface of the connection barrel 14b, the surface of the wire barrel 14a, the exposed surface of the electric wire conductor 18, and the surface of the base end of the connecting portion 14c. Thereby, the coating film 16 is formed on the surface of the connection portion between the wire conductor 18 and the terminal 14.
- the coating film 16 is also formed on the back side of the tab-like connecting portion 14c protruding from the wire barrel 14a of the terminal 14 and the back side of the wire barrel 14a and the insulation barrel 14b. You may do it.
- the anticorrosive agent When applying the anticorrosive agent, it is sufficient that the anticorrosive agent can flow to the extent that it can be applied. Therefore, when applying, the anticorrosive may be appropriately heated, or may be liquefied appropriately using a solvent. Moreover, when apply
- the anticorrosive coating film 16 may be subjected to a crosslinking treatment as necessary for the purpose of increasing heat resistance and mechanical strength.
- a crosslinking treatment there are no particular limitations on the means of crosslinking, such as thermal crosslinking, chemical crosslinking, silane crosslinking, electron beam crosslinking, and ultraviolet crosslinking.
- the anticorrosive mainly contains a specific ethylene- ⁇ -olefin copolymer, it has excellent fluidity when heated. Therefore, it has the property which is easy to apply. Thereby, application
- coating can be accurately performed to the target place. Then, for example, even when the covered electric wire 12 is a thin electric wire (for example, ⁇ 0.8) and the terminal 14 is small (for example, a tab width of 0.64 mm), only the connecting portion between the electric wire conductor 18 and the terminal 14 is accurate. And it can be applied reliably.
- the anticorrosive since the anticorrosive is cooled and solidified after application, it can be fixed in a place where it has been applied over a long period of time, as well as being free from stickiness during handling. Therefore, the anticorrosion effect can be maintained over a long period of time. Further, when the ⁇ -olefin has a polar group, the affinity with the metal material is high, so that the wettability and adhesion to the wire conductor 18 and the terminal 14 are excellent. Also by this, the anticorrosion effect can be maintained over a long period of time.
- the wire harness according to the present invention is formed by bundling a plurality of terminal-coated wires including the terminal-coated wire 10.
- some of the covered wires with terminals out of the plurality of covered wires with terminals may be the covered wires 10 with terminals, or all of the covered wires with terminals of the plurality of terminals.
- the covered electric wire with terminal may be the above-described covered electric wire 10 with terminal.
- the plurality of covered electric wires with terminals may be bundled by tape winding, or may be covered by an external part such as a round tube, a corrugated tube, or a protector.
- the wire harness according to the present invention is suitable for being routed in a vehicle such as an automobile, and is particularly suitable for being routed in an engine room or a vehicle in a wet area.
- a vehicle such as an automobile
- rust is likely to be generated in the connection portion between the electric wire conductor 18 and the terminal 14.
- production of the rust in the connection part of the electric wire conductor 18 and the terminal 14 in the said covered electric wire 10 with a terminal can be suppressed.
- EVA ethylene-vinyl acetate copolymer
- EEA ethylene-ethyl acrylate copolymer
- EMA ⁇ 1> ethylene-methyl acrylate copolymer
- EMMA ethylene-methyl methacrylate copolymer
- Modified EMA ethylene-methyl acrylate-maleic anhydride copolymer
- the terminal-coated wire 1 is connected to the + pole of the 12V power supply 2 and the pure copper plate 3 (1 cm ⁇ 2 cm ⁇ 1 mm) is connected to the ⁇ pole of the 12V power supply 2 to
- the connection portion between the conductor and the terminal and the pure copper plate 3 were immersed in 300 cc NaCl 5% aqueous solution 4 and energized at 12 V for 2 minutes.
- ICP emission analysis of NaCl 5% aqueous solution 4 was performed, and the amount of aluminum ions eluted from the wire conductor of the covered wire 1 with terminals was measured.
- the case where the elution amount was less than 0.1 ppm was “ ⁇ ”, and the case where the elution amount was 0.1 ppm or more was “x”.
- Table 1 shows the types of anticorrosive agents, MFR values, comonomer copolymerization ratios, and anticorrosion test results in Examples and Comparative Examples.
- MFR is a value in 190 degreeC and 21.18N measured based on JISK6922-1.
- Comparative Examples 1 and 2 since the MFR of the anti-corrosive ethylene- ⁇ -olefin copolymer is relatively small, the fluidity is poor and it cannot be applied to cover the exposed wire conductor and the terminal barrel. It was. Therefore, it was inferior to corrosion resistance. Further, in Comparative Example 3, since the anticorrosive agent is made of low-density polyethylene, the coating property or adhesion of the anticorrosive agent to the metal surface is poor. Therefore, it was inferior to corrosion resistance.
- the corrosion resistance was excellent.
- the anticorrosive agent contains an ethylene- ⁇ olefin copolymer, it was confirmed that there was no stickiness.
- a male terminal having a tab-like connecting portion 14c is shown as the terminal 14, but the present invention is not limited to this.
- a female terminal that can be fitted with a male terminal, a tuning fork terminal, or the like may be used.
- the terminal 14 may be crimped only by the wire barrel 14a without having the insulation barrel 14b.
- the method for connecting the wire conductor 12 and the terminal 14 is not limited to crimping by a barrel, and may be a method such as pressure resistance welding, ultrasonic welding, or soldering.
- the conductor 18 which consists of a twisted wire is shown, the conductor 18 may be a single core wire.
Abstract
Description
ポリ塩化ビニル(重合度1300)100質量部、可塑剤としてジイソノニルフタレート40質量部、充填剤として重炭酸カルシウム20質量部、安定剤としてカルシウム亜鉛系安定剤5質量部をオープンロールにて180℃で混合し、ペレタイザーにてペレット状に成形して、ポリ塩化ビニル組成物を調製した。次いで、50mm押出機にて、得られたポリ塩化ビニル組成物で、アルミ合金線を7本撚り合わせたアルミニウム合金撚線よりなる導体(断面積0.75mm)の周囲を0.28mm厚に押出被覆して、被覆電線(PVC電線)を作製した。
作製した被覆電線の端末を皮剥して電線導体を露出させた後、自動車用として汎用されている黄銅製のオス形状の圧着端子(タブ幅0.64mm)を被覆電線の端末に加締め圧着した。次いで、電線導体と端子との接続部分に、下記の各種エチレン-αオレフィン共重合体を塗布して、露出している電線導体および端子のバレルを各種エチレン-αオレフィン共重合体で覆った。これにより、端子付き被覆電線を作製した。なお、エチレン-αオレフィン共重合体を塗布する際には、エチレン-αオレフィン共重合体を230℃に加熱して液状にした。また、塗膜の厚さは0.05mmとした。
・EVA(エチレン-酢酸ビニル共重合体)[三井デュポンポリケミカル製、エバフレックスEV205W(コモノマー14質量%、MFR800)]
・EEA(エチレン-アクリル酸エチル共重合体)[日本ユニカー製、NUC-6090(コモノマー30質量%、MFR1250)]
・EMA<1>(エチレン-アクリル酸メチル共重合体)[三井デュポンポリケミカル製、ニュクレル N2050H(コモノマー20質量%、MFR500)]
・EMMA(エチレン-メタアクリル酸メチル共重合体)[住友化学製、アクリフト CM5021(コモノマー28質量%、MFR450)]
・変性EMA(エチレン-アクリル酸メチル-無水マレイン酸共重合体)[アルケマ製、ボンダイン HX8210(コモノマー10質量%、MFR200)]
・EMA<2>(エチレン-アクリル酸メチル共重合体)[日本ポリエチレン製、レクスパールEMA EB440H(コモノマー20質量%、MFR18)]
・EAA(エチレン-アクリル酸共重合体)[三井デュポンポリケミカル製、ニュクレル N1560(コモノマー15質量%、MFR60)]
・LDPE(低密度ポリエチレン)[東ソ-製、ペトロセン 354(コモノマー0質量%、MFR200)]
図3に示すように、端子付き被覆電線1を12V電源2の+極につなぐとともに、純銅板3(1cm×2cm×1mm)を12V電源2の-極につなぎ、端子付き被覆電線1の電線導体と端子との接続部分および純銅板3を300ccのNaCl5%水溶液4に浸漬し、12Vで2分間通電した。通電後、NaCl5%水溶液4のICP発光分析を行ない、端子付き被覆電線1の電線導体からのアルミニウムイオンの溶出量を測定した。溶出量が0.1ppm未満の場合を「○」とし、溶出量が0.1ppm以上の場合を「×」とした。
Claims (5)
- JIS K6922-1に準拠して測定される190℃、21.18Nにおけるメルトフローレイトが200g/10min.以上のエチレン-αオレフィン共重合体を含有し、前記エチレン-αオレフィン共重合体におけるαオレフィンの共重合比率が10質量%以上であることを特徴とする防食剤。
- 前記αオレフィンは、ビニルエステル、α,β-不飽和カルボン酸アルキルエステル、および、カルボキシル基含有モノマから選択された1種または2種以上であることを特徴とする請求項1に記載の防食剤。
- 請求項1または2に記載の防食剤により電線導体と端子との接続部分が覆われてなることを特徴とする端子付き被覆電線。
- 前記電線導体は、アルミニウムまたはアルミニウム合金よりなる素線を含有してなり、前記端子は、銅または銅合金よりなることを特徴とする請求項3に記載の端子付き被覆電線。
- 請求項3または4に記載の端子付き被覆電線を含むワイヤーハーネス。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010800533063A CN102639751A (zh) | 2009-11-24 | 2010-11-10 | 防腐蚀剂、具有端子的包覆电线和线束 |
DE112010004546T DE112010004546T5 (de) | 2009-11-24 | 2010-11-10 | Korrosionsschutzmittel, beschichtete elektrische Leitung mit Anschluss und Kabelstrang |
US13/500,992 US20120205151A1 (en) | 2009-11-24 | 2010-11-10 | Anticorrosive, coated electric wire with terminal, and wiring harness |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-266527 | 2009-11-24 | ||
JP2009266527A JP5095709B2 (ja) | 2009-11-24 | 2009-11-24 | 端子付き被覆電線およびワイヤーハーネス |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011065229A1 true WO2011065229A1 (ja) | 2011-06-03 |
Family
ID=44066333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/070051 WO2011065229A1 (ja) | 2009-11-24 | 2010-11-10 | 防食剤、端子付き被覆電線およびワイヤーハーネス |
Country Status (5)
Country | Link |
---|---|
US (1) | US20120205151A1 (ja) |
JP (1) | JP5095709B2 (ja) |
CN (1) | CN102639751A (ja) |
DE (1) | DE112010004546T5 (ja) |
WO (1) | WO2011065229A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012028154A (ja) * | 2010-07-23 | 2012-02-09 | Auto Network Gijutsu Kenkyusho:Kk | ワイヤーハーネスの端末構造 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5063750B2 (ja) * | 2010-07-23 | 2012-10-31 | 株式会社オートネットワーク技術研究所 | ワイヤーハーネスの端末構造 |
JP5409545B2 (ja) * | 2010-08-06 | 2014-02-05 | 住友電装株式会社 | 電線接続部の防食構造 |
JP2013089554A (ja) * | 2011-10-21 | 2013-05-13 | Sumitomo Wiring Syst Ltd | 端子付き電線、端子付き電線の製造方法および端子圧着装置 |
WO2014132685A1 (ja) * | 2013-02-27 | 2014-09-04 | 株式会社オートネットワーク技術研究所 | 端子付き被覆電線および端子付き被覆電線の製造方法 |
JP2014165158A (ja) * | 2013-02-28 | 2014-09-08 | Auto Network Gijutsu Kenkyusho:Kk | 端子付き被覆電線及びワイヤーハーネス |
WO2014148071A1 (ja) * | 2013-03-22 | 2014-09-25 | 株式会社オートネットワーク技術研究所 | 端子付き被覆電線 |
JP6056584B2 (ja) | 2013-03-22 | 2017-01-11 | 株式会社オートネットワーク技術研究所 | 端子付き被覆電線、ワイヤーハーネス、及び防食剤 |
JP5741737B2 (ja) * | 2013-10-25 | 2015-07-01 | 株式会社オートネットワーク技術研究所 | 防食剤、端子付き被覆電線及びワイヤーハーネス |
GB2520998B (en) | 2013-12-06 | 2016-06-29 | Schlumberger Holdings | Expandable Reamer |
US10519722B2 (en) | 2014-07-21 | 2019-12-31 | Schlumberger Technology Corporation | Reamer |
GB2528457B (en) | 2014-07-21 | 2018-10-10 | Schlumberger Holdings | Reamer |
GB2528454A (en) | 2014-07-21 | 2016-01-27 | Schlumberger Holdings | Reamer |
GB2528459B (en) | 2014-07-21 | 2018-10-31 | Schlumberger Holdings | Reamer |
GB2528456A (en) | 2014-07-21 | 2016-01-27 | Schlumberger Holdings | Reamer |
GB2528458A (en) | 2014-07-21 | 2016-01-27 | Schlumberger Holdings | Reamer |
JP6354608B2 (ja) * | 2015-01-29 | 2018-07-11 | 株式会社オートネットワーク技術研究所 | 端子付き被覆電線 |
JP6200448B2 (ja) * | 2015-04-20 | 2017-09-20 | 矢崎総業株式会社 | 防食材、端子付き電線及びワイヤーハーネス |
JP6600276B2 (ja) * | 2016-05-20 | 2019-10-30 | 矢崎総業株式会社 | 樹脂組成物及びそれを用いた絶縁電線 |
JP6965595B2 (ja) * | 2017-06-23 | 2021-11-10 | 住友電気工業株式会社 | 端子付電線及びその製造方法 |
JP7052489B2 (ja) * | 2018-03-30 | 2022-04-12 | 株式会社オートネットワーク技術研究所 | 端子付き電線およびワイヤーハーネス |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63230718A (ja) * | 1987-03-19 | 1988-09-27 | Sumitomo Chem Co Ltd | エチレン−α−オレフイン共重合体およびその製造方法 |
JPH0927217A (ja) * | 1995-07-10 | 1997-01-28 | Fujikura Ltd | 防錆性絶縁電線 |
JPH1171536A (ja) * | 1997-06-20 | 1999-03-16 | Mitsui Chem Inc | 防錆処理剤、防錆処理方法および防錆処理金属製品 |
JP2004111058A (ja) * | 2002-09-13 | 2004-04-08 | Furukawa Electric Co Ltd:The | アルミ電線用端子及びコネクタ |
JP2008063539A (ja) * | 2006-09-11 | 2008-03-21 | Du Pont Mitsui Polychem Co Ltd | 熱可塑性樹脂組成物およびその用途 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05159846A (ja) | 1991-12-02 | 1993-06-25 | Sumitomo Wiring Syst Ltd | コネクタへのグリース注入方法と、それに用いるグリース漏出防止カバー |
EP0921154A4 (en) * | 1997-06-20 | 2000-09-06 | Mitsui Chemicals Inc | AQUEOUS DISPERSION COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF, RUST PROTECTION, RUST PROTECTION METHODS AND METAL OBJECTS RESISTANT TO RUST |
JP4895082B2 (ja) * | 2005-07-27 | 2012-03-14 | 株式会社フジクラ | 水密絶縁電線 |
-
2009
- 2009-11-24 JP JP2009266527A patent/JP5095709B2/ja not_active Expired - Fee Related
-
2010
- 2010-11-10 DE DE112010004546T patent/DE112010004546T5/de not_active Withdrawn
- 2010-11-10 US US13/500,992 patent/US20120205151A1/en not_active Abandoned
- 2010-11-10 CN CN2010800533063A patent/CN102639751A/zh active Pending
- 2010-11-10 WO PCT/JP2010/070051 patent/WO2011065229A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63230718A (ja) * | 1987-03-19 | 1988-09-27 | Sumitomo Chem Co Ltd | エチレン−α−オレフイン共重合体およびその製造方法 |
JPH0927217A (ja) * | 1995-07-10 | 1997-01-28 | Fujikura Ltd | 防錆性絶縁電線 |
JPH1171536A (ja) * | 1997-06-20 | 1999-03-16 | Mitsui Chem Inc | 防錆処理剤、防錆処理方法および防錆処理金属製品 |
JP2004111058A (ja) * | 2002-09-13 | 2004-04-08 | Furukawa Electric Co Ltd:The | アルミ電線用端子及びコネクタ |
JP2008063539A (ja) * | 2006-09-11 | 2008-03-21 | Du Pont Mitsui Polychem Co Ltd | 熱可塑性樹脂組成物およびその用途 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012028154A (ja) * | 2010-07-23 | 2012-02-09 | Auto Network Gijutsu Kenkyusho:Kk | ワイヤーハーネスの端末構造 |
Also Published As
Publication number | Publication date |
---|---|
DE112010004546T5 (de) | 2012-10-11 |
US20120205151A1 (en) | 2012-08-16 |
JP5095709B2 (ja) | 2012-12-12 |
CN102639751A (zh) | 2012-08-15 |
JP2011111632A (ja) | 2011-06-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011065229A1 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP5095705B2 (ja) | 端子付き被覆電線およびワイヤーハーネス | |
JP5441826B2 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP5123991B2 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
WO2011108525A1 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP2012174447A (ja) | 自動車用端子圧着電線 | |
JP6131888B2 (ja) | 端子付き被覆電線及びワイヤーハーネス | |
JP2012174449A (ja) | 自動車用端子圧着電線 | |
JP2012028154A (ja) | ワイヤーハーネスの端末構造 | |
WO2013183404A1 (ja) | 端子付き被覆電線及びワイヤーハーネス | |
WO2013011847A1 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP2019179598A (ja) | 端子付き電線およびワイヤーハーネス | |
JP2011113670A (ja) | 端子付き被覆電線の防食方法および端子付き被覆電線の製造方法 | |
JP2015174995A (ja) | 粘着剤組成物、防食端子及び端子付き被覆電線 | |
WO2013011846A1 (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP6131893B2 (ja) | 端子付き電線及びそれに用いる粘着剤 | |
WO2014132538A1 (ja) | 端子付き被覆電線及びワイヤーハーネス | |
JP2010284895A (ja) | 積層体、チューブ、絶縁電線、及びこれらの製造方法 | |
JP6260363B2 (ja) | 端子付き被覆電線 | |
JP2013101935A (ja) | 防食剤、端子付き被覆電線およびワイヤーハーネス | |
JP6107620B2 (ja) | 端子付き被覆電線及びワイヤーハーネス | |
JP2014110151A (ja) | 端子付き被覆電線、ワイヤーハーネス、および防食剤 | |
WO2016084580A1 (ja) | 端子付き被覆電線 | |
JP2013067847A (ja) | 防食剤、端子付き被覆電線及びワイヤーハーネス |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080053306.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10833076 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13500992 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1120100045461 Country of ref document: DE Ref document number: 112010004546 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10833076 Country of ref document: EP Kind code of ref document: A1 |