EP0416131B1 - Insulated electric wire - Google Patents
Insulated electric wire Download PDFInfo
- Publication number
- EP0416131B1 EP0416131B1 EP90904938A EP90904938A EP0416131B1 EP 0416131 B1 EP0416131 B1 EP 0416131B1 EP 90904938 A EP90904938 A EP 90904938A EP 90904938 A EP90904938 A EP 90904938A EP 0416131 B1 EP0416131 B1 EP 0416131B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- wire
- chromium oxide
- base material
- insulated wire
- 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 - Lifetime
Links
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 58
- 239000004020 conductor Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- -1 organic acid salt Chemical class 0.000 claims abstract description 12
- 238000003980 solgel method Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 124
- 239000000463 material Substances 0.000 claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 238000009713 electroplating Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000004804 winding Methods 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000010408 film Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000700 radioactive tracer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910004160 TaO2 Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910006227 ZrO4 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
-
- 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
- H01B7/02—Disposition of insulation
-
- 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
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/065—Insulating conductors with lacquers or enamels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
- H01B3/105—Wires with oxides
Definitions
- the present invention relates to an insulated wire, and more particularly, it relates to an insulated wire such as a distribution wire, a wire for winding or the like which is employed under high-vacuum environment or high-temperature environment such as a high-vacuum apparatus or a high-temperature service apparatus.
- An insulated wire may be applied to equipment such as heating equipment or a fire alarm, for which safety under a high temperature is required. Further, the insulated wire is also used under environment in an automobile, which is heated to a high temperature.
- An insulated wire formed by a conductor which is coated with heat resistant organic resin such as polyimide, fluorocarbon resin or the like has generally been used as such an insulated wire.
- an insulated wire of such a form that a conductor is inserted in an insulator tube of ceramics an MI cable (Mineral Insulated cable) of such a form that a conductor is inserted in a heat resistant alloy tube of a stainless steel alloy etc. which is filled with metal oxide powder of magnesium oxide etc., or the like has been employed for such application.
- a fiber-glass braided insulated wire employing textile glass fiber as an insulating member etc. is listed as an insulated wire for which flexibility is required with heat resistance.
- the highest temperature at which insulability can be maintained is about 200°C at the most. Therefore, it has been impossible to employ such an organic insulated coated wire for application for which guarantee for insulability is required under a high temperature of at least 200°C.
- the insulated wire which is improved in heat resistance through an insulator tube of ceramics has disadvantages such as inferior flexibility.
- the MI cable is formed by a heat resistant alloy tube and a conductor, and hence the outer diameter of the cable is increased with respect to the conductor radius.
- the MI cable has a relatively large section with respect to electric energy allowed by the conductor which is passed through the heat resistant alloy tube.
- the MI cable is wound in the form of a coil, further, it is difficult to improve space factor since the tube of its outer layer is thick as compared with the conductor.
- the fiber-glass braided insulated wire having heat resistance is employed and worked into a prescribed configuration in response to its application, the network of the braid is disturbed to cause a breakdown.
- dust of glass is generated from the glass fiber. This glass dust may serve as a gas adsorption source. Therefore, when the fiber-glass braided insulated wire is used under environment for which a high degree of vacuum is required, it has been impossible to maintain a high degree of vacuum due to the gas adsorption source provided by the glass dust.
- alumite wire prepared by performing anodic oxidation treatment on a wire of aluminum or an aluminum alloy, as an insulated wire which is excellent in heat resistance, insulability and heat dissipativity.
- its base material is restricted to aluminum.
- an inorganic insulating layer formed on the base material is also restricted to aluminum oxide.
- EP-A-0 292 780 describes an electric wire with a coating of a gel film on a conductor.
- EP-A-188 369 describes an insulation with a Keying layer of oxide, such as Al2O3, SiO2, TiO2 and TaO2.
- the present invention has been proposed in order to solve the aforementioned problems, and its object is to provide an insulated wire comprising the following items:
- An insulated wire according to the present invention comprises a base material, a chromium oxide containing layer, and an oxide insulating layer.
- the base material has an outer surface, and includes a conductor.
- the chromium oxide containing layer is formed on the outer surface of the base material.
- the oxide insulating layer is formed by applying a precursor solution of a metallic oxide onto the chromium oxide containing layer by a sol-gel method or an organic acid salt pyrolytic method.
- the chromium oxide containing layer is preferably formed by an electrochemical technique.
- the electrochemical technique includes electrolytic plating or electroless plating.
- the underlayer to be provided with the oxide insulating layer may be a CrO 3-x (1.5 ⁇ X ⁇ 2.5) layer, in order to preferably serve as an adhesion layer.
- the layer formed by the electrochemical technique has a chromium oxide layer as its outermost layer.
- the oxide insulating layer preferably contains silicon oxide, aluminum oxide or zirconium oxide.
- copper or a copper alloy is preferably employed in view of high conductivity and the cost. In consideration of a use at a higher temperature or the like, nickel chromium, silver, iron or a ferroalloy, a stainless steel alloy, or titanium or a titanium alloy is preferably contained in the surface layer of the base material.
- a chrome plated layer is formed on a conductor of copper or a copper alloy etc. as an excellent adhesion layer.
- insulating oxide ceramics such as silicon oxide obtained by heat treatment of a precursor solution of a metallic oxide hardly exhibits adhesion with respect to the chrome plated layer. This is based on recognition of the inventors.
- the ceramics thin film serving as an insulating layer has insufficient adhesion with respect to a base material.
- a layer having a chromium oxide layer as its outermost layer is formed on an outer surface of a base material. Insulating oxide ceramics adheres onto the chromium oxide layer as a layer having excellent adhesion.
- the aforementioned chromium oxide layer is formed by an electrochemical technique.
- a substance obtained by adding a small amount of organic acid to an aqueous solution of chromic anhydride is used as an electrolyte.
- a sergeant bath mainly composed of chromic anhydride or sulfuric acid is known as an electrolytic bath employed for chrome plating, it is different from this bath in the following point: Namely, mineral acid mixed into the electrolytic bath has a function of dissolving chromic anhydride which is generated on the surface of a plated layer in electrolytic plating. Therefore, a glossy metallic chrome layer is plated when a sergeant bath is employed.
- chromium oxide it is necessary to preferentially plate chromium oxide. Therefore, a small amount of organic acid is added to an electrolytic bath employed in the present invention.
- mineral acid such as sulfuric acid
- chromic anhydride concentration is not more than 50 g/l and sulfuric acid concentration is not more than 1 g/l.
- the layer mainly composed of chromium oxide preferably has a roughened surface, in order to further increase adhesion of the thin film.
- the chromium oxide containing layer may be formed by electrolytic plating employing an electrolyte which is prepared by adding sodium citrate, sodium carbonate or the like, for example, to an aqueous solution of sodium chromate.
- the as-formed layer is mainly composed of chromium oxide, which is generated by trivalent reduction of hexavalent chromium contained in the electrolyte. If copper is used as a base material in this electrolytic plating treatment, the base material surface is oxidized and the chromium oxide containing layer is formed in the exterior thereof. However, adhesion of the chromium oxide containing layer with respect to the base material is not reduced by such oxidation of the base material surface.
- Conditions for electrolytic plating for forming the inventive chromium oxide containing layer are different from those for general bright plating in treatment current density etc.
- the current density is set at 10 to 60 A/dm2 in the bright plating, depending on the treatment temperature, the current density is set at 100 to 200 A/dm2 in the present invention.
- a chromium oxide containing layer having a roughened surface can be formed by this condition of the current density.
- an insulating oxide layer is formed by application of a precursor solution of a metallic oxide.
- the precursor solution of a metallic oxide mentioned in this specification is a solution prepared from a metal organic compound, which is broadly classified in correspondence to a sol-gel method or an organic acid salt pyrolytic method, and those of the following two types are included:
- the first type of precursor solution is a solution which is generated by making hydrolytic reaction and dehydration/condensation reaction of a compound containing hydrolyzable metal-oxygen-organic group bonds such as metal alkoxide or acetate of a metal.
- This solution may contain an organic solvent such as alcohol, a raw material compound such as metal alkoxide, and water and a catalyst required for hydrolytic reaction. Further, it generally contains an organic residual group such as alkoxide, dissimilarly to hydroxide sol that is generated from inorganic salt.
- the second type of precursor solution is a solution prepared by dissolving a metal organic compound such as organic acid salt of a metal in an appropriate organic solvent.
- a metal organic compound such as organic acid salt of a metal
- a metallic oxide is generated by pyrolyzation through heating after application. Therefore, a decomposition temperature of the employed metal organic compound must be lower than its boiling point or sublimation point.
- the metal organic compound mentioned in this specification is a concept similar to "metal-organic compounds" described in Journal of Materials Science 12 (1977) pp. 1203 to 1208, for example.
- the applied layer must be left at a temperature higher than the room temperature, for volatilization of the organic solvent and removal of a residual organic substance.
- the temperature of the atmosphere for such leaving must not be higher than the melting point of the metal forming the base material.
- metallic oxide-based ceramics covering by application of a precursor solution of a metallic oxide.
- SiO2, Al2O3, ZrO4, TiO2, MgO or the like can be listed as an example of a metallic oxide formed by this method.
- ethoxide, propoxide, butoxide or the like can be listed as metal alkoxide employed for the first type of precursor solution.
- Metallic salt such as naphtanic acid, caprylic acid, stearic acid, octylic acid or the like is preferable as organic salt employed for the second type of precursor solution.
- the oxide insulating layer formed from the precursor solution of the metallic oxide by the sol-gel method or the organic acid salt pyrolytic method is an oxide which is completely converted to a metallic oxide.
- This oxide is preferably formed by heat treatment under an atmosphere in an oxygen current.
- decomposition of the compound contained in the solution which is applied onto the chromium oxide containing layer is completely terminated at a temperature of about 500°C. If the same is heat treated at a higher temperature, however, reaction between elements forming the chromium oxide containing layer and a metal or semimetal contained in the applied solution is facilitated, whereby adhesion between the chromium oxide containing layer and the oxide layer is improved.
- the oxide insulating layer converted to ceramics exhibits excellent heat resistance/insulability also under a high temperature of at least 500°C.
- the chromium oxide containing layer is excellent in adhesion to the conductor forming the base material. Therefore, adhesion between the oxide insulating layer and the outer surface of the base material is improved as compared with the case of directly forming the oxide insulating layer on the outer surface of the conductor by heat treatment of the precursor solution of the metallic oxide.
- the insulated wire provided according to the present invention has heat resistance/insulability, as well as excellent flexibility.
- the oxide insulating layer formed on the chromium oxide containing layer has a smooth outer surface. Therefore, a high breakdown voltage proportionate to the film thickness can be obtained, while it is possible to reduce a gas adsorption source.
- the chromium oxide containing layer is formed between the base material and the oxide insulating layer. Therefore, combinations with the inorganic insulating layer suitable for various uses can be selected through the chromium oxide containing layer.
- Fig. 1 is a sectional view showing a cross section of an insulated wire according to the present invention in correspondence to Example 1.
- Fig. 2 is a sectional view showing a cross section of an insulated wire according to the present invention in correspondence to Example 2.
- Fig. 3 is a sectional view showing a cross section of an insulated wire according to the present invention in correspondence to Example 3.
- Fig. 4 is a sectional view showing a cross section of an insulated wire according to the present invention in correspondence to Example 4.
- Fig. 5 is a graph showing the result of measurement of surface roughness of a chromium oxide containing layer formed in accordance with Example 3 or Example 4.
- Fig. 6 is a graph showing the result of measurement of surface roughness of a chrome plated layer formed in accordance with Reference Example.
- Electrolytic plating treatment was performed on an outer surface of a copper wire of 2 mm ⁇ in wire diameter.
- an electrolyte was prepared from that having concentration of 40 g/l of chromic anhydride and 0.45 g/l of sulfuric acid.
- the bath temperature was 50°C
- the current density was 140 A/dm2
- the treatment time was two minutes.
- a chromium oxide containing layer was formed on the outer surface of the copper wire with a film thickness of about 1 ⁇ m.
- the wire obtained by (a) was dipped in the coating solution of (b). A step of heating at a temperature of 400°C for 10 minutes was performed ten times on the wire whose outer surface was thus coated with the coating solution. Finally, this wire was heated in an oxygen current of 500°C in temperature for 10 minutes.
- FIG. 1 is a sectional view showing a cross section of the insulated wire obtained according to Example 1.
- a chromium oxide containing layer 2 is formed on an outer surface of a copper wire 1.
- a silicon oxide layer 3 is formed by the sol-gel method as an oxide insulating layer.
- the film thickness of an insulating layer formed by the chromium oxide containing layer 2 and the silicon oxide layer 3 was about 4.0 ⁇ m.
- a breakdown voltage was measured in order to evaluate insulability of the obtained insulated wire. Its breakdown voltage was 800 V under the room temperature, and was 600 V under a temperature of 800°C. Even if this insulated wire was wound on an outer peripheral surface of a cylinder having a diameter of 10 cm, no cracking was caused in the insulating layer.
- the copper wire was used as a cathode and a stainless steel plate was used as an anode to perform electrolytic plating treatment by feeding a direct current of 0.05 A/dm2.
- a solution of about 1l prepared by dissolving 30 g of sodium chromate, 30 g of sodium citrate and 30 g of sodium carbonate in water respectively was used as an electrolyte.
- a copper oxide layer having a film thickness of about 1 ⁇ m was formed on the outer surface of the copper wire, and a chromium oxide containing layer was formed in its exterior with a film thickness of about 0.1 ⁇ m.
- the wire obtained by (a) was dipped in the coating solution of (b).
- a step of heating at a temperature of 400°C for 10 minutes was performed ten times on the wire whose outer surface was thus coated with the coating solution.
- Fig. 2 is a sectional view showing a cross section of the insulated wire obtained according to Example 2.
- a copper oxide layer 12 is formed on the outer surface of a copper wire 11.
- a chromium oxide containing layer 13 is formed in the exterior of this copper oxide layer 12.
- a zirconium oxide layer 14 is formed by the sol-gel method as an oxide insulating layer.
- the film thickness of an insulating layer formed by the copper oxide layer 12, the chromium oxide containing layer 13 and the zirconium oxide layer 14 was about 3.0 ⁇ m.
- a breakdown voltage was measured in order to evaluate insulability of the obtained insulated wire. Its breakdown voltage was 700 V under the room temperature, and was 500 V under a temperature of 700°C. Even if this insulated wire was wound on an outer peripheral surface of a cylinder having a diameter of 10 cm, no cracking was caused in the insulating layer.
- Electrolytic plating treatment was performed on an outer surface of a nickel-plated copper wire of 1.8 mm ⁇ in wire diameter.
- an electrolyte was prepared from that having concentration of 200 g/l of chromic anhydride, 20 g/l of ammonium methavanadate and 6.5 g/l of acetic acid.
- the base material was used as a cathode, while the bath temperature was 50°C, the current density was 150 A/dm2, and the treatment time was two minutes.
- a chromium oxide containing layer was formed on the outer surface of the nickel-plated copper wire with a film thickness of about 1 ⁇ m.
- the center line average roughness Ra was 0.15 ⁇ m and the maximum height Ry was 0.87 ⁇ m in accordance with Surface Roughness of ISO468-1982.
- the surface roughness was measured by using a surface contour measurer DEKTAK3030 made by Sloan Inc., U.S.A., under conditions of a tracer diameter of 0.5 ⁇ m, a stylus pressure of 10 mg, a reference length of 50 ⁇ m, and no use of a cutoff filter. The result of measurement is shown in Fig. 5.
- a coating solution was prepared by dissolving 20 g of 2-ethyl-hexanoic silicate in 100 ml of dibutyl ether.
- Fig. 3 is a sectional view showing a cross section of the insulated wire obtained according to Example 3.
- a nickel-plated copper wire comprising a nickel-plated layer 22 formed on an outer surface of a copper wire 21 is used as a base material.
- a chromium oxide containing layer 23 is formed on the outer surface of this nickel-plated copper wire.
- a silicon oxide layer 24 is formed by an organic acid salt pyrolytic method as an oxide insulating layer.
- the film thickness of an insulating layer formed by the chromium oxide containing layer 23 and the silicon oxide layer 24 was about 5 ⁇ m.
- a breakdown voltage was measured in order to evaluate insulability of the obtained insulated wire.
- the breakdown voltage was 500 V under the room temperature, and was 300 V under a temperature of 800°C. Even if this insulated wire was wound on an outer peripheral surface of a cylinder having a diameter of 5 cm, no cracking was caused in the insulating layer.
- SUS304 stainless steel alloy
- the center line average roughness Ra was 0.15 ⁇ m
- the maximum height Ry was 0.87 ⁇ m in accordance with Surface Roughness of ISO468-1982.
- the measurement was performed by using a surface contour measurer DEXTAK3030 made by Sloan Inc., U.S.A., under conditions of a tracer diameter of 0.5 ⁇ m, a stylus pressure of 10 mg, a reference length of 50 ⁇ m, and no use of a cutoff filter. As the result of this measurement, that shown in Fig. 5 was obtained similarly to Example 3.
- the wire obtained by (a) was dipped in the coating solution of (b).
- a step of heating at a temperature of 500°C for 10 minutes was performed ten times on the wire whose outer surface was thus coated with the coating solution.
- FIG. 4 is a sectional view showing a cross section of the insulated wire obtained according to Example 4.
- a stainless steel clad copper wire having a stainless steel alloy layer 32 on an outer surface of a copper wire 31 is used as a base material.
- a chromium oxide containing layer 33 is formed on the outer surface of the stainless steel clad copper wire.
- an aluminum oxide layer 34 is formed by an organic acid salt pyrolytic method as an oxide insulating layer.
- This aluminum oxide layer 34 consists of an aluminum oxide mixed layer containing aluminum particulates which have been mixed in the coating solution from the start.
- the film thickness of an insulating layer formed by the chromium oxide containing layer 33 and the aluminum oxide layer 34 was about 12 ⁇ m.
- a breakdown voltage was measured in order to evaluate insulability of the obtained insulated wire. Its breakdown voltage was 900 V under the room temperature, and was 700 V under a temperature of 800°C. Even if this insulated wire was wound on an outer peripheral surface of a cylinder having a diameter of 15 cm, no cracking was caused in the insulating layer.
- Electrolytic plating treatment was performed on an outer surface of a nickel-plated copper wire of 1.8 mm ⁇ in wire diameter.
- an electrolyte to be used was prepared from that having concentration of 250 g/l of chromic anhydride and 2.5 g/l of sulfuric acid.
- the base material was used as a cathode, while the bath temperature was 50°C, the current density was 40 A/dm2, and the treatment time was two minutes.
- a chrome containing layer was formed on the outer surface of the nickel-plated copper wire with a film thickness of about 1 ⁇ m.
- the center line average roughness Ra was 0.06 ⁇ m and the maximum height Ry was 0.51 ⁇ m in accordance with Surface Roughness of ISO468-1982.
- the measurement was performed by using a surface contour measurer DEKTAK3030 made by Sloan Inc., U.S.A., under conditions of a tracer diameter of 0.5 ⁇ m, a stylus pressure of 10 mg, a reference length of 50 ⁇ m, and no use of a cutoff filter. The result of this measurement is shown in Fig. 6.
- a glossy metallic chrome layer was formed on the outer surface of the nickel-plated copper wire.
- a coating solution was prepared by dissolving 20 g of 2-ethyl-hexanoic silicate in 100 ml of dibutyl ether.
- the wire obtained by (a) was dipped in the coating solution of (b).
- a step of heating at a temperature of 500°C for 10 minutes was performed on the wire whose outer surface was thus coated with the coating solution, whereby the as-formed insulating layer was separated like a film after heating, and exhibited no adhesion.
- the insulated wire according to the present invention is suitable for a distribution wire, a wire for winding or the like, which is employed under high-vacuum environment or high-temperature environment such as a high vacuum apparatus or a high temperature service apparatus.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Insulated Conductors (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7702889 | 1989-03-28 | ||
JP77028/89 | 1989-03-28 | ||
JP70843/90 | 1990-03-20 | ||
JP2070843A JP2890631B2 (ja) | 1989-03-28 | 1990-03-20 | 絶縁電線 |
PCT/JP1990/000401 WO1990011603A1 (fr) | 1989-03-28 | 1990-03-26 | Fil electrique isole |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0416131A1 EP0416131A1 (en) | 1991-03-13 |
EP0416131A4 EP0416131A4 (en) | 1992-11-25 |
EP0416131B1 true EP0416131B1 (en) | 1994-10-19 |
Family
ID=26411968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90904938A Expired - Lifetime EP0416131B1 (en) | 1989-03-28 | 1990-03-26 | Insulated electric wire |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0416131B1 (ja) |
JP (1) | JP2890631B2 (ja) |
KR (1) | KR940000845B1 (ja) |
AU (1) | AU627859B2 (ja) |
CA (1) | CA2029868C (ja) |
DE (1) | DE69013448T2 (ja) |
DK (1) | DK0416131T3 (ja) |
HK (1) | HK96795A (ja) |
WO (1) | WO1990011603A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2827333B2 (ja) * | 1989-10-13 | 1998-11-25 | 住友電気工業株式会社 | 耐熱絶縁コイルの製造方法 |
US5350638A (en) * | 1991-04-26 | 1994-09-27 | Sumitomo Electric Industries, Ltd. | Electrical insulated wire |
DE69502270T2 (de) * | 1995-02-24 | 1999-01-07 | Sumitomo Electric Industries, Ltd., Osaka | Elektrisches Leiterelement wie ein Draht mit anorganischen Isolierbeschichtung |
JPH1066288A (ja) * | 1996-08-21 | 1998-03-06 | Ebara Corp | 高耐熱モータ |
CN113445088B (zh) * | 2021-06-28 | 2021-12-14 | 沈伟 | 一种具有高吸热性的均热板及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56149775A (en) * | 1980-04-18 | 1981-11-19 | Agency Of Ind Science & Technol | Manufacture of oxide film for solid electrolyte of fuel cell |
JPS60208494A (ja) * | 1984-03-31 | 1985-10-21 | Kawasaki Steel Corp | 溶接性に優れたシ−ム溶接缶用表面処理鋼板 |
CA1295889C (en) * | 1985-01-14 | 1992-02-18 | Richard J. Penneck | Refractory coated article |
CA1295890C (en) * | 1985-01-14 | 1992-02-18 | Stephen J. Duckworth | Electrical wire with refractory coating |
JPS63239150A (ja) * | 1987-03-27 | 1988-10-05 | Sumitomo Electric Ind Ltd | 超電導セラミツクス薄膜の製造方法 |
JP2584626B2 (ja) * | 1987-04-02 | 1997-02-26 | ペルメレツク電極株式会社 | 着色チタン材の製造方法 |
JPS63279524A (ja) * | 1987-05-08 | 1988-11-16 | Sumitomo Electric Ind Ltd | 超電導薄膜の形成方法 |
JPS63281313A (ja) * | 1987-05-12 | 1988-11-17 | Sumitomo Electric Ind Ltd | 耐熱電線 |
JP2642641B2 (ja) * | 1987-09-21 | 1997-08-20 | 株式会社フジクラ | 超電導体 |
-
1990
- 1990-03-20 JP JP2070843A patent/JP2890631B2/ja not_active Expired - Lifetime
- 1990-03-26 AU AU52736/90A patent/AU627859B2/en not_active Ceased
- 1990-03-26 DK DK90904938.9T patent/DK0416131T3/da active
- 1990-03-26 KR KR1019900702515A patent/KR940000845B1/ko not_active IP Right Cessation
- 1990-03-26 CA CA002029868A patent/CA2029868C/en not_active Expired - Fee Related
- 1990-03-26 EP EP90904938A patent/EP0416131B1/en not_active Expired - Lifetime
- 1990-03-26 WO PCT/JP1990/000401 patent/WO1990011603A1/ja active IP Right Grant
- 1990-03-26 DE DE69013448T patent/DE69013448T2/de not_active Expired - Fee Related
-
1995
- 1995-06-15 HK HK96795A patent/HK96795A/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPH0315113A (ja) | 1991-01-23 |
WO1990011603A1 (fr) | 1990-10-04 |
JP2890631B2 (ja) | 1999-05-17 |
DE69013448T2 (de) | 1995-02-23 |
AU5273690A (en) | 1990-10-22 |
EP0416131A1 (en) | 1991-03-13 |
AU627859B2 (en) | 1992-09-03 |
CA2029868C (en) | 1996-09-24 |
DE69013448D1 (de) | 1994-11-24 |
DK0416131T3 (da) | 1995-02-27 |
HK96795A (en) | 1995-06-23 |
KR940000845B1 (ko) | 1994-02-02 |
KR920700456A (ko) | 1992-02-19 |
CA2029868A1 (en) | 1990-09-29 |
EP0416131A4 (en) | 1992-11-25 |
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