EP0377080A2 - Conducteur électrique à isolant polymère - Google Patents

Conducteur électrique à isolant polymère Download PDF

Info

Publication number
EP0377080A2
EP0377080A2 EP89117457A EP89117457A EP0377080A2 EP 0377080 A2 EP0377080 A2 EP 0377080A2 EP 89117457 A EP89117457 A EP 89117457A EP 89117457 A EP89117457 A EP 89117457A EP 0377080 A2 EP0377080 A2 EP 0377080A2
Authority
EP
European Patent Office
Prior art keywords
adhesive
insulated conductor
polymer
peroxide
conductor according
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
Application number
EP89117457A
Other languages
German (de)
English (en)
Other versions
EP0377080B1 (fr
EP0377080A3 (fr
Inventor
Kevin Kirk
Ewald Brückner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WL Gore and Associates GmbH
Original Assignee
WL Gore and Associates GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by WL Gore and Associates GmbH filed Critical WL Gore and Associates GmbH
Publication of EP0377080A2 publication Critical patent/EP0377080A2/fr
Publication of EP0377080A3 publication Critical patent/EP0377080A3/fr
Application granted granted Critical
Publication of EP0377080B1 publication Critical patent/EP0377080B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/301—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen or carbon in the main chain of the macromolecule, not provided for in group H01B3/302
    • 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
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones

Definitions

  • This invention relates to insulated electrical conductors, particularly those conductors that are insulated with polymers. Round cables as well as flat and coaxial cables are to be used as electrical conductors.
  • the siloxanes have 1.3 to 1.95 phenyl and methyl groups per silicon atom, up to half of the phenyl groups can be biphenyl groups and up to 10% of the organic groups can be tolyl, alkyl, ethyl or other groups.
  • the siloxanes are soluble in aromatic, organic solvents or mixtures.
  • the polyamide is denoted by ⁇ -NH - R - NH - (CH2) m - [- NH - R1 - NH - (CH2) m ] n ⁇ -, where m is two or more, n 0 or an integer, R the The residue of an ethylenically unsaturated dicarboxylic acid after removal of the hydroxyl groups and R1 represents the residue of isophthalic, terephthalic or saturated aliphatic acids with 4 to 10 carbon atoms, the hydroxyl groups of which have been removed.
  • a wire is coated with this mixture and cured by removal of the solvent and by heating to form an insulating varnish coating on the wire.
  • Composite materials could be made by firmly joining two sheet members made of the same or different materials, e.g. glass, metals or polymers, by converting the organosilanamide block copolymers described in U.S. Patent No. 3,740,305 to the corresponding polyimides in order to to form firmly bonded materials.
  • the organosilane imides were applied to the surfaces of the sheet members to be bonded, the solvent was removed, and the cyclization reaction was effected by heat.
  • organosiloxanes have the formula wherein R is a monovalent hydrocarbon radical, usually methyl, and n is 0 to 150.
  • organosiloxaneimide block copolymers A much broader and wider variety of organosiloxaneimide block copolymers than those mentioned above has been provided by U.S. Patent 4,522,985; according to this publication, the norbornane and norbornene cores have been used extensively for both the siloxane and diamine regions of the starting materials.
  • Curing under heat for example to cyclize a polyamide into a polyimide directly on the cable, was not a good solution. It is now common to coat a fully cured polyimide tape with a thermoplastic adhesive material, such as a fluorinated ethylene-propylene copolymer. This works very well unless halogen-free insulation is required due to reduced toxicity when burned; it is desirable to remove the outer layer of the thermoplastic adhesive after processing, or to subject the cable to electromagnetic radiation, in which case a halogenated polymer will not work very well under such radiation and a halogenated material must be avoided.
  • a thermoplastic adhesive material such as a fluorinated ethylene-propylene copolymer
  • the invention has for its object to provide an insulation material which has good insulating properties and good adhesiveness when it is applied to the material to be insulated. Furthermore, a method for isolating an electrical conductor is to be specified by means of which the insulation material can be applied to the conductor with good adhesion.
  • the insulation material according to the invention consists of a high temperature-resistant polymer which surrounds an electrical conductor. A completely heat-cured organosiloxaneimide adhesive is applied to this polymer, which surprisingly ensures a good polymer-polymer connection.
  • the polymer is preferably a polyimide, polyphenylene sulfide (PPS) or a polyether ether ketone (PEEK).
  • PPS polyphenylene sulfide
  • PEEK polyether ether ketone
  • the cables according to the invention are particularly suitable for use at high temperatures and under aggressive environmental conditions.
  • the new composite material can be used both as primary insulation and as a jacket.
  • the organopolysiloxaneimide is dissolved in an organic solvent, possibly with organic peroxides and pigments, and the solution is applied to a layer of the fully cured polymer.
  • the solvent is then evaporated and the polymer layer is wrapped around an electrical conductor with the adhesive on top.
  • the polymer layer is preferably cut into a band shape and wound spirally around the electrical conductor.
  • the conductor wrapped in the tape is first of all for a relatively short time heated to a higher temperature to seal the layers of polymer. It is then held at a low temperature for an extended period of time to increase the cross-link curing reaction and to prevent problems such as tarnishing of metal conductors, which can occur at higher temperatures and longer heating times.
  • the preferred organopolysiloxaneimide adhesive is a fully cured material with the formula where Q is a tetravalent radical selected from where D is selected from wherein R4 is a bivalent radical selected from and divalent organic radicals of the general formula wherein R1 and R2 represent alkylenes, usually - (CH2) 3 -, or R4, wherein R represents methyl, phenyl, tolyl or a mixture of aliphatic and aromatic radicals, wherein R3 represents hydrogen or an alkyl radical with 1 to 8 carbon atoms , X from bivalent radicals -CR 3rd 2nd -, C y H 2y -, - CO -, - SO2-, -O-, and -S-, is selected, where y 1 to 5, k 1 to 7, n 1 to 7, m is an integer greater than 1 and p are 0 or 1.
  • the crosslinking reaction is preferably carried out in the presence of a peroxide.
  • Benzoyl peroxides such as bis-2,4-dichlorobenzoyl peroxide, dicumyl peroxide or t-butyl peroxide are particularly suitable as peroxides.
  • the presence of peroxide accelerates the crosslinking reaction and increases chemical resistance to solvents.
  • the crosslinking reaction is initiated by cleavage of the peroxide, as can be seen from the formula below.
  • the radicals formed in this way generate a polymer radical by splitting off hydrogen from the polymer chain. Two of the polymer radicals generated in this way can saturate to form a CC bond, as can be seen from the formula below.
  • a coactivator such as, for example, triallyl cyanurate
  • three-dimensional crosslinking can be achieved, which leads to a thermally more stable product which also has better chemical resistance due to the multiplication of the crosslinking sites.
  • the polymer radical reacts with an allyl group of the cyanurate. The formula is shown below.
  • the crosslinking is only started when the finished product is exposed to a higher temperature, which ensures that no pre-crosslinking takes place during the drying and further processing of the product.
  • the reaction is only triggered when the product is held at 300 ° C for a period of 1 to 3 minutes.
  • the finished products are subjected to post-heating, which normally takes place at 200 ° C for 2 to 3 hours. Insulation produced using this method can be used for mechanical loads up to a permanent temperature of 150 ° C and for only electrical loads up to a permanent temperature of 170 ° C.
  • a low dielectric constant is required to use the insulation material for flat or coaxial cables.
  • the adhesive approach must be modified. This can be done, for example, by adding expanded glass spheres, preferably microspheres, which are hollow on the inside in addition to the mixture mentioned.
  • a coupling agent based on silane is added give.
  • vinyl tris (2-methoxyethoxy) silane (1); 3,4 epoxybutyltriethoxysilane (2); 3-thiocyanatopropyltriethoxysilane (3) or 3-methacryloxypropyltriethoxysilane (4) can be used.
  • the amount of silane used in each case is approximately 0.1 to 0.8% of the weight of glass spheres.
  • the silanes that can be used have the following general formula y-Si-R'-X, where y and X represent the two different reactive centers.
  • the functional group X is linked to an organic intermediate piece R 'with the four-bonded silicon atom.
  • the functional group y is a removable group, in this case either a trimethoxy or a trieethoxysilyl group.
  • the function of silanes as an adhesion promoter is based on the formation of a monomolecular silane layer on the surface of the glass spheres, the functional group y reacting here.
  • the remaining functional group X can react chemically with the plastic matrix or with the crosslinker / coactivator system.
  • a halogen-free flame retardant can also be added.
  • the proportion of the flame retardant can be up to approx. 20 percent by weight. This also makes it possible to obtain a higher layer thickness of the adhesive application and thus to use the coated polymer layer, for example in the form of a film, for the production of ribbon cables.
  • the thickness of the adhesive layer is preferably 50 to 100 microns. This enables the embedding of bare conductors or of fully insulated wires.
  • a roll of polyimide film (DuPont Kapton H-50) is coated with a 2.54 ⁇ m (0.0001 inch) thick layer of an organopolysiloxanimide adhesive which has been dissolved in methylene chloride to give a 5% solids solution .
  • 20% by weight of a green pigment in polyester based on the organopolysiloxaneimide was added to the solution of organopolysiloxaneimide and methylene chloride to color the film. The solvent is evaporated to a to produce dry film.
  • the roll is then cut into evenly wound bobbins with an approximately 1.83 mm (0.072 inch) wide band.
  • the tape is wrapped around a 30 AWG silver plated copper conductor to give a 2.1 wrap construction with a 0.3048 mm (0.012 inch) end diameter.
  • This wrapped structure is connected in an air oven at 300 ° C with a residence time of 50 seconds.
  • the outer adhesive layer which is not covered with a film layer, is washed off the assembly by passing the assembly through a methylene chloride bath to give a green, insulated wire assembly. Tests are carried out on this wire construction with regard to the dielectric in a moist environment, with regard to aging when heated and with regard to the resistance to solvents.
  • the test procedure for dielectric in a humid environment is carried out according to the provisions of MIL-W-81822A, section 4.6.20; the heat resistance test procedure is in accordance with the provisions of MIL-W-81822A, section 4.6.22; and resistance to fluids is determined by the provisions of MIL-W-8l822A, section 4.6.25.
  • the heat resistance of the construction using an organosiloxaneimide adhesive is greater than the heat resistance of a comparable polyester adhesive, but the solvent resistance to 1,1,1-trichloroethane is insufficient.
  • a roll of polyimide film (DuPont Kapton H-100) is covered with a 2.54 ⁇ m (0.0001 inch) thick layer coated from an organopolysiloxaneimide adhesive which was dissolved in methylene chloride to give a 5% solids solution.
  • a red pigment containing chromium is added to the adhesive solution to color the tape. The solvent is evaporated to give a dry film.
  • Another tape is coated exactly as above, except that an organic peroxide (e.g. Luprox 500R dicumyl peroxide) is added in an amount of 10% by weight based on the organopolysiloxaneimide adhesive.
  • an organic peroxide e.g. Luprox 500R dicumyl peroxide
  • Both tapes are cut into evenly wound coils approximately 2.64 mm (0.104 inch) wide.
  • the tapes are wrapped around a 30 AWG silver plated copper conductor to create a 3.2 wrap construction with a finished 0.4064 mm (0.016 inch) diameter.
  • the wrapped superstructures are fired in an air oven with a temperature of 320 ° C and a residence time of 100 seconds.
  • the outer layer of adhesive that is not covered by the film is washed off the assembly by passing the assembly through a methylene chloride bath. A red, insulated wire structure is obtained.
  • the adhesive is more resistant to some solvents than to other solvents.
  • the curing of samples in the presence of peroxide accelerates the crosslinking and thus increases the solvent resistance of the adhesive with respect to solvents which more easily dissolve the adhesive, for example methylene chloride.
  • a roll of PEEK (polyether ether ketone) film is coated with a 0.00254 mm (0.0001 inch) thick layer of an organopolysiloxanimide adhesive dissolved in methylene chloride to form a 5% solids solution. to surrender.
  • a chromium-containing red pigment is added at 25% by weight, based on the organopolysiloxanimide adhesive, in order to color the tape.
  • the solvent is evaporated to give a 5.0 wrap construction with a final diameter of 0.508 mm (0.020 inch).
  • the wrapped structure is heated in an air oven at 300 ° C with a residence time of 100 seconds.
  • the outer adhesive layer which is not covered by a film layer, is washed off the assembly by passing it through a methylene chloride bath so that a red, insulated conductor assembly is obtained.
  • the finished composite insulation material had a tensile strength of 25,000 psi and an elongation of 110%. It also had good heat resistance and good electrical properties.
  • a polyphenylene sulfide film with a layer thickness of about 12 to 100 microns is coated with an adhesive solution.
  • the adhesive solution used as a coating composition contains organopolysiloxane imide as the plastic matrix, bis-2,4-dichlorobenzoyl peroxide as the crosslinker, triallyl cyanurate as the coactivator, and color pigments and methylene chloride as the solvent.
  • the solids concentration is about 20 to 25% by weight, depending on the required layer thickness.
  • the solvent is evaporated, the crosslinking reaction takes place at 300 ° C and a time of 1 to 3 minutes.
  • the finished product is subjected to post-heating, which takes place at 200 ° C for a period of 2 to 3 hours.
  • the end product is a primary insulation material for electrical parts, can be used mechanically for a continuous temperature of at least 150 ° C and electrically for a temperature of at least 170 ° C.
  • Methylene chloride was found to be the best solvent for the uncured organopolysiloxaneimide adhesive.
  • the improved resistance to methylene chloride by means of an organopolysiloxaneimide hardened with the help of peroxide thus eliminates a weak point in the use of this adhesive for the production of wires and cables.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Insulators (AREA)
EP89117457A 1988-12-21 1989-09-21 Conducteur électrique à isolant polymère Expired - Lifetime EP0377080B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28804888A 1988-12-21 1988-12-21
US288048 1988-12-21

Publications (3)

Publication Number Publication Date
EP0377080A2 true EP0377080A2 (fr) 1990-07-11
EP0377080A3 EP0377080A3 (fr) 1991-12-18
EP0377080B1 EP0377080B1 (fr) 1995-12-06

Family

ID=23105529

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89117457A Expired - Lifetime EP0377080B1 (fr) 1988-12-21 1989-09-21 Conducteur électrique à isolant polymère

Country Status (4)

Country Link
EP (1) EP0377080B1 (fr)
AT (1) ATE131310T1 (fr)
DE (2) DE58909529D1 (fr)
ES (1) ES2080058T3 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551747A1 (fr) * 1992-01-10 1993-07-21 General Electric Company Films flexibles de polyétherimide
EP0568923A1 (fr) * 1992-05-08 1993-11-10 PIRELLI CAVI S.p.A. Câble fonctionnant à hautes températures
EP2544194A1 (fr) * 2011-07-07 2013-01-09 Nitto Denko Corporation Matériau de revêtement, fil électrique rectangulaire recouvert et dispositif électrique
EP2544193A3 (fr) * 2011-07-07 2014-11-19 Nitto Denko Corporation Matériau de revêtement, fil électrique supraconducteur et dispositif électrique
EP2544192A3 (fr) * 2011-07-07 2014-11-19 Nitto Denko Corporation Matériau de revêtement, fil électrique supraconducteur et dispositif électrique
EP2544191A3 (fr) * 2011-07-07 2014-11-26 Nitto Denko Corporation Matériau de revêtement, fil électrique rectangulaire recouvert et dispositif électrique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0727966B2 (ja) * 1986-07-04 1995-03-29 日立化成工業株式会社 半導体装置

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0551747A1 (fr) * 1992-01-10 1993-07-21 General Electric Company Films flexibles de polyétherimide
EP0568923A1 (fr) * 1992-05-08 1993-11-10 PIRELLI CAVI S.p.A. Câble fonctionnant à hautes températures
US5437930A (en) * 1992-05-08 1995-08-01 Pirelli Cavi S.P.A. Cable for high operating temperatures
EP2544194A1 (fr) * 2011-07-07 2013-01-09 Nitto Denko Corporation Matériau de revêtement, fil électrique rectangulaire recouvert et dispositif électrique
EP2544193A3 (fr) * 2011-07-07 2014-11-19 Nitto Denko Corporation Matériau de revêtement, fil électrique supraconducteur et dispositif électrique
EP2544192A3 (fr) * 2011-07-07 2014-11-19 Nitto Denko Corporation Matériau de revêtement, fil électrique supraconducteur et dispositif électrique
EP2544191A3 (fr) * 2011-07-07 2014-11-26 Nitto Denko Corporation Matériau de revêtement, fil électrique rectangulaire recouvert et dispositif électrique

Also Published As

Publication number Publication date
DE58909529D1 (de) 1996-01-18
ATE131310T1 (de) 1995-12-15
DE377080T1 (de) 1990-10-18
EP0377080B1 (fr) 1995-12-06
EP0377080A3 (fr) 1991-12-18
ES2080058T3 (es) 1996-02-01

Similar Documents

Publication Publication Date Title
CA1110998A (fr) Isolation de conducteurs
DE1520012C3 (de) Verfahren zur Herstellung von Polykondensaten mit wiederkehrenden Imideinheiten
DE2439490C2 (de) Äthylenvinylacetat-Copolymermasse
DE2832893A1 (de) Siliconharze enthaltende polymermischungen
DE69005936T2 (de) In der Schmelze verarbeitbare, halogenfreie und raucharme Drahtbeschichtungsmasse auf Basis von Silikon-Imid.
DE602004001781T2 (de) Elektrische leitung beschichtet mit einer haftenden schicht und herstellungsprozess davon
DE69328285T2 (de) Thermoplastisches Polyimid, Polyamidsäureee, und thermoschmelzbarer Verbundfilm zum Beziehen von leitenden Drähten
DE3538527A1 (de) Verfahren zur herstellung eines mit vernetzten polyolefinen isolierten kabels
JPS5828688B2 (ja) 導体の被覆方法
EP0377080B1 (fr) Conducteur électrique à isolant polymère
DE2453436C3 (de) Elektrischer Isolierstoff
DE69305563T2 (de) Lackbeschichteter Elektro-Draht und Verfahren zu seiner Herstellung
DE69700977T2 (de) Polyimidvorläuferlösung, Verfahren zu ihrer Herstellung und Verfahren zur Herstellung einer Beschichtung oder eines Films daraus
DE1795638A1 (de) Polyimide
EP0348795A2 (fr) Matériaux composites comportant un matériau de support et des films de polymères électroconducteurs
DE3873128T2 (de) Verfahren zur herstelung eines elektrischen uebertragungslinie.
DE1440862B2 (de) Isolierter elektrischer leiter
DE60314528T2 (de) Verfahren zur herstellung eines modifizierten diisocyanats, verfahren zur herstellung eines selbstschmierenden emaillelackes, verfahren zur herstellung eines lackisolierten elektrischen leiters
JPS58501235A (ja) 難燃性組成物、その製造方法ならびにそのワイヤおよびケ−ブル製品
DE3877963T2 (de) Elektrischer draht.
DE1284336B (de) Verfahren zur Herstellung von hitzegehaerteten Lackisolierungen fuer elektrische Leiter
EP0883881A1 (fr) Fils metalliques laques
US4404331A (en) Enamel having improved coatability and insulated electrical articles produced therefrom
DE3853710T2 (de) Siliciumatome und Imidogruppen enthaltende Oligomere, härtbare Zusammensetzungen und deren Herstellung.
DE1947030C (de) Isoliertes elektrisches Bauteil

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

GBC Gb: translation of claims filed (gb section 78(7)/1977)
ITCL It: translation for ep claims filed

Representative=s name: JACOBACCI CASETTA & PERANI S.P.A.

EL Fr: translation of claims filed
DET De: translation of patent claims
17P Request for examination filed

Effective date: 19901213

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19940801

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19951206

Ref country code: BE

Effective date: 19951206

REF Corresponds to:

Ref document number: 131310

Country of ref document: AT

Date of ref document: 19951215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 58909529

Country of ref document: DE

Date of ref document: 19960118

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2080058

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960122

ITF It: translation for a ep patent filed
ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19960921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19960930

Ref country code: LI

Effective date: 19960930

Ref country code: CH

Effective date: 19960930

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000901

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000905

Year of fee payment: 12

Ref country code: GB

Payment date: 20000905

Year of fee payment: 12

Ref country code: DE

Payment date: 20000905

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000920

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20001006

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010922

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010922

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

EUG Se: european patent has lapsed

Ref document number: 89117457.5

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050921