EP0735187A1 - Une feuille de fibres cellulosiques - Google Patents

Une feuille de fibres cellulosiques Download PDF

Info

Publication number
EP0735187A1
EP0735187A1 EP96302098A EP96302098A EP0735187A1 EP 0735187 A1 EP0735187 A1 EP 0735187A1 EP 96302098 A EP96302098 A EP 96302098A EP 96302098 A EP96302098 A EP 96302098A EP 0735187 A1 EP0735187 A1 EP 0735187A1
Authority
EP
European Patent Office
Prior art keywords
sheet
particles
intercalated graphite
accordance
pressed
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
EP96302098A
Other languages
German (de)
English (en)
Other versions
EP0735187B1 (fr
Inventor
Robert Angelo Mercuri
Brian Mcneil Ford
Thomas William Weber
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.)
Graftech Technology LLC
Original Assignee
Ucar Carbon Technology Corp
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 Ucar Carbon Technology Corp filed Critical Ucar Carbon Technology Corp
Publication of EP0735187A1 publication Critical patent/EP0735187A1/fr
Application granted granted Critical
Publication of EP0735187B1 publication Critical patent/EP0735187B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants

Definitions

  • the present invention relates to a sheet of pressed cellulosic fibers.
  • the present invention relates to a sheet of pressed cellulosic fibers in the form of paper containing dispersed particles of intercalated, i.e. intumescent material graphite which can be applied to a flammable article as a fire-resistant covering.
  • a thermosetting resin is incorporated in the paper to act as an adhesive binder.
  • a continuing effort in the building supply industry is to improve the fire resistance of flammable materials of construction and related materials such as wood products (particle board, oriented strand board), wall board, shipping boxes, bags and like.
  • Such effort has involved the addition of chemicals, such as borates and phosphates to the binder system of the flammable materials, which, at times resulted in degradation of the properties and useful life of the materials.
  • a sheet of pressed cellulosic fibers which contains a dispersion of pressed particles of intercalated graphite, said sheet having a pair of opposed outer surfaces at least a portion of which is formed of pressed particles of intercalated graphite.
  • the present invention thus provides a sheet of pressed cellulosic fibers in the form of a paper sheet containing co-pressed particles of intercalated natural graphite particles, also known as intumescent graphite particles. These particles, upon exposure to high temperature, e.g. a flame, expand in volume more than 50 to 100 times, i.e. exfoliate into vermicular, worm-like structures (called "worms").
  • the cellulosic paper sheet containing the intumescent, i.e. intercalated graphite particles is rendered highly fire-resistant due to the decrease in thermal conductivity of the graphite particles upon the exfoliation which results from exposure to flame.
  • the exfoliated graphite vermicular particles, i.e. worms virtually cover the exposed paper surface and form a flame barrier. Any substrate to which the aforedescribed paper is bonded, or article enclosed in such paper, is provided protection from fire damage.
  • cellulosic fibers e.g. wood, straw, bagasse, flax, cotton and the like are pulped, i.e. separated and suspended in water slurry.
  • Materials such as mineral pigments, sizing, dyes and other coloring chemicals, starches and other fiber bonding materials, are added to the pulp which is then drained, i.e. dewatered, pressed and dried.
  • Fourdrinier machines and evaporative drying by pressing a heated surface on the wet paper are employed to make a cellulosic paper sheet.
  • particles of intercalated natural graphite i.e. intumescent graphite are added to the cellulosic fiber pulp (which may contain other additives such as noted above) and dispersed in the pulp slurry.
  • the added intercalated graphite particles are mostly, i.e. 60% by weight or more, in the size range of 30 to 80 mesh (U.S. screen series) and the amount added is suitably in the range of 40 to 80 grams per square meter of the paper sheet being produced typically from 0.006 to 0.060 inch thick.
  • the paper sheet is prepared by dewatering, pressing and drying in the usual manner.
  • the resulting product is shown in Figure 1 which is a 1:1 scale view of the surface of paper sheet in accordance with the present invention.
  • Figure 2 is an enlarged representation of a sectional side, or edge view, of a paper sheet in accordance with the present invention
  • Figure 2A is a plan view of a surface of the sheet of Figure 2.
  • the paper sheet 10, shown in Figures 1-3 is formed of pressed cellulosic fiber sheet indicated at 20 which contains a dispersion of co-pressed particles of intercalated graphite indicated at 30.
  • the pressing of a wet sheet of cellulosic fibers containing intercalated graphite particles results in some flattening of the intercalated graphite particles, particularly at the surface of the sheet 10 as indicated at 300. This results in at least a portion, e.g.
  • the surface exposed intercalated graphite particles expand in volume, up to 500 times and form a thermal barrier virtually covering the surface exposed to the flame which instantly extinguishes any burning portion of the paper.
  • thermosetting resin e.g. water soluble phenolic resin
  • a thermosetting resin e.g. water soluble phenolic resin
  • the cellulosic fibers and intercalated graphite particles are adhesively bonded due to exposure to drying temperatures of 60 to 100°C which cause a partial setting of the resin.
  • a portion of the partially set resin, in the form of flattened globules, is exposed at the surface as indicated at 400 in Figures 3) and 3(A).
  • the paper containing intercalated graphite and partially set resin is placed in contact with the surface of a flammable element, e.g. wood based, wall board and pressure is applied to the resin containing paper at temperatures of from about 70 to 120°C to fully set the resin and cause adhesive bonding of the intercalated graphite-containing paper to the surface of the flammable element.
  • a flammable wooden substrate is shown at 500 having an outer surface 510 and an overlying intercalated graphite containing paper sheet 10 which has been heated and pressed against surface 510 so that an adhesive layer 520 of thermoset resin is formed which bonds sheet 10 to wooden substrate 500.
  • the resulting article is a flammable wooden element having at its outer surface an adhesively resin bonded sheet of paper which contains a dispersion of intercalated graphite particles 300' at its outer surface.
  • the particles 300 undergo intumescence and expand to form "worms" 3000 shown in Figure 5 which suppress the flame and protect substrate 500 from fire damage.
  • the intercalated graphite included in the present invention is essentially that which is used in the graphite composite wall covering material disclosed in U.S. Patent 5,176,863.
  • graphite is a crystalline form of carbon comprising atoms bonded in flat layered planes with weaker bonds between the planes.
  • the particles of intercalated graphite Upon exposure to high temperature, the particles of intercalated graphite expand in dimension as much as 80 or more times its original volume in an accordion-like fashion in the c-direction, i.e. in the direction perpendicular to the crystalline planes of the graphite.
  • the exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms.
  • Shane et al A common method for manufacturing graphite foil from flexible graphite is described by Shane et al, in U.S. Patent No. 3,404,061 the disclosure of which is incorporated herein by reference.
  • natural graphite flakes are intercalated by dispersing the flakes in a solution containing an oxidizing agent of, e.g. a mixture of nitric and sulfuric acid.
  • the intercalation solution contains oxidizing and other intercalating agents known in the art.
  • Examples include those containing oxidizing agents and oxidizing mixtures, such a solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid.
  • a preferred intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent, i.e. nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like.
  • the intercalation solutions may contain metal halides such as ferric chloride and ferric chloride mixed with sulfuric acid, or halide, such as bromine as a solution of bromine and sulfuric acid or bromine in an organic solvent.
  • the quantity of the intercalation solution may be limited to between 10 to 50 parts of solution per hundred parts of graphite by weight (pph) which permits the washing step to be eliminated as taught and described in U.S. Patent No. 4,895,713 the disclosure of which is also herein incorporated by reference.
  • Particles of exfoliated graphite of intercalated graphite flake possess substantial fire retardant properties. This results from a decrease in thermal conductivity when exposed to high temperature such as in the presence of a fire. This decrease in thermal conductivity is attributable to its expansion at high temperature. An expansion in thickness of 1 to 5 times the unexpanded thickness has been realized from unexfoliated particles of intercalated graphite.
  • Example will further illustrate the present invention: Recycled cellulose fiber was slurried in a solution consisting of 4% by weight w/o Ashland 72115W55 phenolic-based resin in water for 30 seconds in a Waring blender on low speed. Intumescent natural graphite treated flake particles (intercalated graphite), UCAR Grade TG-388, was added and mixed for 5 seconds; excess solution was filtered from the mixture to form a cake which was oven dried at 60°C to remove the water. The cake was then flattened to a paper approximately 0.04 inches thick between heated (60°C) platens.
  • compositions consisted of 4, 6, and 8 grams of treated flake (intercalated flake) per square foot of paper sheet; cellulose 16 grams/square foot of paper sheet; and a resin content of about 2 grams/square foot of paper sheet.
  • the intercalated flake was in the form of particles sized 50% through 40 mesh (U.S. Screen Series).
  • sheets could be bonded to wood, OSB (oriented strand board), or plywood by pressing between platens at about 120°C.
  • compositions were tested in two ways:
  • the invention is amenable to standard Fourdrinier paper processing; prepared paper may be bonded to board products in the hot-pressure-cure step.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP19960302098 1995-03-29 1996-03-27 Une feuille de fibres cellulosiques Expired - Lifetime EP0735187B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41291495A 1995-03-29 1995-03-29
US412914 1995-03-29

Publications (2)

Publication Number Publication Date
EP0735187A1 true EP0735187A1 (fr) 1996-10-02
EP0735187B1 EP0735187B1 (fr) 2001-12-05

Family

ID=23634988

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960302098 Expired - Lifetime EP0735187B1 (fr) 1995-03-29 1996-03-27 Une feuille de fibres cellulosiques

Country Status (6)

Country Link
EP (1) EP0735187B1 (fr)
JP (1) JP3034793B2 (fr)
AU (1) AU700061B2 (fr)
CA (1) CA2172878C (fr)
DE (1) DE69617506T2 (fr)
NO (1) NO961219L (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0949313A1 (fr) * 1998-04-02 1999-10-13 Technical Fibre Products Limited Matériau intumescent
AU777574B2 (en) * 1999-07-08 2004-10-21 E.I. Du Pont De Nemours And Company A method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
WO2005080740A1 (fr) * 2004-02-18 2005-09-01 Environmental Seals Ltd Porte coupe-feu
WO2011047465A1 (fr) * 2009-10-20 2011-04-28 Flamehalt Fire Retardants, Inc. Système pour former une structure murale résistante au feu, et procédé associé
WO2012094723A1 (fr) * 2011-01-13 2012-07-19 Blmh Technologies Inc. Procédé pour former un produit en cellulose ignifuge, et appareil associé
WO2013003944A1 (fr) 2011-07-06 2013-01-10 National Research Counsil Of Canada Matière cellulosique résistante au feu

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4098227B2 (ja) * 2003-09-02 2008-06-11 名古屋油化株式会社 難燃性繊維シートの製造方法、およびそれによって得られた難燃性繊維シートからなる成形物と積層物、並びにその積層物を用いた成形物
DE102015119558A1 (de) 2015-11-12 2017-05-18 Fernando Tahmouresinia Flamm- oder Brandschutzmittel und dessen Herstellung und Verwendung
WO2017118765A1 (fr) 2016-01-09 2017-07-13 Fernando Tahmouresinia Agent retardateur de flamme ou ignifuge et fabrication et utilisation de celui-ci notamment pour produits à base de bois, de cellulose et de polyoléfine
CN109763369A (zh) * 2018-12-29 2019-05-17 湖北烁砺新材料科技有限公司 一种耐火工程纤维的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256801A (en) * 1979-12-14 1981-03-17 Raybestos-Manhattan, Incorporated Carbon fiber/flame-resistant organic fiber sheet as a friction material
EP0109209A2 (fr) * 1982-11-12 1984-05-23 T&N Materials Research Limited Matière flexible sous forme de feuille
EP0112010A1 (fr) * 1982-11-20 1984-06-27 T&N Materials Research Limited Matière flexible sous forme de feuille
EP0408098A2 (fr) * 1989-07-11 1991-01-16 T&N TECHNOLOGY LIMITED Feuille en matière intumescente
DE4007060A1 (de) * 1990-03-07 1991-09-12 Bayer Ag Intumeszierende flaechengebilde
US5176863A (en) * 1991-08-06 1993-01-05 Ucar Carbon Technology Corporation Flexible graphite composite fire retardant wallpaper and method
GB2273100A (en) * 1992-11-18 1994-06-08 Environmental Seals Ltd Intumescent products

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4007075A1 (de) * 1990-03-07 1991-09-12 Bayer Ag Intumeszenzfaehige formteile

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256801A (en) * 1979-12-14 1981-03-17 Raybestos-Manhattan, Incorporated Carbon fiber/flame-resistant organic fiber sheet as a friction material
EP0109209A2 (fr) * 1982-11-12 1984-05-23 T&N Materials Research Limited Matière flexible sous forme de feuille
EP0112010A1 (fr) * 1982-11-20 1984-06-27 T&N Materials Research Limited Matière flexible sous forme de feuille
EP0408098A2 (fr) * 1989-07-11 1991-01-16 T&N TECHNOLOGY LIMITED Feuille en matière intumescente
DE4007060A1 (de) * 1990-03-07 1991-09-12 Bayer Ag Intumeszierende flaechengebilde
US5176863A (en) * 1991-08-06 1993-01-05 Ucar Carbon Technology Corporation Flexible graphite composite fire retardant wallpaper and method
GB2273100A (en) * 1992-11-18 1994-06-08 Environmental Seals Ltd Intumescent products

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0949313A1 (fr) * 1998-04-02 1999-10-13 Technical Fibre Products Limited Matériau intumescent
US6274647B1 (en) 1998-04-02 2001-08-14 Technical Fibre Products Limited Intumescent material
AU777574B2 (en) * 1999-07-08 2004-10-21 E.I. Du Pont De Nemours And Company A method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
WO2005080740A1 (fr) * 2004-02-18 2005-09-01 Environmental Seals Ltd Porte coupe-feu
WO2011047465A1 (fr) * 2009-10-20 2011-04-28 Flamehalt Fire Retardants, Inc. Système pour former une structure murale résistante au feu, et procédé associé
EP2491195A1 (fr) * 2009-10-20 2012-08-29 Blmh Technologies Inc. Système pour former une structure murale résistante au feu, et procédé associé
EP2491195A4 (fr) * 2009-10-20 2014-12-03 Blmh Technologies Inc Système pour former une structure murale résistante au feu, et procédé associé
WO2012094723A1 (fr) * 2011-01-13 2012-07-19 Blmh Technologies Inc. Procédé pour former un produit en cellulose ignifuge, et appareil associé
US8980145B2 (en) 2011-01-13 2015-03-17 Blh Technologies, Inc. Method for forming a fire resistant cellulose product
WO2013003944A1 (fr) 2011-07-06 2013-01-10 National Research Counsil Of Canada Matière cellulosique résistante au feu
US9175147B2 (en) 2011-07-06 2015-11-03 National Research Council Of Canada Fire-resistant cellulosic material

Also Published As

Publication number Publication date
CA2172878A1 (fr) 1996-09-30
NO961219D0 (no) 1996-03-26
CA2172878C (fr) 2002-05-28
JP3034793B2 (ja) 2000-04-17
AU700061B2 (en) 1998-12-17
AU5034696A (en) 1996-10-10
DE69617506T2 (de) 2002-05-16
NO961219L (no) 1996-09-30
DE69617506D1 (de) 2002-01-17
EP0735187B1 (fr) 2001-12-05
JPH0931887A (ja) 1997-02-04

Similar Documents

Publication Publication Date Title
US5443894A (en) Fire retardant oriented strand board structure element
CA1045864A (fr) Panneau composite a la vermiculite resistant au feu
US5176863A (en) Flexible graphite composite fire retardant wallpaper and method
EP0006362B1 (fr) Procédé pour la préparation de produits sous forme de plaques non-combustibles et ne contenant pas d'anuante
CA2172878C (fr) Pellicule resistance au feu
CS229673B2 (en) Fibre compound material and its manufacturing process
CA2294986A1 (fr) Feuille de graphite souple a anisotropie reduite
WO1998041486A1 (fr) Feuille composite de graphite flexible et procede de production
US7858005B2 (en) Method for the production of fire-resistant wood fiber moldings
GB2070089A (en) Thermal insulation
KR20010014424A (ko) 가요성 흑연 복합 시이트 및 제조 방법
EP0971863B1 (fr) Feuille souple composite a base de graphite resistant a l'oxydation et a la corrosion et son procede de fabrication
US5176794A (en) Flame spread barrier made from mechanically delaminated vermiculite sheet
JP3155145B2 (ja) 難燃性シート
EP0333506A2 (fr) Matière fibreuse végétale à inflammation retardée et procédé de fabrication
JPS5921799A (ja) 不燃乃至難燃紙
US3779861A (en) Fireproofing cellulose-containing materials
JP2009173730A (ja) 不燃性テープ
US3269889A (en) Asbestos paper containing carbon and method of making it
JPS58120900A (ja) 耐火性と断熱性とを兼備する無機質繊維製フエルト
US6335089B1 (en) Fibre-clay panel
JPH05148798A (ja) 難燃紙または難燃ボード
JP3654308B2 (ja) 不燃性成形体
JP3155143B2 (ja) 不燃性シート
JPS6283388A (ja) 無機質繊維体

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: A1

Designated state(s): DE FI FR GB IT

17P Request for examination filed

Effective date: 19970324

17Q First examination report despatched

Effective date: 19990312

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FI FR GB IT

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;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: 20011205

Ref country code: FR

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: 20011205

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REF Corresponds to:

Ref document number: 69617506

Country of ref document: DE

Date of ref document: 20020117

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

Ref country code: FR

Payment date: 20020304

Year of fee payment: 7

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UCAR CARBON TECHNOLOGY CORPORATION

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

EN Fr: translation not filed
26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20100330

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20100326

Year of fee payment: 15

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

Ref country code: DE

Payment date: 20100329

Year of fee payment: 15

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

Effective date: 20110327

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

Ref country code: FI

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

Effective date: 20110327

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: 20111001

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69617506

Country of ref document: DE

Effective date: 20111001

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: 20110327