EP1819850B1 - Method to improve release characteristics of elastic polyolefin fibers - Google Patents

Method to improve release characteristics of elastic polyolefin fibers Download PDF

Info

Publication number
EP1819850B1
EP1819850B1 EP05849526A EP05849526A EP1819850B1 EP 1819850 B1 EP1819850 B1 EP 1819850B1 EP 05849526 A EP05849526 A EP 05849526A EP 05849526 A EP05849526 A EP 05849526A EP 1819850 B1 EP1819850 B1 EP 1819850B1
Authority
EP
European Patent Office
Prior art keywords
pdmso
fiber
polyolefin
percent
based material
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.)
Active
Application number
EP05849526A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1819850A1 (en
Inventor
Antonio Batistini
Bryan Launchbury
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.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP1819850A1 publication Critical patent/EP1819850A1/en
Application granted granted Critical
Publication of EP1819850B1 publication Critical patent/EP1819850B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent

Definitions

  • the present invention relates to a method for reducing the amount of die buildup associated with the production of polyolefin based elastic fiber and for improving the unwind or release characteristics of such fiber.
  • the method involves the use of polydimethylsiloxane (PDMSO) in the polyolefin resin.
  • PDMSO polydimethylsiloxane
  • the fiber After the fiber has been formed, the fiber is typically wound on bobbins or spools for later use. Another problem which has been observed with some of these packages is that the fiber tends to stick to the package during unwinding leading to tangles and breaks. It is a goal of the present invention to improve the release or unwind characteristics of the fiber from these packages.
  • Figure 1 is a graph demonstrating the frequency dies needed to be cleaned using different levels of PDMSO.
  • Figure 2 is a graph demonstrating the effect of PDMSO and lubricating oil on the releasability factor.
  • Figure 3 demonstrates the load at break and elongation at break of fibers made in accordance with the present invention.
  • the present invention is a way of improving the fiber spinning and unwinding properties for any polyolefin-based fiber.
  • the olefin polymer for use in the present invention can be any olefin based material capable of forming a fiber, including ethylene-alpha olefin interpolymers, substantially hydrogenated block polymers, propylene alpha olefin interpolymers (including propylene ethylene copolymers), styrene butadiene styrene block polymers, styrene-ethylene/butene-styrene block polymers, ethylene styrene interpolymers, polypropylenes, polyamides, polyurethanes and combinations thereof.
  • the homogeneously branched ethylene polymers described in US 6,437,014 particularly the substantially linear ethylene polymers, are particularly well suited for use in this invention.
  • the present invention is particularly useful for fibers made form linear low density ethylene alpha-olefin copolymers, most preferably those having a density in the range of 0.80 to 0.89 g/cc (as determined by ASTM 1505) and a melt index from 0.5 dg/min to 10 dg/min (as determined by ASTM D1238).
  • Preferred polyolefin materials are sold under the AFFINITY trade name by The Dow Chemical Company, the EXACT trade name sold by Exxon-Mobil Company, or the TAFMER trade name sold by Mitsui Chemical Company.
  • the most preferred polymer is polyethylene with an octene comonomer content of 5 to 30 percent by weight, having a density of about 0.875 g/cc and a melt index of about 3 dg/min.
  • the PDMSO used is a hydroxyl-terminated, ultra high molecular weight poly(dimethylsiloxane).
  • the PDMSO preferably has a molecular weight of approximately 2 million.
  • the PDMSO is conveniently added to the polymer composition in the form of a masterbatch, in a polyethylene based carrier material, in an amount so that the final composition contains from 0.1 percent to 5 percent PDMSO by weight, more preferably from 0.3 percent to 2 percent by weight. Most preferably the final composition contains should contain no less than 0.5 percent by weight PDMSO.
  • the PDMSO can be added to the polymer in any way known to the art.
  • the PDMSO is added prior to extrusion/fiber formation in order to get the benefit of both reduce die build-up and improved unwinding characteristics.
  • the PDMSO may be added to the polyolefin material via a masterbatch with additional polyolefin material as the carrier medium.
  • the addition of the PDMSO reduces die build-up in the extrusion of the polymer and also improves the release characteristics of the fiber from the packages or spools of the fiber. This latter effect can be further improved with the external application of a spin finish.
  • the spin finish can be any lubricating oil and is preferably selected from the group comprising silicones, mineral oils, ester oils with a viscosity range of 1 to 120 cSt, and blends thereof.
  • the method of the present invention leads to spools or packages having improved unwinding or release characteristics.
  • a releasability test was created.
  • the package/spool was placed in contact with a feed or drive roller (friction roller) rotating at a set speed (as provided by spinning the given roller at a speed of 30 rpm), and the filament was unwound onto a winding roller initially rotating at a speed set at three times the speed of the feed roller (that is the draft was 3x). At this speed and draft, no sticking was observed.
  • the winding roller rotational speed was then gradually reduced until the point where the unwinding fiber sticks as indicated by the fiber no longer being removed tangentially from the package/spool.
  • RF releasabilty factor
  • Fibers with the best releasability have very low values on this test (that is they do not stick even at low speeds). It is preferred that the method of the present invention reduce the release-ability value by at least twenty percent (for example if the release-ability factor for a particular fiber was 80 percent without the use of PDMSO, then the method of the present invention will preferably result in a releasability factor of 66 percent or less).
  • Another aspect of the present invention is an elastic polyolefin-based fiber package having a releasabilty of less than 100 percent, more preferably less than 50 percent, still more preferably less than 30 percent most preferably less than 20 percent, using the test just described.
  • fiber was prepared from a base polymer prepared using an INSITE Constrained Geometry Metallocene catalyst.
  • the base polymer was polyethylene with an octene comonomer content of about 35 percent to give a density of 0.875 g/cc with a melt index of 3.0 +/- 0.20 dg/min as determined using ASTM D1238.
  • a masterbatch of 40 percent by weight PDMSO in an ethylene styrene interpolymer was prepared.
  • the master batch was then dry blended into the base polymer to provide the desired level of PDMSO in the fiber.
  • 3 levels of PDMSO were evaluated, 0 percent. 0.5 percent and 1 percent.
  • the polymer was then melt spun into fibers at a melt temperature of 270°C. Each polymer formulation was run for 8 hours and the number of times the spinnerets (dies) had to be cleaned is reported in Figure 1 .

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP05849526A 2004-12-03 2005-12-01 Method to improve release characteristics of elastic polyolefin fibers Active EP1819850B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US63292404P 2004-12-03 2004-12-03
PCT/US2005/044944 WO2006060826A1 (en) 2004-12-03 2005-12-01 Method to improve release characteristics of elastic polyolefin fibers

Publications (2)

Publication Number Publication Date
EP1819850A1 EP1819850A1 (en) 2007-08-22
EP1819850B1 true EP1819850B1 (en) 2009-04-01

Family

ID=35945259

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05849526A Active EP1819850B1 (en) 2004-12-03 2005-12-01 Method to improve release characteristics of elastic polyolefin fibers

Country Status (13)

Country Link
US (1) US20080093768A1 (ko)
EP (1) EP1819850B1 (ko)
JP (1) JP2009508010A (ko)
KR (1) KR20070085655A (ko)
CN (1) CN101068957B (ko)
AT (1) ATE427371T1 (ko)
AU (1) AU2005311589A1 (ko)
BR (1) BRPI0516898B1 (ko)
CA (1) CA2587663A1 (ko)
DE (1) DE602005013689D1 (ko)
ES (1) ES2321219T3 (ko)
TW (1) TW200634188A (ko)
WO (1) WO2006060826A1 (ko)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8835548B2 (en) * 2009-09-16 2014-09-16 Union Carbide Chemicals & Plastics Technology Llc Process for producing crosslinked, melt-shaped articles
CN104055231A (zh) * 2014-06-20 2014-09-24 张连根 一种同时含有丙纶和聚烯烃弹力纤维的针织保暖面料
JP6611323B2 (ja) * 2015-11-16 2019-11-27 花王株式会社 吸収性物品並びに不織布及びその製造方法
TW202020037A (zh) 2018-08-29 2020-06-01 美商陶氏全球科技有限責任公司 用於改良剛性－韌性平衡之聚矽氧增強之乙烯／α－烯烴互聚物
JP6542452B1 (ja) * 2018-09-20 2019-07-10 竹本油脂株式会社 合成繊維用処理剤及び合成繊維

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641822A (en) * 1989-09-18 1997-06-24 Kimberly-Clark Corporation Surface-segregatable compositions and nonwoven webs prepared therefrom
US6448355B1 (en) * 1991-10-15 2002-09-10 The Dow Chemical Company Elastic fibers, fabrics and articles fabricated therefrom
US6194532B1 (en) * 1991-10-15 2001-02-27 The Dow Chemical Company Elastic fibers
JP2862445B2 (ja) * 1992-09-08 1999-03-03 株式会社トクヤマ 樹脂組成物及びその製造方法
US5322728A (en) * 1992-11-24 1994-06-21 Exxon Chemical Patents, Inc. Fibers of polyolefin polymers
US5789473A (en) * 1995-01-17 1998-08-04 Dow Corning Corporation Polyolefin composition containing diorganopolysiloxane process aid
US5824718A (en) * 1995-04-20 1998-10-20 The Dow Chemical Company Silane-crosslinkable, substantially linear ethylene polymers and their uses
DE69631359T2 (de) * 1995-08-08 2004-12-09 FiberVisions, L.P., Wilmington Kardierbare hydrophobische Stapelfaser mit internem Weichmacher und Verfahren zu ihrer Herstellung und zu ihrer Verwendung
US5708084A (en) * 1996-08-28 1998-01-13 Dow Corning Corporation Organic polymers modified with silicone materials
US5902854A (en) * 1996-09-27 1999-05-11 The Dow Chemical Company Polydimethylsiloxane containing polymer blends
BR9908804A (pt) * 1998-03-11 2001-10-30 Dow Chemical Co Fibras produzidas a partir de interpolìmeros eagente de pega
AR018359A1 (es) * 1998-05-18 2001-11-14 Dow Global Technologies Inc Articulo resistente al calor , configurado, irradiado y reticulado, libre de un agente de reticulacion de silano
BR9911213B1 (pt) * 1998-06-01 2010-11-16 método para manufaturar artigo moldado reticulado por irradiação, interpolìmero moldado, artigo de higiene pessoal e de controle de infecções contendo dito interpolìmero.
EP1280856A1 (en) * 2000-05-11 2003-02-05 The Dow Chemical Company Method of making elastic articles having improved heat-resistance
US6762137B2 (en) * 2000-12-21 2004-07-13 Kimberly-Clark Worldwide, Inc. Water repellant meltblown webs and laminates
US20040116018A1 (en) * 2002-12-17 2004-06-17 Kimberly-Clark Worldwide, Inc. Method of making fibers, nonwoven fabrics, porous films and foams that include skin treatment additives
US7273476B2 (en) * 2004-09-13 2007-09-25 The Procter & Gamble Company Diaper with elasticated topsheet

Also Published As

Publication number Publication date
ES2321219T3 (es) 2009-06-03
BRPI0516898A (pt) 2008-09-23
JP2009508010A (ja) 2009-02-26
DE602005013689D1 (de) 2009-05-14
AU2005311589A1 (en) 2006-06-08
KR20070085655A (ko) 2007-08-27
CN101068957B (zh) 2013-05-22
WO2006060826A1 (en) 2006-06-08
CA2587663A1 (en) 2006-06-08
TW200634188A (en) 2006-10-01
CN101068957A (zh) 2007-11-07
BRPI0516898B1 (pt) 2016-04-05
US20080093768A1 (en) 2008-04-24
EP1819850A1 (en) 2007-08-22
ATE427371T1 (de) 2009-04-15

Similar Documents

Publication Publication Date Title
EP1819850B1 (en) Method to improve release characteristics of elastic polyolefin fibers
EP2208821B1 (en) Oil agent composition for carbon fiber precursor acrylic fiber, carbon fiber precursor acrylic fiber bundle, and method for producing the same
US10087560B2 (en) Braid
KR100440529B1 (ko) 폴리프로필렌섬유및이로부터제조된제품
EP0891433B1 (en) Polypropylene fibers and items made therefrom
US5763334A (en) Internally lubricated fiber, cardable hydrophobic staple fibers therefrom, and methods of making and using the same
KR20130037733A (ko) 신규한 이성분 섬유
US6476172B1 (en) Metallocene catalyzed propylene-α-olefin random copolymer melt spun fibers
WO2007101032A2 (en) High tenacity polyolefin ropes having improved cyclic bend over sheave performance
WO2019078170A1 (ja) ポリウレタン弾性繊維、その巻糸体、及びそれを含む製品
US6777496B2 (en) Polymeric additives and polymeric articles comprising said additive
JP2935604B2 (ja) ウレタン弾性糸用油剤
EP1730333B1 (fr) Procede de fabrication d'une bobine avec un monofilament de polypropylene
KR20150126847A (ko) 폴리에틸렌 블렌드를 포함하는 섬유
JPH10158938A (ja) 弾性繊維の油剤付与方法
JP3821604B2 (ja) 無機粒子含有ポリアミド繊維の製造方法
JP2019077979A (ja) 芯鞘複合繊維
JP2788097B2 (ja) ポリウレタン弾性糸用油剤
JP7042328B2 (ja) 溶融異方性芳香族ポリエステルマルチフィラメント
JP2001146683A (ja) 摩擦仮撚加工用ポリエステル繊維の製造方法
JP2902719B2 (ja) ポリウレタン弾性糸の製造方法
JP4223113B2 (ja) 混合紡糸繊維およびその製造方法
JP2001214332A (ja) ポリウレタン弾性繊維
JPH08209459A (ja) ポリエーテルエステル系弾性糸の製造法
JP2021070902A (ja) ポリエチレン繊維

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

17P Request for examination filed

Effective date: 20070703

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LAUNCHBURY, BRYAN

Inventor name: BATISTINI, ANTONIO

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LAUNCHBURY, BRYAN

Inventor name: BATISTINI, ANTONIO

17Q First examination report despatched

Effective date: 20071105

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602005013689

Country of ref document: DE

Date of ref document: 20090514

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2321219

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: SI

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: 20090401

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

Ref country code: PT

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: 20090902

Ref country code: AT

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: 20090401

Ref country code: FI

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: 20090401

Ref country code: LT

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: 20090401

Ref country code: EE

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: 20090401

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

Ref country code: LV

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: 20090401

Ref country code: SE

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: 20090701

Ref country code: PL

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: 20090401

Ref country code: IS

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: 20090801

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

Ref country code: RO

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: 20090401

Ref country code: CZ

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: 20090401

Ref country code: DK

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: 20090401

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

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

Ref country code: SK

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: 20090401

Ref country code: BE

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: 20090401

26N No opposition filed

Effective date: 20100105

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

Ref country code: BG

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: 20090701

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

Ref country code: MC

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

Effective date: 20100701

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: LI

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

Effective date: 20091231

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: 20090702

Ref country code: CH

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

Effective date: 20091231

Ref country code: IE

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

Effective date: 20091201

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: 20091201

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

Ref country code: HU

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: 20091002

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

Ref country code: CY

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: 20090401

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

Ref country code: GB

Payment date: 20121128

Year of fee payment: 8

Ref country code: ES

Payment date: 20121227

Year of fee payment: 8

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

Ref country code: FR

Payment date: 20130107

Year of fee payment: 8

Ref country code: NL

Payment date: 20121208

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20140701

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

Effective date: 20131201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140829

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: 20140701

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: 20131231

Ref country code: GB

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

Effective date: 20131201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20150709

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

Ref country code: ES

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

Effective date: 20131202

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

Ref country code: TR

Payment date: 20201130

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20201110

Year of fee payment: 16

Ref country code: DE

Payment date: 20201118

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005013689

Country of ref document: DE

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: 20220701

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

Effective date: 20211201