EP1819850A1 - Method to improve release characteristics of elastic polyolefin fibers - Google Patents

Method to improve release characteristics of elastic polyolefin fibers

Info

Publication number
EP1819850A1
EP1819850A1 EP05849526A EP05849526A EP1819850A1 EP 1819850 A1 EP1819850 A1 EP 1819850A1 EP 05849526 A EP05849526 A EP 05849526A EP 05849526 A EP05849526 A EP 05849526A EP 1819850 A1 EP1819850 A1 EP 1819850A1
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.)
Granted
Application number
EP05849526A
Other languages
German (de)
French (fr)
Other versions
EP1819850B1 (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

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, hi particular 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 which is hereby incorporated by reference in its entirety), 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 D 1238).
  • Preferred polyolefm 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 can be 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 ideally added prior to extrusion/fiber formation in order to get the benefit of both reduce die build-up and improved unwinding characteristics, but may be added after fiber formation, for example in a spin finish, if only improved unwinding performance is desired.
  • 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.
  • a releasabilty factor (“RF") was then calculated according to the following formula where "r.s.” means rotational speed:
  • 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 polyolefm-based fiber package having a releasabilty of less than 100 percent, more preferably less than 50 percent, most preferably less than 30 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 D 1238 .
  • 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)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

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. In particular the method involves the use of polydimethylsiloxane (PDMSO) in the polyolefin resin.

Description

METHOD TO IMPROVE RELEASE CHARACTERISTICS OF ELASTIC POLYOLEFIN
FIBERS
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, hi particular the method involves the use of polydimethylsiloxane (PDMSO) in the polyolefin resin.
There has been much recent publicity related to cross-linked polyolefin-based elastic fibers, including the news of the Federal Trade Commission establishing a new generic term, "Lastol", to cover such fibers. The production and make-up of these fibers are known in the art, for example as described in US Patents 6,048,935; 6,140,442; 6,194,532;
6,248,851; 6,448,355; 6,436,534; 6,500,540; and 6,559,208, all of which are incorporated by reference in their entirety.
In the production of these fibers, it has been observed that deposits gradually build up on the dies during melt spinning. Periodically, the production must be shut down in order to remove these deposits. It is therefore desirable to reduce or eliminate these buildups.
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.
It has been discovered that the addition of small amounts of polydimethylsiloxane (PDMSO) to the polyolefin fiber prior to fiber formation aids in both of these goals. This result is unexpected as silicones are generally applied to the fiber externally by means of a metering pump or, a kiss roll. Such oils are commonly called spin finishes.
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 (which is hereby incorporated by reference in its entirety), 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 D 1238). Preferred polyolefm 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 can be 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 ideally added prior to extrusion/fiber formation in order to get the benefit of both reduce die build-up and improved unwinding characteristics, but may be added after fiber formation, for example in a spin finish, if only improved unwinding performance is desired. Conveniently, 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. In order to demonstrate this improvement a releasability test was created. For this test, 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. A releasabilty factor ("RF") was then calculated according to the following formula where "r.s." means rotational speed:
RF = (r.s. of winder at point sticking observed) - (r.s. of feed roll) x 100
(r.s. of feed roll )
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 polyolefm-based fiber package having a releasabilty of less than 100 percent, more preferably less than 50 percent, most preferably less than 30 percent using the test just described. EXAMPLES
For these Examples 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 D 1238 .
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. For these examples 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.
As can be seen from Figure 1 , the frequency of cleaning required dropped significantly with the presence of PDMSO.
As the fiber was spun, it was wrapped onto packages, hi some cases an external spin finish of silicone lubricating oil (Takemoto DELION 9535) was applied in an amount of 1.6 percent by weight to the fiber prior to winding onto the package. These packages where then evaluated for their release-ability using the test method described above. An improvement of 35 - 40 percent in the release value was obtained with PDMSO (indicated as "Si" in the figure) alone compared to filament with no lubrication and an improvement of up to 70 percent was observed for PDMSO in combination with external spin finish oil. The results of these experiments are reported in Figure 2.
The load at break (as determined by DIN 53 835 Part 1 and elongation at break (as determined by DIN 53 835 Part 1) of these fibers were measured at 100 mm grip distance at 500 rnm/min separation speed. There was no significant loss of physical properties when using this internal and external lubrication method, as demonstrated in Figure 3.

Claims

WHAT IS CLAIMED IS:
1. In a method for the production of elastic polyolefin-based fibers wherein a polyolefin-based material is extruded and melt spun into a fiber, the improvement comprising incorporating an amount of polydimethylsiloxane (PDMSO) into the polyolefin-based material.
2. The method of Claim 1 wherein the polyolefin-based material comprises an ethylene alpha-olefin copolymer produced using a Metallocene catalyst.
3. The method of Claim 2 wherein the alpha olefin is octene.
4. The method of Claim 3 wherein the polyolefin-based material has a density in the range of 0.8 to 0.89 g/cc and a melt index in the range of 0.5 to 10 dg/min.
5. The method of Claim 2 wherein the PDMSO has an average molecular weight of approximately 2 million.
6. The method of Claim 1 wherein the PDMSO is added in an amount such that the PDMSO comprises from 0.1 to 5.0 per cent by weight of the fiber.
7. The method of Claim 6 wherein the PDMSO is added in an amount such that the PDMSO comprises 0.5 to 1 per cent by weight of the fiber.
8. The method of Claim 2 wherein the PDMSO is added via a masterbatch.
9. The method of Claim 2 further comprising an additional step of adding a lubricating oil to the formed fiber via a spin finish.
10. The method of Claim 1 characterized in that the method results in a releasabilty factor which is at least 20 percent less than a similar fiber without PDMSO.
11. A fiber package having a releasability factor less than 50 percent.
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 true EP1819850A1 (en) 2007-08-22
EP1819850B1 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 (en)
EP (1) EP1819850B1 (en)
JP (1) JP2009508010A (en)
KR (1) KR20070085655A (en)
CN (1) CN101068957B (en)
AT (1) ATE427371T1 (en)
AU (1) AU2005311589A1 (en)
BR (1) BRPI0516898B1 (en)
CA (1) CA2587663A1 (en)
DE (1) DE602005013689D1 (en)
ES (1) ES2321219T3 (en)
TW (1) TW200634188A (en)
WO (1) WO2006060826A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101768730B1 (en) * 2009-09-16 2017-08-16 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크날러지 엘엘씨 Crosslinked, melt-shaped articles and compositions for producing same
CN104055231A (en) * 2014-06-20 2014-09-24 张连根 Knitted thermal fabric containing both polypropylene and polyolefin elastic fibers
JP6611323B2 (en) * 2015-11-16 2019-11-27 花王株式会社 Absorbent article, nonwoven fabric and method for producing the same
TW202020037A (en) 2018-08-29 2020-06-01 美商陶氏全球科技有限責任公司 Silicone enhanced ethylene/alpha-olefin interpolymers for improved stiffness-toughness balance
JP6542452B1 (en) * 2018-09-20 2019-07-10 竹本油脂株式会社 Processing agents for synthetic fibers and synthetic fibers

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
US6194532B1 (en) * 1991-10-15 2001-02-27 The Dow Chemical Company Elastic fibers
US6448355B1 (en) * 1991-10-15 2002-09-10 The Dow Chemical Company Elastic fibers, fabrics and articles fabricated therefrom
JP2862445B2 (en) * 1992-09-08 1999-03-03 株式会社トクヤマ Resin composition and method for producing the same
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
EP0761846B1 (en) * 1995-08-08 2004-01-21 FiberVisions, L.P. Cardable hydrophobic staple fiber with internal lubricant and method of making and using the same
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
EP1068377A1 (en) * 1998-03-11 2001-01-17 The Dow Chemical Company Fibers made from alpha-olefin/vinyl or vinylidene aromatic and/or hindered cycloaliphatic or aliphatic vinyl or vinylidene interpolymers
AR018359A1 (en) * 1998-05-18 2001-11-14 Dow Global Technologies Inc HEAT RESISTANT ARTICLE, CONFIGURED, IRRADIATED AND RETICULATED, FREE FROM A SILANAN RETICULATION AGENT
CA2332558A1 (en) * 1998-06-01 1999-12-09 The Dow Chemical Company Method of making washable, dryable elastic articles
WO2001085843A1 (en) * 2000-05-11 2001-11-15 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006060826A1 *

Also Published As

Publication number Publication date
EP1819850B1 (en) 2009-04-01
BRPI0516898A (en) 2008-09-23
ES2321219T3 (en) 2009-06-03
CN101068957A (en) 2007-11-07
TW200634188A (en) 2006-10-01
ATE427371T1 (en) 2009-04-15
CN101068957B (en) 2013-05-22
AU2005311589A1 (en) 2006-06-08
US20080093768A1 (en) 2008-04-24
CA2587663A1 (en) 2006-06-08
KR20070085655A (en) 2007-08-27
BRPI0516898B1 (en) 2016-04-05
DE602005013689D1 (en) 2009-05-14
WO2006060826A1 (en) 2006-06-08
JP2009508010A (en) 2009-02-26

Similar Documents

Publication Publication Date Title
US6388013B1 (en) Polyolefin fiber compositions
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
US6416699B1 (en) Reduced shrinkage in metallocene isotactic polypropylene fibers
US6476172B1 (en) Metallocene catalyzed propylene-α-olefin random copolymer melt spun fibers
HU226849B1 (en) Polypropylene fibres
US20020103299A1 (en) Polymeric additives and polymeric articles comprising said additive
JP2935604B2 (en) Oil agent for urethane elastic yarn
JP3883621B2 (en) Method for applying oil to elastic fiber
KR20150126847A (en) Fiber comprising polyethylene blend
JPS6221817A (en) Ultra-high speed spinning of polyester fiber
JP2019077979A (en) Core-sheath composite fiber
EP1987179B1 (en) Crosslinked polyethylene elastic fibers
JP3821604B2 (en) Method for producing inorganic particle-containing polyamide fiber
JP2788097B2 (en) Oil agent for polyurethane elastic yarn
US6106942A (en) Liquid crystalline polymer monofilaments having improved adhesion characteristics
JP7042328B2 (en) Melt Anisotropy Aromatic Polyester Multifilament
JPH09188974A (en) Lubricant for polyurethane elastic fiber
JP2001146683A (en) Production of polyester fiber for friction false twisting
JP2001214332A (en) Polyurethane elastic fiber
JP3226057B2 (en) Polyurethane elastic fiber
JPH08209459A (en) Production of polyetherester elastic yarn
JPH1112949A (en) Production of polyether ester-based elastic yarn
JP2003278078A (en) Biodegradable staple fiber

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