AU2005311589A1 - Method to improve release characteristics of elastic polyolefin fibers - Google Patents
Method to improve release characteristics of elastic polyolefin fibers Download PDFInfo
- Publication number
- AU2005311589A1 AU2005311589A1 AU2005311589A AU2005311589A AU2005311589A1 AU 2005311589 A1 AU2005311589 A1 AU 2005311589A1 AU 2005311589 A AU2005311589 A AU 2005311589A AU 2005311589 A AU2005311589 A AU 2005311589A AU 2005311589 A1 AU2005311589 A1 AU 2005311589A1
- Authority
- AU
- Australia
- 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.)
- Abandoned
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 34
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 33
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- 210000004177 elastic tissue Anatomy 0.000 abstract description 3
- 229920005672 polyolefin resin Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000697 Lastol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XRERONKQLIQWGW-UHFFFAOYSA-N but-1-ene;styrene Chemical compound CCC=C.C=CC1=CC=CC=C1 XRERONKQLIQWGW-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
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)
- 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)
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
WO 2006/060826 PCT/US2005/044944 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 ofpolyolefin based elastic fiber and for improving the 5 unwind or release characteristics of such fiber. In 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 10 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 15 order to remove these deposits. It is therefore desirable to reduce or eliminate these build ups. 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 20 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 25 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. 30 Figure 3 demonstrates the load at break and elongation at break of fibers made in accordance with the present invention. -1- WO 2006/060826 PCT/US2005/044944 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 5 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 10 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/co (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 15 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 percerit 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 20 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 25 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. 30 Conveniently, the PDMSO may be added to the polyolefin material via a masterbatch with additional polyolefin material as the carrier medium. -2- WO 2006/060826 PCT/US2005/044944 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 5 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 10 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 15 no longer being removed tangentially from the package/spool. A releasabilty factor ("RF") was then calculated according to the following formnnula 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) 20 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 25 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, most preferably less than 30 percent using the test just described. -3- WO 2006/060826 PCT/US2005/044944 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 5 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. 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 10 at a melt temperature of 270 0 C. Each polymer fornnulation 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. In some cases an external spin 15 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 20 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 mmn grip distance at 500 mm/min separation speed. There was no significant loss of physical properties when 25 using this internal and external lubrication method, as demonstrated in Figure 3. -4-
Claims (11)
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 5 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 10 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. 15
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. 20
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. -5-
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63292404P | 2004-12-03 | 2004-12-03 | |
| US60/632,924 | 2004-12-03 | ||
| PCT/US2005/044944 WO2006060826A1 (en) | 2004-12-03 | 2005-12-01 | Method to improve release characteristics of elastic polyolefin fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2005311589A1 true AU2005311589A1 (en) | 2006-06-08 |
Family
ID=35945259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2005311589A Abandoned AU2005311589A1 (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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112012006018B1 (en) * | 2009-09-16 | 2021-03-02 | Union Carbide Corporation | process for the manufacture of cross-linked fused molded articles |
| 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 |
| ES2887052T3 (en) | 2018-05-03 | 2021-12-21 | Dow Global Technologies Llc | Artificial grass yarn with improved processability and friction management |
| 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 (18)
| 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 |
| DK0761846T3 (en) * | 1995-08-08 | 2004-05-24 | Fibervisions L P | Carteable hydrophobic staple fiber with internal lubricant and method for 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 |
| KR100551782B1 (en) * | 1998-03-11 | 2006-02-13 | 다우 글로벌 테크놀로지스 인크. | Fibers made from alpha-olefin / vinyl or vinylidene aromatic and / or hindered alicyclic 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 |
| RU2226200C2 (en) * | 1998-06-01 | 2004-03-27 | Дау Глобал Текнолоджиз Инк. | Method of manufacturing washable and dryable elastic articles |
| CA2406666A1 (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 |
| KR20040054061A (en) * | 2002-12-17 | 2004-06-25 | 주식회사 이머텍 | Internet Phone System and Method for a Mobile Telephone Service |
| 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 |
-
2005
- 2005-12-01 EP EP05849526A patent/EP1819850B1/en not_active Expired - Lifetime
- 2005-12-01 KR KR1020077012453A patent/KR20070085655A/en not_active Withdrawn
- 2005-12-01 WO PCT/US2005/044944 patent/WO2006060826A1/en not_active Ceased
- 2005-12-01 ES ES05849526T patent/ES2321219T3/en not_active Expired - Lifetime
- 2005-12-01 AU AU2005311589A patent/AU2005311589A1/en not_active Abandoned
- 2005-12-01 BR BRPI0516898A patent/BRPI0516898B1/en not_active IP Right Cessation
- 2005-12-01 AT AT05849526T patent/ATE427371T1/en not_active IP Right Cessation
- 2005-12-01 DE DE602005013689T patent/DE602005013689D1/en not_active Expired - Lifetime
- 2005-12-01 CA CA002587663A patent/CA2587663A1/en not_active Abandoned
- 2005-12-01 CN CN2005800416285A patent/CN101068957B/en not_active Expired - Fee Related
- 2005-12-01 JP JP2007544646A patent/JP2009508010A/en active Pending
- 2005-12-01 US US11/718,614 patent/US20080093768A1/en not_active Abandoned
- 2005-12-02 TW TW094142484A patent/TW200634188A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0516898A (en) | 2008-09-23 |
| ES2321219T3 (en) | 2009-06-03 |
| WO2006060826A1 (en) | 2006-06-08 |
| CA2587663A1 (en) | 2006-06-08 |
| CN101068957B (en) | 2013-05-22 |
| EP1819850A1 (en) | 2007-08-22 |
| JP2009508010A (en) | 2009-02-26 |
| KR20070085655A (en) | 2007-08-27 |
| BRPI0516898B1 (en) | 2016-04-05 |
| US20080093768A1 (en) | 2008-04-24 |
| DE602005013689D1 (en) | 2009-05-14 |
| ATE427371T1 (en) | 2009-04-15 |
| EP1819850B1 (en) | 2009-04-01 |
| TW200634188A (en) | 2006-10-01 |
| CN101068957A (en) | 2007-11-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK4 | Application lapsed section 142(2)(d) - no continuation fee paid for the application |