EP1942213B1 - Fiber comprising an ethylene copolymer - Google Patents
Fiber comprising an ethylene copolymer Download PDFInfo
- Publication number
- EP1942213B1 EP1942213B1 EP07000199A EP07000199A EP1942213B1 EP 1942213 B1 EP1942213 B1 EP 1942213B1 EP 07000199 A EP07000199 A EP 07000199A EP 07000199 A EP07000199 A EP 07000199A EP 1942213 B1 EP1942213 B1 EP 1942213B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- accordance
- polymer component
- present
- ethylene
- 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
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 93
- 229920001038 ethylene copolymer Polymers 0.000 title abstract description 7
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 48
- 239000004711 α-olefin Substances 0.000 claims description 34
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 24
- -1 polypropylenes Polymers 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000007380 fibre production Methods 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 238000009987 spinning Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
Definitions
- the present invention relates to a fiber comprising an ethylene copolymer, a non-woven fabric comprising the fiber, the use of a specific ethylene copolymer for fiber production and a process for preparing a fiber in accordance with the present invention.
- Synthetic fibers are used over a broad range of applications and, in particular, synthetic fibers comprising polyolefins have been developed in the recent past.
- One specific type of synthetic fibers is bicomponent fibers, defining a fiber comprising two different polymers of, for example, different chemical constitution or different physical properties. Typically, these two different polymers are brought together in the spinning process and thereby extruded into a bicomponent fiber.
- bicomponent fiber The basic concept behind a bicomponent fiber is the desire to combine the properties of two different polymers in order to widen the possible fields of application.
- Typical bicomponent fibers are polypropylene/polyethylene fibers. These fibers comprise a low melting temperature component (polyethylene) and a high melting temperature component (polypropylene) which offers specific advantages, for example, when producing a non-woven fabric. If the lower melting temperature component is employed, at least partially as a component being present on the surface of the fiber, the non-woven fabric can be bonded in a simple thermal bonding process requiring far less heat, compared with a thermal bonding process employing pure polypropylene fibers. At the same time, it is ensured that the polypropylene remains intact and provides the desired product strength for the fabric.
- polyethylene low melting temperature component
- polypropylene polypropylene
- Typical advantages associated with the use of such bicomponent fibers are non-woven fabrics with a soft handle which can be produced without chemical binders. Furthermore, non-wovens can be obtained which show a desired degree of bulkiness and the production process of such fabrics is simple and energy efficient.
- the European patent application EP 0696655 A1 discloses a melt adhesive composite fiber which may be used for preparing non-woven fabrics to be employed as surface material for medical supplies and paper diapers.
- the melt adhesive composite fibers as disclosed in the above-mentioned European patent application comprise a polypropylene as a first component and a polyethylene as a second component, which is continuously present on at least a part of the fiber surface along the length of the fiber.
- Typical polyethylenes to be employed in such bicomponent fibers are LLDPE materials, i.e. ethylene copolymers comprising ⁇ -olefins, as well as HDPE materials, which may be homopolymers or copolymers.
- LLDPE materials i.e. ethylene copolymers comprising ⁇ -olefins
- HDPE materials which may be homopolymers or copolymers.
- Examples of such HDPE materials are copolymers of ethylene with 1-octene, which are, for example, disclosed in WO 2005/111291 A1 as suitable component for a bicomponent fiber.
- a commercially available ethylene polymer for use in bicomponent fibers is the polyethylene grade Aspun 6811A of Dow, which is an LLDPE material.
- Bicomponent fibers are also disclosed in US-B1-6391443 or EP-A1-0833002 .
- the present invention aims at providing an improved fiber, fulfilling at least one of the objectives as indicated above.
- the present invention provides the following.
- the present invention provides an improved fiber as defined in claim 1. Preferred embodiments of the fiber are defined in subclaims 2 to 9 as well as the following description.
- the present invention furthermore provides a non-woven fabric comprising the fibers in accordance with the present invention as well as processes for the preparation of the fibers and the non-woven fabrics as defined in claims 10, 11 and 12.
- the present invention provides the use of a specific ethylene copolymer for preparing fibers as indicated in claim 13. Preferred embodiments are again derivable from the present specification.
- the present invention provides a fiber, comprising a first polymer component and a second polymer component, wherein the first and the second polymer component differ from one another at least with respect to one property, such as chemical constitution or physical properties, and wherein the second component is an ethylene- ⁇ -olefin copolymer having a density of from 0.945 to 0.965 g/cm 3 , an MFR 2 of from 15 to 45 g/10 min, and an amount of alpha-olefin of from 1 to 7 wt.-%.
- the first polymer component is selected from the group consisting of polypropylenes and polyesters.
- the weight ratio between the first and the second polymer components is from 30:70 to 70:30.
- the ⁇ -olefin as contained in the ethylene- ⁇ -olefin copolymer of the second polymer component preferably is an ⁇ -olefin having from 3 to 20 carbon atoms, more preferably from 4 to 10 carbon atoms, still more preferably from 4 to 6 carbon atoms and in particular the ⁇ -olefin is 1-hexene.
- the amount of ⁇ -olefin contained in the ethylene- ⁇ -olefin copolymer of the second polymer component of the fiber in accordance with the present invention amounts to about 1 to 7 wt%, preferably 1.25 to 3.5 wt%, and more preferably 1.75 to 3.0 wt%.
- An especially preferred ⁇ -olefin content is in the range of from 2 to 2.6 wt%
- the ethylene- ⁇ -olefin copolymer preferably is a mono-modal copolymer with respect to the molecular weight distribution showing a rather narrow molecular weight distribution (MWD) Mw/Mn of from 1 to 8, more preferably 2 to 5, even more preferably 3.5 to 4.5, such as about 4.
- the density of the ethylene- ⁇ -olefin copolymer typically amounts to from 0.945 to 0.965 g/cm 3 , more preferably 0.945 to 0.960, even more preferably of from 0.947 to 0.955, and in particular of from 0.948 to 0.954.
- the ethylene- ⁇ -olefin copolymer displays an MFR 2 of from 25 to 45 g/10 min, more preferably of from 30 to 45 g/10 min and in particular of from 35 to 42 g/10 min, such as about 39 g/10 min.
- MFR 2 of from 25 to 45 g/10 min, more preferably of from 30 to 45 g/10 min and in particular of from 35 to 42 g/10 min, such as about 39 g/10 min.
- Other highly suitable MFR 2 ranges are from 18 to 30 g/10 min, preferably from 20 to 28 g/10 min, such as about 20 or about 27 g/10 min.
- the ethylene- ⁇ -olefin copolymer of the second polymer component of the fiber in accordance with the present invention has not been subjected to any chemical modification, such as grafting and/or irradiation, which are often employed in the prior art in order to improve the bonding properties or the adhesion to the other polymer component of a bicomponent fiber.
- the fiber in accordance with the present invention preferably is a bicomponent fiber which may be a bicomponent fiber of any type, including core-sheath types, side-by-side types, hollow side-by-side types, orange types, island in sea types, layered types, as well as others, including modifications, such as eccentric core-sheath types, hollow orange types etc.
- Preferred in accordance with the present invention are bicomponent fibers wherein the second polymer component as defined herein at least is partially present at the surface of the fiber.
- core-sheath types are in particular preferred, wherein the second polymer component in accordance with the present invention constitutes the sheath.
- side-by-side types as well as orange types and layered types, since also these bicomponent fiber types ensure that the second polymer component to be employed in accordance with the present invention at least partially is present on the surface of the fiber.
- core-sheath types wherein as identified above, the second polymer component as defined herein constitutes the sheath.
- the ethylene- ⁇ -olefin polymer to be employed in accordance with the present invention as second polymer component preferably has not been subjected to any further modification, such as grafting and/or irradiation. It is in particular preferred if the ethylene- ⁇ -olefin copolymer is employed in the fiber without any further additive beyond the basic stabilization, although it is possible to add typical additives, such as additional stabilizers, coloring agents etc. in usual amounts.
- the ethylene- ⁇ -olefin copolymer (HDPE) to be employed in accordance with the present invention as second polymer component may be prepared using conventional polymerization techniques, in particular employing Ziegler-Natta catalysts. Suitable polymerization conditions and catalysts are known to the skilled person.
- the first polymer component to be employed in accordance with the present invention differs in at least with respect to one property from the second polymer component.
- the first polymer component is selected from the group consisting of polypropylene materials as well as ester materials, such as PET, commonly employed for the preparation of synthetic fibers, in particular bicomponent fibers.
- the first polymer component furthermore may be subjected to any desired kind of pretreatment, such as grafting and/or irradiation in order to improve adhesion or bonding properties.
- the first polymer component furthermore may be compounded, prior to the spinning process, with any desired additives, such as stabilizers, coloring agents, processing aids etc., in usual amounts.
- the wheight ratio between the first polymer component and the second polymer component is from 30:70 to 70:30, including also weight ratios of 50:50 etc.
- the fiber in accordance with the present invention may be prepared in any desired thickness, again depending upon the desired end use.
- Typical thicknesses are known to the skilled person and include in particular the range of from 0.5 to 100 denier, such as from 1 to 50 denier.
- the fibers in accordance with the present invention after spinning, may be subjected to any desired kind of post-treatment, such as stretching, crimping or cutting and the fibers in accordance with the present invention in particular may be subjected directly to a further process for preparing a non-woven fabric.
- the fibers in accordance with the present invention also can be cut at any desired length or may be wound up for any desired kind of post-treatment and/or storage, prior to the further use thereof.
- the present invention also provides a non-woven fabric prepared using the fiber in accordance with the present invention.
- a non-woven fabric can be prepared in accordance with standard techniques known to the skilled person.
- the specific second polymer component as defined herein enables the preparation of fabrics having improved values for tensile strength, compared with a non-woven fabric prepared with the standard market product Aspun 6811A of Dow, which is widely regarded as the best available polyethylene material for bicomponent fiber applications.
- the fibers in accordance with the present invention furthermore provide the possibility to tailor the bonding temperatures required for bonding of the fibers to produce a non-woven fabric which provides the manufacturer of a fiber and a non-woven fabric with a greater latitude for the bonding process, without encountering problems such as sticking.
- the specific ethylene- ⁇ -olefin copolymer to be employed in accordance with the present invention furthermore enables problem-free spinning processes without fiber failures due to gel particles.
- the present invention also provides the use of an ethylene- ⁇ -olefin copolymer as defined herein for the preparation of fibers, preferably bicomponent fibers.
- fibers preferably bicomponent fibers.
- the preferred embodiments as defined above in connection with the fiber and the non-woven fabric also apply with respect to the use as defined herein.
- the present invention finally also provides a process for preparing a fiber in accordance with the present invention as well as a process for preparing a non-woven fabric as defined herein.
- the process in accordance with the present invention comprises the step of providing a first polymer component as defined herein and providing a second polymer component as defined herein, melting the polymer components and extruding the polymer components through a suitable die/spinnerette in order to combine the two polymer components in a bicomponent fiber.
- Suitable process parameters and apparatuses required therefor are known to the skilled person and reference in this respect can be made to the Reicofil ® Bico Technology of Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen Reifen
- Non-woven fabrics can be prepared from fibers in accordance with the present invention by usual processes known to the skilled person, including in particular a treatment step for bonding the fibers by suitable devices such as heated rolls or a calander.
- a suitable process for preparing a non-woven fabric employing the fibers in accordance with the present invention accordingly comprises the steps of providing fibers in accordance with the present invention and bonding the fibers by means of a suitable process as indicated above.
- Sheath/core fibers were produced employing a standard propylene homopolymer (STD PP SB) spunbonded grade (MFR 2 25g/10min) as core component and employing either a commercially available reference product Aspun 6811A of Dow as sheath component or an ethylene- ⁇ olefin copolymer in accordance with the present invention.
- Sheath/core fibers were produced with a weight ratio of the two polymer components of 50:50 with a line speed of 56 m/min and other process parameters as indicated in table 2 below.
- the ethylene- ⁇ -olefin copolymers in accordance with the present invention were HDPE materials comprising 1-hexene, having an MWD of about 4 and produced using a
- the ethylene- ⁇ -olefin copolymers in accordance with the present invention as employed in the examples showed MFR 2 values of 20.0, 27.0 and 38.6, respectively (E1, E2 and E3, respectively).
- the ethylene- ⁇ -olefin copolymers used in accordance with the present invention were produced in a slurry process with a Z/N catalyst and tri-ethyl aluminium as cocatalyst. Pressure was 42 bar and temperature was 95 °C, isobutane was used as diluent.
- melt flow rates were measured according to ISO 1133 with a load of 2.16 kg at 230°C for polypropylene and at 190 °C for polyethylene.
- the melt flow rate is that quantity of polymer in grams which the test apparatus standardised to ISO 1133 extrudes within 10 minutes at a temperature of 230°C or 190 °C respectively, under a load of 2.16 kg.
- Density Densities are measured according to ISO 1183/D.
- Comonomer content is determined in a known manner based on Fourier transform infrared spectroscopy (FTIR) determination calibrated with C13-NMR.
- FTIR Fourier transform infrared spectroscopy
- the die temperature for both polymers was set to 235°C and the connection temperature for the polypropylene and the polyethylene materials were identical to the extrusion temperatures identified above. Fibers with a 2.5 denier thickness were produced and non-woven fabrics of about 42 g/m 2 were prepared.
- the results can be taken from the following table 2.
- the table clearly reveals that the fibers in accordance with the present invention provide non-woven fabrics having increased tensile strength values, compared with the comparative example employing the reference market product.
- the examples in accordance with the present invention did not give rise to any problems during spinning, such as fiber failure, for example, due to the occurrence of gel particles.
- the two grades of ethylene- ⁇ -olefin copolymer having lower MFR 2 values as tested in accordance with the present invention clearly show that also these components enable highly satisfactory tensile strength values, again providing a wide temperature window for the embossing temperature.
- the ethylene- ⁇ -olefin copolymer with MFR 2 of 20.0, for example, enables a satisfactory bonding process with embossing roll temperatures of from 124 to 142°C.
- the present invention enables an improvement with respect to the mechanical properties of a non-woven fabric produced using a fiber in accordance with the present invention while, at the same time, the temperature window for the bonding process is suitably wide providing the manufacturer with a great latitude concerning the process of forming a non-woven fabric.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
- Nonwoven Fabrics (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07000199A EP1942213B1 (en) | 2007-01-05 | 2007-01-05 | Fiber comprising an ethylene copolymer |
DK07000199T DK1942213T3 (da) | 2007-01-05 | 2007-01-05 | Fiber omfattende en ethylencopolymer |
DE602007002148T DE602007002148D1 (de) | 2007-01-05 | 2007-01-05 | Faser mit Ethylencopolymer |
AT07000199T ATE440982T1 (de) | 2007-01-05 | 2007-01-05 | Faser mit ethylencopolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07000199A EP1942213B1 (en) | 2007-01-05 | 2007-01-05 | Fiber comprising an ethylene copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1942213A1 EP1942213A1 (en) | 2008-07-09 |
EP1942213B1 true EP1942213B1 (en) | 2009-08-26 |
Family
ID=38051710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07000199A Active EP1942213B1 (en) | 2007-01-05 | 2007-01-05 | Fiber comprising an ethylene copolymer |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1942213B1 (da) |
AT (1) | ATE440982T1 (da) |
DE (1) | DE602007002148D1 (da) |
DK (1) | DK1942213T3 (da) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130023177A1 (en) * | 2010-03-19 | 2013-01-24 | Dow Blobal Technologies LLC | Bicomponent fibers |
AR122466A1 (es) * | 2020-05-08 | 2022-09-14 | Dow Global Technologies Llc | FIBRAS BICOMPONENTES QUE INCLUYEN INTERPOLÍMEROS DE ETILENO / a-OLEFINA |
WO2024041848A1 (en) | 2022-08-22 | 2024-02-29 | Sabic Global Technologies B.V. | Bicomponent fiber |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4842922A (en) * | 1987-10-27 | 1989-06-27 | The Dow Chemical Company | Polyethylene fibers and spunbonded fabric or web |
TW339377B (en) * | 1996-09-30 | 1998-09-01 | Mitsui Petroleum Chemicals Ind | Flexible nonwoven fabric and laminate thereof |
US6391443B1 (en) * | 2000-05-29 | 2002-05-21 | Chisso Corporation | Polyethylene composite fiber and a non-woven fabric using the same |
JP4315663B2 (ja) * | 2002-10-17 | 2009-08-19 | ユニチカ株式会社 | 芯鞘状複合長繊維よりなる不織布の製造方法 |
ES2393247T3 (es) | 2004-04-30 | 2012-12-19 | Dow Global Technologies Inc. | Fibras mejoradas para materiales no tejidos de polietileno. |
-
2007
- 2007-01-05 DK DK07000199T patent/DK1942213T3/da active
- 2007-01-05 DE DE602007002148T patent/DE602007002148D1/de active Active
- 2007-01-05 EP EP07000199A patent/EP1942213B1/en active Active
- 2007-01-05 AT AT07000199T patent/ATE440982T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DK1942213T3 (da) | 2009-11-02 |
ATE440982T1 (de) | 2009-09-15 |
EP1942213A1 (en) | 2008-07-09 |
DE602007002148D1 (de) | 2009-10-08 |
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