EP2027314A1 - Lyocell staple fiber - Google Patents
Lyocell staple fiberInfo
- Publication number
- EP2027314A1 EP2027314A1 EP07718467A EP07718467A EP2027314A1 EP 2027314 A1 EP2027314 A1 EP 2027314A1 EP 07718467 A EP07718467 A EP 07718467A EP 07718467 A EP07718467 A EP 07718467A EP 2027314 A1 EP2027314 A1 EP 2027314A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- holes
- staple fiber
- cross
- lyocell staple
- filaments
- 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
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 115
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 claims description 33
- 238000007664 blowing Methods 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229920002678 cellulose Polymers 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 9
- 239000004753 textile Substances 0.000 claims description 8
- 230000000712 assembly Effects 0.000 claims description 4
- 238000000429 assembly Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000001143 conditioned effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 240000004533 Hesperis matronalis Species 0.000 claims description 2
- 235000015847 Hesperis matronalis Nutrition 0.000 claims description 2
- 206010021639 Incontinence Diseases 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 238000002350 laparotomy Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 238000009987 spinning Methods 0.000 description 22
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000002904 solvent Substances 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
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
Definitions
- the present invention relates to a Lyocell staple fiber.
- a Lyocell fiber is a celluosic fiber which is spun from a solution from cellulose in an organic solvent, especially in an aqueous tertiary amine-oxide.
- NMMO N-methyl-morpholine-N- oxide
- Lyocell staple fiber is a product resulting from cutting a plurality of (endless) filaments which are obtained by spinning the cellulose solution through a spinneret and precipitating the spun filaments.
- Lyocell fibers typically are essentially round. This is in contrast to standard viscose fibers, which exhibit a rather serrated cross-sectional shape.
- EP 0 301 874 A discloses a process for the manufacture of so-called multi-lobal cellulosic staple fibers.
- a further process for the manufacture of cellulosic staple fibers by spinning of a spinning solution through a spinneret with multi-lobal spinneret holes is disclosed in WO 04/85720.
- Cellulosic fibers of a "Y"- shaped cross-section are also mentioned in GB-A-2 085 304.
- Viscose fibers are quite distinct from Lyocell fibers in terms of their physical and textile properties.
- JP 10-140429 A discloses regenerated cellulose fibers which are produced by spinning a viscose solution through a spinneret exhibiting arrangements of fiber-forming holes which are located adjacent. Upon spinning the solution through the spinneret, the filaments extruded through these fiber-forming holes are fused to form one fiber exhibiting an aiiomal cross-sectional shape.
- a Lyocell staple fibre consisting of a plurality of cut filaments, which is characterized in that at least part of said cut filaments exhibit an overall cross- sectional shape which is a bi- or multi-filar cross-sectional shape resulting from notionally partially overlapping two or more fiber cross-sectional shapes.
- ,bi- or multi-filar cross-sectional shape for the purposes of the present invention, means a cross-sectional shape which results from notionally partially overlapping two or more fiber cross-sectional shapes.
- a bi-filar cross-sectional shape is a shape resulting from partially overlapping two fiber cross-sectional shapes.
- a tri-filar cross-sectional shape is a shape resulting from partially overlapping three fiber cross-sectional shapes, and so on. This resulting cross-sectional shape will in the following also be referred to as the "overall cross-sectional shape", in contrast to the single cross-sectional shapes which are partially overlapped.
- cross-sectional shape of the staple fiber this is to be understood as referring to the overall cross-sectional shape of the filaments which are constituting the staple fiber according to the invention.
- At least part of, and preferably all of said partially overlapped cross-sectional shapes are essentially circular shapes.
- a bi- or multi-filar cross-sectional shape therefore, exhibits several sections in the form of segments of circles, i.e. those segments of the circular shapes which are not overlapped. Furthermore, the bi- or multifilar cross-sectional shape exhibits notches or indentations in those sections where the circular shapes are notionally overlapped. Said two or more partially overlapped circular shapes may have essentially the same diameter. Alternatively, one or more of said partially overlapped circular shapes may have a higher diameter than the rest of said overlapped circular shapes. This means that the overal resulting cross-sectional shape consists of a mixture of smaller and larger circular shapes which are partially overlapped.
- the Lyocell staple fiber according to the present invention may be produced by spinning a cellulose solution through a spinneret wherein at least part of said spinneret orifices consists of an assembly of two or more holes being located adjacent such that when the solution is extruded through said holes, the filaments extruded from said holes are partially fused to form one fused filament.
- a cellulose solution may be extruded through a certain geometrical arrangement of adjacent circular holes with different diameter.
- inventive staple fiber of this kind exhibits surprisingly high crimp values.
- the high crimp of this embodiment of inventive staple fiber results from the fact that, given a certain overall extrusion velocity and a certain overall draw ratio in the air gap, if filaments are extruded from spinning holes with different diameters, the resulting single filaments which are fused together to form a fused filament have different tensile properties, resulting in a certain amount of natural tension and, hence, natural crimp, in the fused filament.
- the overall cross-sectional shape of the fiber according to the invention is a bi-filar cross-sectional shape resulting from notionally overlapping two essentially circular shapes.
- said overall cross-sectional shape is a tri-filar cross- sectional shape resulting from notionally overlapping three essentially circular shapes.
- Said three overlapped circular shapes may be arranged in a row or in the form of a triangle.
- Said triangle preferably may be an essentially isosceles triangle.
- said overall cross-sectional shape is a quadri-filar cross- sectional shape resulting from notionally overlapping four essentially circular shapes.
- Said four overlapped circular shapes may alternatively be arranged in a row, in the form of a square, a parallelogram or a rhombus, or in the form of a triangle, with one of said circular shapes forming the centre of said triangle.
- Lyocell staple fiber comprising filaments with a bi-, tri- or quadri-filar cross-sectional shape as described above may exhibit a decitex of from 0.5 to 8 dtex. Staple fiber of this decitex is especially useful for textile applications.
- staple fiber according to the present invention may be used in a decitex up to 40 dtex or more.
- the overall cross-sectional shape of the staple fiber according to the present invention may also be a multi-filar cross-sectional shape resulting from notionally overlapping five or more, preferably five or seven essentially circular shapes.
- the fibers typically exhibit ' a decitex of higher than 6 dtex.
- At least one of the partially overlapped cross-sectional shapes of the staple fiber according to the present invention may be a non-circular cross-sectional shape.
- the overall cross-sectional shape of a filament component of the staple fiber according to the invention may be a mixture of partially overlapped circular and non-circular cross- sectional shapes or it may even consist exclusively of partially overlapped non-circular cross-sectional shapes.
- Said non-circular cross-sectional shape may be a multilobal, preferably trilobal, or triangular shape.
- An especially preferred embodiment of the staple fiber according to the present invention is characterized in that essentially all of the cut filaments exhibit essentially the same overall cross-sectional shape.
- Staple fiber according to this preferred embodiment has quite uniform properties in terms of its cross-sectional shape and the various physical and textile properties achieved thereby.
- the filament constituting the Lyocell staple fiber according to the invention may at least partly exhibit a bi- or multi-filar cross-sectional shape which is hollow.
- a hollow structure may be obtained by choosing the spinning parameters in terms of size and distance of the spinning holes such that the extruded single filaments are not completely fused, but rather a gap is left in the centre of the formed fused filament.
- Lyocell staple fiber according to the invention has a significantly higher tenacity than comparable standard Lyocell staple fiber of the same decitex.
- Lyocell staple fiber according to the present invention exhibits a fibre tenacity in conditioned state which is higher by at least 15%, preferably at least 20%, than the fibre tenacity of a comparison Lyocell staple fiber of the same decitex, wherein all cut filaments of said comparison Lyocell staple fiber exhibit an essentially round cross-section.
- Lyocell staple fiber according to the present invention has a surprisingly high flexural rigidity.
- Lyocell staple fiber according to the present invention exhibits a decitex-related flexural rigidity of at least 0.5 mN.mm*/tex 2 , preferably more than 0.6 mN.mm 2 /tex 2 .
- the flexural rigidity is measured by a method developed by the applicant.
- the measured value is displayed as the relation of the gradient of the force to path over a linear measuring range, based on the decitex.
- a conditioned fiber is clamped into a clamping bar and cut with a cutting device to a length of exactly 5 mm.
- the clamping bar is moved upwardly at constant speed by an electric gear. Thereby, the fiber is pressed onto a small sensor plate which is adapted to a force sensor. The stiffer the fiber, the higher is the measured force.
- a process for the manufacture of a Lyocell staple fiber comprises the steps of extruding a solution of cellulose dissolved in an aqueous tertiary amine-oxide through a spinneret exhibiting a plurality of spinneret orifices whereby filaments are formed conducting said filaments via an air gap into a precipitation bath drawing said filaments in said air gap blowing air on said filaments in said air gap precipitating said filaments in said precipitation bath cutting said precipitated filaments in order to form cut filaments,
- spinneret orifices consists of an assembly of two or more holes being located adjacent such that when the solution is extruded through said holes, the filaments extruded from said holes are partially fused to form one fused filament.
- At least part of, and more preferably all of said spinneret holes have a circular shape. All of said holes may have the same diameter.
- one or more of said holes may have a higher diameter than the rest of said holes.
- a cross-sectional shape results which is a mixture of partially overlapped smaller and larger circular shapes, as mentioned above.
- the ratio of the cross-sectional area of the hole(s) with the higher diameter to the hole cross-sectional area of the hole(s) with a smaller diameter is preferably from more than 1:1 to 16:1, preferably 1.6 to 1 to 2.7 to 1.
- said spinneret orifice consists of two holes, each having a circular shape.
- Said spinneret orifice may also consist of three holes, each having a circular shape.
- the three holes may be arranged in a row, resulting in an overall flat, oblong cross-sectional shape of the fused filament.
- said said three holes may be arranged in the form of a triangle, preferably an isosceles triangle. If the diameter of all the spinning holes is the same, or especially if the diameter of the hole in the intersection point of the two equal sides of the isosceles triangle is bigger than the diameter of the other two holes, the resulting overall cross-sectional shape of the fused filament will be of a "teddy-bear"-like nature, two of the partially overlapped circular shapes forming the "ears" of the bear, and the circular shape of the filament spun from the hole at the intersection point of the two equal sides of the isosceles triangle forming the "face".
- Said spinneret orifice may also consist of four holes, each having a circular shape.
- the four holes may be arranged in a row, again resulting in an flat and oblong overall cross- sectional shape of the fused filament.
- said four holes may be arranged in the form of a square, a parallelogram, or a rhombus. If the diameter of all the spinning holes is the same, the resulting overall cross- sectional shape of the fused filament will then resemble a square, a parallelogram or a rhombus, respectively.
- Said four holes may also be arranged in the form of a triangle, with one of said holes forming the centre of said triangle. Again, depending on the diameter of the spinning holes employed, a triangular or "teddy-bear"-like shape may result.
- Said spinneret orifice may also consist of five or more holes, preferably five or seven holes, each having a circular shape.
- holes may also consist of five or more holes, preferably five or seven holes, each having a circular shape.
- many different geometrical arrangements of the holes are possible, resulting in a variety of different cross-sectional shapes of the fused filaments, which will be shown in more detail below with reference to the drawings.
- the overall cross-sectional shape of the fused filaments does not only depend on the number and geometrical arrangement of the spinneret holes employed in said spinneret orifice, but there is also a strong correlation to the size of the hole diameters. I.e. by varying the hole diameters or by providing a geometrical arrangement of holes with different diameters, the resulting cross-sectional shape of the fused filament will be strongly influenced.
- At least one of said holes has a non-circular shape.
- Said non-circular shape may be a multilobal, preferably trilobal, or triangular shape.
- all of said spinneret orifices consist of an identical assembly of holes in terms of the geometrical arrangement, the shape and the size of said holes. I.e. in this embodiment all assemblies of holes have the same geometrical arrangement, and the respective sizes and shapes of the holes within said arrangement are the same for all the assemblies.
- these may preferably be positioned in a plurality of parallel rows. Within each of said rows, all assemblies of holes may be oriented essentially parallel to each other.
- the blowing direction should preferably be essentially parallel to the direction of said row in case of a triangle arrangement of said holes, the blowing direction should preferably be essentially parallel to the direction of one of the base lines of said triangle in case of a square arrangement of said holes, the blowing direction should preferably be essentially parallel to the direction of one of the base lines of said square in case of other geometrical arrangement of said holes, the blowing direction should preferably be essentially parallel to the direction of the main orientation axis of said arrangement.
- the diameter of said holes in said hole assembly may be from 35 to 200 ⁇ m.
- the term "diameter” means the diameter of the circle which can be circumscribed around the non-circular shape.
- holes of different diameter may be employed in one hole assembly.
- the distance from the centre of one hole to the centre of the next adjacent hole in said hole assembly may preferably be from 100 to 500 ⁇ rn, preferably from 150 to 250 ⁇ m. The distance may be adjusted by the skilled artisan in dependency of the desired overall cross- sectional shape of the fused filament. By appropriately adjusting the respective distance between the holes and the respective hole diameters, a staple fiber with a hollow cross- sectional shape may be produced.
- the Lyocell staple fiber according to the present invention may be used in a variety of end- uses, such as medical-, hygeniene-, household textiles-, technical- and apparel applications, especially wound dressings, laparotomy pads, bed pads, tampons, sanitary towels, wipes, incontinence products, pillows, duvets, towels, carpets, pile fabrics, damask, satin, insulation materials, reinforcement fibre for polymers, paper or concrete, textile articles, such as knitted or woven textile articles, shirtings, velour, chinos, cotton-like hand fabrics and garments made thereof.
- end- uses such as medical-, hygeniene-, household textiles-, technical- and apparel applications, especially wound dressings, laparotomy pads, bed pads, tampons, sanitary towels, wipes, incontinence products, pillows, duvets, towels, carpets, pile fabrics, damask, satin, insulation materials, reinforcement fibre for polymers, paper or concrete, textile articles, such as knit
- Lyocell staple fiber according to the invention is useful in any application where a stiffer, crisper, more "cotton-like" hand, or altered thermal and moisture management properties or different optics are desirable.
- Figure 1 shows schematically a spinneret orifice suitable for the production of filaments with a bi-filar cross-sectional shape, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifice.
- Figures 2A) and 2B) show schematically two different spinneret orifices suitable for the production of filaments with tri-filar cross-sectional shapes, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 3A) to 3C) show schematically three different spinneret orifices suitable for the production of filaments with a quadri-filar cross-sectional shape, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 4A) to 4B) show schematically two .further spinneret orifices suitable for the production of filaments with a quadri-filar cross-sectional shape, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 5A) to 5B) show schematically two different spinneret orifices suitable for the production of filaments with a cross-sectional shape composed of five fiber cross-sectional shapes, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 6A) to 6B) show schematically two further spinneret orifices suitable for the production of filaments with a cross-sectional shape composed of five fiber cross-sectional shapes, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 7A) to 7B) show schematically two different spinneret orifices suitable for the production of filaments with a cross-sectional shape composed of seven fiber cross-sectional shapes, the preferable direction of blowing air, and possible overall cross-sectional shapes of filaments spun from said spinneret orifices.
- Figures 8A) to 8D) show two embodiments of producing staple fiber according to the invention with a tri-filar cross-sectional shape.
- Figures 9A) to 9B) show a further embodiment of producing staple fiber according to the present invention with a tri-filar cross-sectional shape.
- Figure 10 shows the tri-filar cross-sectional shape of a Lyocell staple fiber according to the present invention.
- Figure 11 shows the tri-filar cross-sectional shape of a further Lyocell staple fiber according to the present invention
- Fig. 12 shows the quadri-filar cross-sectional shape of a Lyocell staple fiber according to the present invention with a hollow structure.
- a spinneret orifice for the production of Lyocell staple fiber with a bi- filar cross-sectional shape consists of two spinneret holes (left side).
- the holes may be of the same or different diameter.
- An optionally smaller hole diameter is indicated by a smaller circle, and vice versa (this applies for all figures 1 to 7).
- the shaded structures shown on the right side of Figure 1 show the two potential overall cross-sectional shapes of a fused filament spun through the spinneret orifice at the left side.
- a bi-filar cross-section composed of two partially overlapping comparatively large circles results.
- a cross-sectional shape such as the shaded structure shown at the right end of Figure 1 results, wherein one larger circle is partially overlapping with a smaller circle.
- the arrow in Figure 1 indicates the preferred direction in which blowing air should be directed onto the extruded filaments such as to achieve the best results in terms of reproducibility and uniformity of the cross-sectional shapes of the fused filaments.
- Figures 2 to 7 are based on the same principal structure as Figure 1 : On the left side, the geometrical arrangement of a spinneret structure is shown. Right therefrom, several possible fiber cross-sectional shapes are shown (shaded structures), in dependence on the respective hole diameters (small or large). Furthermore, in each of these figures, the preferred direction of the blowing air is indicated.
- this shows a tri-f ⁇ lar cross-sectional shape in a row form, if holes of the same diameter are used.
- the blowing direction preferably is essentially parallel to the row.
- Figure 2B shows possible tri-filar cross-section shapes in a triangular configuration. Especially especially if the hole in the intersection point of the two equal sides of the isosceles triangle is bigger (this is indicated by bold lines in the triangular hole configuration on the left side in Figure 2B), a "teddy-bear"-like shape (the shaded structure in the middle) results.
- the blowing direction preferably is essentially parallel to the base line of the triangle of the spinning holes.
- Figures 3A to 3C) show various embodiments of overall quadri-filar cross-sectional shapes. The preferred blowing direction, indicated by the arrow, is preferably the same for all the shown embodiments 3A) to 3C).
- the blowing direction is preferably essentially parallel to the row.
- the blowing direction is preferably essentially parallel to one of the base lines of the square.
- the preferred blowing direction is essentially parallel to the main orientation axis of the geometrical arrangement of the spinneret holes.
- the preferred blowing direction may be essentially parallel to the main diagonal of the square of Figure 3B), or, in the case of Figure 3C), may be essentially parallel to the axis defined by the connection between the uppermost and the lowermost of the holes.
- Figures 6 and 7 show further embodiments, including cross-sectional shapes resulting from spinning the solution through a spinneret orifice with seven adjacent spinneret holes ( Figure 7) and including hollow cross-sectional shapes.
- Figures 8 and 9 demonstrate the influence of the direction of blowing air on the obtainable cross-sectional shape of the staple fiber of the invention.
- a spinneret with various spinneret orifices each consisting of three holes, arranged in the form of a triangle, were used.
- two of the holes had a diameter of 80 ⁇ m, and one of the holes had a diameter of 120 ⁇ m.
- the distance from the center of the bigger hole to the center of the adjacent holes was 250 ⁇ m each.
- FIGS 8 A, 8B, and 9 A respectively, show the respective spinneret configuration and the direction of the blowing air employed.
- Figures 10 and 11 show the cross-sectional shapes of Lyocell staple fiber according to the present invention, produced from a spinneret configuration as described above with regard to Figures 8 and 9.
- a standard spinning solution of 13% cellulose in NMMO was spun at 11O 0 C through the spinneret configuration as described, and was led through an air gap with a length of around 20 mm.
- Blowing air was directed onto the extruded filaments.
- the blowing direction was essentially parallel to the base line of the triangle defined by the two smaller spinneret holes (cf. Figure 9A).
- spinneret orifices having four holes each were employed. Each hole had a diameter of 100 ⁇ m. The distance from the center of one hole to its neighbouring hole was 500 ⁇ m. The holes were arranged in the form of a rhomboid. The blowing air was directed onto the spun filaments essentially parallel to the main orientation axis of the rhomboid (cf. Fig. 4A). A standard spinning solution of 12,3% cellulose in NMMO was spun at 120°C through the spinneret configuration as described, and was led through an air gap with a length of around 20 mm.
- the resulting staple fiber shows excellent uniform cross- sectional shape and has a remarkably reproducible hollow structure.
- Bacell is a TCF-bleached eucalyptus sulfat pulp produced by Bahia Brasil.
- KZO 3 is a TCF-bleached beech sulfite pulp produced by Lenzing AG.
- the Lyocell staple fiber according to the invention has a significantly higher fiber tenacity than a standard Lyocell staple with the same decitex.
- Lyocell staple fiber according to the present invention produced with a spinneret configuration as described with regard to example 1 and Figures 8 and 9, respectively, was compared with various other types of cellulosic fibers in terms of its decitex-related flexural rigidity. The results are shown in table 2:
- Saiccor is a TCF-bleached eucalyptus sulfite pulp, produced by Saiccor South Africa.
- the Modal fiber in the above example was produced according to the teaching of PCT/AT/000493 (not pre-published).
- the Lyocell staple fiber with a tri-x ⁇ lar "teddy-bear"-like cross-sectional shape has a significantly higher decitex-related flex ⁇ ral rigidity than the other cellulosic fibers observed.
- the decitex-related flexural rigidity of the staple fiber according to the invention was higher than 0.5 mN mm 2 /tex 2 in all of the examples.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Woven Fabrics (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0101506A AT503803B1 (en) | 2006-06-14 | 2006-06-14 | LYOCELL STAPLE FIBER |
PCT/AT2007/000256 WO2007143761A1 (en) | 2006-06-14 | 2007-05-29 | Lyocell staple fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2027314A1 true EP2027314A1 (en) | 2009-02-25 |
EP2027314B1 EP2027314B1 (en) | 2014-12-10 |
Family
ID=38531755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07718467.9A Active EP2027314B1 (en) | 2006-06-14 | 2007-05-29 | Lyocell staple fiber |
Country Status (8)
Country | Link |
---|---|
US (2) | US20100021711A1 (en) |
EP (1) | EP2027314B1 (en) |
JP (1) | JP5231404B2 (en) |
CN (2) | CN101501252B (en) |
AT (1) | AT503803B1 (en) |
ES (1) | ES2531985T3 (en) |
TW (1) | TWI480437B (en) |
WO (1) | WO2007143761A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT507387A1 (en) * | 2008-09-22 | 2010-04-15 | Chemiefaser Lenzing Ag | USE OF LYOCELL FIBERS AND ARTICLES CONTAINING LYOCELL FIBERS |
AT507757B1 (en) * | 2008-12-23 | 2015-06-15 | Chemiefaser Lenzing Ag | CELLULOSIC FORM BODIES WITH NON-CIRCULAR CROSS-SECTION AND THEIR USE IN COMPOSITE MATERIALS |
ES2685502T3 (en) | 2010-05-25 | 2018-10-09 | Neste Oyj | Process and microorganisms for lipid production |
KR101455002B1 (en) | 2013-06-28 | 2014-11-03 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
WO2015152594A1 (en) * | 2014-03-31 | 2015-10-08 | 코오롱인더스트리 주식회사 | Lyocell fiber |
KR102205529B1 (en) * | 2014-03-31 | 2021-01-20 | 코오롱인더스트리 주식회사 | Lyocell Fiber |
JP6453575B2 (en) * | 2014-06-18 | 2019-01-16 | ダイセルポリマー株式会社 | Fiber reinforced resin composition |
KR102211219B1 (en) | 2014-06-30 | 2021-02-03 | 코오롱인더스트리 주식회사 | Lyocell Material with Noncircle Cross Section for Cigarette Filter And Manufacturing Method of the same |
KR102211186B1 (en) | 2014-12-31 | 2021-02-03 | 코오롱인더스트리 주식회사 | Lyocell Material Cigarette Filter and Method for the Same |
EP3385435A1 (en) * | 2017-04-03 | 2018-10-10 | Lenzing Aktiengesellschaft | Nonwoven cellulose fiber fabric with different sets of pores |
EP3385428A1 (en) * | 2017-04-03 | 2018-10-10 | Lenzing Aktiengesellschaft | Nonwoven cellulose fiber fabric with fibers having non-circular cross section |
KR102352034B1 (en) * | 2018-06-29 | 2022-01-14 | 코오롱인더스트리 주식회사 | Non-woven Fiber aggregates containing Lyocell Fibers |
CN112981577A (en) * | 2019-12-12 | 2021-06-18 | 连津格股份公司 | Method for producing modal fibers completely chlorine-free |
CN113089112A (en) * | 2019-12-23 | 2021-07-09 | 连津格股份公司 | Spinning machine for producing cellulose fibres and method for operating the same |
EP4189161A1 (en) | 2020-07-29 | 2023-06-07 | Lenzing Aktiengesellschaft | Use of lyocell fibres |
US11795624B2 (en) | 2021-11-01 | 2023-10-24 | Kimberly-Clark Worldwide, Inc. | Through-air dried tissue products comprising regenerated cellulose fiber |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1773969A (en) * | 1928-09-08 | 1930-08-26 | Celanese Corp | Process of and apparatus for making artificial filaments |
DE7005636U (en) * | 1969-02-20 | 1970-05-21 | Bemberg Societa Per Azioni | CELLULOSE ARTIFICIAL THREAD WITH IMPROVED PROPERTIES. |
US4246221A (en) * | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
JPS6017844B2 (en) * | 1978-03-30 | 1985-05-07 | 旭化成工業株式会社 | Acrylic fiber manufacturing method |
JPS6065108A (en) * | 1983-05-09 | 1985-04-13 | Mitsubishi Rayon Co Ltd | Acrylonitrile filament yarn and its production |
SU1341259A1 (en) * | 1985-11-01 | 1987-09-30 | Предприятие П/Я Г-4132 | Apparatus for forming complex profiled yarn |
JPS6426712A (en) * | 1987-07-20 | 1989-01-30 | Mitsubishi Rayon Co | Production of modified cross-section acrylic fiber by dry spinning |
JP2550807B2 (en) * | 1991-08-19 | 1996-11-06 | 東レ株式会社 | Dry-wet spinneret of acrylic cross-section fiber |
US5108838A (en) * | 1991-08-27 | 1992-04-28 | E. I. Du Pont De Nemours And Company | Trilobal and tetralobal filaments exhibiting low glitter and high bulk |
ATA53792A (en) * | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
US5417909A (en) * | 1992-06-16 | 1995-05-23 | Thuringisches Institut Fur Textil- Und Kunststoff-Forschung E.V. | Process for manufacturing molded articles of cellulose |
JPH07305219A (en) * | 1994-05-10 | 1995-11-21 | Toyobo Co Ltd | Production of polynosic fiber with modified cross-section |
JPH083814A (en) * | 1994-06-16 | 1996-01-09 | Toray Ind Inc | Production of liquid crystal polyester fiber |
US6306334B1 (en) * | 1996-08-23 | 2001-10-23 | The Weyerhaeuser Company | Process for melt blowing continuous lyocell fibers |
JP3844089B2 (en) * | 1996-11-07 | 2006-11-08 | 東洋紡績株式会社 | Blended yarn |
JP3832000B2 (en) * | 1996-11-21 | 2006-10-11 | 東洋紡績株式会社 | Modified cross-section regenerated cellulose fiber and process for producing the same |
GB2324064A (en) * | 1997-04-11 | 1998-10-14 | Courtaulds Fibres | Modified lyocell fibre and method of its formation |
DE29709804U1 (en) * | 1997-05-30 | 1997-08-14 | Hoechst Trevira GmbH & Co KG, 65929 Frankfurt | Flame retardant shingle |
US6773648B2 (en) * | 1998-11-03 | 2004-08-10 | Weyerhaeuser Company | Meltblown process with mechanical attenuation |
JP2000190812A (en) * | 1998-12-28 | 2000-07-11 | Toray Ind Inc | Synthetic fiber for seat belt, and seat belt webbing |
JP2001316936A (en) * | 2000-05-10 | 2001-11-16 | Toyobo Co Ltd | Method for producing solvent spun cellulose fiber |
JP2002201526A (en) * | 2000-12-27 | 2002-07-19 | Japan Exlan Co Ltd | Spinneret |
AU2003249903A1 (en) * | 2002-07-09 | 2004-01-23 | Lenzing Aktiengesellschaft | Process for the manufacture of solid regenerated viscose fibres |
AT411863B (en) * | 2002-09-16 | 2004-07-26 | Chemiefaser Lenzing Ag | BLANKET, PREFERABLY QUILTED BLANKET |
AT412654B (en) * | 2003-03-27 | 2005-05-25 | Chemiefaser Lenzing Ag | MASSIVE REGENERATED STANDARD VISCOSE FIBER |
DE10314878A1 (en) * | 2003-04-01 | 2004-10-28 | Zimmer Ag | Method and device for producing post-stretched cellulose filaments |
AT501931B1 (en) * | 2004-12-10 | 2007-08-15 | Chemiefaser Lenzing Ag | CELLULOSE STAPLE FIBER AND ITS USE |
DE102005024433A1 (en) * | 2005-05-24 | 2006-02-16 | Zimmer Ag | Lyocell staple fibers of increased loop strength are obtained by having tertiary amine oxides still present in the spun filaments during the cutting stage |
-
2006
- 2006-06-14 AT AT0101506A patent/AT503803B1/en not_active IP Right Cessation
-
2007
- 2007-05-29 WO PCT/AT2007/000256 patent/WO2007143761A1/en active Application Filing
- 2007-05-29 CN CN200780029500.6A patent/CN101501252B/en not_active Expired - Fee Related
- 2007-05-29 EP EP07718467.9A patent/EP2027314B1/en active Active
- 2007-05-29 ES ES07718467.9T patent/ES2531985T3/en active Active
- 2007-05-29 JP JP2009514588A patent/JP5231404B2/en not_active Expired - Fee Related
- 2007-05-29 CN CN201410458756.0A patent/CN104357928B/en not_active Expired - Fee Related
- 2007-05-29 US US12/304,622 patent/US20100021711A1/en not_active Abandoned
- 2007-05-30 TW TW096119363A patent/TWI480437B/en not_active IP Right Cessation
-
2015
- 2015-09-30 US US14/871,155 patent/US20170121855A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2007143761A1 * |
Also Published As
Publication number | Publication date |
---|---|
ES2531985T3 (en) | 2015-03-23 |
TWI480437B (en) | 2015-04-11 |
CN104357928B (en) | 2018-11-02 |
US20100021711A1 (en) | 2010-01-28 |
WO2007143761A1 (en) | 2007-12-21 |
US20170121855A1 (en) | 2017-05-04 |
JP2009540139A (en) | 2009-11-19 |
CN101501252A (en) | 2009-08-05 |
CN101501252B (en) | 2014-10-29 |
AT503803B1 (en) | 2008-01-15 |
AT503803A4 (en) | 2008-01-15 |
JP5231404B2 (en) | 2013-07-10 |
EP2027314B1 (en) | 2014-12-10 |
CN104357928A (en) | 2015-02-18 |
TW200815633A (en) | 2008-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2027314B1 (en) | Lyocell staple fiber | |
KR0173007B1 (en) | Cellulose fibres | |
EP0001880B1 (en) | Multicomponent polyester feed yarn for draw-texturing, process for the preparation thereof and process of draw-texturing the same | |
WO2013133056A1 (en) | Manufacturing method for composite spinneret and composite fiber | |
EP0951592B1 (en) | Improvements in filament cross sections | |
US5707737A (en) | Cellulose acetate fiber having non-circular cross section, multi-filaments thereof, and process for the production thereof | |
KR20060022643A (en) | Polytrimethylene terephthalate hollow composite staple fibers and process for producing same | |
KR20020015059A (en) | Acrylonitrile-based synthetic fiber and method for production thereof | |
US6964931B2 (en) | Method of making continuous filament web with statistical filament distribution | |
JP4211125B2 (en) | High water absorption, quick drying polyester X-type cross-section fiber | |
JP2006225767A (en) | Polylactic acid multifilament having modified cross section | |
JP3247286B2 (en) | Cellulose acetate multifilament yarn having a special cross section and method for producing the same | |
JPS607045B2 (en) | Polygonal cross-section porous hollow fiber | |
US20070248819A1 (en) | Cellulosic Fibre of the Lyocell Type | |
JP2004052173A (en) | High-strength polyester monofilament and method for producing the same | |
KR102657272B1 (en) | Spinneret and method of manufacturing fiber webs | |
JP2001181957A (en) | Method for producing nonwoven fabric from continuous filament | |
JPS58149318A (en) | Polyester yarn and production thereof | |
JP4351893B2 (en) | Polypropylene mixed fiber crimped yarn, method for producing the same, and carpet | |
JPH0231126B2 (en) | ||
JPH08260223A (en) | Preparation of fiber | |
JP2011195966A (en) | Highly oriented undrawn yarn for separation and monofilament | |
JPS62104907A (en) | Spinneret for melt spinning | |
JPS58109616A (en) | Production of spun-like textured yarn with stretching property | |
JPH08302521A (en) | Cellulose acetate fiber having specific cross section and its production |
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: 20081212 |
|
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 MT NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
17Q | First examination report despatched |
Effective date: 20091002 |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140714 |
|
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 MT 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 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 700720 Country of ref document: AT Kind code of ref document: T Effective date: 20150115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602007039612 Country of ref document: DE Effective date: 20150122 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2531985 Country of ref document: ES Kind code of ref document: T3 Effective date: 20150323 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 700720 Country of ref document: AT Kind code of ref document: T Effective date: 20141210 Ref country code: NL Ref legal event code: VDEP Effective date: 20141210 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20141210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141210 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: 20141210 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20150311 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: 20141210 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: 20141210 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: 20141210 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141210 |
|
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: 20150410 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: 20141210 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: 20141210 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: 20141210 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: 20141210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20141210 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: 20150410 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602007039612 Country of ref document: DE |
|
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: 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: 20141210 |
|
26N | No opposition filed |
Effective date: 20150911 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141210 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 Ref country code: MC 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: 20141210 Ref country code: LU 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: 20150529 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 |
|
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: 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: 20141210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150529 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20141210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT 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: 20141210 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
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; INVALID AB INITIO Effective date: 20070529 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: 20141210 |
|
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: 20141210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20141210 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220520 Year of fee payment: 16 Ref country code: FR Payment date: 20220523 Year of fee payment: 16 Ref country code: DE Payment date: 20220519 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20220725 Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602007039612 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230529 |
|
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: 20231201 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230529 |
|
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: 20230531 |