EP1299581B1 - Polymer filaments having profiled cross-section - Google Patents

Polymer filaments having profiled cross-section Download PDF

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Publication number
EP1299581B1
EP1299581B1 EP01950881A EP01950881A EP1299581B1 EP 1299581 B1 EP1299581 B1 EP 1299581B1 EP 01950881 A EP01950881 A EP 01950881A EP 01950881 A EP01950881 A EP 01950881A EP 1299581 B1 EP1299581 B1 EP 1299581B1
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EP
European Patent Office
Prior art keywords
yarn
portions
filaments
cross
polymer
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Expired - Lifetime
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EP01950881A
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German (de)
English (en)
French (fr)
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EP1299581A1 (en
Inventor
Peter Michael Lancaster
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Invista Technologies Sarl
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Invista Technologies SARL Switzerland
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Publication of EP1299581A1 publication Critical patent/EP1299581A1/en
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    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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

Definitions

  • This invention relates polymer yarn comprising synthetic polymer filaments with an "open hollow" profiled cross section normal to the longitudinal axis of the filament.
  • the invention further relates to spinneret plates for melt extrusion of the filaments, and to methods of manufacture of the filaments by melt extrusion.
  • Textile fibres or filaments from synthetic polymers are produced for apparel uses typically as partially oriented yarn (POY) and drawn yarn.
  • POY will have an elongation to break greater than about 55% and drawn yarn will have a lower elongation.
  • Circular is the most common cross sectional shape for each filament comprising the multifilament yarns of either type, e.g. POY and drawn yarn.
  • Variation on the individual filament cross sectional shapes include trilobed or 6-lobed, disclosed in Japanese Kokoku patent document 01-20243 (Nihon Ester KK ), the scalloped oval cross section as disclosed by in US Patent 5,834,119 (Roop ) and hollow polyamide filaments with a single longitudinal void, disclosed in US Patent 5,604,036 (Bennett et al. ).
  • the present invention provide a polymer yarn, wherein at least a portion of the yarn comprises profiled filament from synthetic polymer having an "open hollow" cross-sectional shape normal to the longitudinal axis of the filament.
  • the cross-section is dimensioned to prevent a first filament from interlocking with a second filament having the same cross-section as defined in claim 1. This means a region proximate to each tip of the cross-section is wider than a spacing between said regions defining an opening to the open hollow cross-section.
  • the profiled cross sectional shape filaments of the polymer yarn of the invention are provided by the novel shape and design of the extrusion capillary.
  • the filaments of the polymer yarn of this invention are prepared directly by melt extrusion of synthetic polymer through a multi-capillary spinneret plate.
  • the term "open hollow” denotes a generally C-shaped or U-shaped cross-section having a hollow center, and a solid region defining wall portion extending around the hollow center to enclose the hollow center, but with an opening in one side of the wall linking the center to the outside of the filament.
  • the opening is narrower than the diameter of the hollow center, thereby forming a throat or constriction between the hollow center and the outside of the filament.
  • the filament comprises a solid part substantially enclosing a central hollow region.
  • An opening leads from the exterior of the filament into the central hollow region.
  • the solid part includes legs that terminate in feet. Confronting surfaces of the feet define the throat (the narrowest dimension) of the opening.
  • the throat of the opening subtends a radial angle alpha ( ⁇ ) of not more than 90°, more preferably not more than 75° and most preferably from 10° to 60°.
  • the radial angle alpha ( ⁇ ) is that angle defined between two rays R 1 and R 2 originating at a point C.
  • the point C is that point lying on the interior surface of the solid part of the filament that lies farthest from a reference line R 3 tangentially connecting the tips of the feet.
  • Each ray R 1 , R 2 extends from the point C and lies tangent to a point on the confronting surfaces of the feet defining the throat of the opening D.
  • the solid part subtends a radial angle equal to 360° minus angle alpha (360° - ⁇ ).
  • the solid part of the cross-section subtends a radial angle of at least 270°. More preferably the solid part subtends a radial angle of at least 300°.
  • the filaments of the polymer yarn according to the present invention are adapted to prevent inter-engagement or stacking of the filaments. For example, hook-like engagement of two cross sections arising from insertion of an end of the solid part of a first filament cross-section through the opening in the cross-section of a second filament is prevented.
  • This provision can be achieved as already described, by making the solid portion of the cross-section subtend a large radial angle, whereby the opening in the filament cross-section is very small.
  • the ends of the solid part of the cross section may be enlarged to inhibit insertion into the opening of other filaments.
  • the solid portion of the cross-section in the filaments of the polymer yarn according to the present invention forms a single continuous curve.
  • the cross-section comprises a "central arcuate" or base portion having first and second ends and two side or “leg” portions.
  • the leg portions extending in substantially side-by-side relationship from the first and second ends of the central arcuate portion.
  • the filament cross sectional shape is characterized by a central arcuate portion 1 (extending horizontally in Figure 1 ) and first and second, generally parallel, elongated leg portions 2,3 (extending vertically in Figure 1 ) joined to the central arcuate portion.
  • the distal portion of each leg (2,3) opposite the juncture with the central arcuate portion 1 defines an enlarged foot portion 4.
  • Each foot portion 4 is characterized by dimension F, the length of the foot, as shown in Figure 1 .
  • the profiled filament cross-section is open in the center. This open portion is bounded on three sides by the leg portions 2,3 and central arcuate base portion 1.
  • the feet portions 4 are oriented in a substantially side-by-side relationship defining an aperture between confronting surfaces of the foot portions with dimension D leading to the open portion, as shown in Figure 1 .
  • the dimension D is less than dimension F.
  • the polymer used to form the profiled polymer filament of the polymer yarn according to the present invention is a polyamide. More preferably, the polyamide polymer has a relative viscosity, by a formic acid method, greater than 40, and still more preferably the relative viscosity of the polyamide by a formic acid method is in the range of 46 to 56.
  • the polyamide is selected from the group consisting of nylon 66 and nylon 6 and copolyamides.
  • the single filament linear density is from 0.5 to 20 dtex, and more preferably it is from 2 to 10 dtex. Most preferably it is less than 4 dtex.
  • the filament cross-sectional shape is substantially constant along the length of the filament.
  • the filament non-uniformity is less than 1 Uster%.
  • the profiled filaments of the polymer yarn according to the present invention provide a lighter unit weight yarn, particularly after texturing by AJT (air jet texturizing) or FTT (false twist texturizing).
  • the yarn incorporates high free volume of air space.
  • the volume of air space contributes to enhanced thermal retention of fabrics and garments produced from the yarn.
  • the yarn when knitted or woven into fabrics provides a less dense fabric than similarly constructed fabrics from solely circular cross section filaments. Furthermore, the yarn exhibits a high moisture wicking capacity.
  • the yarn of the present invention comprises at least 10% by weight of the profiled filaments described, more preferably at least 25% of such filaments, still more preferably at least 50% of such filaments and most preferably it consists essentially of such filaments.
  • the present invention further provides an article comprising at least a portion of the yarn according to the present invention.
  • the article comprises a textile fabric that is knitted or woven from a yarn according to the present invention.
  • a further aspect of the present invention is a spinneret for the production of the profiled open hollow filaments according to the present invention by melt extrusion of polymer into filaments.
  • the spinneret comprises a plate having upper and lower surfaces connected by an assembly of capillaries.
  • the shape, size and configuration of the capillaries are adapted to the melt spinning of filaments according to the present invention.
  • each capillary comprises two adjacent segments as in Figure 3a , whereby the open hollow filament cross section longitudinal to the axis of the filament is obtained as the molten polymer streams from each segment coalesce at a point between the segments or as is the case in the present invention
  • each capillary has an open hollow transverse cross-section as in Figure 3b .
  • a spinneret plate for the production of the profiled open hollow filaments is one with each capillary comprised of two segments in Figure 3a .
  • Each segment is comprised of a straight length portion 30 having at each end a junction with a pair of projecting portions.
  • the pair of projecting portions are of equal area and each comprise a straight portion 31,32 terminating in a round portion 33,34.
  • At the second (opposite the first) end are a pair of unequal area projecting portions.
  • the first unequal area projecting portion is comprised of straight portion 35 and round portion 36 and the second unequal area projecting portion is comprised of straight portion 37 and round portion 38. Therefore, each segment of the capillary has three equivalent projecting portions, two on one end and one on the opposite end.
  • each capillary segment is the mirror image of the other segment. More preferably, each segment is the nonsuperimposable mirror image of the other segment, for example as illustrated by Figure 3a .
  • the nonsuperimposable mirror image relationship means that each segment possesses handiness in the same way as do human left and right hands.
  • the open hollow filament cross section normal to the longitudinal axis of the filament is obtained as the molten thermoplastic polymer streams from each capillary segment coalesce at a point between projecting portions of the two segments. That is, the open hollow filament cross section of the invention is formed as the molten polymer stream coalesces between confronting round portions 38 of the left and right capillary segments shown in Figure 3a .
  • the capillary illustrated by Figure 3b is a spinneret geometry cross section for the production of profiled open hollow filaments.
  • Each capillary has a cross sectional shape comprising a first straight portion 40 with a first end and a second end, opposite each other. Bifurcating from the first end of the first straight portion 40 are a second straight portion 48 and a third straight portion 50.
  • the second straight portion 48 terminates in a round portion 49 and the third straight portion 50 extends to a point of bifurcation; wherein a fourth straight portion 53 and a fifth straight portion 52 extend from this point of bifurcation.
  • the fourth and fifth straight portions having unequal areas and each terminate in round portions 54 and 51.
  • bifurcating from the second end of the first straight portion are a sixth straight portion 41 and a seventh straight portion 43.
  • the sixth straight portion 41 terminates in a round portion 42 and the seventh straight portion 43 extends to a point of bifurcation; wherein an eighth straight portion 46 and a ninth straight portion 44 extend from said point of bifurcation, the eighth and ninth straight portions having unequal areas and each terminate in round portions 45 and 47.
  • the invention provides a process for making drawn yarns and partially oriented yarns (POY) with a modified filament cross section according to the present invention.
  • the process comprises extruding a polyamide melt, typically nylon 66 or nylon 6, of 40 to 60 RV (measured in formic acid), and preferably 48 to 52 RV to form a plurality of filaments.
  • the spinneret according to the invention is maintained at a temperature selected from the range 245 to 295°C, more preferably it is 280°C.
  • Multiple filaments extruded through the spinneret are cooled in a cross flow of air to form solid filaments. These filaments may be treated with oil, converged, interlaced and drawn, or remain undrawn, prior to winding up a multifilament yarn at a speed greater than 3000 meters per minute (m/min).
  • a drawn yarn is prepared by following path A.
  • the melted polymer 10, a polyamide, is pumped to the spin pack 20 and forced through spinneret plate.30 to form filaments 40.
  • the emerging filaments are cooled by a cross flow of air 50, having an air velocity of about 0.15 to 0.5 meters per minute.
  • the cooled filaments are converged into a yarn 60, and an oil and water finish is preferably applied to the resulting yarn bundle at 70.
  • the yarn 60 is forwarded through a first air interlace jet 80 to become intermingled yarn 90.
  • Yarn 90 is forwarded to a first godet 92 (the feed roll) and its associated separator roll, wrapping several times to prevent slippage, and then to a second godet 94 (the draw roll) and its associated separator roll.
  • the draw roll 94 is moving at a surface speed of 60 to 100%, preferably 80%, greater than that of the feed roll 92.
  • the yarn bundle is thereby drawn (elongated), preferably by a total factor of about 1.8, reducing the overall yarn titer to form yarn 100.
  • the drawn yarn 100 is preferably treated by a relaxation device 110 to set the draw and to relax the yarn as is conventionally practised in the art. Any known relaxation device may be employed, including steam, heated fluid, hot tube, hot shoe, heated rolls.
  • the relaxed yarn bundle 120 is optionally passed through a second interlace jet 130 and optionally oiled before the relaxed yarn 140 is wound up on a tube 150 at a winding speed greater than 3000 meters per minute, more preferably about 3800 meters per minute.
  • the resulting drawn yarn has an elongation of 25 to 45%, preferably 40 to 45%, and a tenacity of 35 to 45 cN/tex.
  • a partially oriented yarn is prepared by following path B.
  • the melted polymer 10, a polyamide, is pumped to the spin pack 20 and forced through spinneret plate 30 to form filaments 40.
  • the emerging filaments are cooled by a cross flow of air 50, having an air velocity of about 0.15 to 0.5 meters per minute.
  • the cooled filaments are converged into a yarn 60, and an oil and water finish is preferably applied to the resulting yarn bundle at 70.
  • the yarn 60 is forwarded through a steam atmosphere containing interfloor tube 75, as is known in the art.
  • the steam treated yarn 85 is intermingled at 80 partially wrapped around godet 82 and godet 84, which control any variations in winding tension the yarn may experience.
  • the yarn 115 is wound up as a package of yarn on tube 160 at a speed of about 3800 meters per minute.
  • the POY produced preferably has an elongation of 55 to 85%, preferably 75%, and a tenacity of 25 to 40 cN/tex, preferably about 30 cN/tex.
  • Water Wicking Test Method The principle of the method involves suspending a strip of fabric vertically with its lower end immersed in water. The height to which the water rises up the fabric in measured at fixed time intervals. The fabric samples taken are 300 mm long and 25 mm wide. The samples are conditioned at a relative humidity of 85% +/-5% and 20°C +/-2°C for 16 hours. The maximum rise height of the 20°C +/-2°C water is measured after two minutes. The height is measured from the surface of the water to the point on the fabric of maximum water rise. The mean value of three measurements is reported for each perpendicular fabric direction. Fabric Thickness Test Method : The fabric thickness is the mean distance between upper and lower surfaces of the material measured under a specified pressure.
  • the fabric samples are conditioned as for water wicking.
  • the measuring apparatus used is a Shirley Thickness Gauge with 50 cm 2 presser foot. The pressure foot is allowed to fall under its own momentum onto the fabric. The measurement is repeated ten times and the mean and standard deviation are reported to the nearest 0.05 mm.
  • a first multifilament yarn (Yarn 1A) of 96 dtex and 26 filaments was spun as a POY using the apparatus shown schematically in Figure 5 and a spinneret plate with two segment capillaries according to Fig 3a .
  • Nylon 66 polymer chip of 49.4 RV by the formic acid method, was melted 10 and extruded through a filter pack 20 and through a spinneret plate 30 with 26 capillaries of the segmented cross sectional shape shown in Figure 3a at a spinneret temperature of 280°C.
  • the emerging filaments 40 were cooled by a cross flow of air 50, with an air velocity of 0.45 meters per minute.
  • the quench air was directed, with reference to Fig. 3a , so as to first encounter confronting lobes 38 of the two segment capillary.
  • the cooled filaments 60 were converged into a yarn at 70 where an oil and water finish was applied to the resulting yarn bundle.
  • the converged yarn with the finish applied was forwarded along Path B in Figure 5 .
  • the yarn was passed through a steam atmosphere containing interfloor tube 75.
  • the steam treated yarn 85 was intermingled with apparatus 80.
  • the intermingled yarn 115 was wound up as a package of yarn on tube 160 at a speed of 3800 meters per minute.
  • the POY produced in this way has a yarn linear density of 96 decitex, an elongation to break of about 75% and a tenacity of 30 cN/tex.
  • the cross section of the yarn is shown in Figure 4a .
  • a second multifilament partially oriented yarn (Yarn 1B) of 96 dtex and 26 filaments was spun exactly as the first POY using the apparatus shown schematically in Figure 5 .
  • Yarn 1B a spinneret plate with capillaries according to Fig 3b was used. The elongation and tenacity properties were the same as for the first POY.
  • the cross section of the Yarn 1B is shown in Figure 4b .
  • a comparative multifilament yarn (Yarn 1C) of 96 dtex and 26 filaments was spun in exactly the same way as the first yarn, except for replacing the spinneret plate with one having 26 "circular cross sectional" shaped capillaries.
  • the thermal transmittance test method was essentially that of ASTM D1518-85 (as reapproved 1990). This method measures the time rate of heat transfer from a warm, dry, constant-temperature, horizontal flat-plate up through a layer of the knitted cardigan test material to a relatively calm, cool atmosphere. Thermal resistance was measured and the thermal insulation or CLO value calculated.
  • the "CLO” is a unit of "clothing thermal resistance" in ASTM D1518 and equal to 0.155(°C m 2 W -1 ).
  • the base temperature was 25°C (T 1 ) and the head plate, temperature was 35°C (T 2 ). There was minimal pressure applied to the cardigan knit, 260 Nm -2 during the test procedure. Each sample was tested three times to give the mean result reported in Table 1 below.
  • the primary heater of the texturing machine was 220°C, no secondary heater was used.
  • a draw-textured yarn of 78 decitex and 26 filaments (78f26) was prepared with the texturing machine's 6 mm solid ceramic discs configured to 1/7/1 smooth/working/smooth.
  • the 78f26 yarns were circular knitted into 28 gauge plain interlock fabrics, scoured, dyed and heat set. Fabric samples of 300 mm by 25 mm were taken for water wicking tests.
  • a drawn yarn of 192 decitex and 52 filaments was spun with the apparatus of Figure 5 and using the spinneret plate with 52 capillaries of the cross sectional shape of Figure 3a .
  • Nylon 66 polymer of 49.4 RV (by the formic acid method) was melted 10, extruded through a polymer filter pack 20 and then through the above spinneret 30 maintained at a temperature of 280°C.
  • the extruded filaments 40 were cooled by a cross flow of air 50 flowing at 0.4 meters per minute.
  • the cross flow of air 50 was directed to first encounter confronting lobes 38 of the two segment capillary shown in Fig. 3a .
  • the cooled filaments were converged into a yarn bundle 60 with oil and water application and forwarded along alternative Path A.
  • the yarn was intermingled with an air jet 80, as typically practised in the art.
  • the intermingled yarn 90 was then fed via feed roll 92 and associated separator roll (making several wraps on the roll to prevent slipping) to a second godet 94 and associated separator roll (the draw roll), moving at a surface speed 80% greater than that of the feed roll 92.
  • the intermingled yarn bundle 90 was drawn, by a total factor of 1.8, reducing the overall yarn titer.
  • the drawn yarn 100 was treated by a steam jet 110 to set the draw and to relax the yarn.
  • the relaxed yarn bundle 120 was passed through a second interlace jet 130 and then the yarn 140 was wound up on a tube 150 at a speed of 3800 meters per minute.
  • This process provided cakes of fully drawn yarn (FDY) with a yarn linear density of 192 decitex, a breaking elongation of 42.8%, tenacity of 41 cN/tex.
  • the yarn in dry form had an RV of 50.3 by the formic acid method.
  • Filaments of this 52 filament yarn have a cross sectional shape normal to the longitudinal axis which is substantially similar to those filaments shown in Figure 4a .
  • Yarn 3A was used as the weft yarn of a woven fabric of 3/1 twill weave where the warp yarns were 78 decitex (51 circular filaments). Weaving and fabric finishing details are given in Table 3. As a comparative example, a fully drawn yarn of 192 decitex and 52 filaments was spun in exactly the same way as above but using a spinneret plate with "circular cross section" capillaries, this yarn was called Yarn 3B. A second fabric sample was woven using Yarn 3B in the weft as above. Weaving and fabric finishing details are given in Table 3. The two fabrics were finished identically in greige, dyed and heat-set form.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
EP01950881A 2000-07-10 2001-07-05 Polymer filaments having profiled cross-section Expired - Lifetime EP1299581B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0016926A GB2364667A (en) 2000-07-10 2000-07-10 Polymer filaments having open hollow cross-section
GB0016926 2000-07-10
PCT/US2001/021251 WO2002004720A1 (en) 2000-07-10 2001-07-05 Polymer filaments having profiled cross-section

Publications (2)

Publication Number Publication Date
EP1299581A1 EP1299581A1 (en) 2003-04-09
EP1299581B1 true EP1299581B1 (en) 2008-07-16

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EP01950881A Expired - Lifetime EP1299581B1 (en) 2000-07-10 2001-07-05 Polymer filaments having profiled cross-section

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EP (1) EP1299581B1 (ja)
JP (1) JP2004502882A (ja)
KR (1) KR100761640B1 (ja)
CN (1) CN1291075C (ja)
AT (1) ATE401434T1 (ja)
AU (1) AU2001271834A1 (ja)
BR (1) BR0112503B1 (ja)
CA (1) CA2410555C (ja)
DE (1) DE60134856D1 (ja)
ES (1) ES2310184T3 (ja)
GB (1) GB2364667A (ja)
MX (1) MXPA03000149A (ja)
PL (1) PL205183B1 (ja)
SK (1) SK162003A3 (ja)
TW (1) TW513493B (ja)
WO (1) WO2002004720A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE49773E1 (en) 2013-02-14 2024-01-02 Nanopareil, Llc Hybrid felts of electrospun nanofibers

Families Citing this family (4)

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DE102004036030A1 (de) * 2004-07-23 2006-02-16 Wabco Gmbh & Co.Ohg Faden für akustisches Dämmmaterial, insbesondere für Geräuschdämpfer in Drucklufteinrichtungen
KR101508847B1 (ko) * 2013-10-15 2015-04-08 도레이첨단소재 주식회사 벨벳 직물용 원사 및 그 제조방법
WO2018184378A1 (zh) * 2017-04-07 2018-10-11 优彩环保资源科技股份有限公司 高强高伸复合功能纤维
CN112430871A (zh) * 2020-09-30 2021-03-02 福建凯邦锦纶科技有限公司 一种低卷曲高模瑜伽面料锦纶弹力丝的生产方法

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GB985295A (en) * 1960-04-22 1965-03-03 Celanese Corp Hollow artificial filaments and spinnerets for their production
CA1035496A (en) * 1973-10-12 1978-07-25 Upjohn Company (The) High temperature resistant aromatic copolyimide fibers
JPS5951630B2 (ja) * 1977-01-18 1984-12-14 大和紡績株式会社 羽毛様ポリエステル繊維
JPS56169813A (en) 1980-05-29 1981-12-26 Toyobo Co Ltd Synthetic fiber for wadding
JPS58214549A (ja) * 1982-06-03 1983-12-13 帝人株式会社 機能耐久性に優れた合成繊維マルチフイラメント布帛
JPS6183316A (ja) * 1984-09-28 1986-04-26 Nippon Ester Co Ltd ポリエステル系複合繊維
JP2708428B2 (ja) * 1987-08-21 1998-02-04 帝人株式会社 ポリエステル仮撚捲縮加工糸の製造法
JP2842905B2 (ja) * 1989-12-01 1999-01-06 帝人株式会社 多葉断面弾性フィラメント
JPH08246225A (ja) * 1995-03-06 1996-09-24 Kuraray Co Ltd 異形断面中空繊維およびその製造方法
CA2194225A1 (en) * 1995-05-01 1996-11-07 Hiroyuki Mori Cellulose acetate fiber having noncircular section, assembly thereof, and process for preparing the same
JP3846955B2 (ja) * 1997-01-28 2006-11-15 旭化成せんい株式会社 特殊断面ポリエステル繊維

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE49773E1 (en) 2013-02-14 2024-01-02 Nanopareil, Llc Hybrid felts of electrospun nanofibers

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Publication number Publication date
CA2410555A1 (en) 2002-01-17
TW513493B (en) 2002-12-11
DE60134856D1 (de) 2008-08-28
ATE401434T1 (de) 2008-08-15
CA2410555C (en) 2010-05-25
SK162003A3 (en) 2004-06-08
BR0112503B1 (pt) 2011-06-14
PL362054A1 (en) 2004-10-18
BR0112503A (pt) 2004-08-24
KR100761640B1 (ko) 2007-10-04
EP1299581A1 (en) 2003-04-09
AU2001271834A1 (en) 2002-01-21
PL205183B1 (pl) 2010-03-31
KR20030020918A (ko) 2003-03-10
GB2364667A (en) 2002-02-06
JP2004502882A (ja) 2004-01-29
MXPA03000149A (es) 2003-09-22
CN1500161A (zh) 2004-05-26
WO2002004720A1 (en) 2002-01-17
CN1291075C (zh) 2006-12-20
ES2310184T3 (es) 2009-01-01
GB0016926D0 (en) 2000-08-30

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