WO2004044293A1 - Entangled bicomponent yarn and process for making same - Google Patents

Entangled bicomponent yarn and process for making same Download PDF

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Publication number
WO2004044293A1
WO2004044293A1 PCT/US2003/021615 US0321615W WO2004044293A1 WO 2004044293 A1 WO2004044293 A1 WO 2004044293A1 US 0321615 W US0321615 W US 0321615W WO 2004044293 A1 WO2004044293 A1 WO 2004044293A1
Authority
WO
WIPO (PCT)
Prior art keywords
yarn
filaments
poly
jets
entangled
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.)
Ceased
Application number
PCT/US2003/021615
Other languages
English (en)
French (fr)
Inventor
John A. Rodgers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
INVISTA TECHNOLOGIES SÀRL
EIDP Inc
Original Assignee
INVISTA TECHNOLOGIES SÀRL
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by INVISTA TECHNOLOGIES SÀRL, EI Du Pont de Nemours and Co filed Critical INVISTA TECHNOLOGIES SÀRL
Priority to JP2004551421A priority Critical patent/JP4575778B2/ja
Priority to BR0315717-2A priority patent/BR0315717A/pt
Priority to AU2003253869A priority patent/AU2003253869A1/en
Priority to EP03811191A priority patent/EP1560963A1/en
Publication of WO2004044293A1 publication Critical patent/WO2004044293A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04Blended or other yarns or threads containing components made from different materials
    • D02G3/045Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02JFINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/08Interlacing constituent filaments without breakage thereof, e.g. by use of turbulent air streams
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/56Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads elastic

Definitions

  • This invention relates to polyester bicomponent continuous filaments, more particularly to yarns of such filaments which have high crimp level, high node frequency and node interval constancy, and to a process for making such yarns.
  • United States Patents US2985995 and US3115695 describe jets that can be used to entangle 'flat' fibers
  • United States Patent US4100725 discloses tightly entangled yarns with long entanglement nodes, but such yarns can have inadequate stretch properties.
  • Polyester bicomponent yarns having high crimp levels, little or no twist, and frequent entanglement nodes at highly constant intervals are still needed, as is a process to make them.
  • the present invention provides an entangled continuous filament yarn comprising at least two bicomponent filaments each comprising poly(trimethylene terephthalate) and poly(ethylene terephthalate), wherein the entangled yarn has a node frequency of about 40 to 50 nodes/m, a Crimp Potential of at least about 40%, substantially no twist, and a standard deviation of intervals between nodes of no more than about 1.1 cm.
  • the invention also provides, in a second process aspect, a process for making such a yarn comprising the steps of providing at least two bicomponent continuous filaments each comprising poly(trimethylene terephthalate) and poly(ethylene terephthalate) and having a Crimp Potential of at least about 40%, wherein the filaments are selected from the group consisting of fully drawn and fully oriented; providing at least two jets, each jet comprising a yarn slot, two channels for directing air at the filaments, a first imaginary plane defined by the channels, and a second imaginary plane perpendicular to the yarn slot, wherein an angle ⁇ between the first and second imaginary planes is about -5° to -30°; and passing the filaments through the jets in series at an overfeed of about 2 to 6% to entangle the yarn.
  • FIGURES Figure 1 illustrates in cross-section a jet that can be used in the process of the invention.
  • Figure 2 schematically illustrates a detail of a cross-section of a jet that can be used in the process of the invention.
  • Figure 3 shows fluid orifices of a jet that can be used in the process of the invention.
  • bicomponent continuous filament yarns comprising poly(ethylene terephthalate) and poly(trimethylene terephthalate) can be made with high entanglement levels while retaining high crimp levels, a surprising combination. Further, the intervals between nodes in such entangled yarns are very constant, and the yarn also exhibits substantially no twist. Such entangled yarns are useful in making woven and knit fabrics wherever stretch characteristics are desirable, for example in apparel, accessories, upholstery, and the like.
  • IV means intrinsic viscosity.
  • Fully drawn filament means a bicomponent filament which has been drawn and heat-treated so that it exhibits useful crimp values and is suitable for use without further drawing, for example in weaving, knitting, and the preparation of nonwovens.
  • Fully oriented filament means a filament which has been spun at sufficiently high spinning speed and tension that it requires no drawing or heat-treating to be suitable for use or to exhibit useful crimp values.
  • Drawal speed means the speed of feed rolls used during fiber spinning, which rolls are positioned between the quench zone and the draw rolls.
  • “Countercurrent” or “countercurrently” means not perpendicular to the direction of yarn travel and not with the direction of yarn travel; in other words: against the direction of yarn travel.
  • "Bicomponent filament” means a filament comprising poly(ethylene terephthalate) and poly(trimethylene terephthalate) intimately adhered to each other along the length of the filament, so that the filament cross- section is for example a side-by-side, eccentric sheath-core or other suitable cross-section from which useful crimp can be developed.
  • Such filaments are non-elastomeric in that they do not have a break elongation in excess of 100% independent of any crimp. Rather, they rely on spiral crimp for their elasticity, spontaneously developed by thermal treatment of the filaments.
  • a "snowman" cross-sectional shape can be described as a side-by- side cross-section having a long axis, short axes substantially perpendicular to the long axis, and at least two maxima in the length of the short axes when plotted against the long axis.
  • the poly(ethylene terephthalate) (“2G-T”) and poly(trimethylene terephthalate) (“3G-T”) of which the filaments in the yarn of the invention are comprised have different intrinsic viscosities.
  • 2G-T can have an IV of about 0.45-0.80 dl/g and 3G-T can have an IV of about 0.85- 1.50 dl/g.
  • the ratio of 2G-T to 3G-T can be about 70:30 to 30:70.
  • polyesters in the filaments in the yarn of the invention can be copolyesters, and such copolyesters are included in the meanings of poly(ethylene terephthalate) and poly(trimethylene terephthalate), provided such variants do not have an adverse affect on the amount of crimp in the entangled yarn or on the filaments' processing characteristics..
  • the process of the invention can be used to make an entangled continuous filament yarn that has a node frequency of about 40 to 50 nodes/m and a Crimp Potential of at least about 40% (typically about 55 to 160%).
  • the entangled yarn has a Crimp Potential that is reduced by no more than about 25% relative, compared to the Crimp Potential of the filaments as provided (that is, unentangled).
  • operation of the process can make a yarn that has a standard deviation of the interval between nodes of no more than about 1.1 cm.
  • the polyesters can be copolymers, as described elsewhere herein.
  • the filaments as provided have a Crimp Potential of at least about 40%.
  • Figure 1 shows a cross-section schematic view of a jet that can be used in the process
  • continuous filaments 3a are fed to yarn slot 4 between jet body 1 and plate 5, and entangled yarn 3b emerges in the direction of the arrow.
  • Fluid channel pair 2a or fluid channel pair 2b directs the entangling fluid medium, typically air, against the yarn. Only one member of each channel pair is shown in Figure 1.
  • Each fluid channel can have an internal diameter of about 1.4 to 1.7 mm. Only one channel pair is generally present in jet body 1 ; pairs 2a and 2b indicate alternative arrangements when the jet is oriented in the 'forward' or 'reverse' direction, respectively.
  • channel pair 2a directs the air against the yarn in somewhat the same direction as yarn travel.
  • channel pair 2b directs the air against the yarn in somewhat the opposite direction to yam travel.
  • Each channel pair 2a and 2b defines imaginary planes 7a and 7b, respectively.
  • Angles y are between imaginary planes 7a or 7b and imaginary plane 6, which is perpendicular to yarn slot 4.
  • a positive value of angle ⁇ indicates 'forward' orientation, and a negative value indicates 'reverse' orientation.
  • the present process employs jets having values of ⁇ of -5° to -30° in order to gain higher node frequency and constancy.
  • Jets having values of y of -10° to -25° are preferred.
  • Figure 2 shows at right angles to Figure 1 the relationship among jet body 1 , continuous filament yarn 3 (in cross-section), channel pair 2 (which can be either channel pair 2a or channel pair 2b of Figure 1), yarn slot 4, and plate 5.
  • Width "w" of yarn slot 4 can be about 1.2 to 2.5 mm.
  • Angle ⁇ can be about 80° to 100°.
  • Figure 3 shows that the exit orifices of the members of channel pair 2 as they exit jet body 1 are separated by a distance 'x', which can be about 2.5 to 3.5 mm.
  • the yarn slot of each jet (see Figures 1 and 2) is typically aligned with the axis of the moving yarn for higher node frequency but can optionally be canted slightly off-axis.
  • the jet parts can be of glazed ceramic, for example of alumina, to reduce abrasion of the yarn and to extend the useful life of the jet.
  • the continuous filaments are supplied to the jet(s) at an overfeed of about 2 to 6 %, typically 3% to 5% and can be passed through the jets at a speed of about 1200 to 3000 m/min.
  • the entangling fluid can be air, which can be supplied at a pressure of about 45 to 125 psig (310 to 860 kPa).
  • angle ⁇ can be made more negative, and the air pressure supplied to the jets, the yarn slot width, and the air channel diameter can be increased, to attain the desired node frequency and constancy.
  • a twisting step is unnecessary in the process of the invention, and lack of intentional twist is preferred in order not to add unnecessary expense and to improve downstream processing.
  • the process can be coupled with fiber spinning or operated separately from fiber spinning, as a split process.
  • a finish can be applied to the filaments before they enter the jets, for example at a level of 0.2 to 1.0 wt%, based on filament weight.
  • the bicomponent fiber made by the present process exhibits some crimp.
  • Full crimp development can be attained under dry heat or wet heat conditions in a substantially relaxed state. For example, dry or wet (steam) heating in a tenter frame and wet heating in a dyebath or jig scour can be effective.
  • the frequency of entanglement nodes and standard deviation of the interval between nodes in the samples made in the Examples were determined according to ASTM Test Method D4724, using a "Rapid 400" instrument manufactured by Lenzingtechnik.
  • the entanglement level of a multi-filament yarn was determined by an instrument which inserted a wheel-mounted pin into a sample of moving yarn. Nodes were recorded as a tension increase above a preselected level, as detected by a tensiometer. Since the yarns were 300 denier (333 dtex), the trip force was set at the recommended 25 g. Unless otherwise noted, the following instrument settings were used: Match Steps 50, Tension Scan Interval 1 , and Tension Response Interval 5. Data was obtained on 2000 node intervals or 100 meters, whichever point was reached sooner.
  • Crimp Potential (“CP") and Crimp Shrinkage (“CS”) were determined by measuring the length of a yarn skein under standard loads before and after dry heat treatment.
  • a 7000 denier (7778 dtex) (measured as doubled), 1 ⁇ -inch wide skein sample was prepared from the yarn to be tested.
  • the skein sample was mounted on the magazine of a textured yarn tester (Texturmat-ME, Lawson Hemphill Sales Co.), and a 700g (100mg/d) load was applied for at least 10 seconds. The length of the skein was determined and reported as Li .
  • Crimp Contraction % is calculated as 100 x (L3 - L2)/L3
  • Crimp Potential is related to Crimp Contraction according to the following formula:
  • a Crimp Potential value of 39% is equivalent to a Crimp Contraction value of 30%.
  • Continuous filament bicomponent yarns were melt-spun from poly(ethylene terephthalate) (0.54 dl/g IV, Crystar® 4415, a registered trademark of E. I. du Pont de Nemours and Company) and poly(trimethy!ene terephthalate) (1.02 dl/g IV, Sorona®, a registered trademark of E. I. du Pont de Nemours and Company), subjected to cross- flow quench, withdrawn at 353 ypm (322m/min), drawn 5.1X, heat-treated at 170°C, and wound up at 1720 yards/min (1575 m/min) with a winding tension of about 0.1 to 0.2 gpd (0.09 to 0.18 dN/tex).
  • the weight ratio of 2G-T to 3G-T was 60:40.
  • the yarns had 68 filaments, a total decitex of 333, and a 'snowman' cross-section.
  • Samples 2 through 6 were passed through two jets in series.
  • the entangling fluid was air supplied at about 20°C and 54 psig (372 kilopascal) pressure.
  • the jets were also operated at ambient temperature, that is, about 20°C.
  • the yarn speed at the jets was about 1740 yard/min (1590 m/min), which represented 3.2% overfeed.
  • Continuous bicomponent filaments were melt-spun from poly(ethylene terephthalate) (0.54 dl/g IV, Crystar® 4415, a registered trademark of E. I. du Pont de Nemours and Company) and polyftrimethylene terephthalate) (1.02 dl/g IV, Sorona®, a registered trademark of E. I. du Pont de Nemours and Company), subjected to cross- flow quench, withdrawn at 360 ypm (329 m/min), and simultaneously drawn and heat-treated at 170°C.
  • the weight ratio of 2G-T to 3G-T was 60:40.
  • the yarn had 68 filaments, a total decitex of 333, and a snowman cross-section.
  • the jets had a yarn slot width "w" of 0.040 inches (1.02 mm), an air channel diameter of 0.050 inches (1.27 mm), an angle ⁇ of 0°, an angle ⁇ of 90°, and a distance 'x' between the channel exits of 0.080 inches (2.03 mm).
  • the windup speed was 2390 ypm (2185 m/min).
  • the yarn exhibited 17 nodes/m with a standard deviation of 4.4 cm between nodes, and a Crimp Potential of 68%.
  • Sample 7B the following additional conditions were used.
  • the draw ratio was 5.0X, and finish was applied at 0.8 to 1% based on yarn weight.
  • the yarn had a Crimp Potential of 65%, and a Crimp Shrinkage of 7%.
  • the yarn was passed through two jets of the type shown in Figures 1, 2, and 3 in series.
  • the yarn speed at the jets was about 1740 ypm (1590 m/min), the overfeed was 3.2%, and the pressure of the air fed to the jets was 54 psig (372 kilopascal).
  • the jets had a yarn slot width "w" of 0.080 inches (2.03 mm), an air channel diameter of 0.062 inches (1.57 mm), an angle y of -15°, an angle of 90°, and a distance 'x' between the channel exits of 0.124 inches (3.15 mm).
  • the windup speed was 1720 ypm (1575 m/min).
  • the yarn exhibited 40 nodes/meter with a standard deviation of the node interval of 1.1 cm, and a Crimp Potential of 72%.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Multicomponent Fibers (AREA)
  • Woven Fabrics (AREA)
PCT/US2003/021615 2002-11-14 2003-07-09 Entangled bicomponent yarn and process for making same Ceased WO2004044293A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2004551421A JP4575778B2 (ja) 2002-11-14 2003-07-09 二成分交絡糸およびその製造方法
BR0315717-2A BR0315717A (pt) 2002-11-14 2003-07-09 Fio de filamento contìnuo entrelaçado e processos de fio entrelaçado e tecido
AU2003253869A AU2003253869A1 (en) 2002-11-14 2003-07-09 Entangled bicomponent yarn and process for making same
EP03811191A EP1560963A1 (en) 2002-11-14 2003-07-09 Entangled bicomponent yarn and process for making same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/294,345 US6868662B2 (en) 2002-11-14 2002-11-14 Entangled bicomponent yarn and process to make the same
US10/294,345 2002-11-14

Publications (1)

Publication Number Publication Date
WO2004044293A1 true WO2004044293A1 (en) 2004-05-27

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Family Applications (1)

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PCT/US2003/021615 Ceased WO2004044293A1 (en) 2002-11-14 2003-07-09 Entangled bicomponent yarn and process for making same

Country Status (9)

Country Link
US (1) US6868662B2 (enExample)
EP (1) EP1560963A1 (enExample)
JP (1) JP4575778B2 (enExample)
KR (1) KR20050075003A (enExample)
CN (1) CN1694982A (enExample)
AU (1) AU2003253869A1 (enExample)
BR (1) BR0315717A (enExample)
TW (1) TW200407472A (enExample)
WO (1) WO2004044293A1 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104411871A (zh) * 2012-05-01 2015-03-11 康廷南拓结构塑料有限公司 拆散碳纤维丝束及模塑包含该类纤维的组合物的方法
WO2022005383A1 (en) 2020-07-02 2022-01-06 Ikea Supply Ag A carpet, a carpet pile yarn, and a method for producing the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006099465A (ja) * 2004-09-29 2006-04-13 Toshiba Corp 電子機器の支持装置
US7357985B2 (en) * 2005-09-19 2008-04-15 E.I. Du Pont De Nemours And Company High crimp bicomponent fibers
US7666274B2 (en) * 2006-08-01 2010-02-23 International Paper Company Durable paper
JP6926501B2 (ja) * 2017-02-09 2021-08-25 東レ株式会社 糸条の交絡付与装置およびそれを用いた合繊繊維の製造方法
WO2024211874A1 (en) 2023-04-07 2024-10-10 The Lycra Company Llc Bicomponent yarn with improved bulk and hand-feel and elastic fabrics including the bicomponent yarn

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US3948033A (en) * 1973-02-23 1976-04-06 Imperial Chemical Industries Limited Bulked polyester heteroyarns
EP1059372A2 (en) * 1999-06-08 2000-12-13 Toray Industries, Inc. Soft strech yarns and their method of production
WO2002038847A1 (en) * 2000-11-08 2002-05-16 E. I. Du Pont De Nemours And Company Process for treating knits containing polyester biocomponent fibers

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US2985995A (en) 1960-11-08 1961-05-30 Du Pont Compact interlaced yarn
US3115691A (en) 1961-05-31 1963-12-31 Du Pont Apparatus for interlacing multifilament yarn
US3671379A (en) 1971-03-09 1972-06-20 Du Pont Composite polyester textile fibers
DE2633244A1 (de) 1975-07-25 1977-02-10 Du Pont Garn mit bindungen und verfahren zu seiner herstellung
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TW584680B (en) * 1999-05-28 2004-04-21 Inventa Fischer Ag Device for intermingling, relaxing, and/or thermosetting of filament yarn in a melt spinning process, as well as associated processes and the filament yarn manufactured therewith
US6052878A (en) * 1999-05-28 2000-04-25 E. I. Du Pont De Nemours And Company Methods and apparatus for interlacing filaments and methods of making the apparatus
US6692687B2 (en) 2000-01-20 2004-02-17 E. I. Du Pont De Nemours And Company Method for high-speed spinning of bicomponent fibers
JP3690274B2 (ja) * 2000-12-11 2005-08-31 東レ株式会社 ポリエステル系複合糸およびその製造方法ならびに布帛
ES2258614T3 (es) 2001-02-02 2006-09-01 Asahi Kasei Kabushiki Kaisha Fibra compleja con excelente capacidad de proceso posterior y metodo de fabricacion de la misma.
MXPA03009465A (es) * 2001-04-17 2004-02-12 Asahi Chemical Ind HILO DE TORSIoN FALSA DE FIBRA COMPUESTA DE POLIeSTER Y METODO PARA PRODUCIRLO.

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Publication number Priority date Publication date Assignee Title
US3948033A (en) * 1973-02-23 1976-04-06 Imperial Chemical Industries Limited Bulked polyester heteroyarns
EP1059372A2 (en) * 1999-06-08 2000-12-13 Toray Industries, Inc. Soft strech yarns and their method of production
WO2002038847A1 (en) * 2000-11-08 2002-05-16 E. I. Du Pont De Nemours And Company Process for treating knits containing polyester biocomponent fibers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104411871A (zh) * 2012-05-01 2015-03-11 康廷南拓结构塑料有限公司 拆散碳纤维丝束及模塑包含该类纤维的组合物的方法
WO2022005383A1 (en) 2020-07-02 2022-01-06 Ikea Supply Ag A carpet, a carpet pile yarn, and a method for producing the same
EP4176113A4 (en) * 2020-07-02 2025-06-11 Inter Ikea Systems B.V. CARPETS, THREADS MAKING UP THE VELVET OF A CARPET AND THEIR PRODUCTION PROCESS

Also Published As

Publication number Publication date
JP2006506540A (ja) 2006-02-23
US6868662B2 (en) 2005-03-22
BR0315717A (pt) 2005-09-06
US20040093845A1 (en) 2004-05-20
TW200407472A (en) 2004-05-16
CN1694982A (zh) 2005-11-09
KR20050075003A (ko) 2005-07-19
AU2003253869A1 (en) 2004-06-03
JP4575778B2 (ja) 2010-11-04
EP1560963A1 (en) 2005-08-10

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