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WO2013041183A1 - Fibres de polyester resistantes au boulochage - Google Patents

Fibres de polyester resistantes au boulochage Download PDF

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Publication number
WO2013041183A1
WO2013041183A1 PCT/EP2012/003727 EP2012003727W WO2013041183A1 WO 2013041183 A1 WO2013041183 A1 WO 2013041183A1 EP 2012003727 W EP2012003727 W EP 2012003727W WO 2013041183 A1 WO2013041183 A1 WO 2013041183A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
fiber according
salts
tours
kinkscrew
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/EP2012/003727
Other languages
German (de)
English (en)
Inventor
Jörg Dahringer
Michael Klanert
Andreas LEPPERT
Antonius JAUMANN
Werner Stefani
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.)
Trevira GmbH
Original Assignee
Trevira GmbH
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 Trevira GmbH filed Critical Trevira GmbH
Priority to RU2014116244/05A priority Critical patent/RU2602883C2/ru
Priority to EP12766278.1A priority patent/EP2758567B1/fr
Priority to IN2184CHN2014 priority patent/IN2014CN02184A/en
Priority to CN201280046556.3A priority patent/CN103958750B/zh
Publication of WO2013041183A1 publication Critical patent/WO2013041183A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • the invention relates to a pillar poor polyester fiber, a method for their
  • Polyester fibers have a high strength compared to natural fibers, especially a high transverse strength, possess.
  • Modifications can reduce pilling. These have the goal of preventing the emergence of the pills, or to favor a cancel and remove resulting Pills. Fibers with such a modification are called low-pill fibers. The aim of this invention is to provide such a low-pill fiber.
  • Integrate polycondensation in the molecular chain examples include multifunctional alcohols (pentaerythritol), polybasic acids and silicon or phosphorus compounds.
  • Another route taken is the subsequent hydrolysis of the polyester.
  • hydrolytically active compounds ascids, bases and organic derivatives are added to the polyester.
  • the principle of temporary bridging or branching is that one equips the polyester chain with a thermally or hydrolytically labile bond in the polymer chain, which after spinning, z. B. hydrolytically breaks up when dyeing the textile surface product or the flake.
  • Examples of such temporarily bridged polyesters are found, for. B. in FR-A-2,290,511, where before the transesterification 0.01 to 2 wt .-% diphenylsilanediol, based on dimethyl terephthalate (DMT) is introduced.
  • DMT dimethyl terephthalate
  • Crosslinker silicic acid esters used, known. Due to the correct modification height, excellent pilling behavior (low transverse strength) can be obtained with sufficient strength after staining. However, with multiple staining, or with altered or not constant
  • Pentaerythritol is used.
  • Crosslinking can increase the melt viscosity and thus are too
  • the object of the invention is therefore to provide a novel pillar-poor polyester fibers, which have the required pillar-poor properties,
  • the present invention is a pillar-poor fiber based on polyester containing 0.1 to 10 wt .-% of inorganic particles with a
  • polyester fibers The addition of inorganic or mineral particles in polyester fibers is a common method to modify the fibers to be obtained. Desirable properties such as matting, opacity, color, radiation absorption,
  • low molecular weight raw materials can also be modified in this way.
  • an additional improvement in pill behavior is also possible with raw materials, which can not be further improved due to their already low molecular weight, since otherwise their processability would no longer exist.
  • the additives according to the invention are present in the polyester matrix, so that no unforeseeable events can occur during further processing.
  • a targeted subsequent hydrolysis to improve the pill behavior may have the disadvantage that the desired
  • Suitable polyester materials are in principle all known types suitable for fiber production.
  • Melt-spinnable polyesters consist predominantly of building blocks derived from aromatic dicarboxylic acids and from aliphatic diols. Common aromatic dicarboxylic acid building blocks are the
  • Terephthalic acid and isophthalic acid are particularly suitable.
  • Common diols have 2 to 4 carbon atoms, with ethylene glycol and / or propane-1, 3-diol are particularly suitable.
  • polyester to at least 85 mol% of
  • PET Polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • Glycol units which act as so-called modifiers and which allow the skilled person to influence the physical and chemical properties of the filaments produced targeted. Examples of such
  • Dicarboxylic acid units are radicals of isophthalic acid or of aliphatic dicarboxylic acid, for example glutaric acid, adipic acid, sebacic acid;
  • modifying diol radicals are those of longer-chain diols, eg. Example of propanediol or butanediol, di- or triethylene glycol or, if present in small quantities, of polyglycol having a molecular weight of about 500 to 2000.
  • Particularly advantageous are polyesters which have been flame-retardant modified. Such polyesters are also already well known.
  • the flame-retardant modified polyesters used according to the invention are those in which phosphorus compounds are condensed in the polyester chain, ie they are covalently bonded.
  • Chain links to be understood in the linear chain of the polymer molecule
  • R is alkylene or polymethylene having 2 to 6 carbon atoms or phenyl and R 1 is alkyl having 1 to 6 carbon atoms, aryl, arylalkyl or alkylaryl.
  • R is ethylene and R 1 is methyl, ethyl, phenyl, or o-, m- or p-methylphenyl, in particular methyl or phenyl.
  • Such polyesters are described, for example, in DE-A-39 40 713.
  • polyesters in which the polyester has fused-in phosphorus-containing chain links are, for example, from DE-A-2236 037, DE-A-2242002, DE-A-232800343, DE-A-2346787 and DE-A-2454189.
  • polyesters which are at least 95 mol%
  • PET Polyethylene terephthalate
  • polyesters which are modified with a crosslinker.
  • Such polyesters usually have a molecular weight corresponding to a specific viscosity (n sp ez) of 0.6 to 0.9 measured on solutions of 1 g / l polymer in dichloroacetic acid at 25 ° C.
  • polyesters used to prepare the fiber according to the invention are sufficiently dried and usually have a residual moisture content of less than 500 ppm of water.
  • the inorganic particles used according to the invention are, in particular, mineral materials.
  • the salts of the first and second main groups of the Periodic Table of the Elements are preferred. Especially, the salts of the first and second main groups of the Periodic Table of the Elements are preferred. Especially, the salts of the first and second main groups of the Periodic Table of the Elements are preferred. Especially, the salts of the first and second main groups of the Periodic Table of the Elements are preferred. Especially, the salts of the first and second main groups of the Periodic Table of the Elements are preferred. Especially
  • the chlorides, fluorides, bromides, iodides, carbonates, sulfates, phosphates, nitrates, bicarbonates, sulfites, nitrates and their mixed salts, in particular naturally occurring salts or mixed salts are preferred.
  • the mineral materials used according to the invention but in particular the carbonate salts and / or bicarbonate salts of calcium and / or magnesium, have a particle surface which has a
  • Fatty acid preferably a higher fatty acid of 10 to 28 Carbon atoms, was subjected.
  • the mineral materials used according to the invention but especially the carbonate salts and / or bicarbonate salts of calcium and / or magnesium, have an average particle diameter of
  • the proportion contained therein with a grain size of more than 5 ⁇ may not exceed 1 wt .-%, so that by this the spinning process is not disturbed
  • a suitable particle size analyzer for example is a Microtrac S 3500.
  • Comminution for example grinding, and / or produced by precipitation or crystallization of the underlying salts.
  • the above-described surface treatment with the higher fatty acid prevents aggregation of the mineral materials and ensures the most homogeneous possible distribution in the polyester material of the fiber.
  • Examples of the higher fatty acid may be saturated higher fatty acids
  • the fiber according to the invention preferably has 0.5 to 10% by weight of carbonate salts and / or bicarbonate salts of calcium and / or magnesium having a particle size in the range from 0.5 pm to 5 pm.
  • those which have about 1% by weight of the abovementioned salts are particularly preferred.
  • the fibers of the invention are pillar poor. This property is through
  • Coloring require only a maximum of 800 kinkscrew tours, preferably a maximum of 700 kinkscrew tours, in particular a maximum of 600
  • the fibers according to the invention usually require between 200 and 700 crease scouring tours, preferably 200 to 600 crease scouring tours, in particular 250 to 600 crease scraper tours.
  • the fibers of the invention show in particular an excellent
  • fibers according to the invention preferably have a strength of min. 25cN / tex in combination with the above-mentioned transverse strengths (kinks)
  • the preparation of the fiber of the invention can be accomplished by conventional methods and apparatus, i. essentially without additional
  • mineral material is for example via a mixing extruder in the
  • Polyester compounded Depending on the degree of filling, this compound can serve both as masterbatch and as sole raw material.
  • polyester and the mineral materials or compound described above are provided and melt-spun
  • Nozzle exit surface is tuned to the spinning speed to produce a fiber of the desired denier.
  • the conventionally stretched fibers and filaments can then be crimped, fixed and / or cut to the desired length into staple fibers by generally conventional methods.
  • Withdrawal speed is to produce staple fibers, usually min. 500 meters per minute and max. Spun 2200 meters per minute. In order to produce filaments, they can be removed much higher, at up to 8000 meters per minute.
  • the spinning temperature is typically 255 ° C or more and 305 ° C or less. More preferably, spinning is carried out at about 275-295 ° C.
  • the spinneret is a conventional spinneret of the type used in the art
  • the single denier of the fiber according to the invention is in its final form between 0.6 and 30 dtex, preferably 0.9 to 13 dtex, in particular 0.9 to 8 dtex, the titer due to the higher density of the present
  • inorganic particles increases with increasing dosage.
  • the determination of the titers was carried out in accordance with DIN EN ISO1973.
  • the fibers formed may have round, oval and other suitable cross-sections or other shapes, such as dumbbell, kidney-shaped, triangular or tri- or multilobal cross-sections. Also hollow fibers are possible. Likewise, fibers of two or more polymers can be used.
  • the geometry of the bicomponent fibers can be "core-shell” (centered and eccentric), “side by side”, or “island in the sea”.
  • the large spun fiber cables usually 10-600 ktex, can be used on conventional methods
  • Strip line are stretched, preferably at 10 to 110 m / min
  • the draw ratios are preferably from 1.25 to 4, more preferably from 2.5 to 3.5.
  • the temperature during the stretching is in the range of
  • Glass transition temperature of the tow to be stretched and in the case of polyester is preferably 40.degree. C. to 80.degree. C., particularly preferably 50-70.degree.
  • the V / can extend in one stage or optionally using a
  • two-stage stretching process are carried out (see, for example, US 3,816,486).
  • one or more finishes may be applied using conventional techniques.
  • Stretched fibers can be conventional methods of mechanical
  • Crimping be used with known crimping machines.
  • a mechanical device for fiber crimping is preferred
  • the cable is first heated to a temperature in the range from 50 ° to 100 ° C., preferably 70 ° to 85 ° C., more preferably to about 78 ° C., and with a pressure of the cable entry rollers of 1, 0 to 6, 0 bar, more preferably at about 2.0 bar, a pressure in the crimping of 0.5 to 6.0 bar, more preferably 1, 5- 3.0 bar, with steam at between 1, 0 and 2.0 kg / min., Particularly preferably 1, 5 kg / min. Treated.
  • the smooth, or optionally crimped, fibers are relaxed and / or fixed at 120 ° to 170 ° C in the oven or hot air stream.
  • the smooth, or optionally crimped, fibers are taken up, followed by cutting and possibly hardening and depositing in pressed bales as a flake.
  • the staple fibers of the present invention are preferred on one of the relaxation
  • the fibers of the invention continue to show a very good
  • Crimping (crimping) K1 a measure of the filling of the fiber that is imparted to it through a mechanical crimping process.
  • Fiber filling products in particular of staple fibers, is of importance.
  • the springing property of the fiber becomes
  • Circling in the context of the invention means the following ratio:
  • L k is the length of the crimped staple fiber in the relaxed exposed state and L v is the length of the same, but drawn fiber, that is, the fiber is then practically straight without crimp before.
  • the stretching is carried out using the so-called Entk Hurselungskraft. This will be in
  • the fibers produced according to the invention preferably have one
  • Crimp degree of at least 3 crimps (crimps) per cm preferably 3 sheets per cm to 9.8 sheets per cm and more preferably 3.9 sheets per cm to 8.9 sheets per cm.
  • crimp values of about 5 to 5.5 sheets per cm are particularly preferred.
  • the crimp K1 according to the invention is preferably 15% or more, preferably 17% or more.
  • the fiber loses strength and elongation. However, reduced with
  • polyester fibers of the invention under conventional conditions, i. dispersed at 130 ° C for 60 minutes in acetic acid medium, dyed.
  • the polyester fibers of the invention show
  • the fibers according to the invention, dyed as described above, require only a maximum of 400 crease scouring tours, preferably a maximum of 300
  • the minimum number of crease scrapers, i. until breakage of the fiber is 150 crease scrapers, preferably 190
  • the fibers according to the invention (after dyeing) usually require between 150 and 400 kinkscrew tours, preferably 190 to 400 kinkscrew tours, in particular 190 to 300 kinkscrew tours.
  • the fiber according to the invention after dyeing, show that to a small extent damage to the surface takes place, but this is independent of the pH of the liquor. This indicates that isolated particles on the surface are broken out of the fiber by mechanical stress on the material become.
  • the polyester matrix of the fiber sufficiently integrates the particles to protect them from degradation by the dyeing liquor.
  • the fibers according to the invention require only a maximum of 400 crease scouring tours, preferably a maximum of 300 crease scouring tours, whereas a polyester without the
  • additive according to the invention (coloring as described above) min. 700 kinks to the breakage of the fiber needed.
  • the minimum number of crease scrapers, i. until the fiber breaks, is 150
  • the fibers according to the invention usually require between 150 and 400 kinkscrews, preferably 190 to 400 kinkscrews,
  • the dyed fibers according to the invention show in particular a
  • the fibers according to the invention preferably have a strength of min. 23cN / tex in combination with the
  • From the fibers of the invention can be appropriate textile
  • textile fabric is to be understood in this description in its broadest meaning. It may be all structures containing the fibers of the invention, which after a
  • the nonwoven fabric according to the invention can be constructed from continuous synthetic fibers (filaments) or from staple fibers.
  • staple fibers according to the invention are preferably used, the length of which is generally 1 to 200 mm, preferably 3 to 120 mm, particularly preferably 3 to 60 mm.
  • a low-molecular cross-linked PET raw material is modified with alkaline earth carbonates.
  • the raw material was, as is customary for PET, dried to a residual moisture content of at least 500 ppm.
  • the alkaline earth carbonate was added in the form of a masterbatch.
  • the obtained titre of the spun goods increased with increasing dosage due to the high density of the additive.
  • Titre was determined according to DIN EN ISO1973; Fiber strength and elongation according to DIN EN ISO 5079.
  • the fiber samples were dyed under acid conditions customary for PET at 130 ° C. for 60 minutes.
  • the following table shows the obtained textile data of the colored samples: 0% 1, 25% 2.5% 3.75% 5.0%
  • Knickscheuertouren has reduced by the coloring in all patterns by about half. A reduction in strength and elongation is still present and increases with increasing modification. However, those are
  • the PET matrix of the fiber sufficiently integrates the carbonate particles to protect them from decomposition by the dyeing liquor.
  • the kink chisels are reduced with increasing temperature. However, the dyeing conditions of 130 ° C. and 60 minutes usual for PET are sufficient. A further increase of these two parameters does not lead to an additional reduction of the transverse strength. In addition, it can be stated that the fiber strength is not affected by the dyeing. The fiber strength remains independent of dyeing time, dyeing temperature and pH.
  • the obtained fiber values of the fibers produced are comparable to other commercial low-pill polyester fibers.
  • the following table comparatively shows a few important fiber values.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

Fibres de polyester qui sont modifiées de manière à résister au boulochage par ajout de 0,5 à 10 % en poids de particules inorganiques ayant une taille de l'ordre de 0,5μm à 5μm. Les fibres de polyester résistantes au boulochage selon la présente invention présentent de bonnes propriétés pour des utilisations textiles, lesdites propriétés restant inchangées, même après teinture à haute température dans des liquides acides. Les fibres selon la présente invention permettent de fabriquer des tissus.
PCT/EP2012/003727 2011-09-23 2012-09-05 Fibres de polyester resistantes au boulochage Ceased WO2013041183A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
RU2014116244/05A RU2602883C2 (ru) 2011-09-23 2012-09-05 Полиэфирное волокно с низкой пиллингуемостью
EP12766278.1A EP2758567B1 (fr) 2011-09-23 2012-09-05 Fibres de polyester resistantes au boulochage
IN2184CHN2014 IN2014CN02184A (fr) 2011-09-23 2012-09-05
CN201280046556.3A CN103958750B (zh) 2011-09-23 2012-09-05 低起球的聚酯纤维

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011114237.5 2011-09-23
DE102011114237A DE102011114237A1 (de) 2011-09-23 2011-09-23 Pillarme Polyesterfaser

Publications (1)

Publication Number Publication Date
WO2013041183A1 true WO2013041183A1 (fr) 2013-03-28

Family

ID=46939679

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/003727 Ceased WO2013041183A1 (fr) 2011-09-23 2012-09-05 Fibres de polyester resistantes au boulochage

Country Status (7)

Country Link
EP (1) EP2758567B1 (fr)
CN (1) CN103958750B (fr)
DE (1) DE102011114237A1 (fr)
IN (1) IN2014CN02184A (fr)
PL (1) PL2758567T3 (fr)
RU (1) RU2602883C2 (fr)
WO (1) WO2013041183A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104651972A (zh) * 2015-03-17 2015-05-27 江苏江南高纤股份有限公司 直接纺丝低起球聚酯毛型纤维长丝束的制造方法
CA3201876A1 (fr) 2020-12-21 2022-06-30 Gerhart Huy Poils ayant des additifs de soin buccal contenus dans ceux-ci et procedes de fabrication associes
CN116082614A (zh) * 2022-10-25 2023-05-09 宜昌中盈科技发展有限公司 一种循环再生抗起球阳离子可染聚酯切片的制备方法

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DE2236037A1 (de) 1972-07-22 1974-02-14 Hoechst Ag Schwer entflammbare faeden und fasern aus polyester
DE2242002A1 (de) 1972-08-26 1974-03-07 Hoechst Ag Flammwidrige synthetische lineare polyester sowie geformte gebilde daraus
US3816486A (en) 1969-11-26 1974-06-11 Du Pont Two stage drawn and relaxed staple fiber
DE2328343A1 (de) 1973-06-04 1975-01-02 Hoechst Ag Schwer entflammbare faeden und fasern aus polyester
DE2346787A1 (de) 1973-09-17 1975-03-27 Hoechst Ag Schwer entflammbare lineare polyester, sowie geformte gebilde daraus
DE2454189A1 (de) 1974-11-15 1976-05-26 Hoechst Ag Verfahren zur herstellung schwer entflammbarer linearer polyester
FR2290511A1 (fr) 1974-11-09 1976-06-04 Bayer Ag Fibres en polyesters a pilling faible
DE3940713A1 (de) 1989-12-09 1991-06-13 Hoechst Ag Flammhemmendes vlies mit bindefilamenten
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EP1425444A1 (fr) 2001-06-22 2004-06-09 Trevira Gmbh Fibres de polyester resistantes au boulochage
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Publication number Priority date Publication date Assignee Title
FR1589057A (fr) 1967-04-19 1970-03-23
US3816486A (en) 1969-11-26 1974-06-11 Du Pont Two stage drawn and relaxed staple fiber
DE2236037A1 (de) 1972-07-22 1974-02-14 Hoechst Ag Schwer entflammbare faeden und fasern aus polyester
DE2242002A1 (de) 1972-08-26 1974-03-07 Hoechst Ag Flammwidrige synthetische lineare polyester sowie geformte gebilde daraus
DE2328343A1 (de) 1973-06-04 1975-01-02 Hoechst Ag Schwer entflammbare faeden und fasern aus polyester
DE2346787A1 (de) 1973-09-17 1975-03-27 Hoechst Ag Schwer entflammbare lineare polyester, sowie geformte gebilde daraus
FR2290511A1 (fr) 1974-11-09 1976-06-04 Bayer Ag Fibres en polyesters a pilling faible
DE2454189A1 (de) 1974-11-15 1976-05-26 Hoechst Ag Verfahren zur herstellung schwer entflammbarer linearer polyester
DE3940713A1 (de) 1989-12-09 1991-06-13 Hoechst Ag Flammhemmendes vlies mit bindefilamenten
JPH1077524A (ja) * 1996-09-04 1998-03-24 Toyobo Co Ltd シートベルト用ポリエステル系糸および該糸を用いたシートベルト
US20020014716A1 (en) * 2000-04-04 2002-02-07 Seok Mi Soo Method of producing fiber having functional mineral powder and fiber produced therefrom
US20030088012A1 (en) * 2000-05-22 2003-05-08 Yoshihiro Naruse Polyester fiber and production method of polyester composition.
EP1425444A1 (fr) 2001-06-22 2004-06-09 Trevira Gmbh Fibres de polyester resistantes au boulochage
US20090043022A1 (en) * 2004-12-31 2009-02-12 Hyosung Corporation Polyester Fiber Having Excellent Light-Shielding And Flame Retardant Characteristic And Textile Goods Using The Same
KR20080112597A (ko) * 2007-06-21 2008-12-26 주식회사 코오롱 폴리에스터 섬유
WO2011027732A1 (fr) * 2009-09-03 2011-03-10 東レ株式会社 Cuir artificiel résistant au boulochage

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Also Published As

Publication number Publication date
EP2758567A1 (fr) 2014-07-30
RU2602883C2 (ru) 2016-11-20
RU2014116244A (ru) 2015-10-27
DE102011114237A1 (de) 2013-03-28
IN2014CN02184A (fr) 2015-05-29
EP2758567B1 (fr) 2017-03-01
DE102011114237A8 (de) 2013-07-25
CN103958750A (zh) 2014-07-30
CN103958750B (zh) 2015-12-23
PL2758567T3 (pl) 2017-08-31

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