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WO2009118262A1 - Corps moulés cellulosiques - Google Patents

Corps moulés cellulosiques Download PDF

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Publication number
WO2009118262A1
WO2009118262A1 PCT/EP2009/053198 EP2009053198W WO2009118262A1 WO 2009118262 A1 WO2009118262 A1 WO 2009118262A1 EP 2009053198 W EP2009053198 W EP 2009053198W WO 2009118262 A1 WO2009118262 A1 WO 2009118262A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulosic
cellulose
solvent
maximum tensile
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.)
Ceased
Application number
PCT/EP2009/053198
Other languages
German (de)
English (en)
Inventor
Britta Nicola Zimmerer
Kurt Uihlein
Frank Meister
Birgit Kosan
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.)
Cordenka GmbH and Co KG
Original Assignee
Cordenka GmbH and Co KG
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 Cordenka GmbH and Co KG filed Critical Cordenka GmbH and Co KG
Priority to PL09725538T priority Critical patent/PL2268857T3/pl
Priority to EP09725538A priority patent/EP2268857B1/fr
Priority to ES09725538T priority patent/ES2402442T3/es
Publication of WO2009118262A1 publication Critical patent/WO2009118262A1/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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • 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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • 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
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts

Definitions

  • the present invention relates to cellulosic molded articles having a maximum tensile force of at least 30 cN / tex, prepared by dry-wet deformation of polymer solutions containing predominantly cellulose in a solvent.
  • the present invention relates to so-called technical cellulose multifilament yarns, which are high-strength molded body made of cellulose with a proportion of less than 50% of other polymers and / or additives.
  • the dry-wet deformation is preferably carried out by precipitation.
  • DE-A-4 444 140 in the claims discloses solvent-spun cellulosic filaments of a solution of cellulose in a tertiary amine N-oxide and optionally water having a strength of 50 to 80 cN / tex and an elongation at break of 6 to 25 %. From the corresponding examples, it can be seen, however, that with a maximum tensile strength or tear strength of 65.3 cN / tex, an elongation of 6.3% is associated and results in a tensile strength of 53.2 cN / tex, an elongation of 13%.
  • WO 2006/000197 discloses a process for producing shaped articles from cellulose with ionic liquids as solvent, in which the cellulose is dissolved, the solution is shaped into fibers or films / membranes, the cellulose is regenerated by precipitation in aqueous solutions, the solvent passes through Wash separates and the shape of body dries. According to WO 2006/000197, fibers with very high tensile strengths and moduli in the conditioned and wet state are obtained in this way. According to the table on page 17 of this prior publication, tensile strengths of up to 67.7 cN / tex in the conditioned state are achieved with simultaneous breaking elongations of 9.0%.
  • tear strength tensile strength, breaking strength and maximum tensile force are used interchangeably in this application and refer to the fineness-related force that has to be used for tearing or breaking the cellulosic molding.
  • the elongation of the molded article measured during tearing or breakage of the molded article is based on its original length and referred to as elongation at break, maximum tensile elongation at break or else elongation at break in the form of the percentage increase in length.
  • AV working load in J / g ⁇ : maximum tensile strength in the conditioned state [cN / tex] ⁇ : maximum tensile elongation in the conditioned state [%] of at least 80 J / g, preferably of at least 82 J / g, more preferably of at least 85 J / g g, and most preferably at least 90
  • the shaped bodies according to the invention thus also show at the same time a very high tear strength and a high elongation at break, a combination which is not disclosed in the prior art.
  • Example 3 in WO 2007/128268 discloses fibers of a (60:40) mixture of a cotton linter pulp with polyacrylonitrile, which have a working capacity of about 87 J / g.
  • the fibers described in WO 2007/128268 at the same time have a very low strength of only 25.4 cN / tex and are therefore not suitable for use as technical multifilament yarns.
  • WO 97/33020 shows a working capacity of 41 J / g at a distance between nozzle and godet of 12 m, 38 J / g at 25 m and 45.5 J / g at 48 m. An extrapolation to a distance of 0 would consequently give a working capacity of about 50 to 60 J / g, as also shown in Table 1 of WO 97/33030.
  • WO 02/18682 From the published a few years later WO 02/18682, the skilled artisan can see that between the working capacity of the fibers (product of tensile strength and elongation at break in J / g) and the strain rate is probably a dependency, but this is low.
  • WO 02/18682 contains - despite a corresponding reference thereto - no drawings. If one looks in the corresponding priority application, one recognizes that even at an (extrapolated) strain rate of less than 5 seconds "1 at the specified constant strength of about 41 cN / tex, a working capacity of over 80 J / g would not be achieved.
  • WO 02/18682 recommends to spin at a strain rate in a range between 15 and 40 sec "1 and thus 02/18682 teaches the WO, a working capacity of about 58 to 65 J / g.
  • the maximum tensile force of the claimed molded articles is in a range of 40 to 90 cN / tex, preferably 45 to 85 cN / tex, more preferably 50 to 80 cN / tex, most preferably 55 to 75 cN / tex.
  • Suitable solvents are the known direct solvents for cellulose, such as N-methylmorpholine-N-oxide (NMMO), into consideration. It is likewise preferred if the solvent from which the cellulosic molded bodies are produced is an ionic liquid or mixtures of ionic liquids.
  • NMMO N-methylmorpholine-N-oxide
  • Preferred ionic liquids are those which have imidazolium-based cations and halide or acetate anions, in particular 1, 3-dialkylimidazolium halides and acetates and more preferably 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-yl methylimidazolium acetate and / or mixtures thereof.
  • the cellulosic shaped bodies preferably consist of a pulp which has an ⁇ -cellulose content of greater than 90%, preferably greater than 96%, and particularly preferably greater than 98%. Furthermore, it is advantageous if the cellulose is a pulp which has an average degree of polymerisation (DP), determined by means of the cuoxam method, of> 600, preferably> 650.
  • DP average degree of polymerisation
  • the preparation of the cellulosic molded bodies according to the invention is preferably carried out by enzymatic and / or hydrolytic pretreatment of the pulps used. These pretreatments are used to widen the molecular weight distribution targeted, the molecular weights are reduced.
  • the discontinuity of the spinning solutions can also be adjusted by the targeted mixing of pulps and by the addition of secondary polymers.
  • the cellulosic shaped bodies are filaments or fibers.
  • These fibers or filaments preferably have a cuoxamide DP greater than 550, more preferably greater than 600.
  • the production of the shaped bodies according to the invention is outstandingly successful when the angular velocity (or the shear rate proportional thereto) is in the range of 0.5 to about 2 rad / sec at the "cross-over.” If the solvent used is NMMO, this is the angular velocity preferably between about 1 and 2 rad / sec, for ionic liquids preferably between about 0.5 and 1.
  • the angular velocity at the "cross-over” corresponds to the width molecular weight distribution and the average molecular weight of the polymers involved in the interlocking network.
  • the “cross over” itself is the crossing point between the memory and loss modulus of the master curve (see: Schrempf, C, Schild, G Ruf, H., "Pulp-NMMO solutions and their flow properties", The paper 12 (1995) 748-757).
  • the cellulosic shaped bodies are filaments, they preferably have a DP determined by means of Cuoxam of> 550.
  • the invention is therefore also directed to the use of such cellulosic filaments for the production of technical yarns and for the production of tire cords and of cords and textile reinforcement fabrics.
  • the cellulosic filaments of the present invention are particularly useful for reinforcing elastomers, plastics (e.g., thermoplastics, biopolymers, and biodegradable polymers) and thermosetting molding materials (resins).
  • the clamping length was 20 mm and the pulling speed was 20 mm / min with a preload weight of 0.6 ⁇ 0.06 cN / tex.
  • the measurements were carried out on 50 fibers each.
  • Theological characterization of the cellulosic spinning solutions was carried out using a HAAKE MARS rheometer with cone / plate measuring device (sensor C35 / 4 "or C20 / 4 0 ).
  • Zero shear viscosities were measured by creep using a constant shear stress of 90 Pa at a measurement temperature of 85 ° C.
  • the determination of the average degree of polymerization (DP) of the cellulose was carried out by the Cuoxam method.
  • the intrinsic viscosities [ ⁇ ] (unit ml / g) were determined with the aid of a capillary viscometer and determined according to the following equation of the Cuoxam-DP:
  • Cuprammonium DP 2 ⁇ [ ⁇ ] C uoxam
  • the ⁇ -cellulose content is the part of the pulp which is resistant to 17.5% sodium hydroxide solution in certain types of treatment.
  • the determination of the ⁇ -cellulose content was carried out by treating the pulp with 17.5% aqueous NaOH solution at 20 0 C for 1 h and then washing, drying and reweighing of the pulp.
  • the solids content was determined by precipitation, washing and drying of the cellulose.
  • a lyocell pulp (eucalyptus sulfite pulp, cuoxam DP: 556, ⁇ -cellulose content: 93.8%) was beaten in water at a ratio of 1:20 in water and pressed to a moisture content of 60% by mass.
  • a eucalyptus pulp (8% by mass of moisture, Cuoxam-DP: 556) are dispersed in a liquor ratio of 1:20 to the individual fiber and then pressed to a water content of 60% by mass.
  • the cellulose which is moist by press, is introduced into 380 g of an N-methylmorpholine-N-oxide (NMMO) solution with a water content of 50%, which contains as stabilizers propyl gallate (0.03%, based on the polymer solution to be prepared) and sodium hydroxide solution according to the base consumption Contains substances, introduced and dispersed.
  • NMMO N-methylmorpholine-N-oxide
  • the prepared suspension is placed in a vertical kneader, under shear, increasing temperature of 70 to 95 ° C and decreasing pressure of 750 to 50 mbar the water removed to the level of monohydrate and a microscopically homogeneous cellulose solution having the composition 12.3 mass% Cellulose, 76.0% by mass of NMMO and 11.7% by mass of water.
  • the refractive index of the solution at 50 ° C. was 1.4876.
  • the prepared solution was characterized analytically and formed by dry-wet spinning process into fibers of a fineness of 1.66 dtex. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • the pulp used in Comparative Example 3 (Cuoxam-DP: 798, 98.4% ⁇ -cellulose) was dispersed in water at a ratio of 1:20 in water and adjusted to pH 5.0 by addition of dilute formic acid.
  • an enzymatic pretreatment of the pulp was carried out within 60 minutes with 0.5% of a cellulase with high exoactivity (filter paper activity 90 U / ml), based on cellulose.
  • Enzymatic pretreatment provides only a small reduction in the cuoxam DP of the pulp to a DP of 745, as well as a targeted change in non-uniformity, i. the molecular weight distribution of cellulose.
  • the pulp suspension from the enzyme treatment is pressed after increasing the pH to 11 to a water content of 60% and in each case 78.1 g of this press-moist cellulose used to prepare 12.5% strength cellulose solutions in BMIMCI.
  • the polymer solutions were with very good spinning reliability by dry-wet spinning technology to fibers of a fineness of 1, 78 and 1, 70 dtex deformable.
  • the data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • blends of pulps having a narrow molecular weight distribution and high ⁇ -cellulose contents were prepared.
  • 23.9 g of a pulp (cuoxam-DP: 798, 98.4% ⁇ -cellulose, moisture content: 7%) and 10.1 g of a cotton linter pulp (cuoxam-DP: 443, 98% ⁇ -cellulose) were used.
  • the moist celluloses were suspended in BMIMCI solutions (water content: 30%, stabilizer addition 0.2% NaOH, 0.02% propyl gallate, based on the polymer solution to be prepared) and transferred by means of vertical kneader under dehydration by shear, temperature and vacuum into microscopically homogeneous spinning masses ,
  • the resulting polymer solutions were with very good spinning reliability by dry-wet spinning technology to fibers of a fineness of 1, 81 and 1, 77 dtex deformable.
  • the data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • Examples 4 and 5 carried out an enzymatic pretreatment. After this
  • a cuoxam-DP of cellulose was determined to be 745.
  • Example 9 74.2 g of pretreated, wet cellulose were obtained
  • Tego Phobe 1401 aqueous emulsion of an amino-functional polysiloxane, polymer content: 55%) and thoroughly mixed
  • BMIMCI was converted into a 12.5% by mass, homogeneous dope.
  • the secondary polymers contained polyethylene glycol or polysiloxane each cause a very homogeneous turbidity of the spinning mass and are present in such a finely divided form that microscopically no individual particles could be identified and no adverse effects on the spinning processes took place.
  • the prepared polymer spun masses were characterized analytically and by means of dry-wet spinning process to fibers with finenesses of 1, 97 and 1, 73 dtex deformed. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • the polymer solvent used was a mixture of 2 ionic liquids, BMIMCl and 1-hexyl-3-methylimidazolium chloride (HMIMCI) in a mass ratio of 90:10.
  • the polymer solvent used was a mixture of 2 ionic liquids, BMIMCI and 1-ethyl-3-methylimidazolium acetate (EMIMAc) in a mass ratio of 90:10.
  • a polymer solution was prepared analogously to Example 13 from a cellulose mixture of the pulps used in Example 13 in a mass ratio of 60:40, using as cellulosic solvent a mixture of the ionic liquids BMIMCI and 1-butyl-3-methylimidazolium acetate (BMIMAc) in a mass ratio of 90:10.
  • BMIMCI 1-butyl-3-methylimidazolium acetate
  • a microscopically homogeneous polymer solution was obtained, which was 12.6 % By mass cellulose. This was analytically characterized and formed by dry-wet spinning process to fibers of a fineness of 1, 72 dtex deformed. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne des corps moulés cellulosiques filés avec un solvant à base d'une solution contenant principalement de la cellulose dans un solvant, qui sont caractérisés en ce que les corps moulés cellulosiques présentent une capacité de travail, calculée à partir du produit mathématique de la force de traction à la rupture et de l'allongement à la rupture, d'au moins 80 J/g.
PCT/EP2009/053198 2008-03-27 2009-03-18 Corps moulés cellulosiques Ceased WO2009118262A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL09725538T PL2268857T3 (pl) 2008-03-27 2009-03-18 Celulozowe wyroby kształtowe
EP09725538A EP2268857B1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques
ES09725538T ES2402442T3 (es) 2008-03-27 2009-03-18 Cuerpos celulósicos conformados

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08102964 2008-03-27
EP08102964.7 2008-03-27

Publications (1)

Publication Number Publication Date
WO2009118262A1 true WO2009118262A1 (fr) 2009-10-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/053198 Ceased WO2009118262A1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques

Country Status (5)

Country Link
EP (1) EP2268857B1 (fr)
KR (1) KR101580115B1 (fr)
ES (1) ES2402442T3 (fr)
PL (1) PL2268857T3 (fr)
WO (1) WO2009118262A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130248077A1 (en) * 2010-11-30 2013-09-26 Bridgestone Corporation Purified cellulose fiber, fiber-rubber composite, and tire
JP2013241708A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、補強用コード、ゴム−コード複合体、及びタイヤ
JP2013241707A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp ハイブリッドコード、ゴム−コード複合体、及びタイヤ
JP2013241709A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、ゴム−コード複合体、及びタイヤ
JP2013241705A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、コード、及びゴム−コード複合体、並びに、タイヤ及びランフラットタイヤ
JP2013241706A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp コード、ゴム−コード複合体及びタイヤ
EP2589689A4 (fr) * 2010-06-30 2014-01-22 Kolon Inc Dope pour le filage de fibre cellulosique à haute ténacité, procédé pour la préparation de fibre de filament cellulosique à haute ténacité utilisant un tel dope, et procédé pour la préparation de fibre courte de fibre cellulosique à haute ténacité
WO2014162062A1 (fr) 2013-04-04 2014-10-09 Aalto University Foundation Procédé pour la production d'articles formés en cellulose
EP2853623A4 (fr) * 2012-05-21 2016-01-20 Bridgestone Corp Câble, structure composite de câble en caoutchouc, et pneu
WO2017137284A1 (fr) 2016-02-11 2017-08-17 Basf Se Procédé pour produire des fibres polymères à partir de polymères dissouts dans des liquides ioniques au moyen d'un procédé de filage avec espace d'air
WO2017202834A1 (fr) * 2016-05-25 2017-11-30 Teijin Aramid Gmbh Élément anti-pénétration
WO2018138416A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procédé de fabrication d'une fibre ou d'un film de cellulose
WO2019066070A1 (fr) 2017-09-29 2019-04-04 古河電気工業株式会社 Article moulé
US11578192B2 (en) 2017-09-29 2023-02-14 Furukawa Electric Co., Ltd. Molded article
US11746215B2 (en) 2017-09-29 2023-09-05 Furukawa Electric Co., Ltd. Molded article
US11891498B2 (en) 2017-10-31 2024-02-06 Furukawa Electric Co., Ltd. Molded article provided with a resin part
WO2025210118A1 (fr) 2024-04-03 2025-10-09 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Produits de cellulose régénérée ignifuges

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444140A1 (de) 1994-12-12 1996-06-13 Akzo Nobel Nv Lösungsmittelgesponnene cellulosische Filamente
WO1997033020A1 (fr) * 1996-03-04 1997-09-12 Lenzing Aktiengesellschaft Procede de production de fibres cellulosiques
WO2002018682A1 (fr) * 2000-09-02 2002-03-07 Thüringisches Institut Für Textil - Und Kunststoff - Forschung E.V. Procede de fabrication de fibres cellulosiques et de fils continus cellulosiques
WO2007128268A2 (fr) 2006-05-10 2007-11-15 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Procédé de production de fibres cellulosiques multicomposant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444140A1 (de) 1994-12-12 1996-06-13 Akzo Nobel Nv Lösungsmittelgesponnene cellulosische Filamente
EP0797694B1 (fr) 1994-12-12 1998-08-26 Akzo Nobel N.V. Filaments cellulosiques files dans un solvant
WO1997033020A1 (fr) * 1996-03-04 1997-09-12 Lenzing Aktiengesellschaft Procede de production de fibres cellulosiques
WO2002018682A1 (fr) * 2000-09-02 2002-03-07 Thüringisches Institut Für Textil - Und Kunststoff - Forschung E.V. Procede de fabrication de fibres cellulosiques et de fils continus cellulosiques
WO2007128268A2 (fr) 2006-05-10 2007-11-15 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Procédé de production de fibres cellulosiques multicomposant

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2589689A4 (fr) * 2010-06-30 2014-01-22 Kolon Inc Dope pour le filage de fibre cellulosique à haute ténacité, procédé pour la préparation de fibre de filament cellulosique à haute ténacité utilisant un tel dope, et procédé pour la préparation de fibre courte de fibre cellulosique à haute ténacité
US20130248077A1 (en) * 2010-11-30 2013-09-26 Bridgestone Corporation Purified cellulose fiber, fiber-rubber composite, and tire
JP5851418B2 (ja) * 2010-11-30 2016-02-03 株式会社ブリヂストン 精製セルロース繊維の製造方法、繊維−ゴム複合体の製造方法、及びタイヤの製造方法
EP2647744A4 (fr) * 2010-11-30 2014-05-21 Bridgestone Corp Fibres cellulosiques purifiées, complexe fibre-caoutchouc, et pneu
JP2013241706A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp コード、ゴム−コード複合体及びタイヤ
JP2013241705A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、コード、及びゴム−コード複合体、並びに、タイヤ及びランフラットタイヤ
JP2013241709A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、ゴム−コード複合体、及びタイヤ
JP2013241707A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp ハイブリッドコード、ゴム−コード複合体、及びタイヤ
EP2853623A4 (fr) * 2012-05-21 2016-01-20 Bridgestone Corp Câble, structure composite de câble en caoutchouc, et pneu
JP2013241708A (ja) * 2012-05-21 2013-12-05 Bridgestone Corp 精製多糖類繊維、ゴム−繊維複合体、補強用コード、ゴム−コード複合体、及びタイヤ
WO2014162062A1 (fr) 2013-04-04 2014-10-09 Aalto University Foundation Procédé pour la production d'articles formés en cellulose
WO2017137284A1 (fr) 2016-02-11 2017-08-17 Basf Se Procédé pour produire des fibres polymères à partir de polymères dissouts dans des liquides ioniques au moyen d'un procédé de filage avec espace d'air
WO2017202834A1 (fr) * 2016-05-25 2017-11-30 Teijin Aramid Gmbh Élément anti-pénétration
WO2018138416A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procédé de fabrication d'une fibre ou d'un film de cellulose
US11549200B2 (en) 2017-01-30 2023-01-10 Aalto University Foundation Sr Process for making cellulose fibre or film
WO2019066070A1 (fr) 2017-09-29 2019-04-04 古河電気工業株式会社 Article moulé
US11578192B2 (en) 2017-09-29 2023-02-14 Furukawa Electric Co., Ltd. Molded article
US11597818B2 (en) 2017-09-29 2023-03-07 Furukawa Electric Co., Ltd. Molded article
US11746215B2 (en) 2017-09-29 2023-09-05 Furukawa Electric Co., Ltd. Molded article
EP3689974B1 (fr) * 2017-09-29 2025-04-23 Furukawa Electric Co., Ltd. Article moulé
US11891498B2 (en) 2017-10-31 2024-02-06 Furukawa Electric Co., Ltd. Molded article provided with a resin part
WO2025210118A1 (fr) 2024-04-03 2025-10-09 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Produits de cellulose régénérée ignifuges

Also Published As

Publication number Publication date
ES2402442T3 (es) 2013-05-03
KR20100129293A (ko) 2010-12-08
PL2268857T3 (pl) 2013-01-31
KR101580115B1 (ko) 2016-01-04
EP2268857A1 (fr) 2011-01-05
EP2268857B1 (fr) 2012-09-26

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