EP1705269A1 - Fibres en matière thermoplastique, méthode pour la préparation de cettes fibres, et l'utilisation - Google Patents

Fibres en matière thermoplastique, méthode pour la préparation de cettes fibres, et l'utilisation Download PDF

Info

Publication number
EP1705269A1
EP1705269A1 EP06005377A EP06005377A EP1705269A1 EP 1705269 A1 EP1705269 A1 EP 1705269A1 EP 06005377 A EP06005377 A EP 06005377A EP 06005377 A EP06005377 A EP 06005377A EP 1705269 A1 EP1705269 A1 EP 1705269A1
Authority
EP
European Patent Office
Prior art keywords
melt
fiber material
thermoplastic fiber
polyhydroxyether
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06005377A
Other languages
German (de)
English (en)
Other versions
EP1705269B1 (fr
Inventor
Simon Sutter
Jürg Spindler
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.)
EMS Chemie AG
Original Assignee
EMS Chemie AG
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 EMS Chemie AG filed Critical EMS Chemie AG
Priority to EP20060005377 priority Critical patent/EP1705269B1/fr
Publication of EP1705269A1 publication Critical patent/EP1705269A1/fr
Application granted granted Critical
Publication of EP1705269B1 publication Critical patent/EP1705269B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers

Definitions

  • the present invention relates to a thermoplastic fiber material spun from a raw material containing polyhydroxyether, a process for its preparation, and particular uses therefor.
  • melt spinning process For the production of synthetic fibers from polymers, the melt spinning process is preferred today, because it is particularly economical. Only polymers which can not be melt-removed will be limited to other spinning processes such as e.g. resorting to solution spinning.
  • Melt spinning presupposes that the polymer to be spun is thermoplastic and that it is sufficiently stable in the melt state under pressure and at the required extrusion temperature, that is, it does not degrade, build or crosslink.
  • Polyhydroxyether is a thermoplastic polymer that excellently adheres to many materials and, because of this property, is popular for a variety of applications. At elevated temperatures, however, it is very unstable, which is according to US 3,375,297 limits or even prevents its use in cases where resistance to elevated temperatures is required. Consequently, difficulties are to be expected especially in melt spinning, since the extrusion temperature must be much higher than the softening temperature because of the fine capillaries in the nozzle plate of the spinneret than in other extrusion processes.
  • synthetic fiber yarns especially polyester yarns (PET) are used as auxiliary yarns to stabilize the reinforcing fibers prior to embedding them in the matrix.
  • PET polyester yarns
  • UDs mat-shaped unidirectional layers
  • the auxiliary thread is used to fix the mutually parallel reinforcing fibers in their parallel position and thereby make the clutches as a coherent mats.
  • LM Liquid Molding
  • RV Resin Transfer Molding
  • VARTM Vacuum Assisted Resin Transfer Molding
  • RFI Resin Film Infusion
  • LRI Liquid Resin Infusion
  • RIFT Resin Infusion Flexible Tooling
  • the auxiliary thread has various disadvantages in the finished component.
  • the reinforcing fibers are kinked at the crossing points with the auxiliary thread, whereby they are not oriented ideally in the main force flow direction, which can lead to a significant weakening of the component. Its different physical properties, such as its different thermal expansion coefficient, can weaken the component.
  • Other disadvantages that can occur are shrinkage or a rough surface of the component.
  • GRILON® melts from EMS with low melting point, ideally 60 ° C or 85 ° C. These semi-crystalline yarns melt during curing of the matrix and, depending on the conditions, partially or completely dissolve, so that the reinforcing fibers can better be arranged in the component.
  • the polymeric melt yarn material remains in the component in addition to reinforcing fiber and matrix as a third phase as such. With its other physical properties, such as In turn, a different thermal expansion coefficient, it weakens the component.
  • Polyhydroxy ether sizing agents adhere well to the major reinforcing fibers such as glass fibers and carbon fibers and are compatible with conventional matrix systems based on epoxy, unsaturated polyester, cyanate ester, urethane, phenol, formaldehyde, melamine, or combinations thereof. They are usually applied as aqueous polymer dispersions. They are not suitable for stabilizing the reinforcing fibers or a preform made therefrom before they are embedded in the matrix.
  • the present invention is based on the finding that polyhydroxyethers, despite their low stability to elevated temperatures, can be produced economically even by melt spinning in an economical manner a thermoplastic fiber material having a substantially amorphous structure, which with particular advantage for stabilizing the reinforcing fibers or a thereof prepared preform before it is embedded in the matrix of fiber composites.
  • the polyhydroxyether fiber material dissolves completely in the matrix material at a temperature above its glass transition temperature, thus, for example, the kinking problem with respect to the Reinforcing fibers is eliminated.
  • it crosslinks with the matrix material when it hardens to a homogeneous matrix.
  • the crosslinking takes place on the basis of as well as on the OH-groups repeated many times along the molecular chain.
  • the polyhydroxyether fiber material is thus integrated into the matrix and can no longer adversely affect the mechanical properties of the component.
  • the result is a composite material consisting of only the two phases, namely reinforcing fiber and matrix. The problem of incompatibility of matrix and auxiliary thread or auxiliary thread material is eliminated.
  • thermoplastic fiber material spun from a raw material containing polyhydroxyether, wherein the raw material contains polyhydroxyether as a single polymer, wherein the polyhydroxy ether has a substantially amorphous structure, a molecular weight Mw of 10'000 to 80 ' 000 Daltons and a glass transition temperature T g of not more than 100 ° C.
  • Molecular weight Mw means the weight average of the molecular weight. This value is preferably 20,000 to 60,000 daltons, in particular 30,000 to 55,000 daltons. These polymers are thermoplastic and linear in contrast to the chemically related epoxy, which is of great importance for fiber spinning. Under suitable cooling conditions they solidify completely amorphous. This is advantageous in the above-mentioned use for stabilizing the reinforcing fibers (or a preform made therefrom) prior to their embedding in the matrix of fiber composites, because they are easier to dissolve. Its glass transition temperature Tg (DSC) is typically between 84 ° and 98 ° C and is preferably less than 95 ° C, and more preferably less than 90 ° C.
  • a polyhydroxy ether can be used in which with short, grafted polycaprolactone side chains (eg
  • the glass transition temperature Tg has been reduced e.g. to a value between 30 and 80 ° C, so that this is a few degrees below the curing temperature.
  • a reduction of the glass transition temperature Tg can also be achieved by adding a plasticizer.
  • the fibrous material according to the invention may be a monofilament or contain such, e.g. having a linear density of 20-12,000 dtex, preferably 100-3,000 dtex, and more preferably 200-1,500 dtex.
  • the fibrous material of the present invention may be or may contain a multifilament yarn having a plurality of single filaments, e.g. with a total titre of 20-5,000 dtex, preferably 100-1,500 dtex.
  • the number of individual filaments is e.g. 10-120, preferably 20-50.
  • the fibrous material according to the invention may also be a staple fiber or contain such and, e.g. be further processed by conventional spinning processes to ring yarn, compact yarn, rotor yarn or carded yarn.
  • textile fabrics such as woven fabrics, knitted fabrics, knitted fabrics, nonwovens, felts, scrims or the like.
  • the unit m 3 / kg means that it is the specific blast air consumption relative to the polymer throughput, ie the ratio of the blast air flow rate (in m 3 blast air per unit time) to the polymer mass flow (in kg per same time unit), the throughput goes through the spinning machine or is produced in the form of polymer threads.
  • the melt spinning method according to the present invention may include a method of spinning cables followed by stretching and cutting into staple fibers, a process of single-stage staple fiber staple stretching, bulk continuous filament spinning (BCF), filament spinning of partially oriented yarn (POY) or fully drawn yarn (FDY), electrospinning of microfibers, or even a process of spinning monofilaments in air or in a water bath.
  • BCF bulk continuous filament spinning
  • POY filament spinning of partially oriented yarn
  • FDY fully drawn yarn
  • electrospinning of microfibers or even a process of spinning monofilaments in air or in a water bath.
  • thermoplastic fiber material according to the invention could be produced only by melt spinning.
  • the stated melt spinning process is preferred because of its economy.
  • thermoplastic fiber material as defined above as according to the invention in the manufacture of components from Fiber composites with embedded in a matrix reinforcing fibers for fixing the reinforcing fibers in a defined geometric arrangement before their embedding in the matrix.
  • the reinforcing fibers can in this case be fixed with a thread made of the thermoplastic fiber material, in particular by embroidery, sewing and / or weaving techniques.
  • the reinforcing fibers can also be fixed with a textile fabric made of the thermoplastic fiber material by such a sheet, in particular in the form of a so-called nonwoven fabric made of staple fibers, e.g. sandwiched between the layers of a multi-axial web of reinforcing fibers.
  • a textile fabric made of the thermoplastic fiber material by such a sheet, in particular in the form of a so-called nonwoven fabric made of staple fibers, e.g. sandwiched between the layers of a multi-axial web of reinforcing fibers.
  • a stabilized preform is to use a sheet, e.g. a fabric or a scrim, consisting of a mixture of reinforcing fibers and polyhydroxyether fiber material according to the invention in a hot press above the softening temperature of the polyhydroxyether fiber material to press and shape.
  • the polyhydroxy ether melts fiber material and serves as a hot melt adhesive which stabilizes and holds together the preform after cooling and solidification.
  • the matrix material of the polyhydroxyether melt adhesive remains mechanically stable and only during the curing of the matrix material it dissolves in this and cross-linked with the matrix material to form a homogeneous matrix.
  • the fiber material according to the invention can be used particularly well together with reinforcing fibers of glass, carbon, aramid, polybenzoxazole, polybenzimidazole and / or other, so-called "rigid rod” polymers as well as matrix materials of a crosslinkable resin system such as epoxy resin, unsaturated polyester resin, isocyanate ester resin, phenolic resin, Formaldehyde-phenolic resin, melamine resin or a combination of these resins.
  • a crosslinkable resin system such as epoxy resin, unsaturated polyester resin, isocyanate ester resin, phenolic resin, Formaldehyde-phenolic resin, melamine resin or a combination of these resins.
  • the matrix could also consist entirely of polyhydroxyether.
  • the temperature should be higher than the glass transition temperature Tg of the polyhydroxyether used in the fiber material according to the invention, so that according to the invention the fiber material dissolves in the matrix and crosslinks with it.
  • the polyhydroxyether fiber material according to the invention is preferably produced by melt spinning. Especially preferred is a spin-draw process.
  • the raw material used was a commercially available polyhydroxyether, as sold, for example, by InChem under the name InChemRez® PKHH phenoxy resin, having a molecular weight Mw of 52,000 daltons. Its glass transition temperature Tg (DSC) was 92 ° C. The use of higher or lower molecular weight InChemRez® grade or the use of a similar raw material from another manufacturer would also be possible.
  • the polyhydroxyether polymer was fed in the form of pellets to the spinning machine. If necessary, heat and UV stabilizers or other additives in this phase can still be added via a volumetric or preferably via a gravimetric dosing unit.
  • the pellets were previously dried to a residual moisture of less than 0.01% H 2 O to prevent formation of water vapor bubbles in the melt. In the spun filaments such bubbles lead to defects, which can lead to tearing even at the lowest mechanical stress.
  • a vacuum tumble dryer was used for drying. It was dried for 15 hours at 80 ° C.
  • the residence time should therefore be less than 15 minutes.
  • the residence time is less than 10 minutes and more preferably even less than 8 minutes.
  • the spinning machine and the spinning parameters were suitably designed, i.a. by using only one extruder per spinneret and thus a relatively short melt line and a volume-optimized spinneret.
  • the extruder and spinning head temperature should be adapted to the melt viscosity, respectively to the molecular weight of the polymer, so that the material is sufficiently ductile and no brittle fractures occur immediately after the spinning head, where the spinning distortion is high.
  • InChemRez®-PKHH these are about 100 ° above its initial flow temperature, that is to say at 240 to 300 ° C., preferably at 260 to 280 ° C.
  • the nozzle plate had capillaries with a diameter of 0.5 mm, with diameters of 0.35 to 0.80 mm would also be possible. This resulted in a nozzle pressure of about 50 to 100 bar, which guaranteed a uniform distribution of the melt on all capillaries (nozzle hole bores).
  • the nozzle plate was provided with a diameter of 180 mm with only 40 capillaries.
  • the capillary density was thus smaller than 0.25 holes / cm 2 . It was thus also about 10 times smaller than in melt spinning for example of polyester or polyamide usual.
  • the mutual spacing of the individual filaments emerging from the capillaries was conversely comparatively large and the thread curtain formed by the individual filaments comparatively particularly well permeable. This enabled optimum passage of the blast air flow and thus a very effective cooling of the individual filaments.
  • the blast air consumption was 200 - 300 m 3 / kg.
  • the blowing air was additionally pre-cooled to approx. 16 ° C. As mentioned, was blown in the cross flow. Central blowing would also be possible and possibly even preferable.
  • the convergence length between the nozzle plate and a preparation device before the first godet duo was about 5 m and was thus much larger than those used in melt spinning the usual fiber polymers.
  • the individual filaments had relatively much time for cooling and loss of stickiness.
  • the Galettenduos were heated to fix the multifilament yarn formed from the individual filaments after stretching at temperatures between 80 and 120 ° C.
  • the fixation could be further improved and disturbing shrinkage in further processing can be largely prevented.
  • the polyhydroxyether multifilament yarn thus prepared had the following properties: titres tex 50 Number of individual filaments f 40 Tensile strength N 5.5 tensile strength CN / tex 11 elongation at break % 41 rice energy N cm 102 Glass transition temperature ° C 93
  • Example 2 The same spinning system was used as in Example 1 and the same procedure was followed.
  • the lower melt viscosity allowed reduced spinning temperatures of 200 to 220 ° C at which the material under the spinneret was still sufficiently ductile. At this lower temperature level, gas bubble formation in the melt could be avoided. Thus, no intensive blowing of the filaments was necessary.
  • the lower extrusion temperature required milder cooling conditions to keep the fresh filament stretchable, so the cooling air flow was reduced to 10-50m 3 / kg.
  • the take-off speed was 1500 m / min and only one final stretch could be set by a factor of 1.1 - 1.2.
  • the filaments were air-swirled with a Heberlein Polyjet SP25 for better thread closure.
  • the produced polyhydroxyether multifilament yarn had the following properties: titres tex 50 Number of individual filaments f 28 Tensile strength N 4.7 tensile strength CN / tex 9.4 elongation at break % 38 Glass transition temperature ° C 85
  • Example 1 Due to the lower molecular weight than in Example 1, the yarn had a slightly lower tensile strength, but the spinning process was more stable and the yarn showed hardly any broken individual filaments.
  • Example 1 On a pilot staple fiber line developed and built by EMS-CHEMIE, 10 bobbins of Example 1 were pulled off parallel with this polyhydroxyether multifilament yarn and plied, air-textured and cut into staple fibers with a staple length of 80 mm.
  • the application properties of the polyhydroxyether fiber material were determined by tests as follows:
  • the cross-linking was checked by an extraction test.
  • 10% short cut polyhydroxyether fibers in epoxy (Araldite® PY306 from Huntsman, Araldite® MY0510 from Huntsman, EPICURE TM 3601 from Resolution Performance Products) were dissolved and cured.
  • the cast plate was milled with dry ice cooling and particles less than 60 microns were deposited.
  • a plate without polyhydroxyether fibers and one with 10% polyester fibers (GRILENE® F3 6.7dtex) was prepared and prepared in the same manner.
  • the powder fractions> 60 microns were extracted in m-cresol (Merck) for 2 hours at 95 ° C with stirring.
  • the polyhydroxyether fiber material had completely dissolved under these conditions.
  • the mechanical properties were tested on carbon fiber - epoxy composite panels.
  • a 1200 mm wide UD fabric was produced with a T-700S 6K carbon fiber from Toray. In the shot everyone was 10 mm for fixation a polyhydroxyether multifilament yarn 500 dtex f40 woven.
  • a sample was used with a commercially available Trevira® filament yarn (330 dtex), ie a finer thread, which should be less disturbing due to the thinner cross-section.
  • the bending strength of the sample plate with polyhydroxyether fiber material according to the invention could be improved by 12% compared to the reference plate with polyester filament.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
EP20060005377 2005-03-22 2006-03-16 Matériau fibreux thermoplastique filé à partir d'une matière première contenant un polyhydroxyéther, son procédé de préparation et ses utilisations Active EP1705269B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20060005377 EP1705269B1 (fr) 2005-03-22 2006-03-16 Matériau fibreux thermoplastique filé à partir d'une matière première contenant un polyhydroxyéther, son procédé de préparation et ses utilisations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05006232 2005-03-22
EP20060005377 EP1705269B1 (fr) 2005-03-22 2006-03-16 Matériau fibreux thermoplastique filé à partir d'une matière première contenant un polyhydroxyéther, son procédé de préparation et ses utilisations

Publications (2)

Publication Number Publication Date
EP1705269A1 true EP1705269A1 (fr) 2006-09-27
EP1705269B1 EP1705269B1 (fr) 2008-01-16

Family

ID=36847741

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060005377 Active EP1705269B1 (fr) 2005-03-22 2006-03-16 Matériau fibreux thermoplastique filé à partir d'une matière première contenant un polyhydroxyéther, son procédé de préparation et ses utilisations

Country Status (1)

Country Link
EP (1) EP1705269B1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1904559A1 (fr) 2005-07-05 2008-04-02 Fibre e Tessuti Speciali S.p.A. Matériau composite
WO2011113752A1 (fr) 2010-03-18 2011-09-22 Toho Tenax Europe Gmbh Tissus multiaxiaux présentant des non-tissés polymères
WO2011113751A1 (fr) 2010-03-18 2011-09-22 Toho Tenax Europe Gmbh Tissu multiaxial cousu
CN102965789A (zh) * 2011-08-30 2013-03-13 东丽纤维研究所（中国）有限公司 一种轻薄抗静电防风织物及其生产方法
EP2631337A1 (fr) 2012-02-24 2013-08-28 EMS-Patent AG Structure fibreuse, son procédé de fabrication et son utilisation ainsi que matériau composite la comprenant
DE102013226921A1 (de) * 2013-12-20 2015-06-25 Sgl Automotive Carbon Fibers Gmbh & Co. Kg Vliesstoff aus Carbonfasern und thermoplastischen Fasern
CN105964059A (zh) * 2016-06-22 2016-09-28 东华大学 一种增能的聚乙烯/聚丙烯双组分纺粘滤料及其制备方法
WO2018184992A1 (fr) 2017-04-03 2018-10-11 Toho Tenax Europe Gmbh Procédé pour produire un tissu textile unidirectionnel
WO2020225019A1 (fr) 2019-05-09 2020-11-12 Teijin Carbon Europe Gmbh Matelas multi-axial comprenant une couche intermédiaire discontinue

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3375297A (en) 1965-05-27 1968-03-26 Union Carbide Corp Mixtures of polyhydroxyethers and polyarylene polyethers
US3405199A (en) 1962-12-04 1968-10-08 Union Carbide Corp Flame retarded compositions comprising a thermoplastic polyhydroxyether and a rubber
WO1991001394A1 (fr) 1989-07-25 1991-02-07 Courtaulds Plc Composition d'appret pour fibres
US6020063A (en) 1997-07-31 2000-02-01 Virginia Tech Intellectual Properties, Inc. Composites of thermosetting resins and carbon fibers having polyhydroxyether sizings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3405199A (en) 1962-12-04 1968-10-08 Union Carbide Corp Flame retarded compositions comprising a thermoplastic polyhydroxyether and a rubber
US3375297A (en) 1965-05-27 1968-03-26 Union Carbide Corp Mixtures of polyhydroxyethers and polyarylene polyethers
WO1991001394A1 (fr) 1989-07-25 1991-02-07 Courtaulds Plc Composition d'appret pour fibres
US6020063A (en) 1997-07-31 2000-02-01 Virginia Tech Intellectual Properties, Inc. Composites of thermosetting resins and carbon fibers having polyhydroxyether sizings

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1904559A1 (fr) 2005-07-05 2008-04-02 Fibre e Tessuti Speciali S.p.A. Matériau composite
EP3103906A1 (fr) 2010-03-18 2016-12-14 Toho Tenax Europe GmbH Structure multi-axiale suturee
WO2011113752A1 (fr) 2010-03-18 2011-09-22 Toho Tenax Europe Gmbh Tissus multiaxiaux présentant des non-tissés polymères
WO2011113751A1 (fr) 2010-03-18 2011-09-22 Toho Tenax Europe Gmbh Tissu multiaxial cousu
US8613257B2 (en) 2010-03-18 2013-12-24 Toho Tenax Europe Gmbh Stitched multiaxial non-crimp fabrics
AU2011229316B2 (en) * 2010-03-18 2014-06-12 Toho Tenax Europe Gmbh Multiaxial laid scrim having a polymer nonwoven
RU2562490C2 (ru) * 2010-03-18 2015-09-10 Тохо Тенакс Ойропе Гмбх Мультиаксиальное многослойное нетканое полотно, содержащее полимерный нетканый материал
US9371604B2 (en) 2010-03-18 2016-06-21 Toho Tenax Europe Gmbh Multiaxial non-crimp fabrics having polymer non-wovens
CN102965789A (zh) * 2011-08-30 2013-03-13 东丽纤维研究所（中国）有限公司 一种轻薄抗静电防风织物及其生产方法
CN102965789B (zh) * 2011-08-30 2015-06-17 东丽纤维研究所（中国）有限公司 一种轻薄抗静电防风织物及其生产方法
EP2631337A1 (fr) 2012-02-24 2013-08-28 EMS-Patent AG Structure fibreuse, son procédé de fabrication et son utilisation ainsi que matériau composite la comprenant
US9346943B2 (en) 2012-02-24 2016-05-24 Ems-Patent Ag Fiber structure, method for its manufacture and use as well as fiber-resin composite material
DE102013226921A1 (de) * 2013-12-20 2015-06-25 Sgl Automotive Carbon Fibers Gmbh & Co. Kg Vliesstoff aus Carbonfasern und thermoplastischen Fasern
CN105964059A (zh) * 2016-06-22 2016-09-28 东华大学 一种增能的聚乙烯/聚丙烯双组分纺粘滤料及其制备方法
CN105964059B (zh) * 2016-06-22 2018-01-19 东华大学 一种增能的聚乙烯/聚丙烯双组分纺粘滤料及其制备方法
WO2018184992A1 (fr) 2017-04-03 2018-10-11 Toho Tenax Europe Gmbh Procédé pour produire un tissu textile unidirectionnel
US11047073B2 (en) 2017-04-03 2021-06-29 Toho Tenax Europe Gmbh Method for producing a textile unidirectional fabric
WO2020225019A1 (fr) 2019-05-09 2020-11-12 Teijin Carbon Europe Gmbh Matelas multi-axial comprenant une couche intermédiaire discontinue

Also Published As

Publication number Publication date
EP1705269B1 (fr) 2008-01-16

Similar Documents

Publication Publication Date Title
EP1705269B1 (fr) Matériau fibreux thermoplastique filé à partir d'une matière première contenant un polyhydroxyéther, son procédé de préparation et ses utilisations
US8409486B2 (en) Method for making structural parts with reinforcement fiberes embedded in a matrix material using thermoplastic fibers containing polyhydroxyether
AT395863B (de) Verfahren zur herstellung eines cellulosischen formkoerpers
DE4136694C2 (de) Stärkefaser oder Stärke-modifizierte Faser, Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE69030338T3 (de) Verfahren zur Herstelung von Fasern, Rovings und Matten aus flüssigkristallinen lyotropen Polymeren
EP1888830B1 (fr) Fibre de polypropylene pour le renforcement de materiaux matrices
EP0574870B1 (fr) Procédé de fabrication d'articles moulés en cellulose
WO2019119736A1 (fr) Filament composite à deux composants à haute résistance à structure peau-âme et procédé de préparation s'y rapportant
DE60125964T2 (de) Gekräuselte faser und verfahren zu deren herstellung
WO2001011123A1 (fr) Fils en polyester a resistance elevee et procede de fabrication desdites fibres
EP0031078B2 (fr) Fibres et filaments synthétiques de titre très fin et procédé de filage à sec pour leur fabrication
KR20050003126A (ko) 타이어 코드용 라이오셀 멀티 필라멘트 및 이의 제조방법
DE69726017T2 (de) Bikomponentenfasern in mantelkernstruktur, welche fluor polymere enthalten und verfahren zu deren herstellung und benutzung
EP1658395A1 (fr) Corps moules, en particulier fibres et leurs structures en surface, a proprietes thermoregulatives
WO2019138093A1 (fr) Corps moulé présentant de l'élasthanne incorporé dans de la cellulose et procédé de fabrication
EP1334223B1 (fr) Procede de production de fils synthetiques a base de melanges polymeres
CN113026212A (zh) 一种聚苯硫醚复合无纺布及其制备方法和应用
EP3867425A1 (fr) Polyéthers aromatiques étirés
KR101225557B1 (ko) 리오셀 타입 셀룰로오스 섬유
EP0944750B1 (fr) Fibres de polyacrylonitrile hautement resistantes et a module eleve, leur procede de fabrication et leur utilisation
EP2660372A1 (fr) Fibres thermoplastiques avec une tension de surface réduite
DE10026281A1 (de) Verfahren zur Herstellung von Spinnvliesen
DE10201834B4 (de) Herstellung dimensionsstabiler Polyesterfäden
EP0645479A1 (fr) Fibres de polyacrylonitrile ayant une haute tenacité et un haut module, procédé de leur préparation et leur utilisation
WO1999057348A1 (fr) Fibres et filaments de polyester et procede permettant de les preparer

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20060907

17Q First examination report despatched

Effective date: 20061206

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RTI1 Title (correction)

Free format text: THERMOPLASTIC FIBER MATERIAL SPUN FROM A MATERIAL COMPRISING A POLYHYDROXYETHER, METHOD FOR PREPARING THE SAME, AND ITS USE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20080116

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502006000292

Country of ref document: DE

Date of ref document: 20080306

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2301104

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080516

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080416

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080616

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080416

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080331

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

26N No opposition filed

Effective date: 20081017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080717

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080417

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502006000292

Country of ref document: DE

Representative=s name: BEATE KOENIG, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 502006000292

Country of ref document: DE

Representative=s name: KOENIG, BEATE, DIPL.-PHYS. DR.RER.NAT., DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 502006000292

Country of ref document: DE

Representative=s name: MEISSNER BOLTE PATENTANWAELTE RECHTSANWAELTE P, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20140217

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20140303

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20140319

Year of fee payment: 9

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150316

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502006000292

Country of ref document: DE

Representative=s name: MEISSNER BOLTE PATENTANWAELTE RECHTSANWAELTE P, DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230322

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230321

Year of fee payment: 18

Ref country code: DE

Payment date: 20220620

Year of fee payment: 18

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230412

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230321

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230328

Year of fee payment: 18

Ref country code: ES

Payment date: 20230527

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240320

Year of fee payment: 19