EP1597418B1 - Fibres de polypropylene - Google Patents

Fibres de polypropylene Download PDF

Info

Publication number
EP1597418B1
EP1597418B1 EP04709618A EP04709618A EP1597418B1 EP 1597418 B1 EP1597418 B1 EP 1597418B1 EP 04709618 A EP04709618 A EP 04709618A EP 04709618 A EP04709618 A EP 04709618A EP 1597418 B1 EP1597418 B1 EP 1597418B1
Authority
EP
European Patent Office
Prior art keywords
copolymer
ethylene
propylene
heterophasic
fibres
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.)
Expired - Lifetime
Application number
EP04709618A
Other languages
German (de)
English (en)
Other versions
EP1597418A1 (fr
Inventor
Henk Van Paridon
Nancy Noynaert
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.)
Borealis Technology Oy
Original Assignee
Borealis Technology Oy
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 Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to EP04709618A priority Critical patent/EP1597418B1/fr
Publication of EP1597418A1 publication Critical patent/EP1597418A1/fr
Application granted granted Critical
Publication of EP1597418B1 publication Critical patent/EP1597418B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the present invention relates to novel fibres comprising propylene copolymers. More particularly, the invention relates to fibres comprising heterophasic propylene copolymers, especially heterophasic propylene copolymers containing a propylene random copolymer and an ethylene rubber copolymer.
  • polypropylene is widely used in many fibre and fabric applications. However, it is generally deficient in applications that require high softness. Such applications include nonwoven fabrics for disposable garments or diapers and also for furniture applications. For soft-end use fibre and fabric applications random copolymers have come into use since they can be processed into fibres and fabrics that exhibit improved softness and drape characteristics compared to fibres and fabrics made from propylene homopolymers.
  • the propylene copolymers are described as being an "alloy" from a random propylene copolymer having an ethylene content of 1-5 wt% and a bipolymer having an ethylene content of 10-30 wt%.
  • the propylene copolymer alloy is further described as having a single T g peak, this being an indication as to the miscibility of the random copolymer and the bipolymer.
  • the miscibility of the random copolymer and the bipolymer is disclosed to be a prerequisite for spinnability.
  • fibres from propylene copolymers which fibres shall be characterised by excellent softness.
  • the fibres shall be producible in an economical process, i.e. with high production speeds and without causing processing problems.
  • the fibres of the present invention are characterised by a heterophasic propylene copolymer having at least two discernible T g peaks. Nevertheless, as will be further shown below, these heterophasic propylene copolymers are perfectly spinnable with high uptake speeds and the produced fibres are characterised by excellent softness.
  • the ethylene content may range from 20 - 80 wt% preferably from 20 - 50 wt%, Accordingly, the C 3 -C 8 ⁇ -olefin content may range from 80 - 20 wt%, preferably from 80 - 50 wt%, According to a preferred embodiment the ethylene rubber copolymer is an ethylene propylene rubber (EPR).
  • EPR's are more cost-effective than ethylene rubbers with higher ⁇ -olefins and they can either be synthesised in the second step of a two-step process, where the first step synthesises the matrix polymer or they can be mixed with the matrix polymer in a separate melt blending step.
  • the heterophasic propylene copolymer contains 2 -15 wt%, preferably 5 -12 wt% of the ethylene rubber copolymer. These concentration ranges for the ethylene rubber are preferred, because fibres from heterophasic propylene copolymer with the above amounts of ethylene rubber copolymer offer the best compromise as to spinnability and mechanical properties, which both in general decrease with higher rubber contents, and softness, which generally increases with higher rubber content.
  • the heterophasic propylene copolymer has an MFR of from 0.1 - 50 g/10 min, preferably 2.5 - 30 g/10 min. While in general a wide range of MFR's, e.g.
  • the heterophasic propylene copolymer has an MFR of from 200 - 2000 g/10 min.
  • the production of melt blown nonwoven fabrics of this invention requires MFR's in the range of from 200 - 2000 g/10 min.
  • Heterophasic propylene copolymers having the desired MFR's may be obtained by vis-breaking the low-MFR polymer with e.g. peroxides, or they may be available directly from the polymerisation process by suitable choice of conditions.
  • the fibres of the invention comprise a heterophasic propylene copolymer having an overall ethylene content of from 1.0 -15.0 wt%.
  • the heterophasic propylene copolymers of which the fibres of the invention are comprised preferably show two T g temperatures.
  • the first of these glass transition temperatures preferably is in the range of from -15 to +5°C, more preferably around 0°C.
  • This first T g temperature usually is attributed to the matrix phase and is influenced by the comonomer content of the matrix phase. In the case of ethylene as comonomer it is lower with higher ethylene contents.
  • the second of these glass transition temperatures preferably is in the range of from -35 to -65°C, more preferably from -40 to -60°C and most preferably around -50°C.
  • the second T g usually is attributed to the rubber copolymer of the disperse phase and it is influenced by its molecular weight and its ethylene content.
  • a particularly preferred embodiment refers to a fibre comprising a heterophasic propylene copolymer which contains 80 - 95 wt% of a matrix phase comprising a propylene random copolymer with from 1.0 -15.0 wt% of ethylene and 5 - 20 wt% of a disperse phase comprising an ethylene propylene rubber with from 20 - 40 wt% of ethylene and 80-60 wt% of propylene, the heterophasic propylene copolymer having an overall ethylene content of from 4.0 -12.0 wt% and two distinct T g peaks. Fibres made from these heterophasic propylene copolymer are characterised by superior softness, and contrary to the disclosure of US 6,218,010 , the heterophasic propylene copolymer has two T g peaks.
  • the invention also refers to articles comprising fibres according to the invention.
  • fabric articles include, but are not limited to: nonwoven fabrics for hygiene applications such as diapers, medical gowns and masks; woven fabrics for upholstery and clothing; ropes, twines, carpets.
  • the heterophasic propylene copolymers may be used to produce fibres of the following types; continuous fibre, bulked continuous fibre, staple fibre, monofilament fibre, stretch tape, strapping; and nonwoven fabrics which are spunbonded, meltblown, or produced from staple fibre.
  • the heterophasic propylene copolymers may be produced by multistage process polymerisation of propylene and ethylene and/or an ⁇ -olefin such as bulk polymerisation, gas phase polymerisation, slurry polymerisation, solution polymerisation or combinations thereof using conventional catalysts.
  • Those processes are well known to one skilled in the art.
  • a preferred process is a combination of bulk slurry loop reactor(s) and gas phase reactor(s).
  • the matrix polymer can be made either in loop reactors or in a combination of loop and gas phase reactor.
  • the polymer produced in this way is transferred into another reactor and the disperse phase is polymerised.
  • this polymerisation step is done in a gas phase polymerisation.
  • a suitable catalyst for the polymerisation of the heterophasic copolymer is any stereospecific catalyst for propylene polymerisation which is capable of polymerising and copolymerising propylene and comonomers at a temperature of 40 to 110°C and at a pressure from 10 to 100 bar.
  • Ziegler Natta catalysts as well as metallocene catalysts are suitable catalysts.
  • One skilled in the art is aware of the various possibilities to produce such heterophasic systems and will simply find out a suitable procedure to produce suitable heterophasic polymer systems which are used in the present invention.
  • the heterophasic propylene copolymer may also be produced by mixing and melt blending a propylene random copolymer with an ethylene rubber copolymer.
  • a heterophasic propylene copolymer prepared as explained above, may be subjected to a controlled rheology (CR) process well known in the art, whereby the copolymer is visbroken into a resin having a narrower molecular weight distribution and lower average molecular weight in order to facilitate fibre spinning.
  • the molecular weight (MW) of the visbroken heterophasic copolymer determines the level of melt viscosity and the ultimate desirable physical properties of the fibre.
  • the MFR of the visbroken copolymer as determined by the MFR test (ISO 1133) may vary within a wide range from fractional to about 2000 g/10 minutes.
  • the CR process is preferably carried out by using organic peroxides, such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane).
  • organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
  • the compounds used in the CR process are added to the polymer and the polymer is , for example, visbroken during the extrusion step.
  • the CR process may also convert the polymer granules to pellets for easier feeding into the fibre spinning extruder.
  • Additives such as stabilizers, pigments, fillers, antioxidants, ultra-violet screening agents, nucleating agents, certain processing oils and the like may optionally be added; however, this should not be considered a limitation of the present invention.
  • the heterophasic copolymer is then drawn to a fine diameter fibre by one of several well known in the art modifications of the basic melt-extrusion fibre process.
  • This process consists of the steps of (1) continuously feeding the heterophasic copolymer to a melting screw extruder; (2) At the end of the screw, a spinning pump meters the melted polymer through a filter to a spinneret where the melted polymer is extruded under pressure through capillaries, typically at a rate of about 0.3-1.0 grams per hole per minute; the capillaries, depending upon the desired fibre product, may vary widely in number, size and shape; (3) solidifying the fibres by transferring the heat to a surrounding medium; and (4) winding of the solidified fibres onto packages.
  • Further processing typically includes orienting the fibres by drawing them to many times their original length. Also, a variety of thermal and texturing treatments well known in the art may be employed, depending on the desired final properties of the fibre. Embodiments of the present invention fibres can be drawn into fine diameter fibres at generally high drawdown speed, without the individual fibres sticking together below the crystallization point.
  • a particular embodiment of the present invention involves the use of the heterophasic copolymers for spunbonded fabrics.
  • the spunbonding process is one which is well known in the art of fabric production. Generally, continuous fibres are extruded, laid on an endless belt, and then bonded to each other, and often times to a second layer such as a melt blown layer, often by a heated calander roll, or addition of a binder, or by a mechanical bonding system (entanglement) using needles or hydro jets.
  • a typical spunbond process consists of a continuous filament extrusion, followed by drawing, web formation by the use of some type of ejector, and bonding of the web.
  • the heterophasic copolymer is visbroken using peroxide into a resin having a narrower molecular weight distribution and about 25 MFR. During this step the polymer granules are converted into pellets.
  • the pelletised 25 MFR heterophasic copolymer resin is then fed into an extruder. In the extruder, the pellets simultaneously are melted and forced through the system by a heating melting screw. At the end of the screw, a spinning pump meters the melted polymer through a filter to a spinneret where the melted polymer is extruded under pressure through capillaries, at a rate of 0.3-1.0 grams per hole per minute.
  • the spinneret contains up to 6000 capillaries per metre of die width, measuring 0.4-0.6 mm in diameter.
  • the polymer is melted at about 30°C -120°C above its melting point to achieve sufficiently low melt viscosity for extrusion.
  • the fibres exiting the spinneret are quenched and drawn into fine fibres measuring 10 - 40 microns in diameter by cold air jets, reaching filament speeds of up to 5000 metres per minute.
  • the solidified fibre is laid randomly on a moving belt to form a random netlike structure known in the art as web. After web formation the web is bonded to achieve its final strength using a heated textile calander known in the art as thermobond calander.
  • the calander consists of two heated steel rolls; one roll is plain ant the other bears a pattern of raised points.
  • the web is conveyed to the calander wherein a fabric is formed by pressing the web between the rolls at a bonding temperature of about 130°C -150°C.
  • Crystallisation temperatures are determined by DSC measurement according to ISO 3146 at a cooling rate of 10 K/min after a first heating to 200°C.
  • the shear thinning index SHI is calculated from the flow curve ⁇ ( ⁇ ) at 200°C - which can be determined with a capillary rheometer according to ISO 11443 or calculated from the complex shear viscosity determined with a plate-plate rheometer according to ISO 6271-10 using the "Cox-Merz rule" relating the shear viscosity to the dynamic viscosity as described in W.P. Cox & E.H. Merz, J.Polym.Sci. 28(1958) 619-623 .
  • the SHI (0/50) is defined as the ratio between the zero shear viscosity ( ⁇ 0 ) and the viscosity at a stress ( ⁇ ) value of 50000 Pa.
  • the shear thinning index is proportional to the broadness of the molecular weight distribution (MWD) of the polymer. At very high values it can reflect the bimodality of the molecular weight distribution (i.e. the MWD curve shows two maxima or one maximum and a pronounced shoulder). For reasons of processability and homogeneity the higher molecular weight tail will be limited in practice.
  • MWD molecular weight distribution
  • the melt flow rates were measured with a load of 2.16 kg at 230°C.
  • the melt flow rate is that quantity of polymer in grams which the test apparatus standardised to ISO 1133 extrudes within 10 minutes at a temperature of 230 °C under a load of 2.16 kg.
  • Ethylene content in propylene polymer was measured by Fourier transmission infrared spectroscopy (FTIR).
  • FTIR Fourier transmission infrared spectroscopy
  • a thin film of the sample was prepared by hot-pressing.
  • the area of -CH2- absorption peak (800 - 650 cm-1) was measured with Perkin Elmer FTIR 1600 - spectrometer.
  • the method was calibrated by ethylene content data measured by 13 C NMR.
  • xylene solubles fraction For the determination of the xylene solubles fraction, 2.0 g of polymer are dissolved in 250 ml p-xylene at 135°C under agitation. After 30 ⁇ 2 min the solution is allowed to cool for 15 min at ambient temperature and then to settle for 30 min at 25 ⁇ 0.5°C. The solution is filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml flask is evaporated in nitrogen flow and the residue is dried under vacuum at 90 °C until constant weight is achieved.
  • XS largely correlates to the rubber content of the heterophasic polymer.
  • the tests are carried out in accordance with ISO 6721-2 on specimens of 60x10x1 mm cut from compression moulded plaques.
  • a temperature range of at least -100 to +150°C. is covered, using a heating rate of 1°C/min.
  • the storage modulus G' and the tangent of the loss angle tan( ⁇ ) are the primary results of the tests; from tan( ⁇ ) the temperatures - peak position and peak broadness - of the various mobility transitions, such as the glass transition temperature T g , in the systems, which can be attributed to the phases present, can be determined.
  • the mechanical properties of the fibres were determined on a Textechno Statimat M. according to ISO 5079.
  • the gauge length used has been 100 mm for fibres and 200 mm for nonwoven, the speed was 100 m/min.
  • the tensile test method which was used for nonwoven was Edana 20.2-89.
  • Example 1 (invention, propylene/ethylene random heterophasic copolymer)
  • a continuous multistage process was used.
  • the process comprised a prepolymerisation step, a loop reactor and a fluidized bed gas phase reactor.
  • the catalyst used was highly active, stereospecific transesterified MgCl 2 -supported Ziegler-Natta catalyst prepared according to US 5,234,879 at a titanisation temperature of 135°C.
  • the catalyst was contacted with a co-catalyst (triethylaluminium, TEAL), and an external donor (di-cyclopentyl dimethoxysilane) with the Al/Ti ratio of 200 and an Al/Donor ratio of 10, to yield a catalyst system.
  • TEAL triethylaluminium
  • an external donor di-cyclopentyl dimethoxysilane
  • the catalyst system and propylene were fed into the prepolymerisation reactor which was operated at ca. 30°C and ca. 30 bar.
  • the prepolymerised catalyst was used in the subsequent polymerisation reactors.
  • Propylene, ethylene and hydrogen and the prepolymerised catalyst were fed into the loop reactor which was operated as bulk reactor at a temperature of ca. 70°C and a pressure of ca. 30 bar. Then, the polymer slurry stream was fed from the loop reactor into the gas phase reactor which was operated at a temperature of ca. 70°C and a pressure of ca. 20 bar. More propylene, ethylene and hydrogen were fed into the gas phase reactor to control the desired properties of the final polymer.
  • the process comprised a prepolymerisation step and a loop reactor.
  • the catalyst used was highly active, stereospecific transesterified MgCl 2 -supported Ziegler-Natta catalyst prepared according to US 5,234,879 at a titanisation temperature of 135°C.
  • the catalyst was contacted with a co-catalyst (triethylaluminium, TEAL), and an external donor (di-cyclopentyl dimethoxysilane) with the Al/Ti ratio of 200 and an Al/Donor ratio of 10, to yield a catalyst system.
  • TEAL triethylaluminium
  • an external donor di-cyclopentyl dimethoxysilane
  • the catalyst system and propylene were fed into the prepolymerisation reactor which was operated at ca. 30 C and ca. 30 bar.
  • the prepolymerised catalyst was used in the subsequent polymerisation reactors.
  • Propylene, ethylene and hydrogen and the prepolymerised catalyst were fed into the loop reactor which was operated as bulk reactor at a temperature of ca. 70°C and a pressure of ca. 30 bar.
  • the product was degassed before being fed to an extruder for pelletisation.
  • Spinning trials have been performed on a Fourné long spin pilot line.
  • the spinneret used has 52 holes, each having a diameter of 0.5 mm.
  • the throughput per hole has been kept constant at 0.3 g/hole ⁇ min.
  • the take-up speed has been increased stepwise until fibre break.
  • the data of the maximum take-up speeds are shown in table 1. Fibre samples have been taken and mechanical properties have been tested. The results can be seen in Fig. 1 and 2 .
  • Polymer 3 has been evaluated on a Reicofil 3.1 pilot line. It was run on a single beam at a melt temperature of 257°C at the die and a throughput of 180 kg/m/h. Spinning stability was good and at a cabin pressure of 6916 Pa the filament titer was 1.6 denier.
  • the mechanical properties obtained on a 17 g/m 2 web are listed in Table 2 below. Table 2 MD tensile strength (N/5cm) 32.75 CD tensile strength (N/5cm) 22.08 MD elongation (%) 67.57 CD elongation (%) 72.88
  • the samples used for determining softness were yarns produced at 1000 m/min and 235°C from the spinnability test. 600 m of yarn are wound on a reel, doubled (i.e. folded) and the ends secured between 3 cardboard sheets. Evaluation of softness was by black box panel. Seven persons tested each fibre material and marked their tactile impressions on a scale from 1-5. "1" means that the fibre has about the same softness as a fibre from a propylene homopolymer produced under the same conditions. "5" means that the fibre is very much softer than a fibre from a propylene homopolymer produced under the same conditions. The results are shown in Table 3. Table 3 Polymer-no. 1 2 3 4 softness relative to homopolymer persons tester no. 1 1 5 5 1 tester no. 2 1 5 5 1 tester no. 3 1 5 5 1 tester no. 4 1 5 5 1 tester no. 5 1 5 5 1 tester no. 6 1 5 5 1 tester no. 7 1 5 5 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Multicomponent Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dental Preparations (AREA)
  • Materials For Medical Uses (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (9)

  1. Fibre comprenant un copolymère hétérophasique de propylène contenant
    a) 80-99 % en poids d'une phase formant matrice comprenant un copolymère statistique de propylène avec 0,2-15 % en poids d'éthylène et/ou d'au moins une α-oléfine en C4 - C8 et
    b) 1-20 % en poids d'une phase dispersée comprenant un copolymère caoutchouc d'éthylène avec 20-80 % en poids d'éthylène et 80-20 % en poids d'au moins une α-oléfine en C3 - C8,
    dans laquelle le copolymère hétérophasique possède au moins deux pics Tg.
  2. Fibre selon la revendication 1, caractérisée en ce que le copolymère caoutchouc d'éthylène est un caoutchouc d'éthylène-propylène.
  3. Fibre selon l'une quelconque des revendications 1 et 2, caractérisée en ce que le copolymère hétérophasique statistique de propylène contient 2-15 % en poids , de préférence 5-12 % en poids, du copolymère caoutchouc d'éthylène.
  4. Fibre selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le copolymère hétérophasique de propylène possède un MFR de 0,1 - 50 g/10 min, de préférence de 2,5 - 30 g/10 min.
  5. Fibre selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le copolymère hétérophasique de propylène possède un MFR de 200 - 2000 g/10 min.
  6. Fibre selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le copolymère hétérophasique de propylène possède une teneur totale en éthylène de 1,0 - 15,0 % en poids.
  7. Fibre selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le copolymère hétérophasique de propylène possède une première Tg dans la plage de -15 à +5°C, de préférence aux environs de 0°C, et une seconde Tg dans la plage de -35 à -65°C, de préférence de -40 à -60°C, et plus particulièrement aux environs de -50°C.
  8. Fibre selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le copolymère hétérophasique de propylène contient 80-95 % en poids d'une phase formant matrice comprenant un copolymère statistique de propylène avec 1,0-15,0 % en poids d'éthylène et 5-20 % en poids d'une phase dispersée comprenant un caoutchouc d'éthylène-propylène avec 20-40 % en poids d'éthylène et 80-60 % en poids de propylène, le copolymère hétérophasique de propylène ayant une teneur totale en éthylène de 4,0-12,0 % en poids et deux pics Tg distincts.
  9. Objets comprenant des fibres selon l'une quelconque des revendications 1 à 8, en particulier des tissus non-tissés, par exemple des couches, des blouses et masques médicaux ; des tissus tissés, par exemple des tapisseries d'ameublement, des vêtements, des cordes, des ficelles et des tapis.
EP04709618A 2003-02-26 2004-02-10 Fibres de polypropylene Expired - Lifetime EP1597418B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04709618A EP1597418B1 (fr) 2003-02-26 2004-02-10 Fibres de polypropylene

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP03004115 2003-02-26
EP03004115A EP1452630A1 (fr) 2003-02-26 2003-02-26 Fibres de polypropylène
PCT/EP2004/001210 WO2004076726A1 (fr) 2003-02-26 2004-02-10 Fibres de polypropylene
EP04709618A EP1597418B1 (fr) 2003-02-26 2004-02-10 Fibres de polypropylene

Publications (2)

Publication Number Publication Date
EP1597418A1 EP1597418A1 (fr) 2005-11-23
EP1597418B1 true EP1597418B1 (fr) 2008-12-17

Family

ID=32748793

Family Applications (2)

Application Number Title Priority Date Filing Date
EP03004115A Withdrawn EP1452630A1 (fr) 2003-02-26 2003-02-26 Fibres de polypropylène
EP04709618A Expired - Lifetime EP1597418B1 (fr) 2003-02-26 2004-02-10 Fibres de polypropylene

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP03004115A Withdrawn EP1452630A1 (fr) 2003-02-26 2003-02-26 Fibres de polypropylène

Country Status (6)

Country Link
EP (2) EP1452630A1 (fr)
AT (1) ATE417948T1 (fr)
DE (1) DE602004018464D1 (fr)
DK (1) DK1597418T3 (fr)
PL (1) PL378558A1 (fr)
WO (1) WO2004076726A1 (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1935938A1 (fr) * 2006-12-18 2008-06-25 Borealis Technology Oy Appareil électronique
EP2025712A1 (fr) * 2007-08-09 2009-02-18 Borealis Technology Oy nouvelles compositions de polyoléfine et bandes, fibres et filaments étirés fabriqués à partir de celles-ci
DE602007003738D1 (de) * 2007-10-11 2010-01-21 Borealis Tech Oy Weiche Polypropylenzusammensetzung mit Soft-Touch-Gefühl
WO2009058477A1 (fr) * 2007-10-31 2009-05-07 Exxonmobil Chemical Patents Inc. Fibres en polypropylène pour non-tissé
EP2151512A1 (fr) * 2008-08-01 2010-02-10 Total Petrochemicals Research Feluy Fibres et non-tissés dotés d'une rugosité de surface améliorée
PL2174980T5 (pl) * 2008-10-07 2019-04-30 Borealis Ag Polipropylen heterofazowy o dużej płynności
EP2223943B1 (fr) * 2009-02-25 2011-10-19 Borealis AG Polymère de propylène multimodal, composition le contenant et son procédé de fabrication
WO2015022127A1 (fr) 2013-08-14 2015-02-19 Borealis Ag Composition de propylène ayant une résistance au choc améliorée à basse température
JP2016528368A (ja) 2013-08-21 2016-09-15 ボレアリス・アクチェンゲゼルシャフトＢｏｒｅａｌｉｓ Ａｇ 高い剛性および靭性を有する高流動ポリオレフィン組成物
CN105452365B (zh) 2013-08-21 2018-04-17 博里利斯股份公司 具有高刚度和韧性的高流动聚烯烃组合物
PT2853563T (pt) 2013-09-27 2016-07-14 Borealis Ag Filmes adequados para processamento de bopp a partir de polímeros com xs elevada e tm elevado
ES2568615T3 (es) 2013-10-11 2016-05-03 Borealis Ag Película para etiquetas orientada en la dirección de la máquina
WO2015059229A1 (fr) 2013-10-24 2015-04-30 Borealis Ag Homopolymère pp à bas point de fusion ayant une haute teneur en regioerreurs et un poids moléculaire élevé
ES2644829T3 (es) 2013-11-22 2017-11-30 Borealis Ag Homopolímero de propileno de baja emisión con alto flujo de masa fundida
CN105793298B (zh) 2013-12-04 2019-06-28 博里利斯股份公司 用于熔喷纤维的不含邻苯二甲酸酯的pp均聚物
CN105980457B (zh) 2013-12-18 2019-03-22 博里利斯股份公司 具有改善的刚性/韧性平衡的bopp膜
CN105829364B (zh) 2014-01-17 2017-11-10 博里利斯股份公司 用于制备丙烯/1‑丁烯共聚物的方法
CN112225997B (zh) 2014-02-06 2023-09-22 北欧化工公司 高冲击强度的柔性共聚物
PL3102634T3 (pl) * 2014-02-06 2020-11-16 Borealis Ag Miękkie i przezroczyste kopolimery odporne na uderzenia
EP2907841A1 (fr) 2014-02-14 2015-08-19 Borealis AG Composition de polypropylène
ES2659731T3 (es) * 2014-05-20 2018-03-19 Borealis Ag Composición de polipropileno para aplicaciones en interiores de automóviles
CN111424360A (zh) * 2020-04-23 2020-07-17 吴宁西 一种具备长效可反复使用的n90级别口罩及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ5693A3 (en) * 1992-01-23 1993-10-13 Himont Inc Elastic yarn of polypropylene polymer and articles made therefrom
IT1264840B1 (it) * 1993-06-17 1996-10-17 Himont Inc Fibre adatte per la produzione di tessuti non tessuti con migliorate caratteristiche di tenacita' e sofficita'
US6235664B1 (en) * 1997-03-04 2001-05-22 Exxon Chemical Patents, Inc. Polypropylene copolymer alloys for soft nonwoven fabrics
EP1041111A1 (fr) * 1997-12-11 2000-10-04 Sumitomo Chemical Company, Limited Composition d'elastomere thermoplastique, poudre, pastilles et articles moules
DE69927221T2 (de) * 1998-01-29 2006-07-13 Sumitomo Chemical Co., Ltd. Thermoplastische elastomerzusammensetzung in pulverform, pulverformverfahren unter verwendung derselben und formteile

Also Published As

Publication number Publication date
EP1597418A1 (fr) 2005-11-23
WO2004076726A1 (fr) 2004-09-10
ATE417948T1 (de) 2009-01-15
EP1452630A1 (fr) 2004-09-01
DK1597418T3 (da) 2009-03-30
DE602004018464D1 (de) 2009-01-29
PL378558A1 (pl) 2006-05-02

Similar Documents

Publication Publication Date Title
EP1597418B1 (fr) Fibres de polypropylene
EP0964889B1 (fr) Alliage de copolymeres de polypropylene son procede de fabricaton et utilisations de l'alliage
EP0192897B1 (fr) Mélange de polyéthylène et de polypropylène
US6218010B1 (en) Polypropylene copolymer alloys for soft nonwoven fabrics
EP2631269B1 (fr) Qualité de fibre dotée d'une amélioration de la performance de filature et des propriétés mécaniques
EP2126168B1 (fr) Fibres de polypropylène et non-tissés spunbound (voie fondue directe) en polypropylène présentant des propriétés améliorées
US9702060B2 (en) Method of producing polypropylene spunbond fibers
JP4212469B2 (ja) 改善された性質を持つプロピレンポリマー樹脂
US5549867A (en) Distribution enhanced polyolefin meltspinning process and product
JP5727615B2 (ja) ファイバー用途で使用するのに適したエチレン／α−オレフィンインターポリマー、およびそれから作製されたファイバー
KR20090087880A (ko) 고점착성 슬릿 필름, 모노필라멘트 및 섬유를 생산하기 위한 수지 조성물
JP3287571B2 (ja) 弾性繊維、生地およびそれらから製造される製品
EP2176341B1 (fr) Nouvelles compositions de polyoléfine et rubans, fibres et filaments produits à partir de ces compositions
EP0658577B1 (fr) Résines à base d'homopolymère de propylène ayant un taux élevé de stéréoséquences
WO2006000404A1 (fr) Nouvelles fibres de polypropylene
Bhat et al. Development of structure and properties during spunbonding of propylene polymers
WO2020058462A1 (fr) Composition de polypropylène pour applications de fibres filées par fusion

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

17P Request for examination filed

Effective date: 20050810

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 IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: VAN PARIDON, HENK

Inventor name: NOYNAERT, NANCY

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

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 IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

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

REF Corresponds to:

Ref document number: 602004018464

Country of ref document: DE

Date of ref document: 20090129

Kind code of ref document: P

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

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: 20081217

Ref country code: NL

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: 20081217

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: 20081217

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

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: 20090328

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: 20081217

Ref country code: BE

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: 20081217

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: 20090317

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: 20081217

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081217

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: 20090317

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: 20090518

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

Ref country code: MC

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

Effective date: 20090228

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: 20081217

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: LI

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

Effective date: 20090228

Ref country code: CH

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

Effective date: 20090228

26N No opposition filed

Effective date: 20090918

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 NON-PAYMENT OF DUE FEES

Effective date: 20090210

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: 20090318

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

Ref country code: LU

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

Effective date: 20090210

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: 20090618

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081217

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: 20081217

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

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

Ref country code: FR

Payment date: 20230220

Year of fee payment: 20

Ref country code: DK

Payment date: 20230220

Year of fee payment: 20

Ref country code: CZ

Payment date: 20230203

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20230223

Year of fee payment: 20

Ref country code: GB

Payment date: 20230220

Year of fee payment: 20

Ref country code: DE

Payment date: 20230216

Year of fee payment: 20

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

Effective date: 20230602

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602004018464

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EUP

Expiry date: 20240210

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20240209

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

Ref country code: CZ

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240210

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240209