WO1999015721A1 - Industrial yarn pa 6.6 with little cotton waste - Google Patents

Industrial yarn pa 6.6 with little cotton waste Download PDF

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Publication number
WO1999015721A1
WO1999015721A1 PCT/CH1997/000357 CH9700357W WO9915721A1 WO 1999015721 A1 WO1999015721 A1 WO 1999015721A1 CH 9700357 W CH9700357 W CH 9700357W WO 9915721 A1 WO9915721 A1 WO 9915721A1
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WO
WIPO (PCT)
Prior art keywords
tex
fluff
industrial yarn
yarn
strength
Prior art date
Application number
PCT/CH1997/000357
Other languages
German (de)
French (fr)
Inventor
Luzius Berger
Klaus Fischer
José LUVIZOTTO
Original Assignee
Rhodia Filtec 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
Priority to CH00862/94A priority Critical patent/CH688554A5/en
Priority to DE59706528T priority patent/DE59706528D1/en
Priority to KR1020007002980A priority patent/KR20010024200A/en
Priority to DK97939933T priority patent/DK1017889T3/en
Priority to US09/509,092 priority patent/US6210799B1/en
Priority to PL97339373A priority patent/PL339373A1/en
Application filed by Rhodia Filtec Ag filed Critical Rhodia Filtec Ag
Priority to EP97939933A priority patent/EP1017889B1/en
Priority to SK409-2000A priority patent/SK4092000A3/en
Priority to ES97939933T priority patent/ES2171995T3/en
Priority to AT97939933T priority patent/ATE213789T1/en
Priority to JP2000513006A priority patent/JP2001517741A/en
Priority to PCT/CH1997/000357 priority patent/WO1999015721A1/en
Publication of WO1999015721A1 publication Critical patent/WO1999015721A1/en

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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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present invention relates to a PA 6.6 industrial yarn consisting of filaments with a total titer of 900 to 2100 dtex, produced by melt spinning of polyamide 6.6 with a pellet viscosity RV> 75, at a winding speed v S p, which must meet the following conditions:
  • the level of the fluff is an essential quality feature for an industrial yarn.
  • polyamide industrial yarns generally have too high a fluff level in the order of more than 1.5 fluff per km.
  • the fluff level is strongly dependent on the moisture content of the polyamide polymer which is fed to the extruder.
  • moisten PA 66 polymer before the extruder or in the melt. The aim is to ensure constant melt quality.
  • the addition of moisture is controlled via moist N2 or as direct water metering, whereby the melt pressure upstream of the spinning pump can be used as a controlled variable.
  • the object of the invention is to provide a PA 66 industrial yarn with a strength of at least 84 cN / tex, which has a minimum of fluff with the fastest possible processing.
  • the PA 6.6 filament has a strength of> 84 cN / tex and less than 1.5 lint / km.
  • the water content of the polymer granules before the extruder is in the range from 0.04 to 0.14% by weight, in particular 0.06 to 0.12% by weight.
  • a polyamide 6.6 polymer post-condensed to a relative viscosity (RV) of approx. 93 was charged with different amounts of water before the extruder, so that the resulting total moisture of the polymer varies between 0.16 and 0.02%.
  • the winding speed was 2750 m / min in all batches.
  • the throughput was constant 46 kg / h.
  • the strength Ft was also constant at 85 cN / tex.
  • the relative granule viscosity was measured in 90% formic acid according to ASTM method D 789-81.
  • the fluff test was carried out with the Warpstop 4050 from Protechna, FRG. 24 wraps / tests were evaluated.
  • Fig. 1 the number of fluff is plotted against the water content in the PA 6.6 polymer granulate before melting.
  • Curve 1 shows the dependency for a titer of dtex 940 with a granulate RV of 93 and a throughput of 46 kg / h;
  • Curve 2 shows the course of the fluff under otherwise identical conditions for a titer of dtex 1400, whose curve course tends to be the same.
  • the fluff level is initially increased with increasing water content of the Original polymer drastically reduced.
  • a water content of 0.02% the moisture from the dryer, there are 5 fluff per kilometer at a winding speed of 2750 m / min.
  • a water content of about 0.09% surprisingly minimum values are achieved with regard to fluff.
  • the fluff numbers increase again sharply.
  • the yarns listed in Examples 1-3 are referred to as SHT yarns (Super High Tenacity), the yarns listed in Examples 4 and 5 are referred to as HT yarns.
  • SHT yarns Super High Tenacity
  • HT yarns a polymer with a relative pellet viscosity RV 93 was spun.
  • the polyamide yarn according to the invention has a lint number that is half that of the prior art.
  • the yarn is preferably suitable for the production of cord fabrics for use in rubber, for example for conveyor belts, drive belts and automobile tires.

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

Abstract

Industrial yarn PA 6.6 comprised of filaments having a global yarn count of at least 900-2100 tex, which is made by submitting wet granulate PA 6.6 to a melt spinning-drawing process, is characterized by a strength of > 84 cN/tex for less than 1.5 linters/1 km. Said yarn is used preferably in the production of cord fabric with a rubber ply.

Description

Flusenarmes PA 6.6 Industrieqarn Low-fluff PA 6.6 industrial yarn
Die vorliegende Erfindung betrifft ein PA 6.6-Industrie- garn, bestehend aus Filamenten mit einem Gesamttiter von 900 bis 2100 dtex, hergestellt durch Schmelzspinnstrecken von Polyamid 6.6 mit einer Granulatviskosität RV > 75, bei einer Spulgeschwindigkeit vSp , die folgende Bedingungen erfüllen muss :The present invention relates to a PA 6.6 industrial yarn consisting of filaments with a total titer of 900 to 2100 dtex, produced by melt spinning of polyamide 6.6 with a pellet viscosity RV> 75, at a winding speed v S p, which must meet the following conditions:
vsp = (Ft0/ Ftx)3 * vspo, wobei Ft = Festigkeit, Ft0 =v sp = (Ft 0 / Ft x ) 3 * v spo , where Ft = strength, Ft 0 =
84 cN/tex, Ftx = eff Ft in cN/tex und vSp0= 2750 m/min (1)84 cN / tex, Ft x = eff Ft in cN / tex and v S p 0 = 2750 m / min (1)
bedeuten, unter Zugabe von Wasser sowie ein Verfahren zur Herstellung eines flusenarmen Industriegarns .mean with the addition of water and a process for producing a lint-free industrial yarn.
Neben der Serimetrie stellt das Niveau der Flusen ein wesentliches Qualitätsmerkmal für ein Industriegarn dar. Bei Spulgeschwindigkeiten von mehr als 2750 m/min weisen Polyamidindustriegarne in der Regel ein zu hohes Flusenniveau in der Grössenordnung von mehr als 1 , 5 Flusen pro km auf. Zur Reduktion der Flusenzahlen musste man bisher die Spinngeschwindigkeit herabsetzen, was Produktivitätseinbussen bringt. Es wurde nun gefunden, dass das Flusenniveau neben der Spinn- und Spulgeschwindigkeit stark vom Feuchtigkeitsgehalt des Polyamidpolymers abhängt, welches dem Extruder zugeführt wird. Es ist bekannt, PA 66 Polymer vor dem Extruder oder in der Schmelze zu befeuchten. Ziel ist dabei jeweils die Sicherstellung konstanter Schmelzequalität. Die Feuchtigkeitszugabe erfolgt dabei geregelt über feuchten N2 oder als direkte Wasserzudosierung, wobei der Schmelzedruck vor der Spinnpumpe als Regelgrösse benutzt werden kann.In addition to the serimetry, the level of the fluff is an essential quality feature for an industrial yarn. At winding speeds of more than 2750 m / min, polyamide industrial yarns generally have too high a fluff level in the order of more than 1.5 fluff per km. In order to reduce the number of fluff, it was previously necessary to reduce the spinning speed, which means a loss in productivity. It has now been found that, in addition to the spinning and winding speed, the fluff level is strongly dependent on the moisture content of the polyamide polymer which is fed to the extruder. It is known to moisten PA 66 polymer before the extruder or in the melt. The aim is to ensure constant melt quality. The addition of moisture is controlled via moist N2 or as direct water metering, whereby the melt pressure upstream of the spinning pump can be used as a controlled variable.
Die Beeinflussung von physikalischen Eigenschaften von schmelzbaren Polyamiden durch Depolymerisation mittels Feuchtigkeit ist aus der EP-B-0 092 898 bekannt. Dort wird durch Zugabe von Wasser die Viskosität konstant gehalten. Die Aufgabe wird in der Herstellung einer Polymerschmelze mit konstanten physikalischen Eigenschaften gesehen.The influencing of physical properties of meltable polyamides by depolymerization by means of moisture is known from EP-B-0 092 898. There the viscosity is kept constant by adding water. The task is seen in the production of a polymer melt with constant physical properties.
Aufgabe der Erfindung ist es, ein PA 66 Industriegarnen mit einer Festigkeit von wenigstens 84 cN/tex zur Verfügung zu stellen, welches bei möglichst schneller Verarbeitung ein Minimum an Flusen aufweist.The object of the invention is to provide a PA 66 industrial yarn with a strength of at least 84 cN / tex, which has a minimum of fluff with the fastest possible processing.
Diese Aufgabe wird erfindungsgemäss dadurch gelöst, dass das PA 6.6-Filament bei einer Festigkeit von > 84 cN/tex und weniger als 1,5 Flusen/km aufweist.This object is achieved according to the invention in that the PA 6.6 filament has a strength of> 84 cN / tex and less than 1.5 lint / km.
In einer Variante mit einer Granulatviskosität RV > 90, einer Feuchtigkeit >0.06 % und einer Festigkeit Ft > 90 cN/tex, kann bei einer Spinngeschwindigkeit Sp0 grösser als die aus der Formel (1) berechnete Spinngeschwindigkeit ein Industriegarn mit hohem Titer und überraschend niedriger Flusenzahl erhalten werden, welche folgender Formel entspricht:In a variant with a pellet viscosity RV> 90, a moisture> 0.06% and a strength Ft> 90 cN / tex, an industrial yarn with a high titer and surprisingly can be produced at a spinning speed S p 0 greater than the spinning speed calculated from the formula (1) low fluff number can be obtained, which corresponds to the following formula:
Flusen Fl < (Ftx/Ft0 )3 * vspx/vspo * Ttx/Tt0, wobei (2 T Ttt0o = ddeerr TTiitteerr 994400 uunndd TTtt-x, der Titer bei der Spulgeschwindigkeit vSpX bedeuten. Der Vorteil liegt in einem tiefen Flusenniveau, das bei Einsatz von trockenem PA 66 Polymergranulat sonst nur bei tiefen Spinnstreckgeschwindigkeiten erzielt werden kann.Fluff Fl <(Ft x / Ft 0 ) 3 * v spx / v spo * Tt x / Tt 0 , where (2 T Ttt 0 o = ddeerr TTiitteerr 994400 and TTtt-x mean the titer at the winding speed v S p X . The advantage lies in a low level of fluff, which when using dry PA 66 polymer granulate can otherwise only be achieved at low spin stretching speeds.
Es ist besonders vorteilhaft, wenn der Wassergehalt des Polymergranulat vor dem Extruder im Bereich von 0,04 - 0,14 Gew.-%, insbesondere 0.06 - 0.12 Gew.-% beträgt.It is particularly advantageous if the water content of the polymer granules before the extruder is in the range from 0.04 to 0.14% by weight, in particular 0.06 to 0.12% by weight.
Die Erfindung soll anhand eines Beispiels näher erläutert werden.The invention will be explained in more detail using an example.
Ein auf ein relative Viskosität (RV) von ca. 93 nachkondensiertes Polyamid 6.6 Polymer wurde vor dem Extruder mit unterschiedlichen Wassermengen beaufschlagt, so dass die resultierende Gesamtfeuchte des Polymers zwischen 0.16 und 0.02 % variiert. Die Spulgeschwindigkeit betrug in allen Ansätzen 2750 m/min. Der Durchsatz war konstant 46 kg/h. Die Festigkeit Ft war mit 85 cN/tex ebenfalls konstant .A polyamide 6.6 polymer post-condensed to a relative viscosity (RV) of approx. 93 was charged with different amounts of water before the extruder, so that the resulting total moisture of the polymer varies between 0.16 and 0.02%. The winding speed was 2750 m / min in all batches. The throughput was constant 46 kg / h. The strength Ft was also constant at 85 cN / tex.
Die Messung der relativen Granulatviskosität erfolgte in 90%-iger Ameisensäure nach ASTM-Methode D 789-81.The relative granule viscosity was measured in 90% formic acid according to ASTM method D 789-81.
Der Flusentest erfolgte mit dem Warpstop 4050 der Firma Protechna, BRD. Es wurden 24 Wickel/Test ausgewertet.The fluff test was carried out with the Warpstop 4050 from Protechna, FRG. 24 wraps / tests were evaluated.
Die Ergebnisse sind in Fig. 1 dargestellt. In Fig. 1 ist die Flusenzahl gegen den Wassergehalt im PA 6.6 Polymergranulat vor dem Schmelzen aufgetragen. Die Kurve 1 zeigt die Abhängigkeit für einen Titer von dtex 940 mit einer Granulat-RV von 93 und einem Durchsatz von 46 kg/h; Kurve 2 zeigt den Flusenverlauf unter ansonsten gleichen Bedingungen für einen Titer von dtex 1400, dessen Kurvenverlauf tendenziell gleich ist.The results are shown in Fig. 1. In Fig. 1, the number of fluff is plotted against the water content in the PA 6.6 polymer granulate before melting. Curve 1 shows the dependency for a titer of dtex 940 with a granulate RV of 93 and a throughput of 46 kg / h; Curve 2 shows the course of the fluff under otherwise identical conditions for a titer of dtex 1400, whose curve course tends to be the same.
Wie aus der Fig. 1 weiter ersichtlich ist, wird das Flusenniveau zunächst mit zunehmendem Wassergehalt des Vorlagepolymers drastisch reduziert. Bei einem Wassergehalt von 0,02 %, der Feuchtigkeit ab Trockner, ergeben sich bei einer Spulgeschwindigkeit von 2750 m/min Flusenzahlen um 5 Flusen pro Kilometer. Bei einem Wassergehalt von etwa 0,09 % werden in Bezug auf Flusen überraschenderweise Minimalwerte erreicht. Bei weiter zunehmendem Wassergehalt nehmen die Flusenzahlen wieder stark zu.As can also be seen from FIG. 1, the fluff level is initially increased with increasing water content of the Original polymer drastically reduced. With a water content of 0.02%, the moisture from the dryer, there are 5 fluff per kilometer at a winding speed of 2750 m / min. With a water content of about 0.09%, surprisingly minimum values are achieved with regard to fluff. As the water content continues to increase, the fluff numbers increase again sharply.
Weitere Beispiele sind in der folgenden Tabelle I aufgeführt.Further examples are listed in Table I below.
Tabelle ITable I
Figure imgf000006_0001
Figure imgf000006_0001
* ohne Zugabe von Wasser* without adding water
Die in den Beispielen 1-3 aufgeführten Garne sind als SHT-Garne (Super High Tenacity) , die in den Beispielen 4 und 5 aufgeführten Garne sind als HT-Garne bezeichnet. Bei allen Beispielen wurde ein Polymer mit einer relativen Granulatviskosität RV 93 verponnen.The yarns listed in Examples 1-3 are referred to as SHT yarns (Super High Tenacity), the yarns listed in Examples 4 and 5 are referred to as HT yarns. In all examples, a polymer with a relative pellet viscosity RV 93 was spun.
Daraus ist ersichtlich, dass die Flusenzahl von weniger als 1,5 Flusen pro km bei einem Wassergehalt von 0.04 bis 0.14, und von weniger als 1 Fluse pro km bei einem Wassergehalt von 0.08 bis 0.11 erreicht wird. Das erfin- dungsgemässe Polyamidgarn weist gegenüber dem Stand der Technik eine um die Hälfte geringere Flusenzahl auf. Das Garn ist bevorzugt zur Herstellung von Kordgeweben für den in Gummi-Einsatz, beispielsweise für Transportbänder, Treibriemen und Automobilreifen geeignet. It can be seen that the fluff count is less than 1.5 fluff per km with a water content of 0.04 to 0.14, and less than 1 fluff per km with a water content of 0.08 to 0.11. The polyamide yarn according to the invention has a lint number that is half that of the prior art. The yarn is preferably suitable for the production of cord fabrics for use in rubber, for example for conveyor belts, drive belts and automobile tires.

Claims

Patentansprüche claims
1. PA 6.6-Industrιegarn, bestehend aus Filamenten mit ei- nem Gesamttiter von 900 bis 2100 dtex, hergestellt durch Schmelzspinnstrecken von Polyamid 6.6 mit einer Granulatv skosität RV > 75, bei einer Spulgeschwm- digkeit vsp , die folgende Bedingungen erfüllen muss:1. PA 6.6 industrial yarn, consisting of filaments with a total titer of 900 to 2100 dtex, produced by melt spinning of polyamide 6.6 with a pellet viscosity RV> 75, at a winding speed v sp , which must meet the following conditions:
vsp = (Ft0/ Ftx)3 * vspo, wobei Ft =v sp = (Ft 0 / Ft x ) 3 * v spo , where Ft =
Festigkeit, Ft0 = 84 cN/tex, Ftx = eff Ft m cN/tex und vSp0= 2750 m/mm (1 )Strength, Ft 0 = 84 cN / tex, Ft x = eff Ft m cN / tex and v S p 0 = 2750 m / mm (1)
bedeuten, unter Zugabe von Wasser, dadurch gekennzeichnet, dass das PA 66-Fιlamentgarn bei einer Festigkeit von > 84 cN/tex und weniger als 1,5 Flusen/km aufweist.mean, with the addition of water, characterized in that the PA 66 parliament yarn has a strength of> 84 cN / tex and less than 1.5 lint / km.
2. PA 6.6-Industrιegarn nach Anspruch 1, dadurch gekennzeichnet, dass die Flusenzahl bei einer2. PA 6.6 industrial yarn according to claim 1, characterized in that the fluff number at one
Granulatviskosität RV > 90, einer Feuchtigkeit >0.06 % und einer Festigkeit Ft > 90 cN/tex folgender Formel entspricht:Granulate viscosity RV> 90, moisture> 0.06% and strength Ft> 90 cN / tex corresponds to the following formula:
Flusen Fl < (Ftx/Ft0 )3 * vspx/vspo * Ttx/Tt0, wobei (2) Tt0 der Titer 940 dtx und Ttx der Titer bei der Spulgeschwindigkeit vSpX bedeuten.Fluff Fl <(Ft x / Ft 0 ) 3 * v spx / v spo * Tt x / Tt 0 , with (2) Tt 0 denoting 940 dtx and Tt x denoting the winding speed v S p X.
3. Verfahren zur Herstellung von PA 6.6 Industriegarn mit einem Gesamttiter von 900 bis 2100 dtex durch3. Process for the production of PA 6.6 industrial yarn with a total titer of 900 to 2100 dtex
Schmelzspinnen von Polyamid 6.6 mit einer relativen Granulatviskosität (RV) von wenigstens 75, unter Zudosierung von Wasser, dadurch gekennzeichnet, dass der Wassergehalt des PA 6.6 Polymers nach Zugabe des Wassers vor dem Extruder 0,04 - 0,14 Gew.-% beträgt. Melt spinning of polyamide 6.6 with a relative granular viscosity (RV) of at least 75, with the addition of water, characterized in that the water content of the PA 6.6 polymer after addition of the water before the extruder is 0.04-0.14% by weight.
PCT/CH1997/000357 1994-03-22 1997-09-22 Industrial yarn pa 6.6 with little cotton waste WO1999015721A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
CH00862/94A CH688554A5 (en) 1994-03-22 1994-03-22 Industrial PA 6.6 filaments
KR1020007002980A KR20010024200A (en) 1997-09-22 1997-09-22 Industrial Yarn PA 6,6 with Little Cotton Waste
DK97939933T DK1017889T3 (en) 1997-09-22 1997-09-22 Process for making a lint-poor PA 6.6 industrial yarn
US09/509,092 US6210799B1 (en) 1997-09-22 1997-09-22 Industrial yarn PA 6.6 with little cotton waste
PL97339373A PL339373A1 (en) 1997-09-22 1997-09-22 Industrial yarn pa 6.6 exhibiting minute quantity of lint
DE59706528T DE59706528D1 (en) 1997-09-22 1997-09-22 METHOD FOR PRODUCING A PA 6.6 INDUSTRIAL YARN
EP97939933A EP1017889B1 (en) 1994-03-22 1997-09-22 Process for producing an industrial yarn pa 6.6 with little cotton waste
SK409-2000A SK4092000A3 (en) 1997-09-22 1997-09-22 Industrial yarn pa 6.6 with little cotton waste
ES97939933T ES2171995T3 (en) 1997-09-22 1997-09-22 PROCEDURE FOR THE PRODUCTION OF A PA 6.6 INDUSTRIAL THREAD WITH A WEAKEN.
AT97939933T ATE213789T1 (en) 1997-09-22 1997-09-22 METHOD FOR PRODUCING A LOW LINTING PA 6.6 INDUSTRIAL YARN
JP2000513006A JP2001517741A (en) 1997-09-22 1997-09-22 Low defect 6,6 polyamide industrial yarn
PCT/CH1997/000357 WO1999015721A1 (en) 1994-03-22 1997-09-22 Industrial yarn pa 6.6 with little cotton waste

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH00862/94A CH688554A5 (en) 1994-03-22 1994-03-22 Industrial PA 6.6 filaments
PCT/CH1997/000357 WO1999015721A1 (en) 1994-03-22 1997-09-22 Industrial yarn pa 6.6 with little cotton waste

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WO1999015721A1 true WO1999015721A1 (en) 1999-04-01

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH688554A5 (en) * 1994-03-22 1997-11-14 Rhone Poulenc Filtec Ag Industrial PA 6.6 filaments

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE826615C (en) * 1947-05-10 1952-01-03 Du Pont Process for the production of threads or fibers from synthetic, linear polyamides
EP0092898A2 (en) * 1982-04-28 1983-11-02 E.I. Du Pont De Nemours And Company Process for remelting polyamides
EP0382569A2 (en) * 1989-02-10 1990-08-16 E.I. Du Pont De Nemours And Company Method for controlling polymer viscosity
WO1993005097A1 (en) * 1991-09-03 1993-03-18 Allied-Signal Inc. A process for controlling the melt viscosity of polyamides during melt processing
CH688554A5 (en) * 1994-03-22 1997-11-14 Rhone Poulenc Filtec Ag Industrial PA 6.6 filaments

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE826615C (en) * 1947-05-10 1952-01-03 Du Pont Process for the production of threads or fibers from synthetic, linear polyamides
EP0092898A2 (en) * 1982-04-28 1983-11-02 E.I. Du Pont De Nemours And Company Process for remelting polyamides
EP0382569A2 (en) * 1989-02-10 1990-08-16 E.I. Du Pont De Nemours And Company Method for controlling polymer viscosity
WO1993005097A1 (en) * 1991-09-03 1993-03-18 Allied-Signal Inc. A process for controlling the melt viscosity of polyamides during melt processing
CH688554A5 (en) * 1994-03-22 1997-11-14 Rhone Poulenc Filtec Ag Industrial PA 6.6 filaments

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EP1017889B1 (en) 2002-02-27
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