EP0878567B1 - Polyolefin fibres and polyolefin yarns and textile materials thereof - Google Patents

Description

The invention relates to melt-processed polyolefin fibers and Polyolefin yarns of high strength and elongation, especially not post-drawn Polyolefin fibers and polyolefin yarns, and textile fabrics made therefrom.

Fibers, yarns and textile fabrics made of polypropylene are known (US 3,092 891; Films, fabrics and nonwovens made of polypropylene ", p.175-189, VDI-Verlag Düsseldorf 1979; Moore, P., Polypropylene Handbook "pp. 350-358, Carl Hanser Verlag Munich 1996).

The manufacturing process for fibers and yarns based on polypropylene differ in spinning speed and aftertreatment Strands.

Known manufacturing processes for polypropylene staple fibers Melt spinning is the rapid spinning process and the short spinning process.

In the production of staple fibers based on polypropylene according to Fast spinning process, already known as a quick spinning process for spinning of polyester or polyamide threads, the filaments are moving at high speed (500 to 2000 m / min.) Withdrawn from the spinneret. Because with this procedure If the polypropylene macromolecules are not fully oriented, the produced filaments are stretched in a further operation. This mostly takes place in combination with other post-processing steps.

In the production of staple fibers based on polypropylene according to Short spinning is used at very low spinning speeds (30 to 150 m / min) worked, so the cooling zones of the spinning systems can be very short are dimensioned [Schweitzer, A., Chemiefaser / Textilindustrie 88 (1986), 671-674]. The low spinning speeds enable direct continuous Feeding the filaments brought together into spinning cables on the stretching and Downstream equipment.

This is also done using the technology of the rapid spinning process "Preoriented Yarn Spinning" ["Pre-Oreinted-Yarn (POY) Spinning"], which involves the threads emerging from the spinneret after passing through the blow shaft of high-speed godets or directly from the winder at 1000 to 5000 m / min drawn off and wound on packages. The fiber properties are significantly due to the orientation introduced from the melt-shaped Condition determined [Wulfhorst, B., Chemiefaser / Textilindustrie 92 (1990), 971-976]. This orinting effect results from the difference between Extrusion speed and the take-off or winding speed.

Comparable conditions for influencing the basic fiber properties apply also for the spunbond process. In the spunbond process, the filaments through the cooling zone either through accelerated downpipe air or compressed air operated nozzles removed [Fourne ', F., chemical fiber textile industry 95: 811-822 (1993)]. The undrawn filaments produced are in flat, unordered form placed on a sieve-shaped conveyor belt and in one Post-processing step by applying thermal bonding (by means of Calender consolidation) or needling processes for spunbonding further processed.

A special variant of the nonwoven production is the blown fiber (melt-blow) Spinning technology, in which the thread formation with application of a highly heated Luttstromes around the capillary nozzle openings takes place [Fourne ', F. Chemical fibers / textile industry 81 (1979), 445-449]. The air flow divides the molten polymer thread in many small individual vials with very little Diameter and at the same time causes stretching of the individual threads. The Further processing of the fibers deposited on the screen conveyor belt or Filaments are made using spunbond technology.

When producing high-strength filament yarns (Fully Drawn Yarn (FDY)), the Filaments are removed from the spinneret using godets and placed in Successor devices from stretching device and winder further processed. The Production of high tenacity filament yarns can be carried out using either the short spinning method or also take place after the fast spinning process. In addition to stretching In the bulked continuous filament "process, a three-dimensional crimp by texturing devices [Bussmann, M., chemical fibers / textile industry 35 (1986) 87, 668-672].

The properties of the fibers, yarns and textile fabrics are determined by the Manufacturing process and the polypropylene used determined.

The addition of nucleating agents leads to a decrease in the strength of the Fibers (Richeson, G., ANTEC'96, 2305-2311). Formulations with fillers such as Calcium carbonate [Nago, S., J. Appl. Polymer Sci. 62 (1996), 81-86] or Poly (methylsesquioxane) [Nago, S., J. Appl. Polymer sci. 61 (1996), 2355-2359] result in microporous fibers after spinning and drawing. Fibers increased Heat resistance can be achieved by spinning polypropylene blends Polyethylene terephthalate [Qin, Y., J. Appl. Polymer sci. 61 (1966), 1287-1292] or with Prepare liquid crystalline polymers [Qin, Y., Polymer 34 (1993), 3597].

Polypropylene fibers have the disadvantage of being relatively low Tensile elongation. An addition of elastomers such as ethylene-propylene rubber or Ethylene propylene diene rubber leads to an increase in elongation, however at the same time a sharp drop in the strength of the polypropylene fibers and Game polypropylene.

EP-A 0 412 518 discloses grafted ethylene-propylene copolymers which have been prepared with the aid of hydrolyzable silanes. You are connected. However, crosslinked copolymers are not suitable for spinning. According to EP-A 0 517 810, blends with high impact strength can be produced if they contain a PP with a very broad molecular weight distribution, namely an M _w / M _n ratio of 8 to 60. Furthermore, DE-A 195 06 083 describes nonwovens made from cellulose staple fibers and PP staple fibers, the PP fibers containing up to 15% of a PP grafted with maleic anhydride, and WO 96/26308 describes dyeable polyolefin fibers which contain a polymer containing polar monomers contain a double bond, contain grafted PP.

The object of the present invention was to develop Polyolefin fibers and polyolefin yarns of high strength and elongation, in particular of undrawn polyolefin fibers and yarns, and therefrom manufactured textile fabrics.

A) 0,05 bis 10 Masse%, vorzugsweise 0,2 bis 3 Masse%, modifizierten Propylenpolymeren mit Schmelzindices von 0,1 bis 50 g/10 min bei 230 °C/2,16 kg, bevorzugt 1 bis 40 g/10 min bei 230 °C/2,16 kg, und einem Quotienten aus der Grenzviscosität des modifizierten Polypropylens und der Grenzviscosität des nichtmodifizierten Polypropylens mit weitgehend gleichem Molmassen-Gewichtsmittel von 0,20 bis 0,95, die

a) durch Behandlung von Propylen-Homopolymeren und/oder Copolymeren aus Propylen und Ethylen bzw. alpha -Olefinen mit 4 bis 18 C-Atomen sowie von Mischungen der genannten Polypropylene mit mehrfunktionell ethylenisch ungesättigten Monomeren in Gegenwart ionisierender Strahlung bzw. thermisch zerfallenden Radikalbildnern, oder

b) durch Umsetzung von funktionalisierten Polypropylenen, bevorzugt von Säureund/oder Säureanhydridgruppen enthaltenden Polypropylenen, mit mehrfunktionellen Verbindungen entgegengesetzter Reaktivität, bevorzugt mit C2- bis C16 - Diaminen und/ oder C2- bis C16 - Diolen, oder

c) durch hydrolytische Kondensation von Polypropylenen, die hydrolysierbare Silangruppen enthalten,
hergestellt worden sind,
und andererseits aus

B) 99,95 bis 90 Masse%, vorzugsweise 99,8 bis 97 Masse%, nichtmodifizierten Propylenpolymeren, wobei die nichtmodifizierten Propylenpolymere aus

1) üblichen Propylenpolymeren, bevorzugt unter Anwendung von Ziegler-Natta-Katalysatoren oder Metallocenkatalysatoren hergestellten Propylenhomopolymeren und/oder Copolymeren aus Propylen, Ethylen und/oder alpha -Olefinen mit 4 bis 18 C-Atomen mit einem Propylengehalt von 80,0 bis 99,9 Masse% in Form von statistischen Copolymeren, Blockcopolymeren und/oder statistischen Blockcopolymeren, mit Schmelzindices von 0,1 bis 300 g/10 min bei 230 °C/2,16 kg, bevorzugt 1 bis 100 g/10 min bei 230 °C/ 2,16 kg, die in den Polyolefinfasern und Polyolefingarnen und daraus hergestellten textilen Flächengebilden zu 50 bis 99 Masse%, enthalten sein können, und/oder

2) einer Polyolefinmischung mit einem Mw/Mn-Verhältnis von 2 bis 6 und einem Schmelzindex von 1 bis 40 g/10 min bei 230 °C/2,16 kp, die aus

2.1) 60 bis 98 Masse% eines kristallinen Copolymeren aus 85 bis 99,5 Masse% Propylen und 15 bis 0,5 Masse% Ethylen und/oder einem alpha -Olefin der allgemeinen Formel CH2=CHR, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist,

2.2) 2 bis 40 Masse% eines elastischen Copolymers aus 20 bis 70 Masse% Ethylen und 80 bis 30 Masse% Propylen und/oder einem alpha -Olefin der allgemeinen Formel CH2=CHR, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist, besteht,

wobei die Polyolefinmischung in den Polyolefinfasern und Polyolefingarnen und daraus hergestellten textilen Flächengebilden bis 99 Masse%, bevorzugt 10 bis 80 Masse%, enthalten sein kann,
bestehen,
und wobei weiterhin in den Polyolefinfasern und Polyolefingarnen und daraus hergestellten textilen Flächengebilden 0,01 bis 5 Masse% Hilfsstoffe, bezogen auf die Polyolefine, enthalten sein können.The object according to the invention was achieved by melt processing polyolefin fibers and polyolefin yarns of high strength and elongation, in particular non-post-stretched polyolefin fibers and polyolefin yarns with capillary titers of 1 to 10 dtex and tensile strains of over 130% at tensile strengths of at least 15 cN / tex, and textile fabrics made therefrom, the Polyolefin fibers and polyolefin yarns and textile fabrics made therefrom according to the invention
consist of polypropylene mixtures,
the one out

A) 0.05 to 10% by mass, preferably 0.2 to 3% by mass, of modified propylene polymers with melt indices of 0.1 to 50 g / 10 min at 230 ° C./2.16 kg, preferably 1 to 40 g / 10 min at 230 ° C / 2.16 kg, and a quotient of the intrinsic viscosity of the modified polypropylene and the intrinsic viscosity of the unmodified polypropylene with largely the same molar mass weight average from 0.20 to 0.95, the

a) by treatment of propylene homopolymers and / or copolymers of propylene and ethylene or alpha-olefins having 4 to 18 carbon atoms and of mixtures of the polypropylenes mentioned with polyfunctionally ethylenically unsaturated monomers in the presence of ionizing radiation or thermally decomposing radical formers, or

b) by reaction of functionalized polypropylenes, preferably of polypropylenes containing acid and / or acid anhydride groups, with polyfunctional compounds of opposite reactivity, preferably with C2 to C16 diamines and / or C2 to C16 diols, or

c) by hydrolytic condensation of polypropylenes which contain hydrolyzable silane groups,
have been manufactured
and on the other hand

B) 99.95 to 90% by mass, preferably 99.8 to 97% by mass, of unmodified propylene polymers, the unmodified propylene polymers being composed of

1) conventional propylene polymers, preferably propylene homopolymers and / or copolymers made from propylene, ethylene and / or alpha-olefins having 4 to 18 carbon atoms and having a propylene content of 80.0 to 99.9, prepared using Ziegler-Natta catalysts or metallocene catalysts % By mass in the form of statistical copolymers, block copolymers and / or statistical block copolymers, with melt indices from 0.1 to 300 g / 10 min at 230 ° C / 2.16 kg, preferably 1 to 100 g / 10 min at 230 ° C / 2.16 kg, which can be contained in the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom to 50 to 99 mass%, and / or

2) a polyolefin mixture with an Mw / Mn ratio of 2 to 6 and a melt index of 1 to 40 g / 10 min at 230 ° C / 2.16 kp, which consists of

2.1) 60 to 98 mass% of a crystalline copolymer of 85 to 99.5 mass% propylene and 15 to 0.5 mass% ethylene and / or an alpha -olefin of the general formula CH2 = CHR, where R is a linear or branched alkyl radical Is 2 to 8 carbon atoms,

2.2) 2 to 40 mass% of an elastic copolymer of 20 to 70 mass% ethylene and 80 to 30 mass% propylene and / or an alpha -olefin of the general formula CH2 = CHR, where R is a linear or branched alkyl radical having 2 to 8 carbon atoms is, exists

the polyolefin mixture in the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom can be up to 99% by mass, preferably 10 to 80% by mass,
consist,
and wherein the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom may further contain 0.01 to 5% by mass of auxiliaries, based on the polyolefins.

The in the polyolefin fibers and polyolefin yarns high strength and elongation and textile fabrics produced therefrom may contain modified propylene polymers A) are propylene polymers which are characterized by radical Coupling reactions or polymer-analogous reactions of functionalized Polypropylenes were made.

The starting products for the modified propylene polymers A) are preferred Propylene homopolymers as well as copolymers of propylene and alpha olefins with 2 to 18 carbon atoms and mixtures of the polypropylenes mentioned. Especially preferred starting products for these modified propylene polymers are Polypropylene - homopolymers, statistical propylene - copolymers, propylene block copolymers and / or propylene statistical block copolymers.

modifizierte Polypropylene durch Umsetzung von Polypropylenen mit Bismaleimidoverbindungen in der Schmelze (EP 574 801 ; EP 574804),

modifizierte Polypropylene durch Behandlung von Polypropylenen mit mehrfunktionell ethylenisch ungesättigten Monomeren unter Einwirkung ionisierender Strahlung (EP 678527),

modifizierte Polypropylene durch Behandlung von Polypropylenen mit mehrfunktionell ethylenisch ungesättigten Monomeren in Gegenwart von Peroxiden in der Schmelze (EP 688817; EP 450342).

Examples of these modified propylene polymers A) produced by radical coupling reactions are:

modified polypropylenes by reacting polypropylenes with bismaleimido compounds in the melt (EP 574 801; EP 574804),

modified polypropylenes by treating polypropylenes with polyfunctionally ethylenically unsaturated monomers under the action of ionizing radiation (EP 678527),

modified polypropylenes by treating polypropylenes with polyfunctionally ethylenically unsaturated monomers in the presence of peroxides in the melt (EP 688817; EP 450342).

The modified propylene polymers produced by polymer-analogous reactions A) can be implemented by implementing functionalized polypropylenes Create multifunctional compounds of opposite reactivity.

modifizierte Polypropylene durch Umsetzung von Maleinsäureanhydridgepfropftem Polypropylen mit Diaminen oder Polyglycolen (EP 177401; JP 08 176 365), modifizierte Polypropylene durch Umsetzung von Säure- oder Säureanhydridgruppen enthaltenden Polypropylenen mit Epoxy-, Hydroxy- oder Aminogruppen enthaltenden Polymeren (EP 307684; EP 299486).

Examples of modified propylene polymers A) produced by polymer-analogous reactions are:

modified polypropylenes by reacting maleic anhydride-grafted polypropylene with diamines or polyglycols (EP 177401; JP 08 176 365), modified polypropylenes by reacting polypropylenes containing acid or acid anhydride groups with polymers containing epoxy, hydroxyl or amino groups (EP 307684; EP 299486).

The modified propylene polymers A) can also by hydrolytic Condensation of polypropylenes containing hydrolyzable silane groups, getting produced. Examples are those in DE 4107635 or US 47 14 716 described products.

1) Polypropylenpartikel in Form von Pulvern, Granulaten oder Griessen mit einer bevorzugten Korngrösse im Bereich von 0,001 bis 7 mm, die aus

1.1) Propylen-Homopolymeren, insbesondere aus Propylen-Homopolymeren mit bimodaler Molmassenverteilung, Molmassen-Gewichtsmitteln Mw von 500000 bis 1500000 g/mol, Molmassen-Zahlenmitteln Mn von 25000 bis 100000 g/mol und Mw / Mn -Werten von 5 bis 60, die in einer Reaktorkaskade unter Einsatz von Ziegler-Natta-Katalysatoren oder Metallocenkatalysatoren hergestellt wurden, und/oder aus

1.2) Copolymeren aus Propylen und alpha -Olefinen mit 2 bis 18 C-Atomen, bevorzugt aus statistischen Propylen-Copolymeren, Propylen-Blockcopolymeren, statistischen Propylen-Blockcopolymeren und/oder elastomeren Polypropylenen, oder aus Mischungen der genannten modifizierten Polypropylene, bestehen,

in einem kontinuierlichen Mischer mit 0,05 bis 3 Masse%, bezogen auf die eingesetzten Polypropylene, an Acylperoxiden, Alkylperoxiden, Hydroperoxiden Peroxycarbonaten und/oder Perestern als thermisch zerfallende Radikalbildner, deren thermischer Zerfall bevorzugt unterhalb 210°C abgeschlossen ist und die gegebenenfalls mit inerten Lösungsmitteln verdünnt sind, unter Erwärmung auf 30 bis 100 °C, bevorzugt auf 70 bis 90°C, gemischt worden sind,

2) leichtflüchtige bifunktionelle Monomere, insbesondere C4- bis C10- Diene und/oder C7- bis C10- Divinylverbindungen, durch die Polypropylenpartikel aus der Gasphase, bevorzugt in kontinuierlichen Durchflussmischem als kontinuierliche Gas-Feststoff-Absorber, bei einer Temperatur T von 20°C bis 120 °C, vorzugsweise von 60 bis 100°C, und einer mittleren Sorptionszeit von tau s von 10s bis 1000 s, bevorzugt 60 s bis 600 s, sorbiert worden sind, wobei in den Polypropylenpartikeln der Anteil der bifunktionell ungesättigten Monomeren 0,01 bis 10 Masse%, bevorzugt 0,05 bis 2 Masse%, bezogen auf die eingesetzten Polypropylene, beträgt, nachfolgend

3) die Polypropylenpartikel, in denen die Acylperoxide, Alkylperoxide, Hydroperoxide, Peroxycarbonate und/oder Perester als thermisch zerfallende Radikalbildner und die bifunktionell ungesättigten Monomere sorbiert worden sind, unter einer Atmosphäre aus Inertgas und diesen leichtflüchtigen bifunktionellen Monomeren bei 110°C bis 210 °C in kontinuierlich arbeitenden Knetern oder Extrudern, vorzugsweise in Doppelschneckenextrudern, aufgeschmolzen worden sind und die thermisch zerfallenden Radikalbildner dabei zersetzt worden sind,

4) die Schmelze danach auf 220°C bis 300 °C erwärmt worden ist, wobei nichtumgesetzte Monomere und Zerfallsprodukte entfernt worden sind, und

5) die Schmelze in an sich bekannter Weise granuliert worden ist,
und bei dem vor dem Verfahrensschritt 1) und/oder 5) und /oder vor bzw. während des Verfahrensschrittes 3) und/oder 4) als weitere Hilfsstoffe 0,01 bis 2,5 Masse% Stabilisatoren, 0,1 bis 1 Masse% Antistatika, 0,2 bis 3 Masse% Pigmente, 0,05 bis 1 Masse% Nukleierungsmittel und/oder 0,01 bis 5 Masse% Verarbeitungshilfsmittel, bezogen auf das eingesetzte Polypropylen, zugesetzt worden sind.

For the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom, modified propylene polymers A), which are obtained by treating propylene homopolymers and / or copolymers of propylene and ethylene or alpha-olefins having 4 to 18 carbon atoms and mixtures of the polypropylenes mentioned, are used were produced with polyfunctionally ethylenically unsaturated monomers in the presence of thermally decomposing radical images, in particular those modified propylene polymers which have been prepared by a continuous process in which

1) Polypropylene particles in the form of powders, granules or semolina with a preferred grain size in the range from 0.001 to 7 mm, which

1.1) Propylene homopolymers, in particular from propylene homopolymers with a bimodal molecular weight distribution, weight average molecular weights Mw from 500,000 to 1,500,000 g / mol, number average molecular weights Mn from 25,000 to 100,000 g / mol and Mw / Mn values from 5 to 60 were produced in a reactor cascade using Ziegler-Natta catalysts or metallocene catalysts, and / or

1.2) copolymers of propylene and alpha-olefins having 2 to 18 carbon atoms, preferably of statistical propylene copolymers, propylene block copolymers, statistical propylene block copolymers and / or elastomeric polypropylenes, or of mixtures of the modified polypropylenes mentioned,

in a continuous mixer with 0.05 to 3 mass%, based on the polypropylenes, of acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates and / or peresters as thermally decomposing radical formers, the thermal decomposition of which is preferably completed below 210 ° C. and which may be inert Solvents are diluted, mixed with heating to 30 to 100 ° C, preferably to 70 to 90 ° C,

2) volatile bifunctional monomers, in particular C4 to C10 dienes and / or C7 to C10 divinyl compounds, through the polypropylene particles from the gas phase, preferably in continuous flow mixers as continuous gas-solid absorbers, at a temperature T of 20 ° C. up to 120 ° C, preferably from 60 to 100 ° C, and an average sorption time of tau s from 10s to 1000 s, preferably 60 s to 600 s, the proportion of the bifunctionally unsaturated monomers in the polypropylene particles being 0.01 to 10% by mass, preferably 0.05 to 2% by mass, based on the polypropylenes used, is below

3) the polypropylene particles in which the acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates and / or peresters have been sorbed as thermally decomposing radical formers and the bifunctionally unsaturated monomers, under an atmosphere of inert gas and these volatile bifunctional monomers at 110 ° C. to 210 ° C. have been melted in continuously operating kneaders or extruders, preferably in twin-screw extruders, and the thermally decomposing radical formers have been decomposed in the process,

4) the melt is then heated to 220 ° C to 300 ° C, removing unreacted monomers and decomposition products, and

5) the melt has been granulated in a manner known per se,
and in which before the process step 1) and / or 5) and / or before or during process step 3) and / or 4) as further auxiliaries 0.01 to 2.5% by mass of stabilizers, 0.1 to 1% by mass Antistatic agents, 0.2 to 3 mass% of pigments, 0.05 to 1 mass% of nucleating agent and / or 0.01 to 5 mass% of processing aids, based on the polypropylene used, have been added.

The for the production of this preferred modified propylene polymer A) Polypropylenes used consist in particular of propylene homopolymers and / or copolymers of propylene and alpha-olefins with 2 to 18 carbon atoms and from mixtures of the polypropylenes mentioned. Be particularly preferred Polypropylene particles made of polypropylenes with bimodal molar mass distribution, which in a reactor cascade using Ziegler-Natta catalysts or Metallocene catalysts were produced with weight average molecular weights Mw of 500,000 to 1,500,000 g / mol, number-average molecular weights Mn from 25,000 to 100,000 g / mol and Mw / Mn values of 5 to 60, preferably with weight average molar mass Mw from 600,000 to 1,000,000 g / mol, number-average molecular weights Mn from 30,000 to 100000 g / mol and Mw / Mn values from 15 to 35.

Acylperoxide wie Benzoylperoxid, 4-Chlorbenzoylperoxid, 3-Methoxybenzoylperoxid und/oder Methylbenzoylperoxid;

Alkylperoxide wie Allyl-tert.butylperoxid, 2,2-Bis(tert.butylperoxybutan), 1,1-Bis(tert.butylperoxi)-3,3,5-trimethylcyclohexan, n-Butyl-4,4-bis(tert.butylperoxi)valerat, Diisopropylaminomethyl-tert.amylperoxid, Dimethylaminomethyl-tert.amylperoxid, Diethylaminomethyl-tert.butylperoxid, Dimethylaminomethyl-tert.butylperoxid, 1.1-Di(tert.amylperoxi)cyclohexan, tert.Amylperoxid, tert.Butylcumylperoxid, tert.Butylperoxid, und/oder 1-Hydroxybutyl-n-butylperoxid;

Perester und Peroxycarbonate wie Butylperacetat, Cumylperacetat, Cumylperpropionat, Cyclohexylperacetat, Di-tert.butylperadipat, Ditert.butylperazelat, Di-tert.butylperglutarat, Di-tert.butylperphthalat, Ditert.butylpersebazat, 4-Nitrocumylperpropionat, 1-Phenylethylperbenzoat, Phenylethylnitroperbenzoat, tert.Butylbicyclo-(2,2,1)heptanpercarboxylat, tert.Butyl-4-carbomethoxyperbutyrat, tert.Butylcyclobutanpercarboxylat, tert.Butylcyclohexylperoxycarboxylat, tert.Butylcyclopentylpercarboxylat, tert.Butylcyclopropanpercarboxylat, tert.Butyldimethylpercinnamat, tert.Butyl-2-(2,2-diphenylvinyl)perbenzoat, tert. Butyl-4-methoxyperbenzoat, tert.Butylperbenzoat, tert.Butylcarboxicyclohexan, tert.Butylpernaphthoat, tert.Butylperoxiisopropylcarbonat, tert.Butylpertoluat, tert. Butyl-1-phenylcyclopropylpercarboxylat, tert.Butyl-2-propylperpenten-2-oat, tert.Butyl-1-methylcypropylpercarboxylat, tert.Butyl-4-nitrophenylperacetat, tert.Butylnitrophenylperoxycarbamat, tert.Butyl-N-succinimidopercarborylat, tert.Butylpercrotonat, tert.Butylpermaleinsäure, tert.Butylpermethacrylat, tert.Butylperoctoat, tert.Butylperoxyisopropylcarbonat, tert.Butylperisobutyrat, tert.Butylperacrylat und/oder tert.Butylperpropionat;

Examples of the thermally decomposing radical formers used in the production of this preferred modified propylene polymer A) are:

Acyl peroxides such as benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and / or methylbenzoyl peroxide;

Alkyl peroxides such as allyl tert-butyl peroxide, 2,2-bis (tert-butyl peroxybutane), 1,1-bis (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert. butylperoxi) valerate, diisopropylaminomethyl-tert.amylperoxide, dimethylaminomethyl-tert.amylperoxide, diethylaminomethyl-tert.butylperoxide, dimethylaminomethyl-tert.butylperoxide, 1.1-di (tert.amylperoxi) cyclohexane, tert.amylperoxide, tert.butylcuryl peryl and / or 1-hydroxybutyl-n-butyl peroxide;

Peresters and peroxycarbonates such as butylperacetate, cumylperacetate, cumylperpropionate, cyclohexylperacetate, di-tert.butylperadipate, ditert.butylperazelate, di-tert.butylperglutarate, di-tert.butylperphthalate, ditert.butylpersrocate, 1-nitroperylate, per-perylate, 4-nitroperobate, Butylbicyclo- (2,2,1) heptane percarboxylate, tert.butyl-4-carbomethoxyperbutyrate, tert.butylcyclobutane percarboxylate, tert.butylcyclohexylperoxycarboxylate, tert.butylcyclopentylpercarboxylate, tert.butylcyclopropane percarboxylate, tert.butyldimethylpercinnamper diphenylvinyl) perbenzoate, tert. Butyl 4-methoxyperbenzoate, tert.butylperbenzoate, tert.butylcarboxicyclohexane, tert.butylpersaphthoate, tert.butylperoxiisopropyl carbonate, tert.butylpertoluate, tert. Butyl-1-phenylcyclopropyl percarboxylate, tert.butyl-2-propylperpentene-2-oate, tert.butyl-1-methylcypropylpercarboxylate, tert.butyl-4-nitrophenylperacetate, tert.butylnitrophenylperoxycarbamate, tert.butyl-N-succinimidopercutylperotonate, tert-butylpermaleic acid, tert-butyl permethacrylate, tert-butyl peroctoate, tert-butyl peroxyisopropyl carbonate, tert-butyl perisobutyrate, tert-butyl peracrylate and / or tert-butyl per-propionate;

Mixtures of these thermally decomposing are also advantageous Radical generator in the manufacture of this preferred modified Propylene polymer A) used.

Divinylverbindungen wie Divinylanilin, m-Divinylbenzen, p-Divinylbenzen, Divinylpentan und/oder Divinylpropan;

Allylverbindungen wie Allylacrylat, Allylmethacrylat, Allylmethylmaleat und/oder Allylvinylether;

Diene wie Butadien, Chloropren, Cyclohexadien, Cyclopentadien, 2,3-Dimethylbutadien, Heptadien, Hexadien, Isopren, und/oder 1,4-Pentadien ;

In the production of this preferred modified propylene polymer A), which may be present in the polyolefin fibers, polyolefin yarns and textile fabrics produced therefrom, all bifunctionally unsaturated monomer compounds sorbable from the gas phase which can be polymerized with the aid of free radicals can be used as bifunctionally unsaturated monomers , The following bifunctionally unsaturated monomers are preferably used:

Divinyl compounds such as divinylaniline, m-divinylbenzene, p-divinylbenzene, divinylpentane and / or divinylpropane;

Allyl compounds such as allyl acrylate, allyl methacrylate, allyl methyl maleate and / or allyl vinyl ether;

Dienes such as butadiene, chloroprene, cyclohexadiene, cyclopentadiene, 2,3-dimethylbutadiene, heptadiene, hexadiene, isoprene, and / or 1,4-pentadiene;

Mixtures of these unsaturated monomers are also advantageous in the Production of this preferred modified propylene polymer A) used.

Sorption of these volatile bifunctionally unsaturated monomers takes place at the production of this preferred modified propylene polymer A) According to the invention, in particular in continuous flow mixers continuous gas-solid absorber.

In the production of this preferred variant of the modified Propylene polymers A) are heated and melted Polypropylene particles in which the acyl peroxides, alkyl peroxides, hydroperoxides and / or Perester as a thermally decomposing radical generator and the bifunctional unsaturated monomers are sorbed, under an atmosphere of volatile bifunctionally unsaturated monomers preferably in continuously operating Kneading or extruding, preferably in twin screw extruders.

The as unmodified propylene polymers B) in the in the polyolefin fibers and Polyolefin yarns and textile fabrics made therefrom, if necessary contained conventional propylene polymers 1) preferably consist of propylene homopolymers with an Mw / Mn ratio of 2 to 4.5 and / or copolymers from propylene and alpha-olefins with 2 to 18 carbon atoms and from mixtures of called polypropylene.

The in the high tenacity and polyolefin fibers and polyolefin yarns Elongation and textile fabrics produced therefrom, if necessary auxiliaries contained are preferably 0.01 to 2.5% by mass of stabilizers, 0.1 to 1 Mass% antistatic, 0.2 to 3 mass% pigments, 0.05 to 1 mass% Nucleating agents and / or 0.01 to 1 mass% processing aids. This Auxiliaries can already be used in the melt processing Components A) and / or B) may be included or additionally these components be added.

Mixtures of 0.01 to 0.6% by mass are preferred as stabilizers. phenolic antioxidants, 0.01 to 0.6% by mass of 3-arylbenzofuranones, 0.01 to 0.6 mass% processing stabilizers based on phosphites, 0.01 to 0.6 % By mass High temperature stabilizers based on disulfides and thioethers and / or 0.01 to 0.8 mass% of sterically hindered amines (HALS) are used.

Suitable phenolic antioxidants are 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-isoamylphenol, 2,6, -di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-diisopropylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2-tert-butyl-4,6-dioctadecylphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4,4-hexadecyloxyphenol, 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 3 (3,5-di-tert-butyl - 4-hydroxyphenyl) propionic acid octadecyl ester, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'di-tert.butyl-4-hydroxybenzyl) and / or pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate.

In particular, 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one is a benzofuranone derivative suitable.

Bis-2,2,6,6 tetramethyl-4-piperidyl sebazate and / or are the HALS compounds Poly - ([1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-2,4, diyl) [2,2,6,6-tetramethylpiperidyl) amino] -hexamethylen- 4- (2,2,6,6-tetramethyl) piperidyl) imino] particularly suitable.

Calcium stearate, magnesium stearate and / or can be used as processing aids Waxes are used.

A) 0,05 bis 10 Masse%, vorzugsweise 0,2 bis 3 Masse%, modifizierten Propylenpolymeren mit Schmelzindices von 0,1 bis 50 g/10 min bei 230 °C/2,16 kg, bevorzugt 1 bis 40 g/10 min bei 230 °C/2,16 kg, und einem Quotienten aus der Grenzviscosität des modifizierten Polypropylens und der Grenzviscosität des nichtmodifizierten Polypropylens mit weitgehend gleichem Molmassen-Gewichtsmittel von 0,20 bis 0,95, die

a) durch Behandlung von Propylen-Homopolymeren und/oder Copolymeren aus Propylen und Ethylen bzw. alpha -Olefinen mit 4 bis 18 C-Atomen sowie von Mischungen der genannten Polypropylene mit mehrfunktionell ethylenisch ungesättigten Monomeren in Gegenwart ionisierender Strahlung bzw. thermisch zerfallenden Radikalbildnern, oder

b) durch Umsetzung von funktionalisierten Polypropylenen, bevorzugt von Säureund/oder Säureanhydridgruppen enthaltenden Polypropylenen, mit mehrfunktionellen Verbindungen entgegengesetzter Reaktivität, bevorzugt mit C2- bis C16 - Diaminen und/ oder C2- bis C16 - Diolen, oder

c) durch hydrolytische Kondensation von Polypropylenen, die hydrolysierbare Silangruppen enthalten,
hergestellt worden sind,
und andererseits aus

B) 99,95 bis 90 Masse%, vorzugsweise 99,8 bis 97 Masse%, nichtmodifizierten Propylenpolymeren, wobei die nichtmodifizierten Propylenpolymere aus

1) üblichen Propylenpolymeren, bevorzugt unter Anwendung von Ziegler-Natta-Katalysatoren oder Metallocenkatalysatoren hergestellten Propylenhomopolymeren und/oder Copolymeren aus Propylen, Ethylen und/oder alpha -Olefinen mit 4 bis 18 C-Atomen mit einem Propylengehalt von 80,0 bis 99,9 Masse% in Form von statistischen Copolymeren, Blockcopolymeren und/oder statistischen Blockcopolymeren, mit Schmelzindices von 0,1 bis 300 g/10 min bei 230 °C/2,16 kg, bevorzugt 1 bis 100 g/10 min bei 230 °C/ 2,16 kg, die in den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne und daraus hergestellten textilen Flächengebilden zu 50 bis 99 Masse%, enthalten sein können, und/oder

2) einer Polyolefinmischung mit einem Mw/Mn-Verhältnis von 2 bis 6 und einem Schmelzindex von 1 bis 40 g/10 min bei 230 °C/2,16 kp, die aus

2.1) 60 bis 98 Masse% eines kristallinen Copolymeren aus 85 bis 99,5 Masse% Propylen und 15 bis 0,5 Masse% Ethylen und/oder einem alpha -Olefin der allgemeinen Formel CH2=CHR, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist,

2.2) 2 bis 40 Masse% eines elastischen Copolymers aus 20 bis 70 Masse% Ethylen und 80 bis 30 Masse% Propylen und/oder einem alpha -Olefin der allgemeinen Formel CH2=CHR, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist, besteht,

wobei die Polyolefinmischung in den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne und daraus hergestellten textilen Flächengebilden bis 99 Masse%, bevorzugt 10 bis 80 Masse%, enthalten sein kann, bestehen,
und wobei weiterhin den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingame und daraus hergestellten testen Flächengebilden 0,01 bis 5 Masse% Hilfsstoffe, bezogen auf die Polyolefine, zugesetzt werden können. The polyolefin fibers and polyolefin yarns of high strength and elongation, in particular non-post-stretched polyolefin fibers and polyolefin yarns with capillary titers of 1 to 10 dtex and tensile elongations above 130% at tensile strengths of at least 15 cN / tex, and textile fabrics made therefrom are known in a process by processing polypropylene mixtures Melt spinning plants made of plasticizing extruders, spinning pumps, melt distributors, spinnerets, blow chutes and successor devices with the process steps
Melting at melt temperatures of 185 to 310 ° C,
Transfer of the melt to the spinnerets by means of a melt pump,
Extrusion into the blow duct,
Deduction as threads and further processing in successor devices, whereby according to the invention
Polypropylene blends are used that are made from one hand

A) 0.05 to 10% by mass, preferably 0.2 to 3% by mass, of modified propylene polymers with melt indices of 0.1 to 50 g / 10 min at 230 ° C./2.16 kg, preferably 1 to 40 g / 10 min at 230 ° C / 2.16 kg, and a quotient of the intrinsic viscosity of the modified polypropylene and the intrinsic viscosity of the unmodified polypropylene with largely the same molar mass weight average from 0.20 to 0.95, the

a) by treatment of propylene homopolymers and / or copolymers of propylene and ethylene or alpha-olefins having 4 to 18 carbon atoms and of mixtures of the polypropylenes mentioned with polyfunctionally ethylenically unsaturated monomers in the presence of ionizing radiation or thermally decomposing radical formers, or

b) by reaction of functionalized polypropylenes, preferably of polypropylenes containing acid and / or acid anhydride groups, with polyfunctional compounds of opposite reactivity, preferably with C2 to C16 diamines and / or C2 to C16 diols, or

c) by hydrolytic condensation of polypropylenes which contain hydrolyzable silane groups,
have been manufactured
and on the other hand

B) 99.95 to 90% by mass, preferably 99.8 to 97% by mass, of unmodified propylene polymers, the unmodified propylene polymers being composed of

1) conventional propylene polymers, preferably propylene homopolymers and / or copolymers made from propylene, ethylene and / or alpha-olefins having 4 to 18 carbon atoms and having a propylene content of 80.0 to 99.9, prepared using Ziegler-Natta catalysts or metallocene catalysts % By mass in the form of statistical copolymers, block copolymers and / or statistical block copolymers, with melt indices from 0.1 to 300 g / 10 min at 230 ° C / 2.16 kg, preferably 1 to 100 g / 10 min at 230 ° C / 2.16 kg, which can be contained in the polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom to 50 to 99 mass%, and / or

2) a polyolefin mixture with an Mw / Mn ratio of 2 to 6 and a melt index of 1 to 40 g / 10 min at 230 ° C / 2.16 kp, which consists of

2.1) 60 to 98 mass% of a crystalline copolymer of 85 to 99.5 mass% propylene and 15 to 0.5 mass% ethylene and / or an alpha -olefin of the general formula CH2 = CHR, where R is a linear or branched alkyl radical Is 2 to 8 carbon atoms,

2.2) 2 to 40 mass% of an elastic copolymer of 20 to 70 mass% ethylene and 80 to 30 mass% propylene and / or an alpha -olefin of the general formula CH2 = CHR, where R is a linear or branched alkyl radical having 2 to 8 carbon atoms is, exists

the polyolefin mixture in the polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics produced therefrom can be up to 99% by mass, preferably 10 to 80% by mass,
and wherein furthermore 0.01 to 5% by mass of auxiliaries, based on the polyolefins, can be added to the polypropylene mixtures for the production of the polyolefin fibers and polyolefin gams and test fabrics made therefrom.

In particular, plasticizing extruders are for melting the mixtures Single screw extruder or twin screw extruder with screw lengths of 28 up to 30 D, preferably with flanged static or dynamic mixers, suitable. The temperature control and speed make shear rates from 10 <2> s <-1> to 10 <3> s <-1>.

For even melt dosing in the plasticizing extruder melted mixture over the melt distributor to the capillary tool Diphenyl-heated melt pumps are preferred for use at 240-310 ° C heated melts used.

For the production of staple fibers from the polypropylene blends, the According to the invention, fibers are drawn off with the aid of high-speed godets and in Successor devices from stretching unit, crimper, fixing unit and Cutting machine processed by stretching, crimping and cutting, whereby in short spinning lines (slow spinning) with numbers of nozzle holes from 2000 to 70000 Hole / nozzle the thread take-off speeds to 60 to 250 m / min and in Long spinning lines (conventional high-speed spinning lines) Number of nozzle holes from 800 to 3500 holes / nozzle the thread take-off speeds can be set to 350 to 4000 m / min.

With short spinning systems, the crimping takes place in a stuffer box, at Long spinning lines over crimper, the crimp is two-dimensional.

In long spinning systems, which are particularly suitable for finer titers, these are Processing of the polypropylene mixtures into fibers and further processing Staple fibers in Reckstrasse as a successor to separate processes. The extruded threads are first brought together into fiber cables and in Jugs placed before further processing takes place in Reckstrasse.

For the production of three-dimensional crimped yarns from bulked continuous Filament "type with titers of 300 to 4000 dtex, the fibers are made from the Polypropylene mixtures according to the invention with the help of high-speed godets deducted in successor devices from stretching device, hot air texturing chamber, Relaxation device, tangle device and winder by stretching, Hot air testing, crimping and tangling Thread take-off speeds of 1000 to 4000 m / min further processed. The Tangelung saves a separate two-way process.

For the production of high-strength filament yarns of the fully drawn yarn type Strength values up to 10 cN / dtex, total titles from 40 to 3000 dtex and Capillary titers from 3 to 14 dtex become the threads from the polypropylene mixtures deducted in accordance with the invention with the help of high-speed godets Successor devices from stretching device and winder further processed, whereby in Short spinning lines the thread take-off speeds to 60 to 450 m / min and in Langspinnanlagen the thread take-off speeds to 350 to 4000 m / min can be set.

For the production of multifilament yarns, the threads are made from According to the invention, polypropylene mixtures are used in downstream devices Cables and winders processed further.

Filament yarns of the "pre-oriented yarn" type ("pre-oriented yarn" type) with Capillary titers from 2 to 6 dtex and total titers up to 500 dtex according to the invention by further processing the fibers from the Polypropylene blends in downstream devices made up of a deflection system and winder and optionally interposed godets Thread take-off speeds of 1000 to 5000 m / min.

Textile fabrics in the form of nonwovens are according to the invention Extraction of the fibers from the polypropylene mixtures in the blow duct using air by processing the threads into spunbonded nonwovens in successor devices Screen conveyor belt, calender or needling device and winder Flat, disorderly laying down of the fibers on the sieve-shaped conveyor belt and application of thermal bonding or needling processes to achieve the required strength and dimensional stability. Across from Staple fiber nonwovens have this spunbonded fabrics a significantly cheaper lengthways / crossways - strength ratio.

According to the invention, application forms a special variant of nonwoven production a highly heated airflow around the capillary nozzle openings during the extrusion of the Fibers from the polypropylene mixtures from the capillary tool in the Blowing shaft. The air flow stretches the melted thread out of the Polyolefin mixture with simultaneous division into many individual vials Fiber diameters from 0.5 to 12 µm. The further processing of the on the The screen conveyor belt of the deposited fibers is analogous to the spunbond production. Of of particular importance in this meltblowing variant of nonwoven production from the Polyolefin blends is the temperature and shear rate profile of the Melt processing facility that must be set so that the Melt a degradative reduction in viscosity to a melt index 150g / 10 min at 230 ° C / 2, 16 kp.

1 Extruder

2 Spinnpumpe

3 Spinndüsen

4 Blasschacht

5 Abzugseinrichtung

6 Wickler

For the production of non-post-stretched polyolefin fibers and polyolefin yarns, the process according to the invention is exemplarily explained by a process diagram according to drawing 1. The reference symbols have the following meaning:

1 extruder

2 spinning pump

3 spinnerets

4 blow chute

5 trigger device

6 winders

Preferred extruders (1) for melting the polyolefin mixtures are Single screw extruder with high homogenization effect with screw lengths of 28 up to 36 D, preferably with flanged static or dynamic mixers, used.

Preferred dimensions of the spinnerets (3) are spinnerets with Inside diameters from 0.35 to 1.5 mm.

In the take-off device (5) the take-off can be done directly via the winder (6) or below Intermediate switching of high-speed godets. preferred Withdrawal speeds for capillary titers from 2.5 to 5 dtex are 2500 to 3500 m / min.

mehrschichtige Textilien, bevorzugt in Kombination mit Naturfasern, mit hohem Tragekomfort und Wärmerückhaltevermögen, insbesondere für Trikotagen, Sportund Freizeitbekleidung,

Strickwaren mit hohem Wärmerückhaltevermögen,

hochfeste technische Gewebe hoher Scheuerfestigkeit und Dimensionsstabilität im Nasszustand, bevorzugt in Form von Tauwerken, Gurten und Filtergeweben,

Heimtextilien wie Teppichböden hoher Pflegeleichtigkeit und geringer elektrostatischer Aufladbarkeit sowie Möbelbezugsstoffe, insbesondere für Gartenmöbel,

Viesstoffe im Medizin- und Hygienebereich wie OP-Kittel und Windelhüllen,

Geotestilvliese für Strassen- und Eisenbahnbau und zur Baustellenbefestigung,

Vliesbänder zur Beseitigung von Ölhavarien,

elastische Hygieneartikel.

Preferred areas of application of the polyolefin fibers, polyolefin yarns and textile fabrics produced therefrom are:

multilayer textiles, preferably in combination with natural fibers, with high wearing comfort and heat retention capacity, especially for jersey days, sports and leisure clothing,

Knitwear with high heat retention,

high-strength technical fabrics with high abrasion resistance and dimensional stability when wet, preferably in the form of ropes, belts and filter fabrics,

Home textiles such as carpets with easy care and low electrostatic chargeability as well as upholstery fabrics, especially for garden furniture,

Nonwovens in the medical and hygiene sector such as surgical gowns and diaper sleeves,

Geotestil fleece for road and railway construction and for construction site fastening,

Fleece tapes for removing oil spills,

elastic hygiene articles.

The invention is illustrated by the following examples:

example 1

In a spinning plant according to drawing 1, a polyolefin mixture, which consists of 99 % By mass of an unmodified polypropylene homopolymer (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 1 mass% of a modified polypropylene (Melt index 5.5 g / 10 min at 230 ° C / 2.16 kg, quotient of the intrinsic viscosity (in Decalin at 135 ° C) of the modified polypropylene and the intrinsic viscosity of the unmodified polypropylene with largely the same molar mass weight average 0.74), 0.25 mass% 2-tert-butyl-4,6-diisopropylphenol, 0.2 mass% Up to - 2,2,6,6 - tetramethyl-4-piperidyl sebazate and 0.2 mass% calcium stearate (Auxiliaries based in each case on the sum of the propylene polymers) at one Melt temperature of 275 ° C melted in the extruder transferred from the spinning pump to the spinnerets and at a temperature of Spinning nozzles of 292 ° C through the blow shaft, the one with compressed air Temperature of 20 ° C is cooled, with a withdrawal speed of 3000 m / min deducted by high-speed godets and wound up.

The resulting undrawn polypropylene yarn has a total titer of 252 dTex, a tensile strength of 19.5 cN / tex and an elongation of 202%.

Example 2

In a spinning system according to drawing 1, a polyolefin mixture, which consists of 89 % By mass of an unmodified polypropylene homopolymer (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 10 mass% of an unmodified heterophasic statistical propylene-ethylene block copolymer (ethylene content 33 mol%, Melt index 8 g / 10 min at 230 ° C / 2.16 kg), 1 mass% of a modified Polypropylene (melt indices 5.5 g / 10 min at 230 ° C / 2, 16 kg, quotient from the Intrinsic viscosity (in decalin at 135 ° C) of the modified polypropylene and Intrinsic viscosity of the unmodified polypropylene with largely the same Molar mass weight average 0.74), 0.25 mass% 2-tert-butyl-4,6-diisopropylphenol, 0.25 mass% bis - 2,2,6,6 - tetramethyl-4-piperidyl sebazate and 0.1 mass% Magnesium stearate (auxiliary substances in each case based on the sum of Propylene polymers) at a melt temperature of 275 ° C in the extruder melted. With the spinning pump, the melt becomes the spinnerets transferred and at a temperature of the spinnerets of 275 ° C by the Blow duct, which is cooled with compressed air at a temperature of 20 ° C, with a take-off speed of 3000 m / min due to high-speed godets stripped and wound up.

The resulting undrawn polypropylene yarn has a total titer of 253 dTex, a tensile strength of 18.5 cN / tex and an elongation of 195%.

Example 3 (comparative example)

In a spinning system according to drawing 1, a polypropylene compound that is made 100% by mass of an unmodified polypropylene homopolymer (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 0.2% by mass of pentaerythritol tetrakis [3- (3,5-ditert.butyl-4-hydroxyphenyl)] propionate, 0.2 mass% bis - 2,2,6,6 tetramethyl-4-piperidyl sebazate and 0.2% by mass of magnesium stearate (auxiliary materials in each case on the polypropylene homopolymer) at a melt temperature of 280 ° C in Extruder melted. The melt becomes the with the spinning pump Spinnerets transferred and at a temperature of the spinnerets of 290 ° C the blow duct, which is cooled with compressed air at a temperature of 20 ° C is, with a take-off speed of 3000 m / min by high-speed Stripped and wound up godets.

The resulting undrawn polypropylene yarn has a total titer of 254 dtex, a tensile strength of 23.7 cN / tex and an elongation of 124%.

Example 4: Production of the modified propylene polymer:

In a continuous heatable continuous mixer, a powdered Polypropylene homopolymer (melt index of 0.2 g / 10 min at 230 ° C / 2.16 kp, average particle diameter 0.55 mm) continuously metered. Furthermore, in the continuous mixer 0.1% by weight calcium stearate and 0.09% by weight Bis (tert.butylperoxy) -2,5-dimethylhexane, in each case based on the polypropylene homopolymer, dosed continuously. With homogeneous mixing at 45 ° C becomes the one loaded with thermally decomposing radical generator and auxiliary Polypropylene homopolymer with a residence time of 6 min at 45 ° C by a Butadiene-nitrogen mixture with 1.1% by weight of butadiene, based on the Polypropylene homopolymer, sorptively loaded, after transfer into one Twin screw extruder, the powdered reaction mixture is in contact with the metered-in butadiene-nitrogen mixture with the addition of 0.1% by mass of Irganox 1010 and 0.1 mass% Irgaphos 168 at a melt temperature of 235 ° C melted, after a rough degassing with dosing of water as Entrainer subjected to fine degassing, discharged and granulated.

The resulting modified polypropylene has an IR spectroscopic determined bound butadiene content of 1.0% by weight and a Melt index of 0.85 g / 10 min at 230 ° C / 2.16 kp.

Processing of the polyolefin mixture:

In a laboratory spinning system consisting of a plasticizing extruder, melt pump, capillary tool, blow chute, take-off device and winder, a polypropylene mixture is made up of 99 mass% of a polypropylene homopolymer (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 1 mass % of a modified polypropylene (melt index of 0.85 g / 10 min at 230 ° C / 2.16 kp, content of bound butadiene 1.0% by weight), 0.25% by mass of 2-tert-butyl-4.6 -diisopropylphenol, 0.2 mass% bis - 2,2,6,6 - tetramethyl-4-piperidyl sebazate and 0.2 mass% calcium stearate (auxiliaries in each case based on the sum of the propylene polymers) melted at a melt temperature of 272 ° C. in the extruder The melt is transferred to the spinnerets with the melt pump and drawn off at a spinning nozzle temperature of 290 ° C through the blow shaft, which is cooled with compressed air at a temperature of 20 ° C, at a take-off speed of 3000 m / min by high-speed godets and wound up.
The resulting filament yarn of the EMR1.1 pre-oriented yarn type has a total titer of 252 dtex, a tensile strength of 19.5 cN / tex and a tensile elongation of 202%.

Example 5 (comparative example)

In a laboratory spinning system according to Example 1, a polypropylene compound that is 100% by mass of an unmodified polypropylene homopolymer (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 0.2% by mass of pentaerythritol tetrakis [3- (3,5-ditert.butyl-4-hydroxy-phenyl)] propionate, 0.2 mass% bis - 2,2,6,6-tetramethyl-4-piperidyl sebazate and 0.2% by mass of magnesium stearate (auxiliaries in each case based on the polypropylene homopolymer) at a melt temperature of 275 ° C in Plasticizing extruder melted. The melt is closed with the melt pump transferred to the spinnerets and at a temperature of the spinnerets of 290 ° C through the blow duct, which with compressed air at a temperature of 20 ° C is cooled, with a take-off speed of 3000 m / min by high-speed Stripped and wound up godets.

The resulting filament yarn from EMR1.1 pre-oriented yarn type has a total titer of 254 dtex, one Tensile strength of 23.7 cN / tex and an elongation of 124%.

Example 6 Production of the modified propylene polymer:

A powdery random polypropylene copolymer (melt index of 0.85 g / 10 min at 230 ° C / 2.16 kp, average particle diameter 0.85 mm) is continuously metered into a continuous heatable continuous mixer. Furthermore, 0.05% by weight of hydrotalcite, 0.05% by weight of calcium stearate and 0.45% by weight of tert-butyl peroxybenzoate, in each case based on the polypropylene copolymer, are metered continuously into the continuous mixer. With homogeneous mixing at 70 ° C., the polypropylene homopolymer loaded with thermally disintegrating radical generator and auxiliary material is at a residence time of 4 min at 70 ° C. by the inflowing divinylbenzene / nitrogen mixture with 0.35% by weight divinylbenzene, based on the polypropylene -Homopolymer, sorptively loaded. After transfer to the twin-screw extruder, the pulverulent reaction mixture is melted in contact with the metered-in divinylbenzene / nitrogen mixture with the addition of 0.1% by mass of Irganox 1010 and 0.1% by mass of Irgaphos 168 at a melt temperature of 225 ° C., after a rough degassing Dosing of water as an entrainer undergoes fine degassing, discharged and granulated.
The resulting modified polypropylene copolymer has a content of bound divinylbenzene, determined by IR spectroscopy, of 0.32% by weight and a melt index of 1.35 g / 10 min at 230 ° C./2.16 kp.

Processing of the polyolefin mixture:

In a high-speed laboratory spinning system made of plasticizing extruder, Melt pump, capillary tool, blow duct, extraction device and Storage jug is a polypropylene mixture made of 89% by mass Polypropylene homopolymers (melt index 18.2 g / 10 min at 230 ° C / 2.16 kg), 10 Mass% of a reactor blend (ethylene content 33 mol%, melt index 8 g / 10 min at 230 ° C / 2.16 kg), consisting of a crystalline propylene-ethylene copolymer and an elastic ethylene-propylene copolymer, 1 mass% of one modified polypropylene (content of bound divinylbenzene of 0.32 mass %, Melt index of 1.35 g / 10 min at 230 ° C / 2.16 kp), 0.25 mass% 2-tert-butyl-4,6-diisopropylphenol, 0.25 mass% bis-2,2,6,6-tetramethyl-4-piperidyl sebazate and 0.1% by mass of magnesium stearate (auxiliary substances in each case based on the sum of the Propylene polymers) at a melt temperature of 280 ° C in the extruder melted. The melt becomes the spinnerets with the melt pump transferred and at a temperature of the spinnerets of 285 ° C by the Blow duct, which is cooled with compressed air at a temperature of 20 ° C, with a take-off speed of 3000 m / min due to high-speed godets deducted and placed in a jug.

The discarded is used for the discontinuous production of staple fibers Polypropylene thread in a laboratory post-processing line made of stretching unit, crimper and cutting machine of a stretch by 850% and two-dimensional Rippled and cut into segments. One after the stretching unit has a non-crimped sample (thread diameter 0.2 mm) a tensile strength of 540 MPa and an elongation of 46%.

The fiber segments are thermobonded on a laboratory calender a nonwoven processed, which has a basis weight of 60 g / m 2 and a longitudinal / transverse strength ratio of 2.6: 1.

Claims (10)

1. Polyolefin fibres and polyolefin yarns of high strength and elongation which have been produced by melt processing, especially undrawn polyolefin fibres and polyolefin yarns having filament linear densities of 1 to 10 dtex and tensile elongations above 130% at tensile strengths of at least 15 cN/tex, and textile sheetlike structures produced therefrom, characterized in that the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom consist of polypropylene mixtures which on the one hand consist of

   A) 0.05 to 10 mass%, preferably 0.2 to 3 mass%, of modified propylene polymers having melt indices of 0.1 to 50 g/10 min at 230°C/2.16 kg, preferably 1 to 40 g/10 min at 230°C/2.16 kg, and a ratio of 0.20 to 0.95 for the limiting viscosity of the modified polypropylene to the limiting viscosity of the non-modified polypropylene having substantially the same molar mass weight average, which have been produced

   a) by treatment of propylene homopolymers and/or copolymers of propylene and ethylene or alpha-olefines having 4 to 18 carbon atoms and also of mixtures of the said polypropylenes with multifunctionally ethylenically unsaturated monomers in the presence of ionizing radiation or thermally decomposing free-radical formers, or

   b) by reaction of functionalized polypropylenes, preferably of polypropylenes containing acid and/or acid anhydride groups, with multifunctional compounds of opposite reactivity, preferably with C2- to C16-diamines and/or C2- to C16-diols, or

   c) by hydrolytic condensation of polypropylenes which contain hydrolyzable silane groups, and on the other hand consist of

   B) 99.95 to 90 mass%, preferably 99.8 to 97 mass%, of non-modified propylene polymers, wherein the non-modified propylene polymers consist of

   1) customary propylene polymers, preferably Ziegler-Natta-catalytically or metallocene-catalytically produced propylene homopolymers and/or copolymers of propylene, ethylene and/or alpha-olefines having 4 to 18 carbon atoms having a propylene content of 80.0 to 99.9 mass% in the form of random copolymers, block copolymers and/or random block copolymers, having melt indices of 0.1 to 300 g/10 min at 230°C/2.16 kg, preferably 1 to 100 g/10 min at 230°C/2.16 kg, which may be present in the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom at 50 to 99 mass%, and/or

   2) a polyolefin mixture having an Mw/Mn ratio of 2 to 6 and a melt index of 1 to 40 g/10 min at 230°C/2.16 kgf, which consists of

   2.1) 60 to 98 mass% of a crystalline copolymer of 85 to 99.5 mass% of propylene and 15 to 0.5 mass% of ethylene and/or an alpha-olefine of the general formula CH2=CHR, wherein R is a linear or branched alkyl radical having 2 to 8 carbon atoms, 2.2) 2 to 40 mass% of an elastic copolymer of 20 to 70 mass% of ethylene and 80 to 30 mass% of propylene and/or an alpha-olefine of the general formula CH2=CHR, wherein R is a linear or branched alkyl radical having 2 to 8 carbon atoms,

   wherein the polyolefin mixture may be present in the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom at up to 99 mass%, preferably 10 to 80 mass%,
   and wherein the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom may further contain 0.01 to 5 mass% of auxiliaries, based on the polyolefins.
2. Polyolefin fibres and polyolefin yarns which have been produced by melt processing and textile sheetlike structures produced therefrom according to Claim 1, characterized in that the modified polypropylene polymers A) produced by treatment of propylene homopolymers and/or copolymers of propylene and ethylene or alpha-olefines having 4 to 18 carbon atoms and also of mixtures of the said polypropylenes with multifunctionally ethylenically unsaturated monomers in the presence of thermally decomposing free-radical formers consist of modified propylene polymers which have been produced by a continuous process wherein

   1) polypropylene particles in the form of powders, granules or pellets having a preferred particle size in the range from 0.001 to 7 mm, which consist of

   1.1) propylene homopolymers, especially propylene homopolymers having a bimodal molar mass distribution, molar mass weight averages Mw of 500000 to 1500000 g/mol, molar mass number averages Mn of 25000 to 100000 g/mol and Mw/Mn values of 5 to 60, which have been produced in a reactor cascade using Ziegler-Natta catalysts or metallocene catalysts, and/or of

   1.2) copolymers of propylene and alpha-olefines having 2 to 18 carbon atoms, preferably of random propylene copolymers, propylene block copolymers, random propylene block copolymers and/or elastomeric polypropylenes, or of mixtures of the said modified polypropylenes,
   have been mixed in a continuous mixer with 0.05 to 3 mass%, based on the polypropylenes used, of acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates and/or peresters as thermally decomposing free-radical formers whose thermal decomposition is preferably completed at below 210°C and which have optionally been diluted with inert solvents, by heating at 30 to 100°C, preferably at 70 to 90°C,

   2) volatile bifunctional monomers, especially C4-to C10-dienes and/or C7- to C10-divinyl compounds, have been sorbed by the polypropylene particles from the gas phase, preferably in continuous through-flow mixers as continuous gas-solids absorbers, at a temperature T of 20°C to 120°C, preferably of 60 to 100°C, and an average sorption time of tau s of 10 s to 1000 s, preferably 60 s to 600 s,
   wherein the fraction of the bifunctionally unsaturated monomers in the polypropylene particles is 0.01 to 10 mass%, preferably 0.05 to 2 mass%, based on the polypropylenes used, then

   3) the polypropylene particles in which the acyl peroxides, alkyl peroxides, hydroperoxides, peroxycarbonates and/or peresters as thermally decomposing free-radical formers and the bifunctionally unsaturated monomers have been sorbed have been melted under an atmosphere of inert gas and these volatile bifunctional monomers at 110°C to 210°C in continuous kneaders or extruders, preferably in twin-screw extruders, and the thermally decomposing free-radical formers have been decomposed in the process,

   4) the melt has subsequently been heated at 220°C to 300°C to remove unconverted monomers and decomposition products, and

   5) the melt has been pelletized in a conventional manner,

   and wherein 0.01 to 2.5 mass% of stabilizers, 0.1 to 1 mass% of antistats, 0.2 to 3 mass% of pigments, 0.05 to 1 mass% of nucleators and/or 0.1 to 5 mass% of processing aids based on the polypropylene used have been added as further auxiliaries before process step 1) and/or 5) and/or before or during step 3) and/or 4).
3. Polyolefin fibres and polyolefin yarns which have been produced by melt processing and textile sheetlike structures produced therefrom according to Claim 1 or 2, characterized in that the non-modified propylene polymers 1) consist of propylene homopolymers having an Mw/Mn ratio of 2 to 4.5 and/or copolymers of propylene and alpha-olefines having 2 to 18 carbon atoms and also of mixtures of the said polypropylenes.
4. Polyolefin fibres and polyolefin yarns which have been produced by melt processing and textile sheetlike structures produced therefrom according to one or more of Claims 1 to 3, characterized in that the auxiliaries present therein are 0.01 to 1 mass% of nucleators, 0.01 to 2.5 mass% of stabilizers, 0.1 to 1 mass% of antistats, 0.2 to 3 mass% of pigments, 1 to 4.5 mass% of flame retardants and/or 0.01 to 1 mass% of processing aids, all percentages being based on the sum total of the polyolefins.
5. Process for the production of polyolefin fibres and polyolefin yarns of high strength and elongation, especially of undrawn polyolefin fibres and polyolefin yarns having filament linear densities of 1 to 10 dtex and tensile elongations above 130% at tensile strengths of at least 15 cN/tex, and of textile sheetlike structures produced therefrom, by processing of polypropylene mixtures in known melt-spin ranges consisting of plastifying extruder, spinning pump, melt distributor, spinneret dies, quench chimney and downstream equipment using the process steps of
   melting at melt temperatures of 185 to 310°C, transferring the melt by melt pump to the spinneret dies,
   extrusion into the quench chimney,
   withdrawing as strands and further processing in downstream equipment
   characterized in that
   the polypropylene mixtures used, which on the one hand consist of

   A) 0.05 to 10 mass%, preferably 0.2 to 3 mass%, of modified propylene polymers having melt indices of 0.1 to 50 g/10 min at 230°C/2.16 kg, preferably 1 to 40 g/10 min at 230°C/2.16 kg, and a ratio of 0.20 to 0.95 for the limiting viscosity of the modified polypropylene to the limiting viscosity of the non-modified polypropylene having substantially the same molar mass weight average, which have been produced

   a) by treatment of propylene homopolymers and/or copolymers of propylene and ethylene or alpha-olefines having 4 to 18 carbon atoms and also of mixtures of the said polypropylenes with multifunctionally ethylenically unsaturated monomers in the presence of ionizing radiation or thermally decomposing free-radical formers, or

   b) by reaction of functionalized polypropylenes, preferably of polypropylenes containing acid and/or acid anhydride groups, with multifunctional compounds of opposite reactivity, preferably with C2- to C16-diamines and/or C2- to C16-diols, or

   c) by hydrolytic condensation of polypropylenes which contain hydrolyzable silane groups, and on the other hand consist of

   B) 99.95 to 90 mass%, preferably 99.8 to 97 mass%, of non-modified propylene polymers, wherein the non-modified propylene polymers consist of

   1) customary propylene polymers, preferably Ziegler-Natta-catalytically or metallocene-catalytically produced propylene homopolymers and/or copolymers of propylene, ethylene and/or alpha-olefines having 4 to 18 carbon atoms having a propylene content of 80.0 to 99.9 mass% in the form of random copolymers, block copolymers and/or random block copolymers, having melt indices of 0.1 to 300 g/10 min at 230°C/2.16 kg, preferably 1 to 100 g/10 min at 230°C/2.16 kg, which may be present in the polypropylene mixtures for the production of the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom at 50 to 99 mass%, and/or

   2) a polyolefin mixture having an Mw/Mn ratio of 2 to 6 and a melt index of 1 to 40 g/10 min at 230°C/2.16 kgf, which consists of

   2.1) 60 to 98 mass% of a crystalline copolymer of 85 to 99.5 mass% of propylene and 15 to 0.5 mass% of ethylene and/or an alpha-olefine of the general formula CH2=CHR, wherein R is a linear or branched alkyl radical having 2 to 8 carbon atoms,

   2.2) 2 to 40 mass% of an elastic copolymer of 20 to 70 mass% of ethylene and 80 to 30 mass% of propylene and/or an alpha-olefine of the general formula CH2=CHR, wherein R is a linear or branched alkyl radical having 2 to 8 carbon atoms,

   wherein the polyolefin mixture may be present in the polypropylene mixtures for the production of the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom at up to 99 mass%, preferably 10 to 80 mass%,
   and wherein the polypropylene mixtures for the production of the polyolefin fibres and polyolefin yarns and textile sheetlike structures produced therefrom may further contain 0.01 to 5 mass% of auxiliaries, based on the polyolefins.
6. Process for the production of polyolefin fibres and polyolefin yarns and of textile sheetlike structures produced therefrom according to Claim 5, characterized in that the strands are withdrawn by means of high speed godets and

   A) are processed in downstream equipment comprising drawing unit, crimper, setting unit and cutting machine by drawing, crimping and cutting to form staple fibres, the strand withdrawal speeds being set at 60 to 250 m/min in short spin ranges and at 350 to 4000 m/min in long spin ranges, or

   B) are processed in downstream equipment comprising drawing means, texturing means, relaxing means, tangling means and winder by drawing, hot air texturing, crimping and tangling to form three-dimensionally crimped yarns, the strand withdrawal speeds being set to 1000 to 4000 m/min, or

   C) are processed in downstream equipment comprising drawing means and winder by drawing to form high-strength filament yarns of the fully drawn type, the strand withdrawal speeds being set at 60 to 450 m/min in short spin ranges and at 350 to 4000 m/min in long spin ranges, or

   D) are processed in downstream equipment comprising cabler and winder to form multifilament yarns,

   and optionally are further processed to form textile multifilaments and/or textile sheetlike structures.
7. Process for the production of polyolefin fibres and polyolefin yarns and of textile sheetlike structures produced therefrom according to Claim 5, characterized in that the strands are processed in downstream equipment comprising deflecting system and winder with or without in-between godet to form yarns of the partially oriented yarn type, the strand withdrawal speeds being set to 1000 to 5000 m/min.
8. Process for the production of polyolefin fibres and polyolefin yarns and of textile sheetlike structures produced therefrom according to Claim 5, characterized in that the withdrawal of the extruded strands is effected by air jet with or without the extruded strands of liquid melt being quenched with a hot air stream around the spinneret die openings, and the afterprocessing of the laid-down strands or fibres after this withdrawal process is effected in downstream equipment comprising conveyor belt, calender or kneading means and winder by thermobonding or needling operations to form respectively spunbonded or meltblown webs as textile sheetlike structures.
9. Use of polyolefin fibres and polyolefin yarns and of textile sheetlike structures produced therefrom according to one or more of Claims 1 to 4 for the production of multilayered textiles, preferably in combination with natural fibres, industrial textiles, preferably in the form of rigging, high-strength webbing and filter cloths, home textiles, preferably of carpeting and furniture covering, nonwovens in the medical and hygiene sector and of geotextiles.
10. Use of polyolefin fibres and polyolefin yarns and of textile sheetlike structures produced therefrom according to one or more of Claims 1 to 4 for the production of elastic hygienic goods.

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