EP0878567A2 - Polyolefin fibres and polyolefin yarns and textile materials thereof - Google Patents

Abstract

The claims cover polyolefin fibres and yarns with high strength and elongation at break produced by melt processing, especially fibres with capillary titres of 1-10 dtex, elongation at break > 130% and tensile strength NOTLESS 15 cN/tex that are not redrawn, and textile fabrics produced from them. They consist of polypropylene mixtures containing 0.05-10, preferably 0.2-3 wt.% modified propylene polymers (I) with melt indices of 0.1-50, preferably 1-40 g/10 minutes at 230 degrees C/2.16 kg and a ratio of intrinsic viscosity of (I) to the intrinsic viscosity of the unmodified polypropylene of the same weight average molecular weight (Mw) of 0.20-0.95. (I) are obtained by (a) treating propylene homopolymers and/or copolymers of propylene and ethylene and/or 4-18 carbon (C) alpha -olefins with polyfunctional ethylenically unsaturated monomers in the presence of ionising radiation and/or thermal free radical initiators; or (b) reacting functionalised polypropylene, preferably containing acid and/or acid anhydride groups, with polyfunctional compounds of opposite reactivity, preferably 2-16 C diamines and/or 2-16 C diols. Also claimed is a method of making these materials.

Description

The invention relates to melt-processed polyolefin fibers and High tenacity and elongation polyolefin yarns, especially non-post-drawn ones Polyolefin fibers and polyolefin yarns, and textile fabrics made therefrom.

Folien, Gewebe und Vliesstoffe aus Polypropylen", S.175-189, VDI-Verlag Düsseldorf 1979; Moore, P., Polypropylene-Handbook" S. 350-358, Carl-Hanser-Verlag München 1996).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 post-treatment of the spun threads.

Known manufacturing processes for polypropylene staple fibers by melt spinning are the fast spinning process and the short spinning process.

In the production of staple fibers based on polypropylene using the fast spinning process, already known as a rapid spinning process for spinning 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 Withdrawn from the spinneret.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 using the short spinning process at very low spinning speeds (30 to 150 m / min) worked, so the cooling zones of the spinning systems can be dimensioned very short [Schweitzer, A., Chemiefaser / Textilindustrie 88 (1986), 671-674]. The low spinning speeds allow a direct continuous Feeding the filaments brought together into spinning cables on the stretching and Succession facilities.

This is also done according to the technology of the fast spinning process Preoriented Yarn Spinning "[ Pre-Oreinted-Yarn (POY) spinning] ", in which the threads emerging from the spinneret after passing through the blow chute are drawn off from high-speed godets or directly from the winder at 1000 to 5000 m / min and wound on packages. The fiber properties are largely determined by the orientation introduced from the melt-like state [Wulfhorst, B., Chemiefaser / Textilindustrie 92 (1990), 971-976]. This orinting effect results from the difference between the extrusion speed and the take-off or take-up speed.

Comparable conditions for influencing the basic fiber properties also apply to the spunbonded process. In the spunbonded nonwoven process, the filaments are drawn off through the cooling zone either by accelerated downpipe air or compressed air-operated nozzles [Fourne ' , F., Chemiefaser-Textilindustrie 95 (1993), 811-822]. The undrawn filaments produced are deposited in a flat, disordered form on a sieve-shaped conveyor belt and further processed into spunbonded fabric in a post-processing step by applying thermal bonding (by means of calender strengthening) or needling processes.

A special variant of the nonwoven production is the blown fiber (melt-blow) spinning technology, in which the thread formation takes place with the application of a highly heated lutte stream around the capillary nozzle openings [Fourne ' , F. Chemical fibers / textile industry 81 (1979), 445-449]. The air flow divides the molten polymer thread into many small individual fibers with a very small diameter and at the same time causes the individual threads to stretch. The further processing of the fibers or filaments deposited on the wire conveyor belt is carried out in accordance with the spunbond technology.

In the production of high-strength filament yarns [Fully Drawn Yarn (FDY)], the filaments are drawn off from the spinneret with the help of godets and processed in downstream devices consisting of a stretching device and a winder. High-strength filament yarns can be produced using both the short spinning process and the fast spinning process. In addition to stretching, the Bulked continuous filament "process a three-dimensional crimp by texturing devices [Bussmann, M., Chemiefaser / Textilindustrie 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] after spinning and stretching microporous fibers. Fibers with increased heat resistance can be achieved by spinning polypropylene blends with 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 a relatively low tensile elongation. An addition of elastomers such as ethylene-propylene rubber or ethylene-propylene-diene rubber leads to an increase in stretch, but at the same time a sharp drop in the strength of the polypropylene fibers and polypropylene yarns.

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 polyolefin 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. α-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 Säure- und/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 α-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 bis 99 Masse%, bevorzugt 50 bis 99 Masse%, enthalten sein können, und/oder

2) einer Polyolefinmischung mit einem M_w/M_n-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 α-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 α-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, und/oder

3) weitgehend amorphen Polypropylenen oder Propylen-Copolymeren mit einem Anteil an kristallinem Polypropylen bzw. kristallinem Propylen-Copolymer unter 10 Masse% , einer Schmelzenthalpie unter 40 J/g und einem Schmelzindex von 0,1 bis 100 g/10 min bei 230°C/2,16 kg, wobei das weitgehend amorphe Polypropylen ein Homopolymer des Propylens und/oder ein Copolymer des Propylens aus mindestens 80 Mol % Propylen und höchstens 20 Mol % eines oder mehrerer α-Olefine der allgemeinen Formel CH₂=CHR ist, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist, die in den Polyolefinfasern und Polyolefingarnen und daraus hergestellten textilen Flächengebilden bis 50 Masse% enthalten sein können, und/oder

4) nichtisotaktischen Propylen-Homopolymeren mit einem Schmelzpunkt von 145 bis 165°C, einer Schmelzviscosität über 200000 cps bei190°C, einer Kristallisationswärme von 4 bis 10 cal/g und einem löslichen Anteil in Diethylether von 35 Masse% bis 55 Masse%, die in den Polyolefinfasern und Polyolefingarnen und daraus hergestellten textilen Flächengebilden bis 50 Masse% enthalten sein können,

bestehen,
oder nur aus nichtmodifizierten Propylenpolymeren B) bestehen, wobei die Komponenten 3) und/oder 4) in Anteilen von 5 bis 50 Masse% und die verbleibenden Komponenten im Gemisch von 95 bis 50 Masse% enthalten sind,
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 of 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 produced therefrom, the Polyolefin fibers and polyolefin yarns and textile fabrics made therefrom according to the invention
either 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 α-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 C ₂ to C ₁₆ diamines and / or C ₂ to C ₁₆ 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 α-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 up to 99% by mass, preferably 50 to 99% by mass, and / or

2) a polyolefin mixture with an M _w / M _n 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 α-olefin of the general formula CH ₂ = CHR, where R is a linear or branched alkyl radical with 2 to 8 carbon atoms,

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

wherein 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, and / or

3) largely amorphous polypropylenes or propylene copolymers with a proportion of crystalline polypropylene or crystalline propylene copolymer below 10% by mass, an enthalpy of fusion below 40 J / g and a melt index from 0.1 to 100 g / 10 min at 230 ° C. / 2.16 kg, the largely amorphous polypropylene being a homopolymer of propylene and / or a copolymer of propylene composed of at least 80 mol% of propylene and at most 20 mol% of one or more α-olefins of the general formula CH ₂ = CHR, where R is a linear or branched alkyl radical having 2 to 8 carbon atoms, which can be contained in the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom up to 50% by mass, and / or

4) non-isotactic propylene homopolymers with a melting point of 145 to 165 ° C, a melt viscosity above 200000 cps at 190 ° C, a heat of crystallization of 4 to 10 cal / g and a soluble content in diethyl ether of 35% to 55% by weight The polyolefin fibers and polyolefin yarns and textile fabrics produced therefrom can contain up to 50% by mass,

consist,
or consist only of unmodified propylene polymers B), components 3) and / or 4) being present in proportions of 5 to 50% by mass and the remaining components in a mixture of 95 to 50% by mass,
and wherein the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom may further contain 0.01 to 5% by weight of auxiliaries, based on the polyolefins.

The high strength and elongation and in the polyolefin fibers and polyolefin yarns modified textile fabrics produced therefrom, if any, contain any modified ones Propylene polymers A) are propylene polymers by radical coupling reactions or polymer-analogous reactions of functionalized polypropylenes were manufactured.

The starting products for the modified propylene polymers A) are preferred Propylene homopolymers as well as copolymers of propylene and α-olefins 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 statistical propylene 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 realized by implementing functionalized polypropylenes with multifunctional ones Make connections 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 polypropylene grafted with maleic anhydride 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 M_w von 500000 bis 1500000 g/mol, Molmassen-Zahlenmitteln M_n von 25000 bis 100000 g/mol und M_w / M_n -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 α-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 Durchflußmischern 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 τ_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 produced 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 stated polypropylenes with polyfunctionally ethylenically unsaturated monomers in the presence of thermally decomposing radical formers, 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

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

1.2) copolymers of propylene and α-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% by 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 C ₄ - to C ₁₀ - dienes and / or C ₇ - to C ₁₀ - divinyl compounds, through the polypropylene particles from the gas phase, preferably in continuous flow mixers as continuous gas-solid absorbers, at a temperature T. from 20 ° C. to 120 ° C., preferably from 60 to 100 ° C., and an average sorption time of τ _s from 10 s to 1000 s, preferably 60 s to 600 s, with the proportion of the bifunctionally unsaturated in the polypropylene particles Monomers is 0.01 to 10% by mass, preferably 0.05 to 2% by mass, based on the polypropylenes used, 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,

4) the melt is then heated to 220 ° C to 300 ° C, whereby unreacted monomers and decomposition products have been removed, 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 polypropylenes used for the production of this preferred modified propylene polymer A) consist in particular of propylene homopolymers and / or copolymers of propylene and α-olefins having 2 to 18 carbon atoms and of mixtures of the polypropylenes mentioned. Polypropylene particles of polypropylenes with a bimodal molar mass distribution, which were produced in a reactor cascade using Ziegler-Natta catalysts or metallocene catalysts, with a molar mass weight average M _w of 500,000 to 1,500,000 g / mol and a molar mass number average M _n of 25,000 to 100,000 are particularly preferred g / mol and M _w / M _n values from 5 to 60, preferably with weight average molecular weights M _w from 600,000 to 1,000,000 g / mol, number average molecular weights M _n from 30,000 to 100,000 g / mol and M _w / M _n - 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, Di-tert.butylperazelat, Di-tert.butylperglutarat, Di-tert.butylperphthalat, Di-tert.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.perylperoxide, tert.perylutoxide , and / or 1-hydroxybutyl-n-butyl peroxide;
• Peresters and peroxycarbonates such as butyl peracetate, cumyl peracetate, cumylperpropionate, cyclohexylperacetate, di-tert.butylperadipate, di-tert.butylperazelate, di-tert.butylperglutarate, di-tert.butylperphthalate, di-tert.butylpersrocate, 1-nitylperebate, 4-nitylperebate, Phenylethylnitroperbenzoate, tert.butylbicyclo- (2,2,1) heptane percarboxylate, tert.butyl-4-carbomethoxyperbutyrate, tert.butylcyclobutane percarboxylate, tert.butylcyclohexylperoxycarboxylate, tert.butylcyclopentylpercarboxylate, tert.butylcyclopropanutamate (benzyl) 2,2-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.butylperoctoate, tert.butylperoxyisopropyl carbonate, tert.butylperisobutyrate, tert.butylperacrylate and / or tert.butylperpropionate;

Mixtures of these thermally decomposing radical formers are also advantageous in the production 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 monomers 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.

These highly volatile bifunctionally unsaturated monomers are sorbed in the production of this preferred modified propylene polymer A) according to the invention, in particular in continuous flow mixers as continuous Gas-solid absorber.

In the production of this preferred variant of the modified propylene polymers A) the heating and melting of the polypropylene particles takes place in which the acyl peroxides, alkyl peroxides, hydroperoxides and / or peresters as thermally disintegrating radical formers and the bifunctionally unsaturated monomers are sorbed under an atmosphere of volatile bifunctionally unsaturated Monomers preferably in continuously operating kneaders or extruders, preferably in twin-screw oars.

The propylene polymers B) which are present as non-modified propylene polymers B) in the conventional propylene polymers 1) which may be present in the polyolefin fibers and polyolefin yarns and the textile fabrics made therefrom preferably consist of propylene homopolymers with an M _w / M _n ratio of 2 to 4.5 and / or copolymers Propylene and α-olefins with 2 to 18 carbon atoms and from mixtures of the polypropylenes mentioned.

The as unmodified propylene polymers B) in the polyolefin fibers and polyolefin yarns and fabric made therefrom, optionally as Component 2) contained polyolefin mixture of crystalline copolymers and Elastic copolymers are, for example, those in EP 400333 or EP 472946 described polymer mixtures.

The as unmodified propylene polymers B) in the polyolefin fibers and polyolefin fibers and fabric made therefrom, optionally as Component 3) contained amorphous polypropylenes are in particular stereoblock polypropylenes, which, for example, using highly active, metal oxide fixed Ziegler-Natta catalysts [Collette, J., Macromolecules 22 (1989), 3851-3858; DE 2830160] or soluble Ziegler-Natta catalysts [de Candia, F., Macromol. Chem. 189 (1988), 815-821], optionally under the following Reactive modification (EP 636863) and / or degradation (EP 640 850) will.

The as unmodified propylene polymers B) in the polyolefin fibers and polyolefin yarns and fabric made therefrom, optionally as Component 4) contained non-isotactic propylene homopolymers are in particular elastomeric high molecular propylene homopolymers, for example those in Products described in EP 475 307 or EP 475 308.

Unmodified propylene polymers B) are particularly preferred in the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom Polyolefin blends that combine several of the unmodified polyolefin components 1) to 4) included.

The in high tenacity and in 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 % Antistatic, 0.2 to 3% pigment, 0.05 to 1% nucleating agent and / or 0.01 to 1 mass% processing aid. These excipients can already be used in the components used in melt processing A) and / or B) can be contained or additionally added to these components.

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 - Octadecyl 4-hydroxyphenyl) propionate, 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] -hexamethylene- 4- (2,2,6,6-tetra-methyl) piperidyl) imino] especially suitable.

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

• Aufschmelzen bei Massetemperaturen von 185 bis 310°C,
• Überführung der Schmelze mittels Schmelzepumpe zu den Spinndüsen,
• Extrusion in den Blasschacht,
• Abzug als Fäden und Weiterverarbeitung in Nachfolgeeinrichtungen hergestellt, wobei erfindungsgemäß

entweder Polypropylenmischungen eingesetzt werden, die einerseits aus

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. α-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 Säure- und/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 α-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 bis 99 Masse%, bevorzugt 50 bis 99 Masse%, enthalten sein können, und/oder

2) einer Polyolefinmischung mit einem M_w/M_n-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 α-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 α-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, und/oder

3) weitgehend amorphen Polypropylenen oder Propylen-Copolymeren mit einem Anteil an kristallinem Polypropylen bzw. kristallinem Propylen-Copolymer unter 10 Masse%, einer Schmelzenthalpie unter 40 J/g und einem Schmelzindex von 0,1 bis 100 g/10 min bei 230°C/2, 16 kg, wobei das weitgehend amorphe Polypropylen ein Homopolymer des Propylens und/oder ein Copolymer des Propylens aus mindestens 80 Mol % Propylen und höchstens 20 Mol % eines oder mehrerer α-Olefine der allgemeinen Formel CH₂=CHR ist, wobei R ein linearer oder verzweigter Alkylrest mit 2 bis 8 Kohlenstoffatomen ist, die in den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne und daraus hergestellten textilen Flächengebilden bis 50 Masse% enthalten sein können, und/ oder

4) nichtisotaktischen Propylen-Homopolymeren mit einem Schmelzpunkt von 145 bis 165°C, einer Schmelzviscosität über 200000 cps bei190°C, einer Kristallisationswärme von 4 bis 10 cal/g und einem löslichen Anteil in Diethylether von 35 Masse% bis 55 Masse%, die in den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne und daraus hergestellten textilen Flächengebilde bis 50 Masse% enthalten sein können,

bestehen,
oder Polypropylenmischungen eingesetzt werden, die nur aus nichtmodifizierten Propylenpolymeren B) bestehen, wobei die Komponenten 3) und/oder 4) in Anteilen von 5 bis 50 Masse% und die verbleibenden Komponenten in den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne und daraus hergestellten textilen Flächengebilde in Anteilen von 95 bis 50 Masse% enthalten sind,
und wobei weiterhin den Polypropylenmischungen zur Herstellung der Polyolefinfasern und Polyolefingarne 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 produced 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

either polypropylene blends are used which are made up of 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 α-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 C ₂ to C ₁₆ diamines and / or C ₂ to C ₁₆ 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 α-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 up to 99% by mass, preferably 50 to 99% by mass, and / or

2) a polyolefin mixture with an M _w / M _n 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 α-olefin of the general formula CH ₂ = CHR, where R is a linear or branched alkyl radical with 2 to 8 carbon atoms,

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

wherein the polyolefin mixture in the polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom can be up to 99% by mass, preferably 10 to 80% by mass, and / or

3) largely amorphous polypropylenes or propylene copolymers with a proportion of crystalline polypropylene or crystalline propylene copolymer below 10% by mass, an enthalpy of fusion below 40 J / g and a melt index from 0.1 to 100 g / 10 min at 230 ° C. / 2, 16 kg, the largely amorphous polypropylene being a homopolymer of propylene and / or a copolymer of propylene composed of at least 80 mol% propylene and at most 20 mol% of one or more α-olefins of the general formula CH ₂ = CHR, where R is a linear or branched alkyl radical having 2 to 8 carbon atoms, which can be contained in the polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom up to 50% by mass, and / or

4) non-isotactic propylene homopolymers with a melting point of 145 to 165 ° C, a melt viscosity above 200,000 cps at 190 ° C, a heat of crystallization of 4 to 10 cal / g and a soluble content in diethyl ether of 35% to 55% by weight The polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics produced therefrom can contain up to 50% by mass,

consist,
or polypropylene mixtures are used which consist only of unmodified propylene polymers B), components 3) and / or 4) in proportions of 5 to 50% by mass and the remaining components in the polypropylene mixtures for the production of the polyolefin fibers and polyolefin yarns and textile fabrics made therefrom contained in proportions of 95 to 50% by mass
and 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 yarns and test fabrics produced therefrom.

Single-screw extruders or twin-screw extruders with screw lengths of 28 to 30 D, preferably with flanged static or dynamic mixers, are particularly suitable as plasticizing extruders for melting the mixtures. Temperature control and speed set shear rates from 10 ² s ^-1 to 10 ³ s ^-1 .

For uniform melt dosing of those melted in the plasticizing extruder Mixing via the melt distributor to the capillary tool is preferred Diphenyl-heated melt pumps for the melts heated to 240-310 ° C used.

For the production of staple fibers from the polypropylene blends, the Fibers drawn off according to the invention 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, being 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 systems (conventional high-speed spinning systems) with numbers of nozzle holes the thread take-up speeds from 800 to 3500 holes / nozzle 350 to 4000 m / min can be set.

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 preferably 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 yarn from Bulked Continuous Filament "type with titers of 300 to 4000 dtex, the fibers from the polypropylene mixtures are drawn off according to the invention with the aid of high-speed godets in successor devices from stretching device, hot air texturing chamber, relaxing device, tangle device and winder by stretching, hot air testing, crimping and tangling at thread take-off speeds of 1000 to 4000 m / min further processed, the tangling saves a separate twisting process.

For the production of high tenacity filament yarn from Fully drawn yarn type with strength values up to 10 cN / dtex, total titers from 40 to 3000 dtex and capillary titers from 3 to 14 dtex, the threads from the polypropylene mixtures are drawn off according to the invention with the aid of high-speed godets in successor devices consisting of stretching device and winder, in short spinning systems the thread take-off speeds are set to 60 to 450 m / min and in long spinning systems the thread take-off speeds are set to 350 to 4000 m / min.

For the production of multifilament yarns, the threads are made from Polypropylene mixtures according to the invention in successor devices Cables and winders processed further.

Filament yarn from Pre-oriented yarn type ( Preoriented yarn "type) with capillary titers from 2 to 6 dtex and total titers up to 500 dtex are produced according to the invention by further processing the fibers from the polypropylene mixtures in downstream devices from a deflection system and winder and optionally interposed godets at 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. Opposite staple fiber fleeces these spunbonded fabrics have a significantly cheaper lengthways / crossways Strength ratio.

According to the invention, application forms a special variant of nonwoven production a highly heated air flow around the capillary nozzle openings during the extrusion of the Fibers from the polypropylene mixtures from the capillary tool in the Blow duct. 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. From 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, which 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 exemplified by a process diagram according to drawing 1. The reference symbols have the following meaning:

1 extruder

2 spinning pump

3 spinnerets

4 blow duct

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 inner 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 under Intermediate switching of high-speed godets. Preferred take-off 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, Sport- und 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:

• multi-layer textiles, preferably in combination with natural fibers, with high wearing comfort and heat retention, 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 system 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% bis - 2,2,6,6 - tetramethyl-4-piperidyl sebazate and 0.2% by mass of calcium stearate (auxiliaries in each case to the sum of the propylene polymers) at a melt temperature of 275 ° C in Extruder melted. The melt becomes the with the spinning pump Spinnerets transferred and at a temperature of the spinnerets of 292 ° C the blow chute, which is cooled with compressed air at a temperature of 20 ° C, with a take-off speed of 3000 m / min through high-speed godets stripped 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 (Melting 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 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, 0.25 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 the propylene polymers) at a melt temperature melted at 275 ° C in the extruder. The melt is with the Spinning pump transferred to the spinnerets and at a temperature of the spinnerets of 275 ° C through the blow shaft, which with compressed air has a temperature of 20 ° C is cooled, with a take-off speed of 3000 m / min high-speed godets removed 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-di-tert-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 substances in each case based on the Polypropylene homopolymer) at a melt temperature of 280 ° C in the extruder melted. The melt becomes the spinnerets with the spinning pump transferred and at a temperature of the spinnerets of 290 ° 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 254 dtex, a tensile strength of 23.7 cN / tex and an elongation of 124%.

Example 4:

Production of the modified propylene polymer:
A powdery polypropylene homopolymer (melt index of 0.2 g / 10 min at 230 ° C / 2.16 kp, average particle diameter 0.55 mm) is continuously metered into a continuous heatable continuous mixer. In addition, 0.1% by weight of calcium stearate and 0.09% by weight of bis (tert-butylperoxy) -2,5-dimethylhexane, based in each case on the polypropylene homopolymer, are continuously metered into the continuous mixer. With homogeneous mixing at 45 ° C., the polypropylene homopolymer loaded with thermally disintegrating radical generator and auxiliary is held for 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 being transferred to a twin-screw extruder, the pulverulent reaction mixture is melted in contact with the metered-in butadiene-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 235 ° C, after a rough degassing Dosing of water as an entrainer undergoes 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 based in each case on the sum of the propylene polymers) melted in the extruder at a melt temperature of 272 ° C. . The melt is transferred to the spinnerets with the melt pump and, at a temperature of the spinnerets of 290 ° C., is drawn off 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 from 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 mass% of pentaerythritol tetrakis [3- (3,5-di-tert-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 the plasticizing extruder melted. The melt becomes the melt with the melt pump Spinnerets transferred and at a temperature of the spinnerets of 290 ° C the blow chute, which is cooled with compressed air at a temperature of 20 ° C, with a take-off speed of 3000 m / min through high-speed godets stripped and wound up.

The resulting filament yarn from Pre-oriented yarn type has a total titer of 254 dtex, a tensile strength of 23.7 cN / tex and a tensile 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 consisting of a plasticizing extruder, a melt pump, a capillary tool, a blow chute, an extraction device and a storage can, a polypropylene mixture is made up of 89% by mass of a polypropylene homopolymer (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% of 2-tert-butyl-4,6-diisopropylphenol , 0.25% by mass of bis-2,2,6,6-tetramethyl-4-piperidyl sebazate and 0.1% by mass of magnesium stearate (auxiliaries in each case based on the sum of the propylene polymers) melted at a melt temperature of 280 ° C. in the extruder. The melt is transferred to the spinnerets with the melt pump and drawn off at a spinning nozzle temperature of 285 ° 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 placed in a jug.

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

The fiber segments are further processed on a laboratory calender by thermal bonding to form a nonwoven fabric that has a basis weight of 60 g / m ² and a longitudinal / transverse strength ratio of 2.6: 1.

Claims (5)

Polyolefin fibers and polyolefin yarns of high strength and elongation produced by melt processing, in particular non-post-stretched polyolefin fibers and polyolefin yarns with capillary titers of 1 to 10 dtex and tensile strains over 130% at tensile strengths of at least 15 cN / tex, and textile fabrics made therefrom, characterized in that the polyolefin fibers and Polyolefin yarns and textile fabrics made from them
either 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 α-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 reacting functionalized polypropylenes, preferably polypropylenes containing acid and / or acid anhydride groups, with polyfunctional compounds of opposite reactivity, preferably with C ₂ -C ₁₆ -diamines and / or C ₂ -C ₁₆ -diols, or Polyolefin fibers and polyolefin yarns produced by melt processing and textile fabrics made therefrom according to Claim 1, characterized in that the treatment of propylene homopolymers and / or copolymers of propylene and ethylene or .alpha.-olefins having 4 to 18 carbon atoms and mixtures of the mentioned polypropylenes with polyfunctionally ethylenically unsaturated monomers in the presence of thermally disintegrating radical formers, modified propylene polymers A) consist of 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 1.1) Propylene homopolymers, in particular from propylene homopolymers with a bimodal molecular weight distribution, weight average molecular weights M _w of 500,000 to 1,500,000 g / mol, number average molecular weights M _n of 25,000 to 100,000 g / mol and M _w / M _n values of 5 to 60, which were produced in a reactor cascade using Ziegler-Natta catalysts or metallocene catalysts, and / or from 1.2) copolymers of propylene and α-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% by 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 C ₄ - to C ₁₀ - dienes and / or C ₇ - to C ₁₀ - divinyl compounds, through the polypropylene particles from the gas phase, preferably in continuous flow mixers as continuous gas-solid absorbers, at a temperature T. from 20 ° C. to 120 ° C., preferably from 60 to 100 ° C., and an average sorption time of τ _s from 10 s to 1000 s, preferably 60 s to 600 s, with the proportion of the bifunctionally unsaturated in the polypropylene particles Monomers is 0.01 to 10% by mass, preferably 0.05 to 2% by mass, based on the polypropylenes used, 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 working kneaders or extruders, preferably in twin-screw ovens, and the thermally decomposing radical formers have been decomposed, 4) the melt is then heated to 220 ° C to 300 ° C, whereby unreacted monomers and decomposition products have been removed, 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. Polyolefin fibers and polyolefin yarns produced by melt processing and textile fabrics made therefrom according to claim 1 or 2, characterized in that the unmodified propylene polymers 1) from propylene homopolymers with an M _w / M _n ratio of 2 to 4.5 and / or copolymers Propylene and α-olefins with 2 to 18 carbon atoms as well as mixtures of the polypropylenes mentioned. Polyolefin fibers and yarns produced by melt processing and textile fabrics made therefrom according to one or more of the claims 1 to 3, characterized in that the auxiliary substances contained 0.01 to 1 Mass% nucleating agent, 0.01 to 2.5 mass% stabilizers, 0.1 to 1 mass% Antistatic agents, 0.2 to 3% by mass of pigments, 1 to 4.5% by mass of flame retardant and / or 0.01 to 1 mass% processing aids, each based on the total of the polyolefins. Process for the production of polyolefin fibers and polyolefin yarns of high strength and elongation, in particular of undrawn 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 by processing polypropylene mixtures in known 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 facilities characterized in that
either polypropylene blends are used which are made up of 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 α-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 reacting functionalized polypropylenes, preferably polypropylenes containing acid and / or acid anhydride groups, with polyfunctional compounds of opposite reactivity, preferably with C ₂ -C ₁₆ -diamines and / or C ₂ -C ₁₆ -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 α-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 Mass% in the form of

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