CN110678588A

CN110678588A - Polyketone fibres, their production and use

Info

Publication number: CN110678588A
Application number: CN201880032725.5A
Authority: CN
Inventors: A·H·费舍尔; P·海克恩伯纳; B·努吉尔格
Original assignee: Beilun Co Ltd
Current assignee: Beilun Co Ltd
Priority date: 2017-05-30
Filing date: 2018-05-18
Publication date: 2020-01-10
Also published as: EP3631056A1; PL3631056T3; US20200080236A1; ES2891998T3; KR20200038427A; EP3631056B1; FI3631057T3; EP3631057B1; EP3631057A1; DE202017002839U1; WO2018219494A1; JP2020521893A; WO2018219494A8; PT3631056T; WO2018219495A1; MX2019014377A

Abstract

Melt spun fibers comprising a thermoplastic aliphatic polyketone as a first polymer and a selected polymeric component as a second polymer are described. The fibers are unique in excellent mechanical properties such as good bend recovery, very good sliding properties, high hydrolysis resistance and high abrasion resistance.

Description

Polyketone fibres, their production and use

The present invention relates to melt-spun fibers consisting of a composition comprising a selected polyketone, their manufacture and different uses of these fibers.

For technical applications, synthetic yarns composed of melt-spun polymers are preferred. For cost reasons, there has long been a reliance on known standard polymers, for example polyolefins, such as Polyethylene (PE), polypropylene (PP), polyamides, such as polyamide 6(PA6), polyamide 6.6(PA6.6), or polyesters, such as polyethylene terephthalate (PET), as long as the yarns composed of these polymers are able to meet the desired requirements.

In technical applications it is generally desirable to have a fabric planar structure with low sliding friction. Additional properties, such as a certain dyeing, stability against decomposition by thermal loading or irradiation, in particular mechanical properties (such as increased impact strength, lower elongation at break, increased abrasion resistance, dimensional stability, flexural strength or flexural recovery) are often also desired.

Fibers composed of aliphatic polyketones and fibers composed of combinations of aliphatic polyketones with selected other polymers are known.

EP 0310171 a2 describes melt-spun fibers composed of these materials, for example from ethylene/propylene/-CO-terpolymers. These fibers have high tensile strength and E modulus and are suggested for use as tire cord or for making spun nonwoven fabrics. The latter are suitable for the production of roofing underlayments (Dachuntspannbahnen) or for use as construction industry fabrics.

DE 19757607 a1 discloses polyamide/polyketone blends which can be processed into yarns or fibers. Multicomponent fibers are not disclosed.

DE 19853707 a1 discloses stabilized aliphatic polyketones which can be present in particular as fibers.

Aliphatic polyketones which can be present in particular as fibers and can be stabilized with antioxidants are known from WO 94/20562 a1 and WO 99/41437 a 1.

CN 106521704 a describes a mixture of aliphatic polyketones and polyoxymethylenes, which may be present in particular as fibers and may be stabilized with antioxidants. Multicomponent fibers are not disclosed.

WO 2016/190594 a2 and WO 2016/190596 a2 disclose wet-spun fibers composed of ethylene/propylene/-CO-terpolymers, which have excellent strength and elongation values and which are furthermore distinguished by high water and heat resistance and good thermal conductivity. Different uses are proposed as fields of use of these fibers, for example for the production of ropes, hoses, nets, spun nonwovens, airbags or protective linings, and also as construction industry fabrics, as reinforcing fibers in composites, as tape elements, safety nets, conveyor belts, fishing lines or tennis racket lines.

In the case of wet spinning, the dissolved polymer is spun into a yarn through a spinning capillary. The solvent is recovered as completely as possible and returned to the manufacturing process. It is still unavoidable that a small proportion of the solvent used remains in the finished fiber. It is desirable to provide solvent-free fibers. This avoids any potential safety risk due to the presence of solvent residues in the fibres; in addition, higher crystallinity can be achieved by melt spinning, which can favorably affect the mechanical properties of the fiber.

On the other hand, processing by melt spinning is generally carried out at significantly higher temperatures than wet spinning. Wet spinning may result in accelerated decomposition or crosslinking reactions of the polymer, which in turn adversely affects the properties of the produced fibers or may result in crosslinking reactions of the polymer, which may limit its processability in an extrusion process.

It has surprisingly been found that the degree of crosslinking of the polymers can be controlled and thus can be specifically modified by a combination of matched processing parameters (temperature, shear force, throughput, spinning delay (Spinverzug), degree of stretching, immobilization, holding time)It is good at the thermomechanical properties of the fibres, such as their heat resistance, hydrolysis resistance, chemical resistance, abrasion resistance, flexural strength, flexural recovery, modulus, creep behaviour and tendency to bias

Dimensional stability describes the tendency of a fiber to exhibit a change in length under stress and at a certain temperature. Dimensional stability results from the combination of tensile modulus and creep properties of the fibers (e.g., monofilaments).

It has been found that the dimensional stability of aliphatic polyketone based fibres can be achieved by suitable addition. Selected polymeric additives dispersed in a matrix composed of aliphatic polyketones may be used herein. In this case, for example, the surface of the fibrils and/or fibers can be modified by the dispersed phase.

In the combination of aliphatic polyketones and selected other polymers, the individual polymer components complement each other in a synergistic manner. Thus, for example, excellent mechanical properties (high modulus, low creep, low biasing tendency) are imparted to the fibers by the other polymers and less sliding friction and improved abrasion resistance are imparted by the aliphatic polyketones.

It has also been found that textured surfaces (such as textiles or strands) having filaments composed of aliphatic polyketones or multicomponent filaments with aliphatic polyketones as the shell and other polymers as the core have very low sliding friction and very high abrasion resistance both in the dry state and in the wet state.

It has also been found that fibers composed of selected conventional polymers and aliphatic polyketones can be combined into the following fibers: the fibers are unique in low sliding friction and high bending strength.

Multicomponent fibers having selected properties can thus be obtained, for example fibers having a core/shell structure in which the shell is composed of an aliphatic polyketone and the core is composed of a polyester, for example polyethylene terephthalate, or of a polycarbonate, or of an aliphatic polyketone having a higher melting point than the aliphatic polyketone of the shell. By changing the melting point of the shell polymer, the adhesive properties can be set specifically, for example.

Due to the inherent chemical resistance and good barrier properties of aliphatic polyketones, core-shell fibers with high chemical resistance can be produced.

That is, hot melt variants can be produced that have a low melting point and thus have the potential of thermal bonding with the substrate or with other monofilaments in a fabric construction (e.g., a textile or hook fabric). Furthermore, fibers with a low coefficient of friction and very high abrasion resistance are produced.

The object of the present invention is to provide such fibers with the above-mentioned performance characteristics.

It is another object of the present invention to provide a spinning process for making such fibers.

The invention relates in a first embodiment to a melt-spun fibre comprising a thermoplastic aliphatic polyketone as a first polymer and a polyolefin, a polyester, a polyurethane, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene oxide, a polyphenylene ketone, a polyphenylene ether ketone, a liquid crystal polymer and/or an aliphatic polyketone as a second polymer, wherein the melting point of the aliphatic polyketone, if present as the second polymer, is at least 5 ℃, preferably at least 10 ℃, particularly preferably at least 20 ℃ higher than the melting point of the aliphatic polyketone of the first polymer.

The invention relates in a second embodiment to melt-spun fibres comprising a thermoplastic aliphatic polyketone as a first polymer and a polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylketone, liquid crystal polymer and/or an aliphatic polyketone as a second polymer, wherein the polymers are present in the form of two or more fibre components which are spatially separated from one another but arranged in relation to one another, and wherein the melting point of the aliphatic polyketone, in the case of comprising an aliphatic polyketone as a second polymer, is at least 5 ℃, preferably at least 10 ℃, particularly preferably at least 20 ℃ higher than the melting point of the aliphatic polyketone of the first polymer.

The invention relates in a third embodiment to a melt spun fiber comprising a thermoplastic aliphatic polyketone as a matrix polymer and polysiloxane or poly (meth) acrylate particles dispersed therein.

The aliphatic polyketones used according to the invention are of the formula-R₁Homopolymers or copolymers of recurring structural units of-CO-, in which R is₁Represents a divalent aliphatic group, preferably a divalent aliphatic group having two to six carbon atoms. Preference is given to the radical R₁Having the formula-C_nH_2n-, where n is 2,3 or 4, especially 2 or 3.

Preference is given to using monomers having different radicals R in the polymer chain₁Copolymers of, for example, having the group-C₂H₄And has the group-C₃H₇-。

Particular preference is given to using thermoplastic ethylene/propylene/-CO-terpolymers as aliphatic polyketones.

Aliphatic polyketones are semi-crystalline polymers having one melting point in Differential Scanning Calorimetry (DSC). For the purposes of this specification, DSC analysis was performed according to ASTM D3418. The heating rate here was 10K/min.

It is likewise particularly preferred to use aliphatic polyketones having a melting range of 199 to 220 ℃ and an MFI value of 6 to 60g/10 min (according to ASTM-D1238) at 240 ℃ and 2.16 daN.

The aliphatic polyketones used according to the invention are polymers known per se which have also been used in fiber manufacture.

In a preferred embodiment, the melt spun fiber of the present invention comprises an antioxidant.

Sterically hindered phenols and/or HALS (hindered amine light stabilizers) and/or phosphites may be used as antioxidants, optionally in combination with costabilizers.

Sterically hindered phenol-based antioxidants which are preferably used are sterically hindered alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol or 2, 6-di-tert-butyl-4-methoxyphenol; sterically hindered alkylthiomethylphenols, for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, sterically hindered hydroxylated thiodiphenyl ethers, for example 2,2' -thio-bis (6-tert-butyl-4-methylphenol), 4,4' -thio-bis- (6-tert-butyl-3-methylphenol), 4,4' -thio-bis- (6-tert-butyl-2-methylphenol), 4,4' -thio-bis- (3, 6-di-sec-amylphenol), 4,4' -bis- (2, 6-dimethyl-4-hydroxyphenyl) disulfide; sterically hindered alkylene diphenols, such as 2,2' -methylene-bis- (6-tert-butyl-4-methylphenol); sterically hindered benzyl phenols, such as 3,5,3',5' -tetra-tert-butyl-4, 4' -dihydroxydibenzyl ether; sterically hindered hydroxybenzylated malonates, for example dioctadecyl-2, 2-bis- (3, 5-di-tert-butyl-2-hydroxybenzyl) malonate; sterically hindered hydroxybenzyl aromatics, for example 1,3, 5-tris- (3, 5-di-tert-butyl) -4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 1, 4-bis- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5, 6-tetramethylbenzene, 2,4, 6-tris- (3, 5-di-tert-butyl) -4-hydroxybenzyl) phenol; sterically hindered phenolic triazine compounds, for example 2, 4-bis-octylmercapto-6- (3, 5-di-tert-butyl-4-hydroxyphenylamino) -1,3, 5-triazine; sterically hindered phenolic benzyl phosphates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzyl phosphate; alkyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate; esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono-or polyhydric alcohols; esters of beta- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono-or polyhydric alcohols; esters of 3, 5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols; amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N ' -bis- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N ' -bis- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine or N, N ' -bis- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Preferred co-stabilizers include organic phosphites and/or organic phosphonites. Which are known per se as costabilizers for oxidation resistance.

The proportion of antioxidant is generally between 0.05 and 10% by weight relative to the total amount of fibres. The proportion of antioxidants is preferably from 0.1 to 5% by weight, in particular from 0.5 to 3% by weight.

In a first embodiment, the fibers of the invention comprise, in addition to the thermoplastic aliphatic polyketone, at least one polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenolone, polyphenyleneketone, liquid crystal polymer and/or a further aliphatic polyketone as a second polymer. In the second embodiment of the invention, it is also possible to use polyamides and/or polyoxymethylenes as second polymer.

The proportion of aliphatic polyketone as the first polymer in the fibers of the invention is generally between 5 and 90% by weight, relative to the total amount of the fibers. The proportion of aliphatic polyketone as first polymer is preferably from 10 to 80% by weight, in particular from 20 to 50% by weight.

The proportion of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer, further aliphatic polyketone, polyamide and/or polyoxymethylene as second polymer in the fibers of the invention is generally between 10 and 95% by weight, relative to the total amount of the fibers. The proportion of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer, further aliphatic polyketone, polyamide and/or polyoxymethylene as second polymer is preferably from 20 to 90% by weight, in particular from 50 to 80% by weight.

The polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylsulfones, polyphenylene oxides, polyphenylketones, polyphenylene oxide ketones, liquid crystal polymers, further aliphatic polyketones, polyamides and/or polyoxymethylenes used according to the invention are polymers known per se which have also been used for fiber production.

Examples of polyolefins are homopolymers or copolymers derived from ethylene and/or propylene, optionally in combination with additional ethylenically unsaturated aliphatic hydrocarbons, such as alpha-olefins having from four to eight carbon atoms. Polyethylene and polypropylene may exist in different densities and crystallinities. All of these modifications are basically suitable for use according to the invention.

Examples of polyesters are thermoplastic polymers derived from aliphatic, cycloaliphatic and/or aromatic diacids or polyester derivatives (e.g., alkyl esters) composed thereof and aliphatic, cycloaliphatic and/or aromatic diols (e.g., ethylene glycol, propylene glycol and/or butylene glycol).

Other examples of polyesters are polyesters of the thermoplastic elastomer type (TPE-PE), such as polyesters comprising repeating structural units of ethylene terephthalate and comprising repeating structural units of polyethylene terephthalate. TPE-PE is known to those skilled in the art.

Other examples of polyesters are polycarbonates. Preferably, polycarbonate is used. Polycarbonates are orthopolyesters of carbonic acid comprising the repeating structural unit- [ R-O-CO-O ] -, where R is the radical of a dihydric organic alcohol or phenol after removal of the two alcohol groups. R is preferably the radical of an aromatic dihydroxy compound (i.e.a diphenol). Preferred radicals R are derived from 2, 2-bis- (4-hydroxyphenyl) propane (bisphenol A), bis- (4-hydroxyphenyl) methane (bisphenol F), bis- (4-hydroxyphenyl) sulfone (bisphenol S), dihydroxydiphenyl sulfide, tetramethylbisphenol A or 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (BPTMC).

The properties of the polycarbonates produced can be varied by using mixtures of the abovementioned components. The co-condensation product of bisphenol a and BPTMC yields a highly transparent and heat-resistant molded plastic. It is also possible to add higher functionality alcohols/phenols, such as 1,1, 1-tris (4-hydroxyphenyl) ethane (THPE). This makes it possible to add chain branches which advantageously influence the structural viscosity during processing of the material.

It is also preferred to use aromatic-aliphatic polyester homopolymers or copolymers. Examples thereof are polyethylene terephthalate homopolymers or copolymers comprising units of ethylene terephthalate. That is, these preferred polymers are derived from ethylene glycol and optionally additional alcohols and terephthalic acid or its constituent polyester diffractors (e.g., esters or chlorides of terephthalic acid).

These polyesters may contain structural units derived from other suitable diols in addition to or in place of ethylene glycol. Typically represented by aliphatic and/or cycloaliphatic diols, such as propylene glycol, 1, 4-butanediol, cyclohexanedimethanol or mixtures thereof.

These polyesters may comprise structural units derived from other suitable dicarboxylic acids or derivatives from which the polyesters are constructed, in addition to or in place of terephthalic acid or derivatives from which it constitutes the polyesters. They are typically represented by aromatic and/or aliphatic and/or cycloaliphatic dicarboxylic acids, such as naphthalenedicarboxylic acid, isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid or mixtures thereof.

That is, fibers comprising other polyesters such as polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate homopolymers, or copolymers comprising polyethylene naphthalate units can also be made.

These thermoplastic polyesters are known per se. The structural units of the thermoplastic copolyester are preferably the above-mentioned diols and dicarboxylic acids or derivatives constituting the polyester of corresponding structures.

The following polyesters are preferably used: the solution viscosity (IV value) is at least 0.60dl/g, preferably 0.80 to 1.05dl/g, particularly preferably 0.80 to 0.95dl/g (measured in dichloroacetic acid (DCE) at 25 ℃).

The polyesters used according to the invention may also be derived from hydroxycarboxylic acids.

Examples of polyamides which can be used in the second embodiment of the invention are thermoplastic polymers derived from aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or their polyamide-constituting derivatives (such as salts thereof) and aliphatic, cycloaliphatic and/or aromatic diamines (such as hexamethylenediamine).

Further examples of polyamides are polyamides of the thermoplastic elastomer type (TPE-PA), such as polyamides comprising recurring structural units of hexamethylene terephthalamide and recurring structural units of polyethylene glycol terephthalamide. TPE-PA is known to those skilled in the art.

The polyamides preferably used are semi-crystalline aliphatic polyamides which can be prepared starting from aliphatic diamines and aliphatic dicarboxylic acids and/or cycloaliphatic lactams having at least 5 ring members or the corresponding amino acids.

Aliphatic dicarboxylic acids, preferably adipic acid, 2, 4-and 2,4, 4-trimethyladipic acid, azelaic acid and/or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2, 4-and 2,4, 4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bis-aminomethylcyclohexanes, aminocarboxylic acids, preferably amino acids or the corresponding lactams, come into consideration as reactants. Copolyamides of various ones of the monomers are also included. Caprolactam is particularly preferably used, and epsilon-caprolactam is very particularly preferably used.

The aliphatic homo-or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9, polyamide 10.9, polyamide 10.10, polyamide 11 or polyamide 12.

The polyesters and polyamides used according to the invention may also be derived from hydroxycarboxylic acids or aminocarboxylic acids.

An example of a polyoxymethylene that may be used in the second embodiment of the present invention is one comprising the formula-CH₂-homopolymers or copolymers of recurring structural units of O-.

Examples of polyurethanes are homopolymers or copolymers derived from aromatic or (cyclo) aliphatic diisocyanates and (cyclo) aliphatic or aromatic diols. The polyurethane comprises, for example, the formula-C₆H₄-NH-CO-O-C₂H₄-repeating structural units of-O-CO-NH-.

Other examples of polyurethanes are thermoplastic elastomer-type polyurethanes (TPE-PU). TPE-PU is known to those skilled in the art.

An example of polyphenylene sulfide is a polyphenylene sulfide, e.g. comprising a para-C₆H₄Homopolymers or copolymers of S-repeating structural units.

An example of a polyphenylsulfone is a polyphenylsulfone, e.g. comprising a para-C₆H₄-SO_x-homopolymers or copolymers of repeating structural units, wherein x represents a number between 1 and 2. Examples of polyphenylene ethers are polyphenylene ethers, e.g. comprising para-C₆H₄-homopolymers or copolymers of repeating structural units of O-.

Examples of polyphenyleneketones are polyparaphenylenones, e.g. comprising para-C₆H₄-homopolymers or copolymers of CO-repeating structural units.

Examples of polyphenylene ether ketones are polyphenylene ether ketones, e.g. comprising para-C₆H₄-CO-repeat structural unit and para-C₆H₄-copolymers of repeating structural units of O-.

Examples of liquid crystalline polymers are liquid crystalline aromatic polyesters, such as homopolymers or copolymers comprising repeating structural units derived from p-hydroxybenzoic acid.

In the fibers of the present invention, the first polymer and the second polymer may be present as a polymer mixture, or the polymers may be present in the form of two or more fiber components that are spatially separated from each other but are arranged in relation to each other.

Preferred are fibers in which the first polymer and the second polymer are present as a polymer mixture, wherein one of the polymers (preferably the aliphatic polyketone) constitutes a matrix and the other polymer is dispersed in the matrix in the form of fibrils.

An example of such an embodiment is a fiber that is present in the form of an island fiber in the sea, i.e. in which the polymer component is arranged in the form of fibrils in the polymeric matrix component. Here, the fibrils are preferably oriented in the longitudinal direction of the fiber and thereby increase the tensile strength and modulus of the fiber.

The tensile modulus of a monofilament consisting of aliphatic polyketones can thus be increased significantly, for example by metering in 1 to 7% of a liquid-crystalline polyester (see example 4).

As an example of a fiber in which the polymer is present in the form of two or more fiber components which are spatially separated from each other but arranged in relation to each other, mention may be made of a multicomponent fiber.

That is, the at least two polymers in the fibers of the present invention may be present as a polymer mixture or the at least two polymers may be present in the form of two or more fiber components that are spatially separated from each other but are arranged in relation to each other. An example of the latter embodiment is a multicomponent fiber, which may be present, for example, as a core-shell fiber or as a side-by-side fiber.

Preference is given to fibers comprising a mixture of aliphatic polyketones and polycarbonates.

The following fibers are preferred: wherein one of said polymer components, preferably a polymer different from the aliphatic polyketone, is present in the form of fibrils in the polymer matrix component.

The following fibers are particularly preferred: wherein the aliphatic polyketone forms a polymer matrix and a further polymer selected from a polyolefin, a polyester, a polyphenolone and/or a liquid crystal polymer is present in the form of fibrils in the polymer matrix component. Very particularly preferably, these fibers comprise a liquid-crystalline polymer as further polymer.

It is also preferred to use core-shell fibers having a shell composed of an aliphatic polyketone and a core composed of a polyolefin, a polyester, a polyurethane, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene oxide, a polyphenylene ketone, a polyphenylene ether ketone, a liquid crystal polymer, a further aliphatic polyketone, a polyamide and/or a polyoxymethylene, wherein in the case of an aliphatic polyketone being present in the core its melting point is at least 5 ℃, preferably at least 10 ℃ and particularly preferably at least 20 ℃ higher than the melting point of the aliphatic polyketone in the shell.

Particularly preferred are core-shell fibers having a shell composed of aliphatic polyketones and a core composed of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.

Also preferred are side-by-side fibers having a fiber portion composed of aliphatic polyketone and a further fiber portion composed of polyolefin, polyester, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer, further aliphatic polyketone, polyamide and/or polyoxymethylene which is in contact with the fiber portion, wherein in the case of aliphatic polyketone being present in the further fiber portion its melting point is at least 5 ℃, preferably at least 10 ℃, particularly preferably at least 20 ℃ higher than the melting point of the aliphatic polyketone in the further fiber portion. Also particularly preferred are side-by-side fibers having a fiber portion composed of aliphatic polyketone and a further fiber portion composed of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone in contact with the fiber portion.

Also preferred are side-by-side fibers having a fiber portion composed of aliphatic polyketones and a further fiber portion composed of polyolefins, polyesters, polyphenylene sulfides, polyphenylsulfones, polyphenylene oxides, polyphenylene ketones, polyphenylene ether ketones and/or liquid crystal polymers in contact with the fiber portion.

Very particular preference is given to core-shell fibers in which the shell comprises aliphatic polyketones as polymer and the core comprises one or more of the above-mentioned second polymers and also at least one additive in the core and/or the shell, which additive imparts a certain functionality to the fiber.

Very particular preference is furthermore given to side-by-side fibers in which one fiber fraction comprises an aliphatic polyketone as polymer and the other fiber fraction comprises one or more of the above-mentioned second polymers and also at least one additive which imparts a certain functionality to the fibers.

Also particularly preferred are core-shell fibers having a shell composed of an aliphatic polyketone and having a core composed of a further aliphatic polyketone whose melting point is at least 5 ℃, preferably at least 10 ℃ and in particular at least 20 ℃ higher than the melting point of the aliphatic polyketone in the shell.

Thus, for example, fibers with good thermal stability are produced by a core-shell structure having a core composed of a polyester (such as PET or polycarbonate) or of an aliphatic polyketone with a higher melting point than the melting point of the shell polymer. Compared to fibers composed of aliphatic polyketones, they are distinguished by a high tensile and flexural modulus and thus high stability, for example in the case of core-shell fibers with PET in the shell. These fibers typically exhibit good dimensional stability under stress at temperatures up to 150 ℃.

In a third embodiment of the invention, the following fibers are provided: wherein the fiber surface is modified by selected polymer particles in the form of dispersed in the matrix polymer. The functionalization and texturing of the surface can be achieved by metering in silicone particles (e.g. PMSQ particles) and/or poly (meth) acrylate particles (e.g. crosslinked PMMA microspheres). Typical diameters of these particles vary in the range of 0.2 to 100 μm. It is thus possible to produce microtexturing of the surface and to modify the surface properties of the fibers. Thereby reducing the friction surface area mainly and improving the friction performance significantly. Furthermore, the dust resistance of the fibers is improved.

In this embodiment, the invention relates to fibers, in particular monofilaments, comprising a matrix composed of aliphatic polyketones and, distributed therein, particles composed of polysiloxanes and/or of poly (meth) acrylates having a diameter of from 200nm to 100 μm.

The particles may have any configuration. Examples thereof are configurations with rotational symmetry, in particular spherical, but also irregular configurations. The particles are present as a micropowder. The diameter of the particles varies in the range from 0.2 to 100. mu.m, preferably from 1 to 50 μm. In the case of particles with varying diameters, the diameter value relates to the maximum diameter of the particle.

Preferred are monofilaments comprising spherical particles of silicone, the diameter of which is 1 to 50 μm.

The particles are present as a micropowder in dispersed form in the matrix polymer. Generally, from 0.001 to 8% by weight, preferably from 0.02 to 5% by weight, of particles are metered into the matrix polymer. The particles are present as a heterogeneous phase in the matrix polymer. The particles may be present as individual particles in the matrix polymer and/or as aggregates of different individual particles.

Polysiloxanes used according to the present invention are a group of synthetic polymers in which silicon atoms are linked via oxygen atoms. The polysiloxanes used according to the invention are also referred to as silicones. In this case, these may be linear or crosslinked polysiloxanes or else polysiloxanes having a cage structure, so-called silsesquioxanes.

Preference is given to using a catalyst comprising the repeating structural unit-SiR¹R²Linear or crosslinked polysiloxanes of the formula R¹SiO_3/2In which R is¹Is represented by C₁-C₆Alkyl (especially methyl) and R²Is represented by C₁-C₆Alkyl or phenyl (especially methyl or phenyl).

Very particular preference is given to monofilaments comprising polysiloxanes which are linear or crosslinked polydimethylsiloxanes or polymethylsilsesquioxanes.

The poly (meth) acrylates used according to the invention are a group of synthetic polymers derived from esters of acrylic acid and/or esters of methacrylic acid. Furthermore, the poly (meth) acrylates may still have further monomer units which are copolymerized with esters of acrylic acid and/or with esters of methacrylic acid. The poly (meth) acrylates used according to the invention may be linear or, preferably, crosslinked with one another.

Preference is given to using homopolymers or copolymers of methyl acrylate or methyl methacrylate as poly (meth) acrylates.

Examples of such additives are conductive additives, lubricants, anti-adhesion agents, foaming agents for the foaming or porous fibre surface, pigments and/or fillers.

Preferred multicomponent fibres comprise a fraction consisting of aliphatic polyketones, which predominantly improve the sliding properties and a further fraction consisting of one or more of the above-mentioned polymer types, in particular polyesters, very particularly preferably TPE-PE, or in particular polyurethanes, very particularly preferably TPE-PU, in contact with it, wherein the second polymer component predominantly improves other properties, for example improved grip properties by TPE-PE or TPE-PU or hot tack properties by copolyesters.

The aliphatic polyketones and/or further polymers used according to the invention (selected from the group consisting of polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylsulfones, polyphenylene ethers, polyphenyleneketones, polyphenylene ether ketones, liquid crystal polymers, further aliphatic polyketones, polyamides and/or polyoxymethylenes) may comprise additional additives which impart the desired properties to the fibers produced. Examples of such additives are UV stabilizers, pigments, dyes, fillers, matte agents, reinforcing materials, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and/or further polymers different from aliphatic polyketones, polyolefins, polyesters, polyphenylene sulfides, polyphenylsulfones, polyphenylene ethers, polyphenyleneketones, polyphenylene ether ketones, liquid crystal polymers, further aliphatic polyketones, polyamides and/or polyoxymethylenes. These additives are known to the person skilled in the art.

Examples of preferred UV stabilizers are UV-absorbing compounds, such as benzophenones or benzotriazoles, or compounds of the HALS (hindered amine light stabilizers) type.

Examples of preferred pigments are carbon black, titanium dioxide or iron oxide.

Examples of preferred dyes are anionic dyes, acid dyes, metal complex dyes, cationic or basic dyes and dispersion dyes.

Examples of preferred fillers are carbonates such as chalk or dolomite, silicates such as talc, mica, kaolin, or sulfates such as barite, or oxides and hydroxides such as quartz flour, crystalline silica, aluminum hydroxide or magnesium oxide, zinc oxide or calcium oxide.

An example of a preferred matte finish is titanium dioxide.

An example of a preferred reinforcing material is glass fiber.

Examples of preferred crosslinking agents are polycarboxylic acids and esters thereof, polyols, polycarbonates or polycarbodiimides.

An example of a preferred crystallization accelerator is a carboxylic acid ester.

Examples of preferred lubricants are polyolefin waxes, fatty acids or salts thereof, fatty alcohols, fatty acid esters, silicones, polymethacrylate pellets, polysiloxanes and, in particular, PMSQ, as described in EP 2,933,361 a 1.

Examples of preferred flame retardants are phosphorus-containing compounds, organic halogen compounds, nitrogen-containing organic compounds, or combinations thereof.

Examples of preferred antistatic agents are carbon black, graphite, graphene or carbon nanotubes.

Examples of preferred hydrolysis stabilizers are carbodiimides or epoxidized compounds.

Examples of preferred processing aids are waxes or long-chain carboxylic acids or salts thereof, aliphatic, aromatic esters or ethers.

Examples of preferred plasticizers are diethylhexyl phthalate, alkyl sulfonates of phenols, triethyl citrate, diethylhexyl adipate or diethyloctyl adipate.

Examples of preferred impact modifiers are thermoplastic elastomers, such as thermoplastic copolyamides, thermoplastic polyester elastomers, thermoplastic copolyesters, olefin-based thermoplastic elastomers, styrene copolymers, such as SBS, SEBS, SEPS, SEEPS, MBS, ABS, SAN or SBK, urethane-based thermoplastic elastomers, olefin-based thermoplastic vulcanizates or crosslinked thermoplastic elastomers, in particular PP/EPDM, or polycarbonates.

Examples of preferred other polymers are fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoroethylene copolymer or polychlorotrifluoroethylene.

The proportion of these additional additives in the fibers of the invention can generally be up to 10% by weight, relative to the total amount of fibers. These additives are preferably used in an amount of 1 to 5% by weight.

In a preferred embodiment, the invention relates to a melt-spun core-shell fiber comprising a shell composed of a thermoplastic ethylene/propylene/-CO-terpolymer and a core composed of a polyolefin, a polyester, a polyurethane, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene ether, a polyphenylketone, a polyphenylketoneketone, a liquid crystal polymer, a further aliphatic polyketone, a polyamide and/or a polyoxymethylene, wherein the amount of the shell is from 5 to 50% by weight and the amount of the core is from 95 to 5% by weight, and wherein the core and/or the shell optionally can also comprise up to 10% by weight in total of additives, in particular sterically hindered phenols, UV stabilizers, pigments, dyes, fillers, matte agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, Impact modifier and/or fluoropolymer, wherein the percentage values are relative to the total amount of the fibers.

Within the scope of the present description, the term "fiber" is to be understood as a thread-like structure which is thin compared to its length. Typically, the ratio of fiber length to diameter is at least 5: 1. Fibers in the sense of this specification may be continuous (and therefore referred to as monofilaments) and may be cut to a limited length (and therefore referred to as bristles or chopped fibers). The fibers may also be present in the form of a plurality of monofilaments or a plurality of staple fibers. The invention preferably relates to the fibers in the form of monofilaments, bristles or chopped fibers.

The cross-sectional shape of the fibers of the present invention may be arbitrary. It may be of irregular, point-symmetrical or axisymmetric cross-section, for example circular, elliptical or n-polygonal cross-section, where n is equal to or greater than 3. The cross-sectional shape of the fibers may also be multi-lobed.

The fiber strength (Titer) of the present invention can be expressed by the yarn weight. Here 1dtex corresponds to a fiber mass of 1g per 10km of fiber length. Typical yarn weights vary from 1 to 100000 dtex.

The titer of the monofilaments, bristles or chopped fibers preferred according to the invention is preferably to 10dtex and can be varied in a wider range. The preferred fiber strength of the monofilaments, bristles or chopped fibers varies in the range of 10 to 30000dtex, especially in the range of 45 to 20000 dtex.

The components required for the production of the fibers according to the invention are known per se, partly commercially available or can be produced according to methods known per se.

The fibers according to the invention are preferably used for producing textile flat structures, in particular woven, nonwoven, knitted, wire or hook fabrics. The manufacture of these planar structures is carried out according to known techniques.

The manufacture of the fibers of the invention can be carried out by essentially known melt spinning processes, combined with one or more stretches of the obtained fibers and a stationary phase.

The invention also relates to a method for producing the polyketone fibres.

In a first embodiment of the process according to the invention, the polyketone starting material and the sterically hindered phenol are metered into an extruder and extruded in molten form through a die plate. The die plate may have one or more spinning capillaries. The resulting filaments are drawn from the spinning capillary. The withdrawal speed is generally from 1 to 120m/min, in particular from 5 to 50 m/min.

The sterically hindered phenol and/or other additives may be metered in the form of a masterbatch comprising the additive and a thermoplastic polymer, wherein the polymer is selected from the group consisting of: polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene oxides, polyphenolones, polyphenylene oxides, liquid crystal polymers, further aliphatic polyketones, polyamides and/or polyoxymethylenes.

The die plate is generally a spinning pack which consists of a filter device for the melt-spun substance and a die plate connected downstream.

The temperature of the spinning mass should be selected here such that, on the one hand, sufficient flowability of the spinning mass is ensured and, on the other hand, the thermal loading of the polyketone is also limited, so that crosslinking and decomposition reactions and gel formation in the spinning mass can be kept within limits or can even be prevented completely.

In a first embodiment of the process of the invention, a polyketone feedstock stabilized with an antioxidant may be used, together with selected additional polymers derived from a masterbatch. Here, the temperature of the spinning mass can be in the range from 200 to 300 ℃, preferably from 220 to 240 ℃ on exiting through the spinning capillary.

The diameter of the spinning capillary is selected by the skilled person according to the desired weight of the fibre. Typical diameters vary from 10 μm to 5mm, preferably from 0.1 to 1mm in the case of monofilaments or bristles. These values correspond to the pore diameter at the outlet side of the polymer mass.

One or more stretches with heat action are integrated into the spinning process, which imparts the desired final properties to the yarn. Such a way of working is known to the person skilled in the art.

After spinning, the filaments are preferably drawn several times, in particular with a total draw ratio in the range from 1:3 to 1:15, preferably in the range from 1:4 to 1: 8.

Particularly preferably, the stretching step is followed by at least one relaxation step (fixing step). The drawn monofilaments are subjected to a heat treatment while maintaining the fiber stress, so that the stress built up in the monofilaments can be decomposed.

The produced monofilaments are then fed into a suitable storage die, for example coiled or cut into staple fibres in a cutting device.

In a second embodiment of the process of the invention, the polymer blend consisting of the aliphatic polyketone and of the polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer and/or further aliphatic polyketone is spun as described above by means of a conventional spinning capillary or the aliphatic polyketone is spun on the one hand and the polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether ketone, liquid crystal polymer, further aliphatic polyketone, polyamide and/or polyoxymethylene is spun on the other hand by means of a spinning capillary to produce the multicomponent monofilament. In other respects, the method of the second embodiment corresponds to the process in the first embodiment of the method.

In a second embodiment of the process according to the invention, an antioxidant, preferably a sterically hindered phenol; but can also work without antioxidants.

In a second embodiment, the temperature of the spinning mass should also be selected such that, on the one hand, sufficient flowability of the spinning mass is ensured and, on the other hand, the thermal loading of the polyketone and the further polymer components is also limited, so that crosslinking and decomposition reactions and gel formation in the spinning mass can be kept within limits or can even be prevented completely.

In a second embodiment of the process according to the invention, it is possible to use polymer raw materials which are not necessarily stabilized with antioxidants. Here, the temperature of the spinning mass can be in the range from 200 to 300 ℃, preferably from 220 to 260 ℃, upon exiting through the spinning capillary.

In a third embodiment of the process according to the invention, a blend of aliphatic polyketone and of polysiloxane particles and/or of poly (meth) acrylate particles is spun as described above by means of conventional spinning capillaries.

The present invention relates to a process for the manufacture of polyketone fibres as described above, said process comprising the following measures:

i) mixing in an extruder a thermoplastic aliphatic polyketone with a masterbatch to a spinning mass, the masterbatch comprising a sterically hindered phenol and a polymer selected from the group consisting of: polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene oxides, polyphenylene ketones, polyphenylene ether ketones and/or liquid crystal polymers,

ii) extruding the spinning mass from step i) through a die plate having one or more spinning capillaries, wherein the temperature of the spinning mass on the outlet side of the spinning capillaries is in the range from 200 to 300 ℃, preferably from 220 to 260 ℃,

iii) the formed filaments are drawn off at a drawing speed in the range from 1 to 120m/min, in particular from 5 to 50m/min, the ratio of the drawing speed to the speed at which the spinning mass exits from the spinning capillary preferably being selected to be greater than 1,

iv) stretching the formed monofilament one or more times,

v) optionally relaxing the formed monofilament, and

vi) optionally coiling or cutting the formed monofilament.

i) mixing in an extruder a thermoplastic aliphatic polyketone with: polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene oxides, polyphenylene ketones, polyphenylene ether ketones and/or liquid crystal polymers,

iv) stretching the formed monofilament one or more times,

v) optionally relaxing the formed monofilament, and

vi) optionally coiling or cutting the formed monofilament.

The present invention relates to a further process for the manufacture of polyketone fibres as described above, said process comprising the following measures:

ia) providing a first spin mass in a first extruder, said first spin mass comprising a thermoplastic aliphatic polyketone,

ib) providing a second spinning mass in a second extruder, the second spinning mass comprising a polyolefin, a polyester, a polyurethane, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene ether, a polyphenylene ketone, a polyphenylene ether ketone, a liquid crystal polymer, a further aliphatic polyketone, a polyamide and/or a polyoxymethylene,

ii) extruding the first spinning substance from step ia) and the second spinning substance from step ib) through a die plate having one or more spinning capillaries such that each spinning capillary is flowed through by the first spinning substance and the second spinning substance, wherein the temperature of the first and second spinning substances on the outlet side of the spinning capillaries is in the range from 200 to 300 ℃, preferably from 220 to 260 ℃,

iii) the formed filaments are drawn off at a drawing speed in the range from 1 to 120m/min, in particular from 5 to 50m/min, the ratio of the drawing speed to the speed at which the spinning mass exits from the capillary preferably being selected to be greater than 1,

iv) stretching the formed monofilament one or more times,

v) optionally relaxing the formed monofilament, and

vi) optionally coiling or cutting the formed monofilament.

The present invention furthermore relates to another process for the manufacture of polyketone fibres as described above, said process comprising the following measures:

i) mixing in an extruder a thermoplastic aliphatic polyketone with a masterbatch to a spinning mass, the masterbatch comprising: sterically hindered phenols and silicone particles and/or poly (meth) acrylate particles,

ii) extruding the spinning mass from step i) through a die plate having one or more spinning capillaries, wherein the temperature of the spinning mass on the outlet side of the spinning capillaries is in the range from 200 to 300 ℃, preferably from 220 to 260 ℃.

iv) stretching the formed monofilament one or more times,

v) optionally relaxing the formed monofilament, and

vi) optionally coiling or cutting the formed monofilament.

i) mixing thermoplastic aliphatic polyketones with particles of polysiloxanes and/or poly (meth) acrylates in an extruder to a spinning mass,

iv) stretching the formed monofilament one or more times,

v) optionally relaxing the formed monofilament, and

vi) optionally coiling or cutting the formed monofilament.

The fibers according to the invention are preferably used, in particular in the form of monofilaments, for producing textile flat structures, in particular woven, spiral, non-woven or hook fabrics. The textile planar structure is preferably suitable for use in a screen or a conveyor belt. Another important field of application are fibers for brushes or for oral hygiene and for body cleaning, but also chopped fibers in composite materials with e.g. concrete as matrix material.

The invention therefore also relates to textile flat structures comprising the above-mentioned fibers, in particular in the form of woven fabrics, hook fabrics, knitted fabrics, knits or gauzes.

The fibers of the present invention are unique in excellent mechanical properties such as high tensile modulus and good loop and knot strength, excellent bend recovery and very good slip properties, as well as high abrasion resistance.

The fibers can be used in different fields. It is preferably used in applications where increased wear and high mechanical loads are to be taken into account, in particular in hot and humid environments. Examples thereof are filter cloths for screen fabrics and gas and liquid filters, drying belts (for example for the manufacture of food or especially paper), and brushes for any type of cleaning purpose (for example for household cleaning purposes, for body cleaning, such as oral hygiene, for example as a toothbrush). Other applications are as fluidizing belts, as processing belts for the cardboard industry, as conveyor belts and as processing belts in the manufacture of non-woven fabrics, such as spunbonded, meltblown, airlaid, wet-laid, spunlaced or thermally bonded fabrics, or as chopped fibers for reinforcement of concrete or composites.

The invention also relates to the use of the above-mentioned fibers, in particular in the form of monofilaments, as felt for paper machines, in conveyor belts and in filter screens.

In another preferred embodiment, various stabilizers, such as antioxidants for heat stabilization and/or hydrolytic stabilizers, are added to the fibers of the present invention. This variant is therefore particularly suitable for drying processes in a wet environment, for example in the drying section of a paper machine, and also in other continuously operating industrial drying and filtration processes, such as in the drying of particle boards, pellets to be used as fuel or very generally biomass.

Very particularly preferably, the fibers according to the invention are used in the form of monofilaments as felt for paper machines in the board forming section and/or in the drying section of a paper machine.

These monofilaments are used, for example, in the lower weft yarns (unterschaus) of a forming screen in a paper machine. This can be done 100% as an under weft and/or as a so-called alternating weft (the monofilaments are alternately exchanged with, for example, polyamide, polyester or polyphenylene sulfide monofilaments). Aliphatic polyketones contribute to a significant reduction in the sliding friction and thus to a significant reduction in the drive power of the paper machine, with the result that considerable energy savings are achieved. In addition, the monofilaments of the present invention are more abrasion resistant than similar monofilaments comprising polyethylene terephthalate, polybutylene terephthalate or polycyclohexylene terephthalate or polyamides without the use of aliphatic polyketones.

The fibers of the invention are particularly preferably used in the form of filter fabrics or hook fabrics, as aids for membranes with wide meshes and high dimensional stability (for example as aids for reverse osmosis membranes which have to withstand a continuous pressure of 50 bar) and as process fabrics for the production of paper and nonwovens.

Furthermore, the fibers of the present invention are well suited for use in the manufacture of conveyor belts where a combination of dimensional stability and good sliding properties are required.

Another preferred field of application of the fibres of the invention is their use in brushes, in particular toothbrushes. The fibers of the invention can generally be used here in the form of bristles.

The monofilaments are furthermore present in the form of continuous or chopped strands which are assembled in bundles or as brushes.

The present invention is illustrated in detail by the following examples. These examples are merely illustrative of the invention and should not be construed as limiting.

In the following examples different aliphatic polyketones were used. Here, the shell polymer is of the M630A type (according to ASTM D3418) having a melting point of 222 ℃, or alternatively a low melting variant, such as the M410F type (according to ASTM D3418) having a melting point of 199 ℃, or such as the M620A type (according to ASTM D3418) having a melting point of 207 ℃. The core polymer is, for example, a semi-crystalline PET (polyethylene terephthalate) having a melting point of 254 ℃, or a polycarbonate (for example Makrolon 2456 by Covestro), or an aliphatic polyketone having a high melting point (type M630A by Hyosung), or a blend of these components.

Example 1

A combination of two commercially available aliphatic polyketones: one high melting polyketone in the core (Hyosung model M630A) and one low melting polyketone in the shell (Hyosung model M410F).

To produce such bicomponent monofilaments, the two components are coextruded in one production step. The core/shell ratio, here 70/30, can be set by the relative transport rate. In the process, the monofilament is stretched several times under the effect of temperature. The total draw ratio was chosen to be 1: 3.7.

By the above process bicomponent monofilaments are obtained with the following properties:

combining these two polyketone variants in a monofilament allows for thermally induced physical attachment at the monofilament intersection. The textile structure thus has, for example, an increased shear stability. In addition, such crosslinked structures show thickening at the intersection points. Due to the positive flow properties, this property is of interest, for example, for liquid filtration.

Example 2

Stabilized polyethylene terephthalate (PET) (99.3% Invista type 12 stock with 0.7% Lanxess Stabaxol) was used in the core and aliphatic polyketones (Hyosung type M630A polyketones) were used in the shell.

Such monofilaments are coextruded in one production step.

The core/shell ratio, here 70/30, can be set by the relative transport rate. In the process, the monofilament is stretched several times under the effect of temperature. The total draw ratio was chosen to be 1: 4.3.

combining PET and aliphatic polyketone in monofilaments links properties common to PET to the surface properties of the polyketone. This makes it possible to produce textile structures which have a significantly reduced coefficient of friction and can therefore result in energy savings when used, for example, in conveyor belts. The advantages of PET cores result from the similar processing properties of the filaments in the weaving process as PET, for example from the very same Floating (Floating).

Example 3

Aliphatic polyketones (polyketones of type M630A of Hyosung) were used as matrix polymers. Furthermore, 1.0% by weight of silicone pellets having an average diameter of 8 μm (PMSQ E +580 from Coating Products) were dispersed in the matrix polymer.

The obtained monofilaments showed the following properties:

as shown in EP 2933961 a1, the incorporation of silicone pellets reduces their coefficient of friction against metals or ceramics by the resulting monofilament surface structure. This is also the case when combined with aliphatic polyketones (see next table). The monofilaments of comparative examples V1 to V5 detailed in the table are described further below.

Example numbering	3	V1	V2	V3	V4	V5
							Filament to metal, dry	0.132	0.188	0.211	0.198	0.220	0.384
Monofilament to ceramic, wet	0.163	0.234	0.224	0.206	0.241	0.307

Example 4

The procedure was as in example 3. Aliphatic polyketones (polyketones of type M630A of Hyosung) were used as matrix polymers. As second polymer component up to 7% of a Liquid Crystalline Polymer (LCP) is added a polyester consisting of hydroxybenzoic acid and hydroxynaphthalene carboxylic acid of the Vectra A950 type of Ticona. The obtained monofilament showed the following properties:

the combination of polyketone with LCP shows an increase in E-modulus with an increase in strength. This is due to the synergistic effect of LCP fibrils in the polyketone matrix. The increase in E modulus is shown in the table below. The monofilaments of comparative examples V1 to V2 detailed in the table are described further below.

Comparative examples V1 to V4

Aliphatic polyketones (polyketones of type M630A of Hyosung) were used up to 100%.

For producing monofilaments, polyketones are extruded, spun and drawn under the action of temperature several times.

The following properties are produced depending on the draw ratio:

comparative example 5

Commercially available PET, invitsta, form RT 12 was used at up to 100%. The procedure is as in comparative examples V1 to V4. The obtained monofilaments showed the following properties

	Unit of	Numerical value
			Diameter of	mm	0.6
Fineness of fiber	dtex	3922
			Strength of	cN/tex	36.2
Elongation at break	％	38.8
			Heat shrinkage (10 minutes at 180 ℃ C.)	％	3.6

Claims

1. Melt spun fibers comprising a thermoplastic aliphatic polyketone as a first polymer and a polyolefin, a polyester, a polyurethane, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene ether, a polyphenylene ketone, a polyphenylene ether ketone, a liquid crystal polymer and/or an aliphatic polyketone as a second polymer, wherein in case the aliphatic polyketone is present as the second polymer, its melting point is at least 5 ℃ higher than the melting point of the aliphatic polyketone of the first polymer.

2. Melt-spun fibers comprising a thermoplastic aliphatic polyketone as a first polymer and a polyolefin, a polyester, a polyamide, polyoxymethylene, a polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, a liquid crystal polymer and/or an aliphatic polyketone as a second polymer, wherein the polymers are present in the form of two or more fiber components which are spatially separated from one another but arranged in relation to one another, and wherein the melting point of the aliphatic polyketone is at least 5 ℃ higher than the melting point of the aliphatic polyketone of the first polymer for the case comprising an aliphatic polyketone as a second polymer.

3. Melt-spun fibers comprising a thermoplastic aliphatic polyketone as a matrix polymer and polysiloxane or poly (meth) acrylate particles dispersed therein.

4. Melt-spun fibre according to one of the claims 1 to 3, characterised in that the thermoplastic aliphatic polyketone is an ethylene/propylene/CO-terpolymer.

5. Melt spun fiber according to at least one of claims 1 to 4, characterized in that the fiber comprises an antioxidant, preferably a sterically hindered phenol, optionally in combination with a co-stabilizer.

6. A melt-spun fiber according to one of the claims 1 or 2, characterized in that the polyester is a homopolymer or a copolymer of an aromatic-aliphatic polyester, in particular a polyethylene terephthalate homopolymer or a copolymer comprising ethylene terephthalate units.

7. A melt-spun fiber according to any of claims 1 or 2, wherein the polyester is a polycarbonate.

8. The melt spun fiber according to at least one of claims 1 or 4 to 7, characterized in that the first polymer and the second polymer are present as a polymer mixture, wherein one of the polymers forms a matrix and the other polymer is dispersed in the matrix in the form of fibrils.

9. The melt-spun fiber according to claim 8, wherein the fiber is present as an island-in-the-sea fiber in which the polymer component is arranged in the form of fibrils in the polymeric matrix component.

10. Melt-spun fibers according to at least one of claims 2 or 4 to 7, characterized in that the fibers are present as core-shell fibers having a shell consisting of aliphatic polyketone and a core consisting of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylsulfone, polyphenylene ether, polyphenylketone, liquid crystal polymer and/or further aliphatic polyketone.

11. A melt-spun fiber according to claim 10, characterized in that the fiber is present as a core-shell fiber having a shell consisting of aliphatic polyketone and a core consisting of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylketone, polyphenylketoneketone or another aliphatic polyketone.

12. A melt-spun fibre according to claim 2, characterised in that the fibre is present as side-by-side fibre having a fibre portion consisting of aliphatic polyketone and a further fibre portion in contact with the fibre portion consisting of polyolefin, polyester, polyamide, polyoxymethylene, polyphenylene sulphide, polyphenylsulfone, polyphenylene oxide, polyphenylene ether ketone, liquid crystal polymer and/or a further aliphatic polyketone.

13. A melt-spun fiber according to claim 12, characterized in that the fiber is present as a side-by-side fiber having a fiber portion composed of aliphatic polyketone and another fiber portion composed of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone in contact with the fiber portion.

14. Melt-spun fiber according to at least one of claims 2 or 4 to 7 or 10 to 11, characterized in that the fiber is constituted as a core-shell fiber comprising a shell consisting of a thermoplastic ethylene-/propylene-/CO-terpolymer and a core consisting of a polyolefin, a polyester, a polyamide, a polyoxymethylene, a polyphenylene sulfide, a polyphenylsulfone, a polyphenylene ether, a polyphenylene ketone, a polyphenylene ether ketone, a liquid crystal polymer and/or a further aliphatic polyketone, wherein the amount of the shell is 5 to 50 wt. -% and the amount of the core is 95 to 5 wt. -%, and wherein the core and/or the shell optionally may further comprise additives, in particular sterically hindered phenols, UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, in total up to 10 wt. -% Lubricants, flame retardants, antistatic agents, hydrolytic stabilizers, plasticizers, impact modifiers and/or fluoropolymers, wherein the percentage values are relative to the total amount of the fibers.

15. Melt spun fiber according to at least one of claims 1 to 14, wherein the fiber is present as a monofilament in the form of continuous or chopped and assembled bundles or as a brush.

16. Textile planar structure comprising melt spun fibers according to at least one of claims 1 to 15 in the form of a woven, hook, knit or gauze.

17. Use of the melt spun fiber according to at least one of claims 1 to 15 for screen fabrics, filter cloths for gas and liquid filters, for processing and drying belts and for brushes of any type for cleaning purposes.

18. Use according to claim 17, characterized in that the melt spun fibres are used as a fluidising belt, as a processing belt for the cardboard industry, as a conveyor belt and as a processing belt in the manufacture of non-woven fabrics.

19. Use according to claim 17, wherein the melt spun fibres are used in brushes for household cleaning purposes or in brushes for body cleaning, in particular toothbrushes.

20. Use according to claim 17, wherein the melt spun fibres are used as chopped fibres for concrete and composite reinforcement layers.

21. Use according to claim 17, characterized in that the melt spun fibres are used in monofilament form as felt for paper machines, in conveyor belts and in filter screens.

22. Use according to claim 17, characterized in that the melt spun fibres are used in the form of bristles in brushes, in particular toothbrushes.