DE202017002839U1 - Polyketone fibers, their preparation and use - Google Patents

Abstract

Melt-spun fibers containing thermoplastic aliphatic polyketone and antioxidant.

Description

The present invention relates to melt-spun fibers of selected polyketone-containing compositions, their preparation and various uses of these fibers.

For technical applications, synthetic filaments of melt-spinnable polymers are preferred. For reasons of cost, use is made of standard polymers which have been known for a long time, for example polyolefins such as polyethylene (PE), polypropylene (PP), polyamides such as polyamide 6 (PA 6), polyamide 6.6 (PA 6.6) or polyesters such as polyethylene terephthalate (US Pat. PET), if threads made of these polymers can meet the desired requirements.

In technical applications, a low sliding friction of textile fabrics is often desired. Frequently, additional properties are desired, such as a certain coloration, stability against degradation by thermal stress or by the action of radiation, special mechanical properties such as increased impact strength, low elongation at break, increased abrasion resistance, dimensional stability, bending strength or bending recovery.

Aliphatic polyketone fibers are known.

EP 0 310 171 A2 describes melt spun fibers from these materials, for example ethylene / propylene / CO terpolymers. These fibers have high tensile strengths and moduli of elasticity and are proposed for use as tire cord or for the production of spunbonded nonwovens. The latter are suitable for the production of roof underlays or as geotextiles.

WO 2016/190594 A2 and WO 2016/190596 A2 disclose wet-spun fibers of ethylene / propylene / -CO-terpolymers, which have excellent strength and elongation values and are also distinguished by high water and heat resistance and by good thermal conductivity. As applications for these fibers, various uses are proposed, for example the production of ropes, tubes, nets, spunbonded fabrics, airbags or protective clothing, as well as the use as geotextiles, as reinforcing fibers in composites, as belts, safety nets, conveyor belts, fishing lines or tennis strings.

In wet spinning, the dissolved polymer is spun into threads by a spinning capillary. The solvent is recovered as completely as possible and returned to the manufacturing process. Nevertheless, it can not be avoided that small amounts of the solvent used remain in the finished fiber. It is desirable to provide a solvent-free fiber. This avoids any potential safety hazard caused by the presence of solvent residues in the fiber; In addition, higher degrees of crystallization can be achieved by melt spinning, which can have an advantageous effect on the mechanical properties of the fiber.

On the other hand, processing by melt spinning often has to be done at significantly higher temperatures than when wet spinning. This can lead to accelerated degradation or crosslinking reactions of the polymer, which in turn can adversely affect the properties of the fiber produced or can lead to crosslinking reactions of the polymer, which can limit their processability in the extrusion process.

Surprisingly, it was found that by a combination of adapted process parameters (temperature, shear, throughput, spin delay, degree of stretching, fixation, residence time), the degree of crosslinking of the polymer could be controlled and thereby the thermomechanical properties of the fibers could be specifically improved, such. their heat resistance, hydrolysis resistance, chemical resistance, abrasion resistance, flexural strength, flexural recovery, modulus, creep, and cranking propensity.

In combinations of aliphatic polyketones and selected other polymers, the individual polymer components complement each other in a synergistic manner. Thus, the fibers are replaced by the other polymers e.g. excellent mechanical properties (high modulus, low creep, low tendency to bend) and due to the aliphatic polyketone low sliding friction and increased abrasion resistance.

Furthermore, it has been found that textile surfaces, such as fabric or container, the yarns of aliphatic polyketone or multi-component yarns with aliphatic polyketone as a shell and with the other polymer as the core a very low sliding friction and a very high abrasion resistance in drying and in wet conditions exhibit.

Furthermore, it has been found that fibers of selected conventional polymers with aliphatic polyketones can be combined into fibers which are characterized by a low sliding friction and high flexural strength.

An object of the present invention is to provide such fibers having the above property profile.

Another object of the present invention is to provide a spinning process for producing such fibers.

The present invention in a first embodiment relates to melt spun fibers containing thermoplastic aliphatic polyketone and antioxidant.

The present invention relates in a second embodiment to melt spun fibers containing thermoplastic aliphatic polyketone as the first polymer and polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer as the second polymer.

The aliphatic polyketones used according to the invention are homopolymers or copolymers having repeating structural units of the formula -R ₁ -CO-, where R _{1 is} a divalent aliphatic radical, preferably a divalent aliphatic radical having two to six carbon atoms.

Preferred radicals R ₁ have the formula -C _n H _2n -, in which n is 2, 3 or 4, in particular 2 or 3.

Copolymers having different radicals R ₁ are preferably used in the polymer chain, for example with radicals -C ₂ H ₄ - and with radicals -C ₃ H ₇ -.

The aliphatic polyketone used is particularly preferably a thermoplastic ethylene / propylene / CO terpolymer.

Also particularly preferably used are aliphatic polyketones having a melting range of 199 to 220 ° C and having an MFI value at 240 ° C and 2.16 daN from 6 to 60 g / 10 min (according to ASTM D 1238).

The aliphatic polyketones used according to the invention are polymers which are known per se and have already been used for fiber production.

As antioxidants according to the invention sterically hindered phenols and / or HALS (hindered amine light stabilizer) and / or phosphites are used, which are optionally combined with co-stabilizers.

Preferred antioxidants based on hindered phenols are sterically hindered alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxyphenol; sterically hindered alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, hindered hydroxylated thiodiphenyl ethers, e.g. 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-di-methyl) 4-hydroxyphenyl) disulfide; sterically hindered alkylidene bisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol; sterically hindered benzylphenols, eg 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether; hindered hydroxybenzylated malonates, eg dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxy-benzyl) -malonate; sterically hindered hydroxybenzyl-aromatics, eg 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, e.g. B. 2,4-bis-octylmercapto-6 (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine; sterically hindered phenolic benzylphosphonates, e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbaminsäurealkylester; Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols; Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols; Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols; Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as. N, N'-bis- (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) -hexamethylenediamine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxy -phenylpropionyl) -trimethylenediamine or N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.

Preferred co-stabilizers include organic phosphites and / or organic phosphonites. These are known co-stabilizers for antioxidants.

The content of aliphatic polyketone in the first embodiment of the invention is usually at least 80% by weight based on the total mass of the fiber. Preference is given to proportions of aliphatic polyketone of more than 90 wt .-%, in particular of more than 95 wt .-%.

The proportion of antioxidant in the first embodiment of the invention is usually between 0.05 and 10 wt .-%, based on the total mass of the fiber. Preferred are proportions of antioxidant from 0.1 to 5 wt .-%, in particular from 0.5 to 3 wt .-%.

In the second embodiment of the fibers according to the invention, at least one polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer are used in addition to the thermoplastic aliphatic polyketone.

The proportion of aliphatic polyketone in the second embodiment of the invention is usually between 5 and 90 wt .-%, based on the total mass of the fiber. Preference is given to proportions of aliphatic polyketone of from 10 to 80% by weight, in particular from 20 to 50% by weight.

The proportion of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystal polymer in the second embodiment of the invention is usually between 10 and 95 wt .-%, based on the total mass of the fiber , Preference is given to fractions of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer from 20 to 90% by weight, in particular from 50 to 80% by weight.

The polyolefins, polyesters, polyamides, polyoxymethylenes, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones and / or liquid-crystalline polymers used according to the invention are polymers known per se which have also already been used for fiber production.

Examples of polyolefins are homopolymers or copolymers derived from ethylene and / or from propylene optionally in combination with other ethylenically unsaturated aliphatic hydrocarbons, such as α-olefins having four to eight carbon atoms. Polyethylene and polypropylene can be in different densities and crystallinities. For the use according to the invention, all these modifications are fundamentally suitable.

Examples of polyesters are thermoplastic polymers derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as the alkyl esters, and of aliphatic, cycloaliphatic and / or aromatic dihydric alcohols, such as ethylene glycol, propylene glycol and / or butylene glycol.

Further examples of polyesters are thermoplastic-elastomeric polyesters (TPE-PE), for example polyesters comprising repeating ethylene terephthalate structural units and containing repeating polyethylene glycol terephthalate structural units. TPE-PE are known to the person skilled in the art.

Aromatic-aliphatic polyester homo- or copolymers are preferably used. Examples thereof are polyethylene terephthalate homopolymers or copolymers containing ethylene terephthalate units. These preferred polymers are thus derived from ethylene glycol and optionally further alcohols and from terephthalic acid or its polyester-forming derivatives, such as terephthalic acid esters or chlorides.

In addition to or instead of ethylene glycol, these polyesters may contain structural units derived from other suitable dihydric alcohols. Typical representatives thereof are aliphatic and / or cycloaliphatic diols, for example propanediol, 1,4-butanediol, cyclohexanedimethanol or mixtures thereof.

In addition to or instead of terephthalic acid or its polyester-forming derivatives, these polyesters may contain structural units derived from other suitable dicarboxylic acids or from their polyester-forming derivatives. Typical representatives thereof are aromatic and / or aliphatic and / or cycloaliphatic dicarboxylic acids, for example naphthalenedicarboxylic acid, isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid or mixtures thereof.

It is thus also possible to produce fibers containing other polyesters, such as polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate homopolymer or copolymers comprising ethylene naphthalate units.

These thermoplastic polyesters are known per se. Building blocks of thermoplastic copolyesters are preferably the abovementioned diols and dicarboxylic acids, or correspondingly constructed polyester-forming derivatives.

Preference is given to using polyesters whose solution viscosities (IV values) are at least 0.60 dl / g, preferably from 0.80 to 1.05 dl / g, particularly preferably from 0.80 to 0.95 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).

Examples of polyamides are thermoplastic polymers derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyamide-forming derivatives, such as their salts, and aliphatic, cycloaliphatic and / or aromatic divalent amines, such as hexamethylenediamine.

Further examples of polyamides are thermoplastic-elastomeric polyamides (TPE-PA), for example polyamides containing repeating hexamethylene terephthalamide structural units and containing repeating polyethylene glycol terephthalamide structural units. TPE-PA are known to the person skilled in the art.

Preferably used polyamides are partially crystalline aliphatic polyamides, which can be prepared starting from aliphatic diamines and aliphatic dicarboxylic acids and / or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids.

Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclo-hexylmethanes, diaminodicyclohexylpropanes, bis-aminomethylcyclohexane, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams. Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ε-caprolactam is 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.

Polyesters and polyamides used according to the invention can also be derived from hydroxycarboxylic acids or from aminocarboxylic acids.

Examples of polyoxymethylenes are homo- or copolymers containing recurring structural units of the formula -CH ₂ -O-.

Examples of polyurethanes are homo- or copolymers derived from aromatic or (cyclo) aliphatic diisocyanates and from (cyclo) -aliphatic or aromatic diols. Polyurethanes contain, for example, recurring structural units of the formula -C ₆ H ₄ -NH-CO-OC ₂ H ₄ -O-CO-NH-.

Further examples of polyurethanes are thermoplastic-elastomeric polyurethanes (TPE-PU). TPE-PU are known to the person skilled in the art.

Examples of polyphenylene sulfides are poly-p-phenylene sulfides, for example homopolymers or copolymers containing repeating structural units -para-C ₆ H ₄ -S-.

Examples of polyphenylene sulfones are poly-p-phenylene sulfones, for example homopolymers or copolymers containing repeating structural units -para-C ₆ H ₄ -SO _x -, where x is a number between 1 and 2.

Examples of polyphenylene ethers are poly-p-phenylene ethers, for example homopolymers or copolymers containing repeating structural units -para-C ₆ H ₄ -O-.

Examples of polyphenylene ketones are poly-p-phenylene ketones, for example homopolymers or copolymers containing repeating structural units -para-C ₆ H ₄ -CO-.

Examples of polyphenylene ether ketones are poly-p-phenylene ether ketones, for example copolymers containing recurring structural units - para-C ₆ H ₄ -CO- and recurring structural units -para-C ₆ H ₄ -O-.

Examples of liquid-crystalline polymers are liquid-crystalline aromatic polyesters, for example homopolymers or copolymers containing recurring structural units derived from para-hydroxybenzoic acid.

The at least two polymers in the fiber of the second embodiment of the invention may be present as a polymer blend or in the form of two or more fiber components spatially separated from one another but contiguous. Examples of this latter embodiment are multicomponent fibers which may be present, for example, as core-sheath fibers or as side-by-side fibers.

Preference is given to core sheath fibers with an aliphatic polyketone sheath and with a core of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer.

Particular preference is given to core sheath fibers with an aliphatic polyketone sheath and with a core of polyester, polyamide, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.

Also preferred are side-by-side fibers having an aliphatic polyketone fiber portion and another fiber portion in contact therewith of polyolefin, polyester, polyamide, polyoxymethylene, polyphenylene sulfide, Polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer.

Also particularly preferred are side-by-side fibers having an aliphatic polyketone fiber portion and another fiber portion in contact therewith of polyester, polyamide, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.

Preferred multicomponent fibers comprise a part of aliphatic polyketone and another part in contact therewith of one of the abovementioned types of polymer, in particular polyester, very particularly preferably TPE-PE, in particular polyamide, very particularly preferably TPE-PA, or in particular polyurethane, very particularly preferably TPE-PU, wherein the aliphatic polyketone mainly improves the sliding properties and the second polymer component mainly improves other properties, such as. B improved grip properties mediated e.g. TPE-PE, TPE-PA or TPE-PU or hot melt adhesive properties mediates e.g. by co-polyesters and / or by co-polyamides.

The aliphatic polyketones used according to the invention and / or the further polymers selected from the group consisting of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer may contain additional additives which are the fibers produced give a desired property. Examples of such additives are UV stabilizers, pigments, dyes, fillers, matting agents, reinforcing agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or other polymers which are derived from aliphatic polyketones, polyolefins, Polyesters, polyamides, polyoxymethylenes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones and / or liquid crystalline polymer differ. These additives are known 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 stabilizer") type.

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

Examples of preferred dyes are anionic dyes, acid dyes, metal complex dyes, cationic or basic dyes and disperse 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 or magnesium hydroxides or magnesium, zinc or calcium oxides). ,

An example of a preferred matting agent is titanium dioxide.

An example of a preferred reinforcing material is glass fibers.

Examples of preferred crosslinking agents are polybasic carboxylic acids and their esters, polyhydric alcohols, polycarbonates or polycarbodiimides.

Examples of preferred crystallization accelerators are carboxylic acid esters.

Examples of preferred lubricants are polyolefin waxes, fatty acids or their salts, fatty alcohols, fatty acid esters, silicones, polysiloxanes and in particular PMSQ, as in EP 2,933,361 A1 described.

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 blacks, graphite, graphene or carbon nanotubes.

Examples of preferred hydrolysis stabilizers are carbodiimides or epoxidized compounds.

Examples of preferred processing aids are waxes or longer chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.

Examples of preferred plasticizers are diethylhexyl phthalate, alkyl sulfonic acid esters of phenol, triethyl citrate, diethylhexyl adipate or diethyloctyl adipate.

Examples of preferred toughening 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, thermoplastic vulcanizates or cross-linked olefin-based thermoplastic elastomers, in particular PP / EPDM, or polycarbonate.

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

The proportion of these additional additives in the fiber according to the invention can usually be up to 10 wt .-%, based on the total mass of the fiber. These additional additives are preferably used in amounts of from 1 to 5% by weight.

In a preferred embodiment, the present invention relates to melt spun fibers containing at least 80% by weight of thermoplastic ethylene / propylene / CO terpolymer, from 0.1% to 5% by weight of hindered phenol and from 0.1% to 15% by weight. at least one additional additive selected from the group of UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or fluoropolymers, the percentages being based on the total mass of the Refer fibers.

In another preferred embodiment, the present invention relates to melt spun core sheath fibers comprising a thermoplastic ethylene / propylene / CO terpolymer sheath and a core of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer, wherein the mass of the shell 5 to 50 wt .-% and the mass of the core is 95 to 5 wt .-%, and wherein the core and / or the shell, if necessary, still up to a total of 10 wt. % of additives, in particular hindered phenol, UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or fluoropolymers, wherein the percentages are based on the total mass refer to the fibers.

In the context of this description, the term "fiber" is to be understood as meaning a linear structure which is thin in relation to its length. Typically, the length to diameter ratio of a fiber is at least 5: 1. Fibers in the sense of this description can be endless (and are then called filaments) and can be cut to finite length (and are then called bristles or short cut fibers). Fibers may also be in the form of multiple filaments or in the form of multiple staple fibers. The invention preferably relates to fibers in the form of monofilaments, bristles or short cut fibers.

The cross-sectional shape of the fibers according to the invention can be arbitrary. It may be irregular cross sections, to point or axisymmetric cross sections, for example, round, oval or n-shaped cross-sections, where n is greater than or equal to 3. The cross-sectional shape of the fibers may also be multilobal.

The strength (titer) of the fibers according to the invention can be expressed by the thread weight. 1 dtex corresponds to a fiber mass of 1 g per 10 km fiber length. Typical thread weights range from 1 to 100,000 dtex.

The titer of the inventively preferred monofilaments, bristles or short cut fibers is preferably at least 10 dtex and can vary widely. Preferred titres of monofilaments, bristles or short cut fibers are in the range from 10 to 30,000 dtex, in particular in the range from 45 to 20,000 dtex.

The components required for producing the fibers according to the invention are known per se, some are commercially available or can be prepared by processes known per se.

The fibers according to the invention are preferably used for the production of textile fabrics, in particular of woven, laid, knitted, braided or knitted fabrics. The production of these fabrics is carried out by known techniques.

The production of the fibers according to the invention can be carried out by a basically known melt spinning process, combined with single or multiple stretching and fixing of the fibers obtained.

The invention also relates to a method of the polyketone fibers described above.

In a first embodiment of the process according to the invention, polyketone raw material, together with the sterically hindered phenol, is metered into an extruder and pressed in molten form through a die plate. The nozzle plate may have one or more spinning capillaries. The resulting filament is from the Spin capillary deducted. The take-off speed is usually 1 to 120 m / min, in particular 5 to 50 m / min. Preferably, the take-off speed is selected such that, compared to the exit speed of the spinning mass from the nozzle, a drafting ratio greater than 1 results, which results in a higher crystallinity of the fiber with improved mechanical stability, bending strength and bending recovery. Furthermore, the so selected degree of stretching improves the diameter uniformity of the fiber.

The hindered phenol and / or further additives are preferably added in the form of a masterbatch, for example in the form of a masterbatch containing the additive (s) and a thermoplastic polymer, e.g. Polyketone.

The nozzle plate is usually part of a spin pack consisting of filter devices for the molten spinning mass and the downstream nozzle plate.

The temperature of the dope is to be chosen so that on the one hand sufficient fluidity of the dope is guaranteed, and on the other hand, the thermal stress of the polyketone remains limited, so that crosslinking and degradation reactions and gel formation in the dope to keep within limits or even completely suppressed can be.

In the first embodiment of the process according to the invention, an antioxidant-stabilized polyketone raw material is used. Here, the temperatures of the spinning mass at the exit through the spinning capillary in the range of 200 to 300 ° C, preferably from 220 to 240 ° C, are.

The diameter of a spinning capillary is selected by the skilled person according to the desired fiber weight. Typical diameters are in the range of 10 μm to 5 mm, in monofilaments or bristles preferably in the range of 0.1 to 1 mm. This information corresponds to the diameter of the hole on the exit side of the polymer mass.

Integrated in the spinning process are one or more draws with thermal effects that give the thread the desired end properties. The person skilled in the art knows such procedures.

Preferably, the filament is drawn several times after spinning, in particular with a total draw ratio in the range of 1: 3 to 1:15, preferably in the range of 1: 4 to 1: 8.

Particularly preferably, the stretching stage (s) is followed by at least one relaxation stage (fixing stage). The stretched filaments are thermally treated while maintaining the fiber tension, so that built-in stress in the filament can be reduced.

Subsequently, the filaments produced are fed to a suitable storage form, for example, wound up or cut into staple fibers in a cutting device.

In a second embodiment of the process of the present invention, a polymer blend of aliphatic polyketone and polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer is spun or spun through a conventional spin capillary as described above aliphatic polyketone, on the one hand, and polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer, on the other hand, are spun through a spinning capillary to produce multicomponent filaments. Otherwise, the method of the second embodiment corresponds to the procedure in the first embodiment of the method.

In the second embodiment of the process of the invention, an antioxidant, preferably hindered phenol, may be present in the polymer components; but it can also be worked without the antioxidant.

Also in the second embodiment, the temperature of the dope is to be chosen so that on the one hand sufficient fluidity of the dope is ensured, and on the other hand, the thermal load of the aliphatic polyketone and the other polymer component remains limited, so that crosslinking and degradation reactions and gelation in the Spinnmasse be limited or even completely suppressed.

In the second embodiment of the process according to the invention, it is possible to use polymer raw materials which are not necessarily stabilized with antioxidant. Here, the temperatures of the spinning mass at the exit through the spinning capillary in the range of 200 to 300 ° C, preferably from 220 to 260 ° C, are.

1. i) Vermischen von thermoplastischem aliphatischem Polyketon mit sterisch gehindertem Phenol in einem Extruder zu einer Spinnmasse,
2. ii) Extrudieren der Spinnmasse aus Schritt i) durch eine Düsenplatte mit einer oder mehreren Spinnkapillaren, wobei die Temperatur der Spinnmasse an der Austrittseite der Spinnkapillare(n) im Bereich von 200 bis 300 °C liegt, vorzugsweise von 220 bis 260 °C,
3. iii) Abziehen des gebildeten Filaments mit einer Abzugsgeschwindigkeit im Bereich von 1 bis 120 m/min, insbesondere von 5 bis 50 m/min, vorzugsweise unter Wahl des Verhältnisses von Abzugsgeschwindigkeit zu Austrittsgeschwindigkeit der Spinnmasse aus der Spinnkapillare von größer als 1,
4. iv) ein- oder mehrfaches Verstrecken des gebildeten Filaments,
5. v) gegebenenfalls Relaxieren des gebildeten Filaments, und
6. vi) gegebenenfalls Aufspulen oder Schneiden des gebildeten Filaments.

The invention relates to a process for producing the above-described polyketone fibers of the first embodiment, comprising the following measures:

1. i) mixing thermoplastic aliphatic polyketone with hindered phenol in an extruder into a dope,
2. 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 at the exit side of the spinning capillary (s) is in the range from 200 to 300 ° C., preferably from 220 to 260 ° C.,
3. iii) stripping off the filament formed at a take-off speed in the range from 1 to 120 m / min, in particular from 5 to 50 m / min, preferably by selecting the ratio of draw speed to exit speed of the spinning mass from the spinning capillary of greater than 1,
4. iv) one or more stretching of the formed filament,
5. v) optionally relaxing the formed filament, and
6. vi) optionally winding or cutting the filament formed.

1. i) Vermischen von thermoplastischem aliphatischem Polyketon und Polyolefin, Polyester, Polyamid, Polyoxymethylen, Polyurethan, Polyphenylensulfid, Polyphenylensulfon, Polyphenylenether, Polyphenylenketon, Polyphenylenetherketon und/oder flüssigkristallinem Polymer in einem Extruder zu einer Spinnmasse,
2. ii) Extrudieren der Spinnmasse aus Schritt i) durch eine Düsenplatte mit einer oder mehreren Spinnkapillaren, wobei die Temperatur der Spinnmasse an der Austrittseite der Spinnkapillare(n) im Bereich von 200 bis 300 °C liegt, vorzugsweise von 220 bis 260 °C,
3. iii) Abziehen des gebildeten Filaments mit einer Abzugsgeschwindigkeit im Bereich von 1 bis 120 m/min, insbesondere von 5 bis 50 m/min, vorzugsweise unter Wahl des Verhältnisses von Abzugsgeschwindigkeit zu Austrittsgeschwindigkeit der Spinnmasse aus der Spinnkapillare von größer als 1,
4. iv) ein- oder mehrfaches Verstrecken des gebildeten Filaments,
5. v) gegebenenfalls Relaxieren des gebildeten Filaments, und
6. vi) gegebenenfalls Aufspulen oder Schneiden des gebildeten Filaments.

The invention relates to a process for producing the above-described polyketone fibers of the second embodiment, comprising the following measures:

1. i) mixing thermoplastic aliphatic polyketone and polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer in an extruder into a dope,
2. 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 at the exit side of the spinning capillary (s) is in the range from 200 to 300 ° C., preferably from 220 to 260 ° C.,
3. iii) stripping off the filament formed at a take-off speed in the range from 1 to 120 m / min, in particular from 5 to 50 m / min, preferably by selecting the ratio of draw speed to exit speed of the spinning mass from the spinning capillary of greater than 1,
4. iv) one or more stretching of the formed filament,
5. v) optionally relaxing the formed filament, and
6. vi) optionally winding or cutting the filament formed.

• ia) Bereitstellen einer ersten Spinnmasse enthaltend thermoplastisches aliphatisches Polyketon in einem ersten Extruder,
• ib) Bereitstellen einer zweiten Spinnmasse enthaltend Polyolefin, Polyester, Polyamid, Polyoxymethylen, Polyurethan, Polyphenylensulfid, Polyphenylensulfon, Polyphenylenether, Polyphenylenketon, Polyphenylenetherketon und/oder flüssigkristallines Polymer in einem zweiten Extruder,
• ii) Extrudieren der ersten Spinnmasse aus Schritt ia) und der zweiten Spinnmasse aus Schritt ib) durch eine Düsenplatte mit einer oder mehreren Spinnkapillaren, so dass jede Spinnkapillare von der ersten Spinnmasse und von der zweiten Spinnmasse durchströmt wird, wobei die Temperatur der ersten und der zweiten Spinnmasse an der Austrittseite der Spinnkapillare (n) im Bereich von 200 bis 300 °C liegt, vorzugsweise von 220 bis 260 °C,
• iii) Abziehen des gebildeten Filaments mit einer Abzugsgeschwindigkeit im Bereich von 1 bis 120 m/min, insbesondere von 5 bis 50 m/min, vorzugsweise unter Wahl des Verhältnisses von Abzugsgeschwindigkeit zu Austrittsgeschwindigkeit der Spinnmasse aus der Kapillare von größer als 1,
• iv) ein- oder mehrfaches Verstrecken des gebildeten Filaments,
• v) gegebenenfalls Relaxieren des gebildeten Filaments, und
• vi) gegebenenfalls Aufspulen oder Schneiden des gebildeten Filaments.

The invention relates to a further process for producing the above-described polyketone fibers of the second embodiment, comprising the following measures:

• ia) providing a first dope comprising thermoplastic aliphatic polyketone in a first extruder,
• ib) providing a second dope comprising polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer in a second extruder,
• ii) extruding the first dope of step ia) and the second dope of step iib) through a die plate with one or more spinning capillaries, so that each spinning capillary is flowed through by the first dope and the second dope, the temperature of the first and the second dope on the exit side of the spinning capillary (s) is in the range from 200 to 300 ° C., preferably from 220 to 260 ° C.,
• iii) stripping off the filament formed at a take-off speed in the range from 1 to 120 m / min, in particular from 5 to 50 m / min, preferably by selecting the ratio of draw speed to exit velocity of the spinning mass from the capillary greater than 1,
• iv) one or more stretching of the formed filament,
• v) optionally relaxing the formed filament, and
• vi) optionally winding or cutting the filament formed.

The fibers according to the invention, in particular in the form of monofilaments, are preferably used for the production of textile surface constructions, in particular of woven fabrics, spiral fabrics, laid or knitted fabrics. These textile surface constructions are preferably suitable for use in screens or conveyor belts. Another important field of application are fibers for brushing or for oral hygiene as well as for body care but also short cut fibers in composite materials with e.g. Concrete as a matrix material.

The invention therefore also relates to textile fabrics comprising the fibers described above, in particular textile fabrics in the form of a woven, knitted, knitted, braided or laid fabric.

The fibers of the invention are characterized by a combination of outstanding mechanical properties, such as high tensile modulus and good loop and knot strength, excellent bending recovery, and very good sliding properties and high abrasion resistance.

They can be used in a wide variety of fields. They are preferably used in applications in which increased wear and high mechanical stress, in particular in hot humid environments, can be expected. Examples of this are the use in screen fabrics and filter cloths for gas and liquid filters, in drying tapes, for example for the production of food or especially paper, and in brushes for cleaning purposes of all kinds, for example in the home, in personal care, such as in oral hygiene, e.g. as a toothbrush. Further uses are the use as fluidizing belts, as processing belts for the board industry, as conveyor belts and as process belts in the production of nonwovens, such as spunbond, meltblown, airlaid, wetlaid, spunlaced or thermobonded, or as short-cut fibers for concrete or composite reinforcement.

The invention also relates to the use of the fibers described above, in particular in the form of monofilaments, as papermachine clothing, in conveyor belts and in filtration screens.

In a further preferred embodiment, the fibers of the invention are various stabilizers, e.g. Antioxidants for thermal stabilization and / or hydrolysis stabilizers added. As a result, this variant is particularly suitable for drying processes in a humid environment, e.g. in the dryer section of paper machines as well as in other continuous industrial drying and filtration processes, such as the drying of particle board, of pellets to be used as fuels or more generally of biomass.

The fibers according to the invention are very particularly preferably used in the form of monofilaments as paper machine clothing in the sheet forming section and / or in the dryer section of the paper machine.

These monofilaments are used, for example, in the deficit of forming fabrics in paper machines. This can be done 100% as deficiency or as a so-called interchange (alternating said monofilament alternating with, for example, polyamide, polyester or polyphenylene sulfide monofilaments). The aliphatic polyketone causes a significant reduction in sliding friction and thus a significant reduction in the drive performance of the paper machine, resulting in a significant energy savings result. Furthermore, the monofilament according to the invention is more resistant to abrasion than comparable monofilaments of polyethylene terephthalate, polybutylene terephthalate or polycyclohexane terephthalate or of polyamides without the use of aliphatic polyketone.

Another preferred field of application of the fibers according to the invention is their use in brushes, in particular in toothbrushes. Here, the fibers according to the invention are generally used in the form of bristles.

For this purpose, the monofilaments are in endless or cut and combined into bundles form or as brushes.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0310171 A2 [0005]
• WO 2016/190594 A2 [0006]
• WO 2016/190596 A2 [0006]
• EP 2933361 A1 [0071]

Claims (25)

Melt-spun fibers containing thermoplastic aliphatic polyketone and antioxidant. Melt-spun fibers containing as the first polymer a thermoplastic aliphatic polyketone and as a second polymer a polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer. Melt spun fibers according to one of Claims 1 or 2 , characterized in that the thermoplastic aliphatic polyketone is an ethylene / propylene / CO terpolymer. Melt-spun fibers after at least one of Claims 1 to 3 , characterized in that as antioxidant, a sterically hindered phenol is used, which is optionally combined with co-stabilizers. Melt-spun fibers after Claim 4 characterized in that the sterically hindered phenol is selected from the group of sterically hindered alkylated monophenols, hindered alkylthiomethylphenols, hindered hydroxylated thiodiphenyl ethers, hindered alkylidene bisphenols, hindered benzylphenols, hindered hydroxybenzylated malonates sterically hindered hydroxybenzyl aromatics, sterically hindered phenolic triazine compounds, hindered phenolic benzyl phosphonates, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid alkyl esters, β- (3,5-di- tert-butyl-4-hydroxy-phenyl) -propionic acid with monohydric or polyhydric alcohols, the esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monohydric or polyhydric alcohols, the esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, the esters of 3,5-di-tert-butyl-4-hydroxy-phenyles acetic acid with mono- or polyhydric alcohols, or the amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid. Melt spun fibers according to one of Claims 4 or 5 , characterized in that the co-stabilizer is selected from the group of organic phosphites and / or organic phosphonites. Melt-spun fibers after at least one of Claims 2 to 6 , characterized in that the polyolefin is a homo- or copolymer which is derived from ethylene and / or from propylene optionally in combination with further ethylenically unsaturated aliphatic hydrocarbons. Melt-spun fibers after at least one of Claims 2 to 6 characterized in that the polyester is an aromatic aliphatic polyester homo- or copolymer, in particular a polyethylene terephthalate homopolymer or a copolymer containing ethylene terephthalate units. Melt-spun fibers after at least one of Claims 2 to 6 , characterized in that the polyamide is a partially crystalline aliphatic polyamide derived from aliphatic diamines and aliphatic dicarboxylic acids and / or cycloaliphatic lactams having at least 5 ring members or corresponding amino acids. Melt-spun fibers after at least one of Claims 2 to 9 Characterized in that the first polymer and the second polymer are present as polymer blend or in the form of two or more fiber components, but which are arranged spatially separated from each contiguous with one another. Melt-spun fibers after Claim 10 characterized in that they are present as core sheath fibers with a sheath of aliphatic polyketone and with a core of polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer. Melt-spun fibers after Claim 11 , characterized in that they are present as core sheath fibers with a sheath of aliphatic polyketone and with a core of polyester, polyamide, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone. Melt-spun fibers after Claim 10 characterized in that they are provided as side-by-side fibers with a fiber portion of aliphatic polyketone and another fiber portion in contact therewith of polyolefin, polyester, polyamide, polyoxymethylene, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer Melt-spun fibers after Claim 13 characterized in that it comprises, as side-by-side fibers, a fiber portion of aliphatic polyketone and another fiber portion of polyester, polyamide, polyphenylene sulfide, poly-phenylene ether, Polyphenylene ketone or polyphenylene ether ketone are present. Melt-spun fibers after at least one of Claims 1 to 14 , characterized in that they contain additional additives which are selected from the group of UV stabilizers, pigments, dyes, fillers, matting agents, reinforcing agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or others Polymers which differ from aliphatic polyketones, polyolefins, polyesters, polyamides, polyoxymethylenes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones and / or liquid-crystalline polymers. Melt-spun fibers after at least one of Claims 1 to 15 , characterized in that it comprises at least 80% by weight of thermoplastic ethylene / propylene / CO terpolymer, 0.1 to 5% by weight of sterically hindered phenol and 0.1 to 15% by weight of at least one additional additive selected from the group of UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or fluoropolymers, the percentages being based on the total mass of the fibers. Melt-spun fibers after at least one of Claims 2 to 16 characterized in that they are formed as core-sheath fibers, a thermoplastic ethylene / propylene / CO terpolymer sheath and a core of polyolefin, polyester, polyamide, polyoxymethylene, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystal polymer, wherein the mass of the shell 5 to 50 wt .-% and the mass of the core from 95 to 5 wt .-%, and wherein the core and / or the shell optionally still up to a total of 10 wt .-% of Contain additives, in particular sterically hindered phenol, UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or fluoropolymers, wherein the percentages are based on the total mass refer to the fibers. Melt-spun fibers after at least one of Claims 1 to 17 , characterized in that they are present as monofilaments in endless or cut and bundled form or as brushes. Textile fabrics containing the melt-spun fibers after at least one of Claims 1 to 18 in the form of a fabric, knitted fabric, knitted fabric, braid or loosely. Use of the melt spun fibers after at least one of Claims 1 to 18 for use in screen fabrics, in filter cloths for gas and liquid filters, in process belts and dry belts and in brushes for cleaning purposes of all kinds. Use after Claim 20 , characterized in that the melt-spun fibers are used as Fluidisationsbänder, as processing belts for the carton industry, as conveyor belts and as process belts in the production of nonwovens. Use after Claim 20 , characterized in that the melt-spun fibers are used in brushes for cleaning purposes in the home or in the personal care, in particular in toothbrushes. Use after Claim 20 , characterized in that the melt-spun fibers are used as short-cut fibers for concrete and Kompositarmierung. Use after Claim 20 , characterized in that the melt-spun fibers are used in the form of monofilaments as papermachine clothing, in conveyor belts and in filtration screens. Use after Claim 20 , characterized in that the melt-spun fibers are used in the form of bristles in brushes, in particular in toothbrushes.