Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
• • A—HUMAN NECESSITIES
  • A46—BRUSHWARE
  • A46D—MANUFACTURE OF BRUSHES
  • A46D1/00—Bristles; Selection of materials for bristles
• • A—HUMAN NECESSITIES
  • A46—BRUSHWARE
  • A46D—MANUFACTURE OF BRUSHES
  • A46D1/00—Bristles; Selection of materials for bristles
  • A46D1/02—Bristles details
  • A46D1/0207—Bristles characterised by the choice of material, e.g. metal
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
  • D01D5/082—Melt spinning methods of mixed yarn
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

• the present invention relates to melt spun fibers
• polyolefins such as polyethylene (PE), polypropylene (PP), polyamides such as polyamide 6
• PA 6 polyamide 6.6
• PET polyethylene terephthalate
• 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 and combinations of aliphatic polyketones with selected other polymers are known.
• CONFIRMATION COPY EP 0 310 171 A2 describes melt-spun fibers from these
• Materials such as 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.
• CN 106 521 704 A describes mixtures of aliphatic polyketones and polyoxymethylene which may, inter alia, be present as fibers and which may be stabilized with antioxidants. Multi-component fibers are not disclosed.
• WO 2016/190594 A2 and WO 2016/190596 A2 disclose wet-spun fibers of ethylene / propylene / -CO-terpolymers which are excellent
• 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.
• thermomechanical properties of the fibers could be specifically improved, such B. their heat resistance, hydrolysis resistance, chemical resistance,
• Abrasion resistance, flexural strength, flexural recovery, modulus, creep, and cranking propensity The dimensional stability describes the tendency of a fiber under tension and at a certain temperature to show a change in length. It results from a combination of the tensile modulus and creep properties of the fiber, for example a monofilament.
• the dimensional stability of the aliphatic polyketone-based fibers can be achieved by suitable additives. It is possible to use selected polymeric additives which are dispersed in the matrix of aliphatic polyketone. In this case, for example, fibrils can form from the dispersed phase and / or the surface of the fiber is modified by the dispersed phase.
• 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.
• 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.
• 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.
• multicomponent fibers having selected properties can be obtained, for example, core / sheath fibers wherein the sheath is aliphatic polyketone and the core is polyester, for example polyethylene terephthalate or polycarbonate, or higher melting point aliphatic polyketone than the sheath aliphatic polyketone ,
• adhesive properties can be adjusted in a targeted manner. Due to the intrinsic chemical resistance and good barrier properties of aliphatic polyketones, core-sheath fibers with high chemical resistance can be produced.
• Monofilaments in a textile construct e.g. in woven or knitted fabrics.
• fibers are produced with low coefficients of friction and very good abrasion resistance.
• 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.
• aliphatic polyketone is present as the second polymer whose melting point is at least 5 ° C, preferably at least 10 ° C, more preferably at least 20 ° C higher than the melting point of the aliphatic polyketone of the first polymer.
• the present invention relates 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, liquid crystalline polymer and / or aliphatic polyketone as the second polymer, said polymers being in the form of two or more fiber components spatially separated from each other but contiguous, and if so in that aliphatic polyketone is contained as a second polymer whose melting point is at least 5 ° C, preferably at least 10 ° C, more preferably at least 20 ° C higher than the melting point of the aliphatic polyketone of the first polymer.
• the present invention relates to melt-spun fibers containing thermoplastic aliphatic polyketone as a matrix polymer and dispersing therein particles of polysiloxanes or
• the aliphatic polyketones used in the invention are homo- or copolymers having recurring structural units of the formula -Ri-CO-, where Ri is a divalent aliphatic radical, preferably a bivalent aliphatic radical having two to six carbon atoms.
• Ri is a divalent aliphatic radical, preferably a bivalent aliphatic radical having two to six carbon atoms.
• Preferred radicals R 1 have the formula -C n H 2 n -, in which n is 2, 3 or 4, in particular 2 or 3. Copolymers having different radicals are preferred in the
• Polymer chain used, for example, with radicals -C 2 H 4 - and with radicals
• the aliphatic polyketone used is particularly preferably a thermoplastic ethylene / propylene / CO terpolymer.
• Aliphatic polyketones are partially crystalline polymers that have a melting point in differential thermal analysis (DSC).
• DSC analysis is performed according to ASTM D3418. The heating rate is 10 K / min.
• 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.
• the melt-spun fibers according to the invention contain an antioxidant.
• antioxidants hindered phenols and / or HALS
• antioxidants based on sterically hindered phenols 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'-thiobis (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'
• Preferred co-stabilizers include organic phosphites and / or organic phosphonites. These are known co-stabilizers for antioxidants.
• the proportion of antioxidant is usually between 0.05 and 10 wt .-%, based on the total mass of the fiber. Preference is given to shares
• Antioxidant from 0.1 to 5 wt .-%, in particular from 0.5 to 3 wt .-%.
• the fibers according to the invention comprise, in addition to the thermoplastic aliphatic polyketone, as the first polymer at least one polyolefin, polyester, polyurethane, polyphenylene sulfide,
• Polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer and / or another aliphatic polyketone as a second polymer In the second embodiment of the
• Polyamide and / or polyoxymethylene can also be used as the second polymer.
• the proportion of aliphatic polyketone as the first polymer in the fibers 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 as the first polymer of from 10 to 80% by weight, in particular from 20 to 50% by weight.
• Polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene as the second polymer in the Fibers according to the invention are usually between 10 and 95% by weight, based on the total mass of the fiber. Preference is given to proportions of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone,
• liquid crystalline polymer further aliphatic polyketone, polyamide and / or polyoxymethylene as second polymer from 20 to 90 wt .-%, in particular from 50 to 80 wt .-%.
• polyesters In the polyolefins, polyesters, and
• Polyurethanes polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, liquid-crystalline polymers, other aliphatic polyketones, polyamides and / or
• Polyoxymethylenes are known polymers which have also been used for fiber production.
• polyolefins are homopolymers or copolymers derived from ethylene and / or from propylene optionally in combination with other ethylenically unsaturated aliphatic hydrocarbons, such as ⁇ -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.
• polyesters are thermoplastic polymers derived from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as the alkyl esters, and from
• Alcohols such as ethylene glycol, propylene glycol and / or butylene glycol.
• polyesters are thermoplastic-elastomeric polyesters (TPE-PE), for example polyesters containing repeating ethylene Terephthalate structural units and containing recurring TPE-PE.
• TPE-PE Polyethylene glycol terephthalate structural units.
• TPE-PE are known to the person skilled in the art.
• polycarbonates are polycarbonates. These are preferably used. Polycarbonates are formally carbonic polyesters containing the repeating structural unit - [R-O-CO-O] -, wherein R is a residue of a dihydric organic alcohol or phenol after removal of the two alcohol groups.
• R is the radical of an aromatic dihydroxy compound, ie a bisphenol.
• 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), dihydroxydiphenylsulfide, tetramethyl-bisphenol A or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
• Cocondensates of bisphenol A and BPTMC to highly transparent and heat-resistant plastics are possible, for example, 1, 1, 1-tris (4-hydroxyphenyl) ethane (THPE). This allows the incorporation of chain branches which positively influence the intrinsic viscosity during the processing of the material.
• THPE 1, 1, 1-tris (4-hydroxyphenyl) ethane
• aromatic-aliphatic polyester homopolymers or copolymers are preferred.
• These preferred polymers are thus derived from ethylene glycol and optionally further alcohols and terephthalic acid or their polyester-forming derivatives, such as terephthalic acid esters or chlorides.
• 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.
• 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 are examples of Sebacic acid or mixtures thereof.
• polyesters such as polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate homopolymer or copolymers comprising ethylene naphthalate units.
• 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.
• 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)).
• DCE dichloroacetic acid
• polyamides examples include 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 dihydric amines, such as
• polyamides are thermoplastic-elastomeric polyamides (TPE-PA), for example polyamides containing recurring polyamides
• TPE-PA Hexamethylene terephthalamide structural units and containing repeating polyethylene glycol terephthalamide structural units.
• 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-aminomethyl-cyclohexane, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams.
• 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,
• Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ⁇ -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.
• polyoxymethylenes that can be used in the second embodiment of the invention are homo- or copolymers containing recurring structural units of the formula -CH 2 -O-.
• 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-O-C 2 H 4 -O-CO-NH-.
• thermoplastic elastomers are thermoplastic elastomers
• TPE-PU Polyurethanes
• polyphenylene sulfides are poly-p-phenylene sulfides, for example homopolymers or copolymers containing recurring structural units
• polyphenylene sulfones are poly-p-phenylene sulfones, for example homopolymers or copolymers containing recurring structural units
• polyphenylene ethers are poly-p-phenylene ethers, for example homo- or copolymers containing recurring structural units
• polyphenylene ketones are poly-p-phenylene ketones, for example homopolymers or copolymers containing recurring structural units
• polyphenylene ether ketones are poly-p-phenylene ether ketones, for example copolymers containing repeating structural units -para-CeH 4 -CO- and recurring structural units -para-C 6 H -O-.
• liquid-crystalline polymers are liquid-crystalline aromatic polyesters, for example homopolymers or copolymers comprising recurring structural units derived from para-hydroxybenzoic acid.
• the first polymer and the second polymer may be present as a polymer blend, or the polymers may be in the form of two or more fiber components spaced apart but coextensive.
• Examples of this embodiment are fibers in the form of islet-in-sea fibers, in which a polymer component in the form of fibrils is thus arranged in the polymeric matrix component.
• the fibrils are preferred oriented in the longitudinal direction of the fiber and thereby increase
• multicomponent fibers may be mentioned.
• the at least two polymers in the fiber according to the invention can therefore be present as a polymer mixture or the at least two polymers can be present in the form of two or more fiber components, which are spatially separated from one another but arranged in a continuous manner.
• Examples of this latter embodiment are multicomponent fibers which may be present, for example, as core-sheath fibers or as side-by-side fibers.
• fibers comprising a mixture of aliphatic polyketone and polycarbonate.
• fibers wherein the aliphatic polyketone forms a polymer matrix and another polymer selected from the group of polyolefins, polyesters, polyphenylene ketones, polyphenylene ether ketones and / or liquid crystalline polymers in the form of fibrils in the polymer matrix component.
• these fibers contain as a further polymer, a liquid crystalline polymer.
• core sheath fibers with an overcoat of aliphatic polyketone and with a core of polyolefin, polyester, polyurethane,
• Core sheath fibers with a sheath are particularly preferred
• aliphatic polyketone and having a core of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.
• side-by-side fibers having an aliphatic polyketone fiber portion and another fiber portion in contact therewith of polyolefin, polyester, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone,
• liquid crystal polymer further aliphatic polyketone, polyamide and / or polyoxymethylene, wherein in the event that aliphatic polyketone is present in the further fiber portion whose melting point is at least 5 ° C, preferably at least 10 ° C and especially at least 20 ° C higher than the melting point of the aliphatic polyketone in the other fiber part.
• side-by-side fibers having a fiber portion of aliphatic polyketone and another fiber portion in contact therewith of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.
• side-by-side fibers having a fiber portion of aliphatic polyketone and another fiber portion in contact therewith of polyolefin, polyester, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer.
• core sheath fibers in which the sheath contains aliphatic polyketone as the polymer and the core contains one or more of the abovementioned second polymers and in addition at least one additive is present in the core and / or sheath which gives the fiber a specific functionality gives.
• one fiber part contains aliphatic polyketone as polymer and the other fiber part contains one or more of the abovementioned second polymers and additionally at least one additive which gives the fiber a specific
• core sheath fibers having an aliphatic polyketone sheath and a further aliphatic core
• Polyketone whose melting point is at least 5 ° C, preferably at least 10 ° C and in particular at least 20 ° C higher than the melting point of the aliphatic polyketone in the jacket.
• core-shell structures with cores of polyesters, such as PET or polycarbonate, or aliphatic polyketones of higher melting point than the sheath polymer can produce fibers with good thermal stability.
• These are characterized in comparison with aliphatic polyketone fibers by high tensile and flexural Moduli and therefore by high stability, for example, in core-sheath fibers with PET in the jacket. These fibers often exhibit good dimensional stability under tension at temperatures up to 150 ° C.
• fibers are provided in which the fiber surface is modified by selected polymer particles dispersed in the matrix polymer.
• Functionalization and texturing of the surface can be achieved by addition of polysiloxane particles, such as PMSQ particles and / or
• Poly (meth) acrylate particles such as crosslinked PMMA microspheres can be achieved. Typical diameters of these particles range from 0.2 to 100 pm.
• microtexturing of the surface can be created and the surface properties of the fiber can be modified. Above all, this reduces the friction surface and significantly improves the friction properties. In addition, the cleaning properties of the fiber are improved.
• the invention relates to fibers, in particular
• Monofilaments comprising a matrix of aliphatic polyketone and dispersed therein particles of polysiloxane and / or of poly (meth) acrylate, which have a diameter of 200 nm to 100 pm.
• the particles can have any shape. Examples are particles with rotationally symmetrical shape, in particular spheres, but also with an irregular shape. These particles are present as micropowder. Of the Diameter of these particles is in the range of 0.2 to 100 ⁇ ⁇ ⁇ , preferably from 1 to 50 m. The diameter specification for particles with varying diameters refers to the largest diameter of the particle.
• Preference monofilaments contain spherical particles of polysiloxane whose diameter is from 1 to 50 ⁇ .
• the particles are dispersed as micropowder in the matrix polymer. In general, from 0.001% by weight to 8% by weight, preferably from 0.02% by weight to 5% by weight, of particles are metered into the matrix polymer.
• the particles are present in the matrix polymer as a heterogeneous phase.
• the particles may be present as individual particles in the matrix polymer and / or as aggregates of various individual particles.
• the polysiloxanes used in the invention is a group of synthetic polymers in which silicon atoms via
• Polysiloxanes are also called silicones. These may be linear or crosslinked polysiloxanes or also polysiloxanes with cage structure, so-called silsesquioxanes.
• polysiloxanes which are linear or crosslinked polydimethylsiloxanes or polymethylsilsesquioxane.
• 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. In addition, you can
• Poly (meth) acrylates have further copolymerized with esters of acrylic acid and / or with esters of methacrylic acid monomer units.
• the poly (meth) acrylates used according to the invention may be linear or, preferably, crosslinked poly (meth) acrylates.
• Homopolymers or copolymers of methyl acrylate or of methyl methacrylate are preferably used as the poly (meth) acrylates.
• additives examples include electroconductive additives, lubricants, anti-adhesion agents, blowing agents for producing foamed or porous fiber surfaces, pigments and / or fillers.
• 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, or in particular polyurethane, very particularly preferably TPE-PU, where the aliphatic polyketone mainly the Slip properties improved and the second polymer component mainly improves other properties, such as.
• B improved grip properties mediated e.g. TPE-PE or TPE-PU or hot melt adhesive properties mediates e.g. by co-polyester.
• the aliphatic polyketones used according to the invention and / or the further polymers selected from the group consisting of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ethers, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene may contain additional additives which impart a desired property to the fibers produced. Examples of such additives are UV stabilizers, pigments, dyes, fillers, matting agents, reinforcing agents,
• Crosslinking agents are crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and / or other aliphatic polymers
• Polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, poly phenylene ether ketones, liquid crystalline polymers, other aliphatic polyketones, polyamides and / or polyoxymethylenes differ. These additives are known in the art.
• 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.
• dyes examples include anionic dyes, acid dyes, metal complex dyes, cationic or basic dyes and
• Disperse dyes examples include carbonates, such as chalk or dolomite, silicates, such as talc, mica, kaolin or sulfates, such as baryta, or oxides and hydroxides, such as quartz, 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.
• crosslinking agents are polybasic carboxylic acids and their esters, polyhydric alcohols, polycarbonates or polycarbodiimides.
• crystallization accelerators examples include carboxylic acid esters.
• lubricants examples include polyolefin waxes, fatty acids or their salts, fatty alcohols, fatty acid esters, silicones, polymethacrylate
• Examples of preferred flame retardants are phosphorus-containing
• Examples of preferred antistatic agents are carbon blacks, graphite, graphene or carbon nanotubes.
• hydrolysis stabilizers examples include carbodiimides or epoxidized compounds.
• Examples of preferred processing aids are waxes or
• plasticizers are diethylhexyl phthalate, alkylsulfonic acid esters of phenol, triethyl citrate, diethylhexyl adipate or diethyloctyl adipate.
• plasticizers diethylhexyl phthalate, alkylsulfonic acid esters of phenol, triethyl citrate, diethylhexyl adipate or diethyloctyl adipate.
• preferred impact modifiers are thermoplastic
• thermoplastic copolyamides 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 crosslinked thermoplastic elastomers
• Olefin base especially PP / EPDM, or polycarbonate.
• 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.
• the present invention relates to melt spun core sheath fibers comprising a sheath
• liquid crystalline polymer further aliphatic polyketone, polyamide and / or polyoxymethylene, 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 optionally total may contain up to 10% by weight of additives, especially hindered phenol, UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents,
• Fiber is to be understood as meaning a linear structure which is thin in relation to its length .
• the ratio of length to diameter of a fiber is typically at least 5: 1.
• 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 may be any desired, and may be irregular cross sections, point or axisymmetric cross sections, for example round, oval or rectangular cross sections, where n is greater than or equal to 3.
• the cross sectional shape The fibers can 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 on or
• the invention also relates to a method of the above-described polyketone fibers.
• 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 withdrawn from the spinning capillary.
• Withdrawal speed is usually 1 to 120 m / min, in particular 5 to 50 m / min.
• the hindered phenol and / or further additives may be added in the form of a masterbatch containing the additive (s) and a thermoplastic polymer, the polymer being selected from the group consisting of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone , Polyphenylene ether, polyphenylene ketone, Polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene.
• the nozzle plate is usually part of a spin pack, which consists 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.
• an antioxidant-stabilized polyketone raw material and a selected further polymer derived from the masterbatch are used.
• 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 range from 10 m to 5 mm, monofilaments or bristles preferably from 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.
• the filament is preferably drawn several times after spinning, 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.
• Particular preference is given to the draw step (s) at least a Relaxiercut (fixing) on.
• the stretched filaments are thermally treated while maintaining the fiber tension, so that in
• Filament can reduce built-in voltages. Subsequently, the filaments produced are fed to a suitable storage form, for example, wound up or cut into staple fibers in a cutting device.
• a polymer blend of aliphatic polyketone and of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystal polymer and / or further aliphatic polyketone by a conventional
• an antioxidant preferably sterically hindered, may be present in the polymer components Phenol, to be present; but it can also be worked without the antioxidant.
• 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.
• 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.
• a blend of aliphatic polyketone and of polysiloxane particles and / or of poly (meth) acrylate particles is spun through a conventional spinning capillary as described above.
• the invention relates to a process for producing the polyketone fibers described above, comprising the following measures:
• thermoplastic aliphatic polyketone i) mixing of thermoplastic aliphatic polyketone with
• Polymer selected from the group consisting of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid-crystalline polymer in an extruder to form a dope, 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.,
• the invention relates to a process for producing the polyketone fibers described above, comprising the following measures:
• thermoplastic aliphatic polyketone and polyolefin, polyester, polyurethane, polyphenylene sulfide,
• step 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.,
• the invention relates to a further process for the preparation of the polyketone fibers described above comprising the following measures:
• thermoplastic aliphatic polyketone in a first extruder
• Polyester polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene in a second extruder, ii) extruding the first dope from step ia) and the second dope from step i) a nozzle plate having one or more spinning capillaries, so that each spinning capillary is flowed through by the first spinning mass and by the second spinning mass, the temperature of the first and second spinning masses being on the exit side of the spinning capillary (n) in the range of 200 to 300 ° C. , preferably from 220 to 260 ° C,
• the invention also relates to a process for the preparation of the polyketone fibers described above comprising the following measures: i) mixing thermoplastic aliphatic polyketone with a masterbatch comprising sterically hindered phenol and polysiloxane particles and / or from poly (meth) acrylate particles in an extruder to form a dope,
• step ii) extruding the spinning mass from step i) through a die plate having one or more spinning capillaries, the temperature of the spinning mass at the exit side of the spinning capillary (s) being in the range from 200 to 300 ° C., preferably from 220 to 260 ° C.
• Withdrawal speed in the range of 1 to 20 m / min, in particular from 5 to 50 m / min, preferably with a choice of the ratio of take-off speed to
• the invention relates to a process for producing the polyketone fibers described above, comprising the following measures:
• thermoplastic aliphatic polyketone with polysiloxane particles and / or poly (meth) acrylate particles in an extruder to give a dope
• step ii) extruding the spinning mass from step i) through a die plate with one or more spinning capillaries, wherein the temperature of the spinning mass on the exit side of the spinning capillary (s) is in the range from 200 to 300 ° C, preferably from 220 to 260 Stripping the formed filament with a
• Take-off speed in the range of 1 to 120 m / min, in particular from 5 to 50 m / min, preferably with the choice of the ratio of take-off speed to
• the fibers according to the invention 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
• 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
• Further uses are the use as fluidization belts, as process belts for the board industry, as conveyor belts and as process belts in the production of nonwovens, such as spunbond, meltblown, airlaid, wetlaid,
• 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.
• the fibers according to the invention are subjected to various stabilizers, e.g. Antioxidants to
• 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 100% as a deficit and / or as a so-called interchange (alternately the said
• Monofilament alternating with e.g. Polyamide, polyester or polyphenylene sulfide monofilaments).
• the aliphatic polyketone causes a significant reduction in the sliding friction and thus a significant
• the monofilament according to the invention is more resistant to abrasion than comparable monofilaments of polyethylene terephthalate, polybutylene terephthalate or polycyclohexane terephthalate or aus
• the fibers according to the invention are particularly preferably used in the form of filtration fabrics or knitted fabrics as support for
• Wide mesh membranes with high dimensional stability e.g.
• the fibers of the invention are well suited for the production of conveyor belts, in which a combination of dimensional stability and good sliding properties is required.
• Another preferred field of application of the fibers according to the invention is their use in brushes, in particular in toothbrushes.
• the fibers according to the invention are generally used in the form of bristles.
• the sheath polymers were of the M630A type having a melting point (according to ASTM D3418) of 222 ° C. or alternatively a low melting variant, such as the M410F type having a melting point (according to ASTM D3418) of 199 ° C. or as Type M620A with a melting point (according to ASTM D3418) of 207 ° C.
• the core polymers were, for example, a semi-crystalline PET (polyetheylene terephthalate) having a melting point of 254 ° C. or a polycarbonate (such as Makroion 2456 from Covestro) or a
• high melting point aliphatic polyketone (type M630A from Hyosung) or a blend of these components.
• Example 1 Combination of two commercially available aliphatic polyketones, a higher melting core type M630A from Hyosung Polyketone and a low melting in the shell type M410F from Hyosung Polyketone.
• both components were coextruded in one production step.
• the core / shell ratio can be adjusted, which was 70/30 here.
• the monofilament was stretched several times under the influence of temperature.
• the total draw ratio was 1: 3.7.
• tissue structures have, for example, increased shear stability. Furthermore, such crosslinked structures show thickening at the crossing points. This property is due to positive
• PET Stabilized polyethylene terephthalate
• Such a monofilament was coextruded in one production step.
• the core / shell ratio can be adjusted, which was 70/30 here.
• the monofilament was stretched several times under the influence of temperature.
• the total draw ratio was 1: 4.3
• the combination of PET and aliphatic polyketone in a monofilament combines the usual properties of PET with the surface properties of polyketone.
• tissue structures can be produced, which have a significantly reduced coefficient of friction and thus can lead to energy savings when used for example in conveyor belts.
• the advantage of the PET core results from the analogous processing properties of the monofilament in the Webe process (eg identical
• Aliphatic polyketone type M630A from Hyosung Polyketone was used as the matrix polymer.
• 1.0% by weight of polysiloxane beads - type PMSQ E + 580 from Coating Products - having an average diameter of 8 ⁇ m were dispersed in the matrix polymer.
• the monofilament obtained has the following properties: Unit value
• the matrix polymer used was aliphatic polyketone type M630A from Hyosung Polyketone.
• the second polymer component used was a liquid-crystal polymer (LCP) -polyester of hydroxybenzoic acid and hydroxynaphthalene.
• carboxylic acid type Vectra A950 from Ticona added to 7%.
• the monofilament obtained showed the following properties:
• Aliphatic polyketone type M630A from Hyosung Polyketone was used at 100%.
• the polyketone was extruded, spun and stretched several times under the action of temperature.

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