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EP0665323A2 - Preparation containing aramide fibers and their use - Google Patents

Preparation containing aramide fibers and their use Download PDF

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Publication number
EP0665323A2
EP0665323A2 EP95100370A EP95100370A EP0665323A2 EP 0665323 A2 EP0665323 A2 EP 0665323A2 EP 95100370 A EP95100370 A EP 95100370A EP 95100370 A EP95100370 A EP 95100370A EP 0665323 A2 EP0665323 A2 EP 0665323A2
Authority
EP
European Patent Office
Prior art keywords
aramid fiber
alkyl
fiber according
mono
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95100370A
Other languages
German (de)
French (fr)
Other versions
EP0665323A3 (en
Inventor
Gerhard Stein
Richard Dr. Neuert
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Hoechst AG
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Hoechst AG
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Filing date
Publication date
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Publication of EP0665323A2 publication Critical patent/EP0665323A2/en
Publication of EP0665323A3 publication Critical patent/EP0665323A3/en
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D04H1/4342—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • the present invention relates to aramid fibers coated with a selected preparation and the use of these fibers.
  • Aromatic polyamides - also known as aramids - are known fiber-forming materials with high chemical resistance. Aramid fibers are characterized above all by good mechanical properties, such as high strength and modulus.
  • aramid fibers are usually loaded with so-called preparations in order to improve the processing properties in post-treatment or further processing.
  • preparation systems for aramid fibers are described in WO-A-92-15,747, EP-A-416,486, EP-A-423,703, JP-A-49-62,722, JP-A-51-88,798 and JP-A-58- 46,179 as well as in Research Disclosures 219,001 and 195,028.
  • the fibers treated according to the invention are notable for good thread closure and good antistatic properties of the individual filaments. Preparations are made available that have a low surface or interfacial tension and a low intrinsic color. With the preparations to be used according to the invention, uniform wetting and distribution on the fiber surface is made possible, thread / metal friction is significantly reduced and processing at elevated temperatures, for example at temperatures up to 200 ° C., is made possible.
  • the preparation system according to the invention is characterized by good biodegradability; This enables preparations to be made that are more than 80% biodegradable in accordance with the 28th VwV of the WRMG (Detergents and Cleaning Agents Act).
  • the preparation to be used according to the invention is applied to the aramid fibers in the amount adapted to the particular application. This is usually an amount of 0.2 to 4% by weight, preferably 0.5 to 2% by weight, based on the amount of fiber.
  • aramid fiber preparations In addition to these components A) to C), other constituents customary for preparations can also occur in the aramid fiber preparations according to the invention. Examples of this are corrosion inhibitors, coloring components such as pigments, biocides and preservatives.
  • Component A) can be any anionic antistatic if it contains phosphoric acid ester and / or phosphonic acid ester groups.
  • salts of phosphoric acid esters with monohydric alcohols in particular aliphatic alcohols
  • salts of phosphonic acid esters with monohydric alcohols in particular alkyl or arylphosphonic acid esters with aliphatic alcohols.
  • the aliphatic alcohols which can be used to prepare the phosphoric acid esters or phosphonic acid esters are fatty alcohols which, if appropriate, can also be mono- or polyethylenically unsaturated, in particular aliphatic alcohols having 10 to 20 carbon atoms, such as decanol, dodecanol, tridecanol , Tetradecanol, hexadecanol, octadecanol or eicosanol.
  • compounds which differ from polyalkylene oxides such as polyethylene oxide, polypropylene oxide or polybutylene oxide, can also be used as monohydric alcohols. deduce. The number of repeating alkylene oxide units can be up to 10. Examples of such compounds can be found in EP-A-423,703.
  • Preferred as component A) are salts of a mono- or dialkylphosphoric acid ester, salts of a mono- or diarylphosphoric acid ester, salts of an alkylphosphonic acid ester, salts of an arylphosphonic acid ester or mixtures of these compounds.
  • the salts can be compounds with any cations as counterions.
  • preferred cations are alkali, alkaline earth or quaternary ammonium ions, in particular Na+, K+, diethanolammonium and triethanolammonium.
  • the alkyl radicals in the mono- or diphosphoric acid esters or in the phosphonic acid esters can be any alkyl radicals which can be straight-chain or branched. These are usually alkyl radicals with 1-22 carbon atoms. Examples of any alkyl radicals are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or behenyl. Ethylenically unsaturated residues are also possible.
  • residues derived from polyalkylene oxides can be, for example, residues of the formulas (CH3-CH2-CH2-O) - (CH2-CH2-CH2-O) s - or in particular (CH3-CH2-O) - (CH2-CH2-O) t - act in which s and t are integers between 1 and 9.
  • the phosphoric or phosphonic acid esters particularly preferably have at least one C8-C20-alkyl radical.
  • the aryl radicals in the mono- or diphosphoric acid esters or in the phosphonic acid esters can be any aromatic radicals, preferably aromatic hydrocarbon radicals, in particular phenyl.
  • the aryl radicals can also have one or two inert substituents, for example alkyl radicals or halogen atoms.
  • the alkyl and aryl residues can occur simultaneously within one molecule.
  • Particularly preferred components A) are alkali metal salts, in particular sodium or potassium salts, of alkylphosphonic acid alkyl esters or in particular of mono- or dialkylphosphoric acid esters.
  • alkali metal salts in particular sodium or potassium salts
  • alkylphosphonic acid alkyl esters or in particular of mono- or dialkylphosphoric acid esters.
  • examples of such compounds are the products R Silastol NZ, from Schill and Seilacher GmbH & Co., R Tallopol EM 5198 from Chemische Fabrik Stockhausen GmbH or R Leomin AN from Hoechst AG.
  • Component B) of the preparations to be used according to the invention is a special polyethylene glycol ether ester.
  • R1 can be any alkyl or alkenyl group.
  • the alkenyl groups can be any alkenyl radicals which can be straight-chain or branched. These are usually alkenyl radicals with 2-20 carbon atoms. Examples of any alkenyl radicals are ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl or octadecenyl.
  • R1 is C12-C20 alkyl is particularly preferred.
  • R2 can be hydrogen or any alkyl group.
  • R2 is preferably methyl.
  • Component C) of the preparations to be used according to the invention is a special polyethylene glycol ether, which may optionally also have polyproylene glycol and / or polybutylene glycol units R3 can be any alkyl or alkenyl group or the di-, tri- or tetravalent radical of an optionally ethylenically unsaturated aliphatic alcohol.
  • Examples of possible alkyl groups R3 are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.
  • polyhydric alcohols from which R3 can be derived are glycol, glycerin, trimethylolpropane and penthaerithritol.
  • R3 C12-C20-alkyl is particularly preferred.
  • R4 is usually a polyethylene glycol residue; in the case of trihydric and tetravalent alcohol residues R3, polybutylene glycol residues or preferably polypropylene glycol residues can additionally be present in the molecule.
  • R5 can be any alkyl group.
  • Examples of possible alkyl groups R5 are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.
  • R5 is preferably methyl.
  • the fiber according to the invention can consist of any aramids. These can be aramids which are essentially composed of meta-aromatic monomers.
  • An example of compounds of this type is poly (meta-phenylene-isophthalamide).
  • the fiber-forming material is preferably aramids, which are composed to a substantial extent of para-aromatic monomers. Some of these aramids are not soluble in organic solvents and are therefore usually spun from sulfuric acid.
  • An example of compounds of this type is poly (para-phenylene-terephthalamide).
  • Another preferred group of this type is soluble in organic solvents, especially in polar aprotic solvents.
  • soluble aromatic polyamide is understood to mean an aromatic polyamide that has a solubility in N-methylpyrrolidone of at least 50 g / l at 25 ° C.
  • the polar aprotic organic solvent preferably contains at least one solvent of the amide type, such as, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethylene urea, N, N, N ', N'-tetramethyl maleic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N'-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methylformamide, N, N '-Dimethylpropyleneurea.
  • amide type such as, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethylene
  • the preferred organic solvents for the process according to the invention are N-methyl-2-pyrrolidone, N, N-dimethylacetamide and a mixture of these compounds.
  • Aromatic polyamides are preferably used which are soluble in polar aprotic organic solvents with the formation of isotropic solutions and which have at least two, in particular three different recurring structural units which differ in the diamine units.
  • radicals mean divalent aromatic radicals whose valence bonds are in a para- or in a comparable coaxial or parallel position to one another, they are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynuclear.
  • heterocyclic-aromatic radicals these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.
  • Polynuclear aromatic radicals can be condensed with one another or linearly connected to one another via C-C bonds or via -CO-NH groups.
  • valence bonds which are in a coaxial or parallel position, are directed in opposite directions.
  • An example of coaxial, oppositely directed bonds are the biphenyl-4,4'-ene bonds.
  • An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.
  • Examples of preferred divalent aromatic radicals are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.
  • radicals mean divalent aromatic radicals whose valence bonds are in a meta- or in a comparable angled position to one another, then these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear.
  • heterocyclic-aromatic radicals these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.
  • Polynuclear aromatic radicals can be condensed with one another or via C-C bonds or via bridging groups, e.g. -O-, -CH2-, -S-, -CO- or -SO2- be connected to each other.
  • Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.
  • Smaller proportions for example up to 5 mol% of the monomer units, based on the polymer, can be aliphatic or cycloaliphatic in nature, for example alkylene or cycloalkylene units.
  • Alkylene radicals are to be understood as meaning branched and in particular straight-chain alkylene, for example alkylene with two to four carbon atoms, in particular ethylene.
  • Cycloalkylene radicals are, for example, radicals having five to eight carbon atoms, in particular cycloalkylene.
  • substituents are alkyl, alkoxy or halogen.
  • Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.
  • Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy with one to six carbon atoms, in particular methoxy.
  • radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.
  • Aromatic polyamides based on unsubstituted radicals are preferably used.
  • Terephthalic acid units are preferably used as the dicarboxylic acid unit in the aromatic polyamides containing the recurring structural units of the formulas III, IV and, if appropriate, V.
  • Examples of preferred diamine combinations on which these preferred recurring structural units of the formulas III, IV and V are based are 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro-, 3,3'-dimethyl- or 3 , 3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,3'-dichloro-, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 4,4'-diaminobenzanilide; and 1,4-phenylenediamine
  • Aramides which are derived from such diamine combinations and which can preferably be used according to the present invention are in the EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860.
  • aromatic polyamides to be used according to the invention are known per se and can be produced by processes known per se.
  • Ar 1 is a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position
  • Ar 2 is a divalent one or represents a polynuclear aromatic radical, the free valences of which are in the p-position or in a parallel or coaxial position comparable to this position
  • Ar3 represents a radical of the formula VI -Ar5-X-Ar6- (VI), wherein Ar5 and Ar6 independently of one another represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, or in which Ar6 additionally a divalent mono- or polynuclear aromatic radical represents whose free valences are in the meta position or in an angular position comparable to each other, X is a group of the formula -O-, -S-, -SO2-, -
  • fiber is to be understood in its broadest meaning within the scope of this invention; this includes, for example, continuous fibers (filaments), such as mono- or multifilaments, or staple fibers or pulp.
  • the aramid fibers to be used according to the invention can be produced by processes known per se, as described, for example, in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860 are.
  • the preparation can be applied directly after the threads have been spun out or in the aftertreatment.
  • the application can be carried out by means of known devices, such as dipping, preparation rolls or by spraying.
  • the aramid fibers treated according to the invention can have an organic or inorganic stretching preparation applied to them.
  • the aramid fibers according to the invention are notable for excellent mechanical properties, such as high tear strengths and initial moduli and low elongation at break, and also for the above-mentioned favorable application and processing properties.
  • the fibers of the invention preferably have single filament titers of greater than or equal to 1.0 dtex, in particular from 1 to 20 dtex.
  • the tensile strength of the fibers according to the invention is preferably 140 to 290 cN / tex.
  • the initial modulus, based on 100% elongation, of the fibers according to the invention is preferably 40 to 130 N / tex.
  • the cross-sectional shape of the individual filaments of the fibers according to the invention can be any, for example triangular, tri-or multilobal or in particular elliptical or round.
  • the fibers according to the invention which have excellent mechanical and thermal properties and are notable for high stretchability, can be processed in various ways and used industrially.
  • the aramid fibers according to the invention can be used in particular in the production of textile fabrics for interlacing, twisting, braiding or folding.
  • the aramid fibers according to the invention are preferably used in knitting or weaving.
  • the invention also relates to the use for these purposes.
  • the aramid fibers according to the invention can be processed in particular to give woven fabrics, knitted fabrics, laid fabrics, wickerwork or nonwovens.
  • the preparation-containing aramid fibers according to the invention are distinguished by a number of advantageous properties.
  • the water vapor volatility of the preparations according to the invention was less than 10% at 102 ° C., whereas conventional preparations have water vapor volatilities of up to 25%.
  • the abrasion of the preparations according to the invention e.g. was very slight and dusty when twisted; the abrasion was easily removed and did not form a sticky structure on the deflection elements.
  • An improvement of around 50% was found compared to conventional systems.
  • the thread closure or the transverse adhesion between the filaments of the aramid fibers prepared according to the invention is about 10% higher than in conventional systems.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

Beschrieben werden Aramidfasern mit einer Präparation enthaltend die Bestandteile A) anionisches Antistatikum auf der Basis von Phosphorsäureestern und/oder Phosphonsäureestern, B) Verbindung der Formel I R¹-COO-(CH2-CH2-O-)x-R² (I), und C) Verbindung der Formel II R³-O-(R<4>-O)y-R<5> (II), worin R¹ Alkyl oder Alkenyl bedeutet, x eine ganze Zahl von 2 bis 20, vorzugsweise 3-15 darstellt, und R² Wasserstoff oder Alkyl ist, R³ Alkyl oder Alkenyl bedeutet, y eine ganze Zahl von 1 bis 8 darstellt, R<4> Ethylen ist oder, falls y 2, 3 oder 4 bedeutet, ein Teil der Reste R<4> auch Propylen oder Butylen sein kann, und R<5> Alkyl bedeutet. Die Aramidfasern lassen sich insbesondere bei der Herstellung von textilen Flächengebilden beim Verwirbeln, Zwirnen, Flechten oder Fachen einsetzen.Aramid fibers are described with a preparation containing the components A) anionic antistatic based on phosphoric acid esters and / or phosphonic acid esters, B) compound of the formula I R¹-COO- (CH2-CH2-O-) x-R² (I), and C ) Compound of the formula II R³-O- (R <4 -O) yR <5 (II), in which R¹ is alkyl or alkenyl, x represents an integer from 2 to 20, preferably 3-15, and R² is hydrogen or is alkyl, R³ is alkyl or alkenyl, y represents an integer from 1 to 8, R 4 is ethylene or, if y represents 2, 3 or 4, part of the radicals R 4 may also be propylene or butylene can, and R 5 denotes alkyl. The aramid fibers can be used in particular in the manufacture of textile fabrics by interlacing, twisting, braiding or folding.

Description

Die vorliegende Erfindung betrifft Aramidfasern, die mit einer ausgewählten Präparation beschichtet sind, sowie die Verwendung dieser Fasern.The present invention relates to aramid fibers coated with a selected preparation and the use of these fibers.

Aromatische Polyamide - auch Aramide genannt - sind bekannte faserbildendene Werkstoffe hoher Chemikalienrestistenz. Aramidfasern zeichnen sich vor allem durch gute mechanische Eigenschaften, wie hohe Festigkeiten und Moduli, aus.Aromatic polyamides - also known as aramids - are known fiber-forming materials with high chemical resistance. Aramid fibers are characterized above all by good mechanical properties, such as high strength and modulus.

Aramidfasern werden -wie andere Fasern auch - üblicherweise mit sogenannten Präparationen beaufschlagt, um die Verarbeitungseigenschaften in der Nachbehandlung oder Weiterbearbeitung zu verbessern. Beispiele für Präparationssysteme für Aramidfasern sind in den WO-A-92-15,747, EP-A-416,486, EP-A-423,703, JP-A-49-62,722, JP-A-51-88,798 und JP-A-58-46,179 sowie in den Research Disclosures 219,001 und 195,028 zu finden.Like other fibers, aramid fibers are usually loaded with so-called preparations in order to improve the processing properties in post-treatment or further processing. Examples of preparation systems for aramid fibers are described in WO-A-92-15,747, EP-A-416,486, EP-A-423,703, JP-A-49-62,722, JP-A-51-88,798 and JP-A-58- 46,179 as well as in Research Disclosures 219,001 and 195,028.

Es wurde jetzt gefunden, daß ausgewählte Präparationen Aramidfasern ausgezeichnete Eigenschaften in der Weiterverarbeitung verleihen. Die erfindungsgemäß behandelten Fasern zeichnen sich durch einen guten Fadenschluß und eine gute Antistatik der einzelnen Filamente aus. Es werden Präparationen zur Verfügung gestellt, die eine geringe Oberflächen- bzw. Grenzflächenspannung sowie eine geringe Eigenfarbe aufweisen. Mit den erfindungsgemäße einzusetzenden Präparationen wird eine gleichmäßige Benetzung und Verteilung auf der Faseroberfläche ermöglicht, die Faden-/Metallreibung signifikant herabgesetzt und eine Verarbeitung bei erhöhten Temperaturen, beispielsweise bei Temperaturen bis zu 200 °C, ermöglicht.It has now been found that selected preparations give aramid fibers excellent properties in further processing. The fibers treated according to the invention are notable for good thread closure and good antistatic properties of the individual filaments. Preparations are made available that have a low surface or interfacial tension and a low intrinsic color. With the preparations to be used according to the invention, uniform wetting and distribution on the fiber surface is made possible, thread / metal friction is significantly reduced and processing at elevated temperatures, for example at temperatures up to 200 ° C., is made possible.

Das erfindungsgemäße Präparationssystem zeichnet sich durch gute biologische Abbaubarkeit aus; so lassen sich Präparationen herstellen, die zu mehr als 80 % biologisch abbaubar sind im Sinne der 28. VwV des WRMG (Wasch- und Reinigungsmittel Gesetzes).The preparation system according to the invention is characterized by good biodegradability; This enables preparations to be made that are more than 80% biodegradable in accordance with the 28th VwV of the WRMG (Detergents and Cleaning Agents Act).

Die vorliegende Erfindung betrifft Aramidfasern mit einer Präparation enthaltend die Bestandteile

  • A) anionisches Antistatikum auf der Basis von Phosphorsäureestern und/oder Phosphonsäureestern,
  • B) Verbindung der Formel I



            R¹-COO-(CH₂-CH₂-O-)x-R²   (I),



    und
  • C) Verbindung der Formel II



            R³-O-(R⁴-O)y-R⁵   (II),



worin R¹ Alkyl oder Alkenyl bedeutet, x eine ganze Zahl von 2 bis 20, vorzugsweise 3-15 darstellt, und R² Wasserstoff oder Alkyl st,
R³ Alkyl oder Alkenyl bedeutet, y eine ganze Zahl von 1 bis 8 darstellt,
R⁴ Ethylen ist oder, falls y 2, 3 oder 4 bedeutet, ein Teil der Reste R⁴ auch Propylen oder Butylen sein kann, und
R⁵ Alkyl bedeutet, insbesondere Methyl.The present invention relates to aramid fibers with a preparation containing the components
  • A) anionic antistatic based on phosphoric acid esters and / or phosphonic acid esters,
  • B) Compound of formula I.



    R¹-COO- (CH₂-CH₂-O-) x -R² (I),



    and
  • C) Compound of formula II



    R³-O- (R⁴-O) y -R⁵ (II),



wherein R¹ is alkyl or alkenyl, x represents an integer from 2 to 20, preferably 3-15, and R² is hydrogen or alkyl,
R³ denotes alkyl or alkenyl, y represents an integer from 1 to 8,
R⁴ is ethylene or, if y is 2, 3 or 4, part of the radicals R⁴ can also be propylene or butylene, and
R⁵ means alkyl, especially methyl.

Die erfindungsgemäß einzusetzende Präparation wird in der dem jeweiligen Anwendungszweck angepaßten Menge auf die Aramidfasern aufgebracht. Üblicherweise handelt es sich dabei um Mengen von 0,2 bis 4 Gew.%, vorzugsweise 0,5 bis 2 Gew.%, bezogen auf die Menge der Faser.The preparation to be used according to the invention is applied to the aramid fibers in the amount adapted to the particular application. This is usually an amount of 0.2 to 4% by weight, preferably 0.5 to 2% by weight, based on the amount of fiber.

Die Mengenanteile der einzelnen Komponenten A), B) und C) können innerhalb weiter Grenzen gewählt werden.

  • Komponente A) wird üblicherweise in Mengen von 10 bis 40 Gew.% eingesetzt.
  • Komponente B) wird üblicherweise in Mengen von 20 bis 60 Gew.% eingesetzt.
  • Komponente C) wird üblicherweise in Mengen von 10 bis 40 Gew.% eingesetzt.
The proportions of the individual components A), B) and C) can be selected within wide limits.
  • Component A) is usually used in amounts of 10 to 40% by weight.
  • Component B) is usually used in amounts of 20 to 60% by weight.
  • Component C) is usually used in amounts of 10 to 40% by weight.

Diese Mengenangaben beziehen sich dabei jeweils auf die Gesamtmenge aus Komponenten A), B) und C).These quantities refer to the total of components A), B) and C).

Neben diesen Komponenten A) bis C) können in den erfindungsgemäßen Aramidfaser-Präparationen noch weitere für Präparationen übliche Bestandteile auftreten. Beispiele dafür sind Korrosionsinhibitoren, farbgebende Komponenten, wie Pigmente, Biozide und Konservierungsmittel.In addition to these components A) to C), other constituents customary for preparations can also occur in the aramid fiber preparations according to the invention. Examples of this are corrosion inhibitors, coloring components such as pigments, biocides and preservatives.

Bei Komponente A) kann es sich um ein beliebiges anionisches Antistatikum handeln, sofern diese Phosporsäureester- und/oder Phosphonsäureestergruppen enthält.Component A) can be any anionic antistatic if it contains phosphoric acid ester and / or phosphonic acid ester groups.

Beispiele dafür sind Salze von Phosphorsäureestern mit einwertigen Alkoholen, insbesondere aliphatischen Alkoholen oder Salze von Phosphonsäureestern mit einwertigen Alkoholen, insbesondere Alkyl- oder Arylphosphonsäureestern mit aliphatischen Alkoholen. Bei den aliphatischen Alkoholen, die zur Herstellung der Phosphorsäureester oder Phosphonsäureester eingesetzt werden können, handelt sich sich um Fettalkohole, die gegebenenfalls auch ein- oder mehrfach ethylenisch ungesättigt sein können, insbesondere um aliphatische Alkohole mit 10 bis 20 Kohlenstoffatomen, wie Decanol, Dodecanol, Tridecanol, Tetradecanol, Hexadecanol, Octadecanol oder Eicosanol. Desweiteren können als einwertige Alkohole auch Verbindungen eingesetzt werden, die sich von Polyalkylenoxiden, wie Polyethylenoxid, Polypropylenoxid oder Polybutylenoxid, ableiten. Die Anzahl der wiederkehrenden Alkylenoxydeinheiten kann dabei bis zu 10 betragen. Beispiele für derartige Verbindungen sind in der EP-A-423,703 zu finden.Examples of these are salts of phosphoric acid esters with monohydric alcohols, in particular aliphatic alcohols, or salts of phosphonic acid esters with monohydric alcohols, in particular alkyl or arylphosphonic acid esters with aliphatic alcohols. The aliphatic alcohols which can be used to prepare the phosphoric acid esters or phosphonic acid esters are fatty alcohols which, if appropriate, can also be mono- or polyethylenically unsaturated, in particular aliphatic alcohols having 10 to 20 carbon atoms, such as decanol, dodecanol, tridecanol , Tetradecanol, hexadecanol, octadecanol or eicosanol. Furthermore, compounds which differ from polyalkylene oxides, such as polyethylene oxide, polypropylene oxide or polybutylene oxide, can also be used as monohydric alcohols. deduce. The number of repeating alkylene oxide units can be up to 10. Examples of such compounds can be found in EP-A-423,703.

Bevorzugt als Komponente A) werden Salze eines Mono- oder Dialkylphosphorsäureesters, Salze eines Mono- oder Diarylphosphorsäureesters, Salze eines Alkylphosphonsäureesters, Salze eines Arylphosphonsäureesters oder Gemische dieser Verbindungen.Preferred as component A) are salts of a mono- or dialkylphosphoric acid ester, salts of a mono- or diarylphosphoric acid ester, salts of an alkylphosphonic acid ester, salts of an arylphosphonic acid ester or mixtures of these compounds.

Bei den Salzen kann es sich um Verbindungen mit beliebigen Kationen als Gegenion handeln. Beispiele für bevorzugte Kationen sind Alkali-, Erdalkali- oder quaternäre Ammoniumionen, insbesondere Na⁺, K⁺, Diethanolammonium und Triethanolammonium.The salts can be compounds with any cations as counterions. Examples of preferred cations are alkali, alkaline earth or quaternary ammonium ions, in particular Na⁺, K⁺, diethanolammonium and triethanolammonium.

Bei den Alkylresten in den Mono- oder Diphosphorsäureestern bzw. in den Phosphonsäureestern kann es sich um beliebige Alkylreste handeln, die geradkettig oder verzweigt sein können. Üblicherweise handelt es sich dabei um Alkylreste mit 1-22 Kohlenstoffatomen. Beispiele für irgendwelche Alkylreste sind Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl oder Behenyl. Es sind auch ethylenisch ungesättigte Reste möglich.The alkyl radicals in the mono- or diphosphoric acid esters or in the phosphonic acid esters can be any alkyl radicals which can be straight-chain or branched. These are usually alkyl radicals with 1-22 carbon atoms. Examples of any alkyl radicals are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or behenyl. Ethylenically unsaturated residues are also possible.

Bei den Resten, die sich von Polyalkylenoxiden ableiten, kann es sich beispielsweise um Reste der Formeln (CH₃-CH₂-CH₂-O)-(CH₂-CH₂-CH₂-O)s- oder insbesondere um (CH₃-CH₂-O)-(CH₂-CH₂-O)t- handeln, worin s und t ganze Zahlen zwischen 1 und 9 bedeuten.The residues derived from polyalkylene oxides can be, for example, residues of the formulas (CH₃-CH₂-CH₂-O) - (CH₂-CH₂-CH₂-O) s - or in particular (CH₃-CH₂-O) - (CH₂-CH₂-O) t - act in which s and t are integers between 1 and 9.

Besonders bevorzugt weisen die Phosphor- oder Phosphonsäureester mindestens einen C₈-C₂₀-Alkylrest auf.The phosphoric or phosphonic acid esters particularly preferably have at least one C₈-C₂₀-alkyl radical.

Bei den Arylresten in den Mono- oder Diphosphorsäureestern bzw. in den Phosphonsäureestern kann es sich um beliebige aromatische Reste handeln, vorzugsweise um aromatische Kohlenwasserstoffreste, insbesonder um Phenyl. Die Arylreste können auch ein oder zwei inerte Substituenten aufweisen, beispielsweise Alkylreste oder Halogenatome.The aryl radicals in the mono- or diphosphoric acid esters or in the phosphonic acid esters can be any aromatic radicals, preferably aromatic hydrocarbon radicals, in particular phenyl. The aryl radicals can also have one or two inert substituents, for example alkyl radicals or halogen atoms.

In den Phosphorsäureestern bzw. in den Phosphonsäureestern können die Alkyl- und Arylreste gleichzeitig innerhalb eines Moleküls auftreten.In the phosphoric acid esters or in the phosphonic acid esters, the alkyl and aryl residues can occur simultaneously within one molecule.

Besonders bevorzugte Komponenten A) sind Alkalisalze, insbesondere Natrium- oder Kaliumsalze, von Alkylphosphonsäurealkylestern oder insbesondere von Mono- oder Dialkylphosphorsäureestern. Beispiele für solche Verbindungen sind die Produkte RSilastol NZ, der Firma Schill und Seilacher GmbH & Co., RTallopol EM 5198 der Firma Chemische Fabrik Stockhausen GmbH oder RLeomin AN der Firma Hoechst AG.Particularly preferred components A) are alkali metal salts, in particular sodium or potassium salts, of alkylphosphonic acid alkyl esters or in particular of mono- or dialkylphosphoric acid esters. Examples of such compounds are the products R Silastol NZ, from Schill and Seilacher GmbH & Co., R Tallopol EM 5198 from Chemische Fabrik Stockhausen GmbH or R Leomin AN from Hoechst AG.

Komponente B) der erfindungsgemäß einzusetzenden Präparationen ist ein spezieller Polyethylenglykoletherester.Component B) of the preparations to be used according to the invention is a special polyethylene glycol ether ester.

Bei R¹ kann es sich um eine beliebige Alkyl- oder Alkenylgruppe handeln.R1 can be any alkyl or alkenyl group.

Beispiele für mögliche Alkylgruppen sind weiter oben bei der Beschreibung der Mono- oder Diphosphorsäureester bzw. der Phosphonsäureester aufgeführt.Examples of possible alkyl groups are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.

Bei den Alkenylgruppen kann es sich um beliebige Alkenylreste handeln, die geradkettig oder verzweigt sein können. Üblicherweise handelt es sich dabei um Alkenylreste mit 2-20 Kohlenstoffatomen. Beispiele für irgendwelche Alkenylreste sind Ethylen, Propenyl, Butenyl, Pentenyl, Hexenyl, Heptenyl, Octenyl, Nonenyl, Decenyl, Undecenyl, Dodecenyl, Tridecenyl, Tetradecenyl, Pentadecenyl, Hexadecenyl, Heptadecenyl oder Octadecenyl.The alkenyl groups can be any alkenyl radicals which can be straight-chain or branched. These are usually alkenyl radicals with 2-20 carbon atoms. Examples of any alkenyl radicals are ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl or octadecenyl.

Besonders bevorzugt ist R¹ C₁₂-C₂₀-Alkyl.R¹ is C₁₂-C₂₀ alkyl is particularly preferred.

Bei R² kann es sich um Wasserstoff oder um eine beliebige Alkylgruppe handeln.R² can be hydrogen or any alkyl group.

Beispiele für mögliche Alkylgruppen sind weiter oben bei der Beschreibung der Mono- oder Diphosphorsäureester bzw. der Phosphonsäureester aufgeführt.Examples of possible alkyl groups are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.

R² ist vorzugsweise Methyl.R² is preferably methyl.

Komponente C) der erfindungsgemäß einzusetzenden Präparationen ist ein spezieller Polyethylenglykolether, der gegebenenfalls zusätzlich Polyproylenglykol- und/oder Polybutylenglykoleinheiten aufweisen kann
Bei R³ kann es sich um eine beliebige Alkyl- oder Alkenylgruppe oder um den zwei-, drei- oder vierwertigen Rest eines gegebenenfalls ethylenisch ungesättigten aliphatischen Alkohols handeln.Component C) of the preparations to be used according to the invention is a special polyethylene glycol ether, which may optionally also have polyproylene glycol and / or polybutylene glycol units
R³ can be any alkyl or alkenyl group or the di-, tri- or tetravalent radical of an optionally ethylenically unsaturated aliphatic alcohol.

Beispiele für mögliche Alkylgruppen R³ sind weiter oben bei der Beschreibung der Mono- oder Diphosphorsäureester bzw. der Phosphonsäureester aufgeführt.Examples of possible alkyl groups R³ are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.

Beispiele für mögliche Alkylgruppen R³ sind weiter oben bei der Beschreibung von R¹ aufgeführt.Examples of possible alkyl groups R³ are listed above in the description of R¹.

Beispiele für mehrwertige Alkohole, von denen sich R³ ableiten kann sind Glycol, Glyzerin, Trimethylolpropan und Penthaerithrit.Examples of polyhydric alcohols from which R³ can be derived are glycol, glycerin, trimethylolpropane and penthaerithritol.

Besonders bevorzugt ist R³ C₁₂-C₂₀-Alkyl.R³ C₁₂-C₂₀-alkyl is particularly preferred.

Besonders bevorzugt leitet sich R³ von einem einwertigen Alkohol ab (y = 1).R³ is particularly preferably derived from a monohydric alcohol (y = 1).

Bei R⁴ handelt es sich üblicherweise um einen Polyethylenglycolrest; im Falle drei- und vierwertiger Alkoholreste R³ können zusätzlich Polybutylenglycolreste oder vorzugsweise Polypropylenglycolreste im Molekül vorhanden sein.R⁴ is usually a polyethylene glycol residue; in the case of trihydric and tetravalent alcohol residues R³, polybutylene glycol residues or preferably polypropylene glycol residues can additionally be present in the molecule.

Bei R⁵ kann es sich um eine beliebige Alkylgruppe handeln.R⁵ can be any alkyl group.

Beispiele für mögliche Alkylgruppen R⁵ sind weiter oben bei der Beschreibung der Mono- oder Diphosphorsäureester bzw. der Phosphonsäureester aufgeführt.Examples of possible alkyl groups R⁵ are listed above in the description of the mono- or diphosphoric acid esters or the phosphonic acid esters.

R⁵ ist vorzugsweise Methyl.R⁵ is preferably methyl.

Die erfindungsgemäße Faser kann aus beliebigen Aramiden bestehen. Dabei kann es sich um Aramide handeln, die im wesentlichen aus meta-aromatischen Monomeren aufgebaut sind. Ein Beispiel für Verbindungen dieses Typs ist Poly-(meta-phenylen-isophthalamid).The fiber according to the invention can consist of any aramids. These can be aramids which are essentially composed of meta-aromatic monomers. An example of compounds of this type is poly (meta-phenylene-isophthalamide).

Bei dem faserbildenden Material handelt es sich vorzugsweise um Aramide, die zu einem wesentlichen Anteil para-aromatischen Monomeren aufgebaut sind. Einige dieser Aramide sind in organischen Lösungsmitteln nicht löslich und werden daher üblicherweise aus Schwefelsäure versponnen. Ein Beispiel für Verbindungen dieses Typs ist Poly-(para-phenylen-terephthalamid).The fiber-forming material is preferably aramids, which are composed to a substantial extent of para-aromatic monomers. Some of these aramids are not soluble in organic solvents and are therefore usually spun from sulfuric acid. An example of compounds of this type is poly (para-phenylene-terephthalamide).

Eine Weitere bevorzugte Gruppe dieses Typs ist in organischen Lösungsmitteln, insbesondere in polaren aprotischen Lösungsmitteln, löslich.Another preferred group of this type is soluble in organic solvents, especially in polar aprotic solvents.

Unter löslichem aromatischen Polyamid ist im Rahmen dieser Erfindung ein aromatisches Polyamid zu verstehen, daß bei 25°C eine Löslichkeit in N-Methylpyrrolidon von mindestens 50 g/l aufweist.In the context of this invention, soluble aromatic polyamide is understood to mean an aromatic polyamide that has a solubility in N-methylpyrrolidone of at least 50 g / l at 25 ° C.

Vorzugsweise enthält das polare aprotische organische Lösungsmittel zumindest ein Lösungsmittel vom Amidtyp, wie z.B. N-Methyl-2-pyrrolidon, N,N-Dimethylacetamid, Tetramethylharnstoff, N-Methyl-2-piperidon, N,N'-Dimethylethylenharnstoff, N,N,N',N'-Tetramethylmaleinsäureamid, N-Methylcaprolactam, N-Acetylpyrrolidin, N,N-Diethylacetamid, N-Ethyl-2-pyrrolidon, N,N'-Dimethylpropionsäureamid, N,N-Dimethylisobutylamid, N-Methylformamid, N,N'-Dimethylpropylenharnstoff.The polar aprotic organic solvent preferably contains at least one solvent of the amide type, such as, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethylene urea, N, N, N ', N'-tetramethyl maleic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N'-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methylformamide, N, N '-Dimethylpropyleneurea.

Für das erfindungsgemäße Verfahren sind die bevorzugten organischen Lösungsmittel N-Methyl-2-pyrrolidon, N,N-Dimethylacetamid und eine Mischung dieser Verbindungen.The preferred organic solvents for the process according to the invention are N-methyl-2-pyrrolidone, N, N-dimethylacetamide and a mixture of these compounds.

Bevorzugt setzt man aromatische Polyamide ein, die in polaren aprotischen organischen Lösungsmitteln unter der Ausbildung isotroper Lösungen löslich sind und die mindestens zwei, insbesondere drei verschiedene sich in den Diamineinheiten unterscheidende wiederkehrende Struktureinheiten aufweisen.Aromatic polyamides are preferably used which are soluble in polar aprotic organic solvents with the formation of isotropic solutions and which have at least two, in particular three different recurring structural units which differ in the diamine units.

Dabei handelt es sich insbesondere um Polymere, die die wiederkehrenden Struktureinheiten der Formeln III, IV und gegebenenfalls V aufweisen



        -OC-Ar¹-CO-NH-Ar²-NH-   (III),





        -OC-Ar¹-CO-NH-Ar³-NH-   (IV),





        -OC-Ar¹-CO-NH-Ar⁴-NH-   (V),



worin Ar¹, Ar², Ar³ und Ar⁴ unabhängig voneinander einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellen, dessen freie Valenzen sich in para-Stellung oder in meta-Stellung oder in einer zu diesen Stellungen vergleichbaren parallelen, koaxialen oder gewinkelten Stellung zueinander befinden, und
Ar², Ar³ und gegbenenfalls Ar⁴ im Einzelfall jeweils unterschiedliche im Rahmen der gegebenen Definitionen liegende Bedeutungen annehmen, und wobei die jeweiligen dem Polymeren zugrundeliegenden Monomerbausteine so ausgewählt werden, daß sich ein in organischen Lösungsmitteln lösliches und isotrope Lösungen bildendes aromatisches Polyamid ergibt.These are in particular polymers which have the recurring structural units of the formulas III, IV and, if appropriate, V.



-OC-Ar¹-CO-NH-Ar²-NH- (III),





-OC-Ar¹-CO-NH-Ar³-NH- (IV),





-OC-Ar¹-CO-NH-Ar⁴-NH- (V),



wherein Ar¹, Ar², Ar³ and Ar⁴ independently represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para-position or in the meta-position or in a parallel, coaxial or angled position comparable to these positions, and
Ar², Ar³ and optionally Ar⁴ in each case assume different meanings within the scope of the given definitions, and the respective monomer units on which the polymer is based are selected such that an aromatic polyamide which forms soluble and isotropic solutions in organic solvents is obtained.

Bedeuten irgendwelche Reste zweiwertige aromatische Reste, deren Valenzbindungen sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, so handelt es sich dabei um ein- oder mehrkernige aromatische Kohlenwasserstoffreste oder um heterocyclisch-aromatische Reste, die ein- oder mehrkernig sein können. Im Falle von heterocyclisch-aromatischen Resten weisen diese insbesondere ein oder zwei Sauerstoff-, Stickstoff- oder Schwefelatome im aromatischen Kern auf.If any radicals mean divalent aromatic radicals whose valence bonds are in a para- or in a comparable coaxial or parallel position to one another, they are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be mononuclear or polynuclear. In the case of heterocyclic-aromatic radicals, these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.

Mehrkernige aromatische Reste können miteinander kondensiert sein oder über C-C-Bindungen oder über -CO-NH- Gruppen linear miteinander verbunden sein.Polynuclear aromatic radicals can be condensed with one another or linearly connected to one another via C-C bonds or via -CO-NH groups.

Die Valenzbindungen, die in koaxialer oder parallel zueinander befindlicher Stellung stehen, sind entgegengesetzt gerichtet. Ein Beispiel für koaxiale, entgegengesetzt gerichtete Bindungen sind die Biphenyl-4,4'-en-Bindungen. Ein Beispiel für parallel, entgegegesetzt gerichtete Bindungen sind die Naphthalin-1,5- oder -2,6-Bindungen, während die Naphthalin-1,8-Bindungen parallel gleichgerichtet sind.The valence bonds, which are in a coaxial or parallel position, are directed in opposite directions. An example of coaxial, oppositely directed bonds are the biphenyl-4,4'-ene bonds. An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.

Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, sind einkernige aromatische Reste mit zueinander para-ständigen freien Valenzen, insbesondere 1,4-Phenylen oder zweikernige kondensierte aromatische Reste mit parallelen, entgegengesetzt gerichteten Bindungen, insbesondere 1,4-, 1,5- und 2,6-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit koaxialen, entgegengesetzt gerichteten Bindungen, insbesondere 4,4'-Biphenylen.Examples of preferred divalent aromatic radicals, the valence bonds of which are in para- or in a comparable coaxial or parallel position to one another, are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.

Bedeuten irgendwelche Reste zweiwertige aromatische Reste, deren Valenzbindungen sich in meta- oder in vergleichbarer gewinkelter Position zueinander befinden, so handelt es sich dabei um ein- oder mehrkernige aromatische Kohlenwasserstoffreste oder um heterocyclisch-aromatische Reste, die ein- oder mehrkernig sein können. Im Falle von heterocyclisch-aromatischen Resten weisen diese insbesondere ein oder zwei Sauerstoff-, Stickstoff- oder Schwefelatome im aromatischen Kern auf.If any radicals mean divalent aromatic radicals whose valence bonds are in a meta- or in a comparable angled position to one another, then these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear. In the case of heterocyclic-aromatic radicals, these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.

Mehrkernige aromatische Reste können miteinander kondensiert sein oder über C-C-Bindungen oder über Brückengruppen, wie z.B. -O-, -CH₂-, -S-, -CO- oder -SO₂- miteinander verbunden sein.Polynuclear aromatic radicals can be condensed with one another or via C-C bonds or via bridging groups, e.g. -O-, -CH₂-, -S-, -CO- or -SO₂- be connected to each other.

Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in meta- oder in vergleichbarer gewinkelter Position zueinander befinden, sind einkernige aromatische Reste mit zueinander meta-ständigen freien Valenzen, insbesondere 1,3-Phenylen oder zweikernige kondensierte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 1,6- und 2,7-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 3,4'-Biphenylen.Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.

Geringere Anteile, beispielsweise bis zu 5 Mol % der Monomereinheiten, bezogen auf das Polymere, können aliphatischer oder cycloaliphatischer Natur sein, beispielsweise Alkylen- oder Cycloalkyleneinheiten darstellen.Smaller proportions, for example up to 5 mol% of the monomer units, based on the polymer, can be aliphatic or cycloaliphatic in nature, for example alkylene or cycloalkylene units.

Unter Alkylenresten ist verzweigtes und insbesondere geradkettiges Alkylen zu verstehen, beispielsweise Alkylen mit zwei bis vier Kohlenstoffatomen, insbesondere Ethylen.Alkylene radicals are to be understood as meaning branched and in particular straight-chain alkylene, for example alkylene with two to four carbon atoms, in particular ethylene.

Unter Cycloalkylenresten sind beispielsweise Reste mit fünf bis acht Kohlenstoffatomen zu verstehen, insbesondere Cycloalkylen.Cycloalkylene radicals are, for example, radicals having five to eight carbon atoms, in particular cycloalkylene.

Alle diese aliphatischen, cycloaliphatischen oder aromatischen Reste können mit inerten Gruppen substituiert sein. Darunter sind Substituenten zu verstehen, die die ins Auge gefaßte Anwendung nicht negativ beeinflussen.All of these aliphatic, cycloaliphatic or aromatic radicals can be substituted with inert groups. These are to be understood as substituents that do not negatively influence the envisaged application.

Beispiele für solche Substituenten sind Alkyl, Alkoxy oder Halogen.Examples of such substituents are alkyl, alkoxy or halogen.

Unter Alkylresten ist versweigtes und insbesondere geradkettiges Alkyl zu verstehen, beispielsweise Alkyl mit ein bis sechs Kohlenstoffatomen, insbesondere Methyl.Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.

Unter Alkoxyresten ist verzweigtes und insbesondere geradkettiges Alkoxy zu verstehen, beispielsweise Alkoxy mit ein bis sechs Kohlenstoffatomen, insbesondere Methoxy.Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy with one to six carbon atoms, in particular methoxy.

Bedeuten irgendwelche Reste Halogen, so handelt es sich dabei beispielsweise um Fluor, Brom oder insbesondere um Chlor.If any radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.

Bevorzugt verwendet aromatische Polyamide auf der Basis von unsubstituierten Resten.Aromatic polyamides based on unsubstituted radicals are preferably used.

Als Dicarbonsäureeinheit in den aromatischen Polyamiden enthaltend die wiederkehrenden Struktureinheiten der Formeln III, IV und gegebenenfalls V setzt man vorzugsweise Terephthalsäureeinheiten ein.Terephthalic acid units are preferably used as the dicarboxylic acid unit in the aromatic polyamides containing the recurring structural units of the formulas III, IV and, if appropriate, V.

Beispiele für bevorzugte Diaminkombinationen, die diesen bevorzugten wiederkehrenden Struktureinheiten der Formeln III, IV und V zugrundeliegen, sind 1,4-Phenylendiamin, 4,4'-Diaminodiphenylmethan und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 1,4-Bis-(aminophenoxy)-benzol und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 3,4'-Diaminodiphenylether und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 3,4'-Diaminodiphenylether und 4,4'-Diaminobenzanilid; sowie 1,4-Phenylendiamin, 1,4-Bis-(aminophenoxy)-benzol und 3,4'-Diaminodiphenylether.Examples of preferred diamine combinations on which these preferred recurring structural units of the formulas III, IV and V are based are 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro-, 3,3'-dimethyl- or 3 , 3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,3'-dichloro-, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 4,4'-diaminobenzanilide; and 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,4'-diaminodiphenyl ether.

Aramide, die sich von solchen Diaminkombinationen ableiten und die sich bevorzugt gemäß der vorliegenden Erfindung einsetzen lassen, sind in den EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 und EP-A-424,860 beschrieben.Aramides which are derived from such diamine combinations and which can preferably be used according to the present invention are in the EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860.

Die erfindungsgemäß einzusetzenden aromatischen Polyamide sind an sich bekannt und können mittels an sich bekannter Verfahren hergestellt werden.The aromatic polyamides to be used according to the invention are known per se and can be produced by processes known per se.

Von diesen bevorzugten Aramiden werden besonders diejenigen besonders bevorzugt, worin Ar¹ einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, Ar² einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in p-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, Ar³ einen Rest der Formel VI darstellt



        -Ar⁵-X-Ar⁶-   (VI),



worin Ar⁵ und Ar⁶ unabhängig voneinander einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellen, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, oder worin Ar⁶ zusätzlich einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in meta-Stellung oder in einer Zu dieser Stellung vergleichbaren gewinkelten Stellung zueinander befinden,
X eine Gruppe der Formel -O-, -S-, -SO₂-, -O-Phenylen-O- oder Alkylen ist, und worin
Ar⁴ eine der für Ar² oder Ar³ definierten Bedeutungen annimmt aber von dem jeweils gewählten Rest Ar² oder Ar³ eines Moleküls abweicht.Of these preferred aramids, those in which Ar 1 is a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, Ar 2 is a divalent one or represents a polynuclear aromatic radical, the free valences of which are in the p-position or in a parallel or coaxial position comparable to this position, Ar³ represents a radical of the formula VI



-Ar⁵-X-Ar⁶- (VI),



wherein Ar⁵ and Ar⁶ independently of one another represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, or in which Ar⁶ additionally a divalent mono- or polynuclear aromatic radical represents whose free valences are in the meta position or in an angular position comparable to each other,
X is a group of the formula -O-, -S-, -SO₂-, -O-phenylene-O- or alkylene, and wherein
Ar⁴ assumes one of the meanings defined for Ar² or Ar³ but deviates from the selected Ar² or Ar³ radical of a molecule.

Ganz besonders bevorzugt werden Aramide, worin Ar¹ 1,4-Phenylen ist, Ar² 1,4-Phenylen oder ein zweiwertiger Rest des 4,4'-Diaminobenzanilids ist, Ar⁵ und Ar⁶ 1,4-Phenylen darstellen, X -O-, -CH₂- oder -O-1,4-Phenylen-O- ist und Ar⁴ einen zweiwertigen Rest des 3,4'-Diaminodiphenylethers, 3,3'-Dichlorbenzidins, des 3,3'-Dimethylbenzidins oder des 3,3'-Dimethoxybenzidins darstellt.Aramides in which Ar¹ is 1,4-phenylene, Ar² is 1,4-phenylene or a divalent radical of 4,4'-diaminobenzanilide, Ar⁵ and Ar⁶ are 1,4-phenylene, X are -O-, - Is CH₂- or -O-1,4-phenylene-O- and Ar⁴ represents a divalent radical of 3,4'-diaminodiphenyl ether, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine or 3,3'-dimethoxybenzidine.

Der Begriff "Faser" ist im Rahmen dieser Erfindung in seiner breitesten Bedeutung zu verstehen; dazu zählen also zum Beispiel Endlosfasern (Filamente), wie Mono- oder Multifilamente, oder Stapelfasern oder Pulp.The term "fiber" is to be understood in its broadest meaning within the scope of this invention; this includes, for example, continuous fibers (filaments), such as mono- or multifilaments, or staple fibers or pulp.

Die Herstellung der erfindungsgemäß einzusetzenden Aramidfasern kann nach an sich bekannten Verfahren erfolgen, wie sie beispielsweise in den EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 und EP-A-424,860 beschrieben worden sind.The aramid fibers to be used according to the invention can be produced by processes known per se, as described, for example, in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860 are.

Das Aufbringen der Präparation kann direkt nach dem Ausspinnen der Fäden oder in der Nachbehandlung erfolgen.The preparation can be applied directly after the threads have been spun out or in the aftertreatment.

Das Aufbringen kann mittels bekannter Vorrichtungen, wie Tauchen, Präparationsrollen oder durch Aufsprühen erfolgen.The application can be carried out by means of known devices, such as dipping, preparation rolls or by spraying.

Die erfindungsgemäß behandelten Aramidfasern können mit einer organischen oder anorganischen Verstreckpräparation beaufschlagt sein.The aramid fibers treated according to the invention can have an organic or inorganic stretching preparation applied to them.

Die erfindungsgemäßen Aramidfasern zeichnen sich durch ausgezeichnete mechanische Eigenschaften, wie hohe Reißfestigkeiten und Anfangsmoduli und niedrige Reißdehnungen, sowie durch die oben erwähnten günstigen Anwendungs- und Weiterverarbeitungseigenschaften aus.The aramid fibers according to the invention are notable for excellent mechanical properties, such as high tear strengths and initial moduli and low elongation at break, and also for the above-mentioned favorable application and processing properties.

Die erfindungsgemäßen Fasern weisen vorzugsweise Einzelfilamenttiter von größer gleich 1,0 dtex, insbesondere von 1 bis 20 dtex, auf.The fibers of the invention preferably have single filament titers of greater than or equal to 1.0 dtex, in particular from 1 to 20 dtex.

Die Zugfestigkeit der erfindungsgemäßen Fasern beträgt vorzugsweise 140 bis 290 cN/tex.The tensile strength of the fibers according to the invention is preferably 140 to 290 cN / tex.

Der Anfangsmodul, bezogen auf 100 % Dehnung, der erfindungsgemäßen Fasern beträgt vorzugsweise 40 bis 130 N/tex.The initial modulus, based on 100% elongation, of the fibers according to the invention is preferably 40 to 130 N / tex.

Die Querschnittsform der Einzelfilamente der erfindungsgemäßen Fasern kann beliebig sein, beispielsweise dreieckig, tri- oder multilobal oder insbesondere elliptisch oder rund.The cross-sectional shape of the individual filaments of the fibers according to the invention can be any, for example triangular, tri-or multilobal or in particular elliptical or round.

Die erfindungsgemäßen Fasern, welche hervorragende mechanische und thermische Eigenschaften besitzen und sich durch eine hohe Verstreckbarkeit auszeichnen, können auf die verschiedenste Weise weiterverarbeitet uns industriell eingesetzt werden.The fibers according to the invention, which have excellent mechanical and thermal properties and are notable for high stretchability, can be processed in various ways and used industrially.

Die erfindungsgemäßen Aramidfasern lassen sich aufgrund ihres guten Fadenschlusses und ihrer hervorragenden Antistatikeigenschaften insbesondere bei der Herstellung von textilen Flächengebilden beim Verwirbeln, Zwirnen, Flechten oder Fachen einsetzen. Vorzugsweise werden die erfindungsgemäßen Aramidfasern beim Stricken oder Weben eingesetzt. Die Erfindung betrifft auch die Verwendung für diese Zwecke.Because of their good thread closure and their excellent antistatic properties, the aramid fibers according to the invention can be used in particular in the production of textile fabrics for interlacing, twisting, braiding or folding. The aramid fibers according to the invention are preferably used in knitting or weaving. The invention also relates to the use for these purposes.

Die erfindungsgemäßen Aramidfasern lassen sich insbesondere zu Geweben, Gestricken, Gelegen, Flechtwerken oder Vliesen verarbeiten.The aramid fibers according to the invention can be processed in particular to give woven fabrics, knitted fabrics, laid fabrics, wickerwork or nonwovens.

Wie bereits ausgeführt, zeichnen sich die erfindungsgemäßen präparationshaltigen Aramidfasern durch eine Reihe vorteilhafter Eigenschaften aus.As already stated, the preparation-containing aramid fibers according to the invention are distinguished by a number of advantageous properties.

Versuche haben gezeigt, daß die Temperaturflüchtigkeit der erfindungsgemäßen Präparationen im Bereich von 200-220°C weniger als 10 % betrug, während herkömmliche Präparationen Temperaturflüchtigkeiten bis zu 60 % aufweisen.Experiments have shown that the temperature volatility of the preparations according to the invention was less than 10% in the range from 200-220 ° C., whereas conventional preparations have temperature volatilities of up to 60%.

Desweiteren betrug die Wasserdampfflüchtigkeit der erfindungsgemäßen Präparationen bei 102°C weniger als 10 % während herkömmliche Präparationen Wasserdampfflüchtigkeiten von bis zu 25 % aufweisen.Furthermore, the water vapor volatility of the preparations according to the invention was less than 10% at 102 ° C., whereas conventional preparations have water vapor volatilities of up to 25%.

Ferner wies die Faden-/Metallreibung der erfindungsgemäßen Präparationen um 15-20 % niedrigere Werte auf als mit herkömmlichen Systemen erzielt wurden.Furthermore, the thread / metal friction of the preparations according to the invention was 15-20% lower than was achieved with conventional systems.

Zusätzlich wurde gefunden, daß der Abrieb der erfindungsgemäßen Präparationen z.B. beim Zwirnen sehr gering und staubförmig war; der Abrieb ließ sich leicht entfernen und bildete keinen klebrigen Aufbau auf den Umlenkorganen. Gegenüber herkömmlichen Systemen wurde eine um ca. 50 %ige Verbesserung festgestellt.In addition, it was found that the abrasion of the preparations according to the invention e.g. was very slight and dusty when twisted; the abrasion was easily removed and did not form a sticky structure on the deflection elements. An improvement of around 50% was found compared to conventional systems.

Außerdem wurde gefunden, daß der Fadenschluß bzw. die Querhaftung zwischen den Filamenten der erfindungsgemäßen präparierten Aramidfasern um ca. 10 % höher ist als bei herkömmlichen Systemen.In addition, it was found that the thread closure or the transverse adhesion between the filaments of the aramid fibers prepared according to the invention is about 10% higher than in conventional systems.

Claims (17)

Aramidfaser mit einer Präparation enthaltend die Bestandteile A) anionisches Antistatikum auf der Basis von Phosphorsäureestern und/oder Phosphonsäureestern, B) Verbindung der Formel I



        R¹-COO-(CH₂-CH₂-O-)x-R²   (I),



und C) Verbindung der Formel II



        R³-O-(R⁴-O)y-R⁵   (I),

worin
R¹ C₁-C₂₂-Alkyl oder C₂-C₂₂-Alkenyl bedeutet, x eine ganze Zahl von 2 bis 20, vorzugsweise 3-15 darstellt, und R² Wasserstoff oder C₁-C₂₂-Alkyl ist,
R³ C₁-C₂₂-Alkyl oder C₂-C₂₂-Alkenyl bedeutet, y eine ganze Zahl von 1 bis 8 darstellt,
R⁴ Ethylen ist oder, falls y 2, 3 oder 4 bedeutet, ein Teil der Reste R⁴ auch Propylen oder Butylen sein kann, und
R⁵ C₁-C₂₂-Alkyl bedeutet.Aramid fiber with a preparation containing the components A) anionic antistatic based on phosphoric acid esters and / or phosphonic acid esters, B) Compound of formula I.



R¹-COO- (CH₂-CH₂-O-) x -R² (I),



and C) Compound of formula II



R³-O- (R⁴-O) y -R⁵ (I),



wherein
R¹ is C₁-C₂₂-alkyl or C₂-C₂₂-alkenyl, x represents an integer from 2 to 20, preferably 3-15, and R² is hydrogen or C₁-C₂₂-alkyl,
R³ is C₁-C₂₂-alkyl or C₂-C₂₂-alkenyl, y represents an integer from 1 to 8,
R⁴ is ethylene or, if y is 2, 3 or 4, part of the radicals R⁴ can also be propylene or butylene, and
R⁵ means C₁-C₂₂-alkyl. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß die Menge der Präparation 0,5 bis 4 Gew.%, bezogen auf die Menge der Faser beträgt.Aramid fiber according to Claim 1, characterized in that the amount of the preparation is 0.5 to 4% by weight, based on the amount of the fiber. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß das anionische Antistatikum ein Salz eines Mono- oder Dialkylphosphorsäureesters, ein Salz eines Mono- oder Diarylphosphorsäureesters, ein Salz eines Alkylphosphonsäureesters, ein Salz eines Arylphosphonsäureesters oder ein Gemisch dieser Verbindungen ist.Aramid fiber according to claim 1, characterized in that the anionic antistatic is a salt of a mono- or dialkylphosphoric acid ester, a salt of a mono- or diarylphosphoric acid ester, a salt of an alkylphosphonic acid ester, a salt of an arylphosphonic acid ester or a mixture of these compounds. Aramidfaser nach Anspruch 3, dadurch gekennzeichnet, daß das anionische Antistatikum ein Alkalisalz eines Alkylphosphonsäurealkylesters oder insbesondere ein Alkalisalz eines Mono- oder Dialkylphosphorsäureesters ist.Aramid fiber according to Claim 3, characterized in that the anionic antistatic is an alkali salt of an alkylphosphonic acid alkyl ester or in particular an alkali salt of a mono- or dialkylphosphoric acid ester. Aramidfaser nach Anspruch 4, dadurch gekennzeichnet, daß das anionische Antistatikum ein Kaliumsalz eines Mono- und/oder Dialkylphosphorsäureesters, dessen Alkylgruppen insbesondere 8 bis 20 Kohlenstoffatome aufweisen, ist.Aramid fiber according to Claim 4, characterized in that the anionic antistatic is a potassium salt of a mono- and / or dialkylphosphoric acid ester, the alkyl groups of which in particular have 8 to 20 carbon atoms. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß R¹ C₁₂-C₂₀-Alkyl ist.Aramid fiber according to claim 1, characterized in that R¹ is C₁₂-C₂₀ alkyl. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß R² Methyl ist.Aramid fiber according to claim 1, characterized in that R² is methyl. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß R³ C₁₂-C₂₀-Alkyl ist.Aramid fiber according to claim 1, characterized in that R³ is C₁₂-C₂₀ alkyl. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß R³ ein zwei-, drei- oder vierwertiger Rest eines gegebenenfalls ethylenisch ungesättigten aliphatischen Alkohols ist.Aramid fiber according to claim 1, characterized in that R³ is a divalent, trivalent or tetravalent radical of an optionally ethylenically unsaturated aliphatic alcohol. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß R⁵ Methyl ist.Aramid fiber according to claim 1, characterized in that R⁵ is methyl. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß y 1 ist.Aramid fiber according to claim 1, characterized in that y is 1. Aramidfaser nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Aramid um ein in organischen Lösungsmitteln lösliches aromatisches Polyamid handelt.Aramid fiber according to Claim 1, characterized in that the aramid is an aromatic polyamide which is soluble in organic solvents. Aramidfaser nach Anspruch 12, dadurch gekennzeichnet, daß es sich bei dem aromatischen Polyamid um ein Polymeres handelt, das die wiederkehrenden Struktureinheiten der Formeln III, IV und gegebenenfalls V aufweist



        -OC-Ar¹-CO-NH-Ar²-NH-   (III),





        -OC-Ar¹-CO-NH-Ar³-NH-   (IV),





        -OC-Ar¹-CO-NH-Ar⁴-NH-   (V),



worin Ar¹, Ar², Ar³ und Ar⁴ unabhängig voneinander einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellen, dessen freie Valenzen sich in para-Stellung oder in meta-Stellung oder in einer zu diesen Stellungen vergleichbaren parallelen, koaxialen oder gewinkelten Stellung zueinander befinden, und
Ar², Ar³ und gegbenenfalls Ar⁴ im Einzelfall jeweils unterschiedliche im Rahmen der gegebenen Definitionen liegende Bedeutungen annehmen, und wobei die jeweiligen dem Polymeren zugrundeliegenden Monomerbausteine so ausgewählt werden, daß sich ein in organischen Lösungsmitteln lösliches und isotrope Lösungen bildendes aromatisches Polyamid ergibt.Aramid fiber according to Claim 12, characterized in that the aromatic polyamide is a polymer which has the recurring structural units of the formulas III, IV and, if appropriate, V.



-OC-Ar¹-CO-NH-Ar²-NH- (III),





-OC-Ar¹-CO-NH-Ar³-NH- (IV),





-OC-Ar¹-CO-NH-Ar⁴-NH- (V),



wherein Ar¹, Ar², Ar³ and Ar⁴ independently represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para-position or in the meta-position or in a parallel, coaxial or angled position comparable to these positions, and
Ar², Ar³ and optionally Ar⁴ in each case assume different meanings within the scope of the given definitions, and the respective monomer units on which the polymer is based are selected such that an aromatic polyamide which forms soluble and isotropic solutions in organic solvents is obtained. Aramidfaser nach Anspruch 13, dadurch gekennzeichnet, daß Ar¹ einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, Ar² einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in p-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, Ar³ einen Rest der Formel VI darstellt



        -Ar⁵-X-Ar⁶-   (VI),



worin Ar⁵ und Ar⁶ unabhängig voneinander einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellen, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, oder worin Ar⁶ zusätzlich einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in meta-Stellung oder in einer zu dieser Stellung vergleichbaren gewinkelten Stellung zueinander befinden,
X eine Gruppe der Formel -O-, -S-, -SO₂-, -O-Phenylen-O- oder Alkylen ist, und worin
Ar⁴ eine der für Ar² oder Ar³ definierten Bedeutungen annimmt aber von dem jeweils gewählten Rest Ar² oder Ar³ eines Moleküls abweicht.Aramid fiber according to Claim 13, characterized in that Ar¹ represents a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, Ar² is a divalent mono- or polynuclear aromatic radical Ar³ represents a radical whose free valences are in the p-position or in a parallel or coaxial position comparable to this position, Ar³ represents a radical of the formula VI



-Ar⁵-X-Ar⁶- (VI),



in which Ar⁵ and Ar⁶ independently of one another represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, or in which Ar⁶ additionally a divalent mono- or polynuclear aromatic radical whose free valences are in the meta position or in an angular position comparable to this position,
X is a group of the formula -O-, -S-, -SO₂-, -O-phenylene-O- or alkylene, and wherein
Ar⁴ assumes one of the meanings defined for Ar² or Ar³ but deviates from the selected Ar² or Ar³ radical of a molecule. Aramidfaser nach Anspruch 14, dadurch gekennzeichnet, daß Ar¹ 1,4-Phenylen ist, Ar² 1,4-Phenylen oder ein zweiwertiger Rest des 4,4'-Diaminobenzanilids ist, Ar⁵ und Ar⁶ 1,4-Phenylen darstellen, X -O-, -CH₂- oder - O-1,4-Phenylen-O- ist und Ar⁴ einen zweiwertigen Rest des 3,4'-Diaminodiphenylethers, 3,3'-Dichlorbenzidins, des 3,3'-Dimethylbenzidins oder des 3,3'-Dimethoxybenzidins darstellt.Aramid fiber according to claim 14, characterized in that Ar¹ is 1,4-phenylene, Ar² is 1,4-phenylene or a divalent radical of 4,4'-diaminobenzanilide, Ar⁵ and Ar⁶ are 1,4-phenylene, X represents -O- , -CH₂- or - O-1,4-phenylene-O- and Ar⁴ is a divalent radical of 3,4'-diaminodiphenyl ether, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine or 3,3 ' Represents dimethoxybenzidine. Verwendung der Aramidfasern nach Anspruch 1 bei der Herstellung von textilen Flächengebilden beim Verwirbeln, Zwirnen, Flechten oder Fachen.Use of the aramid fibers according to claim 1 in the manufacture of textile fabrics during interlacing, twisting, braiding or folding. Verwendung der Aramidfasern nach Anspruch 16 beim Stricken, Weben, Wirken oder bei der Vliesherstellung.Use of the aramid fibers according to claim 16 in knitting, weaving, knitting or in the manufacture of nonwovens.
EP95100370A 1994-01-26 1995-01-12 Preparation containing aramide fibers and their use. Withdrawn EP0665323A3 (en)

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