EP0392476B1 - Verwendung von Harzlösungen oder Dispersionen von Harzen zur Oberflächenbehandlung von Polyamidfasern - Google Patents
Verwendung von Harzlösungen oder Dispersionen von Harzen zur Oberflächenbehandlung von Polyamidfasern Download PDFInfo
- Publication number
- EP0392476B1 EP0392476B1 EP90106889A EP90106889A EP0392476B1 EP 0392476 B1 EP0392476 B1 EP 0392476B1 EP 90106889 A EP90106889 A EP 90106889A EP 90106889 A EP90106889 A EP 90106889A EP 0392476 B1 EP0392476 B1 EP 0392476B1
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- European Patent Office
- Prior art keywords
- weight
- diamines
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- fiber
- copolymers
- 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.)
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Classifications
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- 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
- D06M13/322—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 nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents 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
- 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
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- 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
-
- 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
-
- 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 invention proposes the use of solutions which contain polyamide resins on the one hand and polymers bearing acid groups on the other hand, for coating polyamide fibers, before the final processing.
- fibers are understood to mean both continuous fibers and also fiber cuts, fiber composites, yarns, pulp and the like, as well as textile fabrics, be they woven, knitted, knitted or in some other way, for example connected as non-wovens.
- fibers are coated in technology with surface treatment agents, for example epoxy resin preparations or else with other resins. This is described, for example, in US-A-4,557,967 and US-A-4,652,488.
- surface treatment agents for example epoxy resin preparations or else with other resins.
- the associated improvements in the adhesion of the fibers in the matrix are not yet sufficient.
- the treatment of the fibers with epoxides in some cases leads to embrittlement, so that the fibers treated in this way can break or split open in subsequent textile processing steps, such as knitting or weaving; furthermore the water absorption by the fiber is increased.
- DE-A-35 04 804 describes a hot melt adhesive made from polyamides based on dimerized fatty acids, aliphatic amines and modifying additives on the one hand and copolymers of ethylene on the other hand, with an additional 5 to 95% by weight, based on the total mixture, of a copolymer of ethylene , the inner anhydride of an ethylenically unsaturated dicarboxylic acid and optionally (meth) acrylic acid esters and / or vinyl esters are contained.
- the copolymers preferably consist of 50 to 90 wt .-% ethylene, 5 to 30 wt .-% (meth) acrylic acid ester of aliphatic linear or branched primary C1-C18 alcohols and 2 to 30 wt .-% of the inner anhydride of a polymerizable Carboxylic acid.
- a further object of the invention is to provide coated polyamide fibers, in particular aromatic polyamide fibers (aramid fibers), which have better processability in knitting and weaving processes, combined with higher resistance to material fatigue. Furthermore, the fiber composites should be able to absorb less water.
- a further object of the invention is to provide an aromatic polyamide fiber coated with a surface treatment agent, which can be used for most known applications without additional treatment steps.
- a further object of the invention is to provide a coated fibrous polyamide material, in particular a coated fibrous aromatic polyamide material, which has an improved ability to bind to other substrates, such as rubber, while exhibiting satisfactory textile processability, and excellent resistance to material fatigue.
- Another object of the invention is to produce a method for producing such fibrous polyamides, in which the coating with the Surface treatment agent can take place on the never-dried fiber (on line) or on the dried fiber (off line).
- the resin solutions used according to the invention contain, as one of the two main components, a polyamide resin based on long-chain branched dicarboxylic acids, in particular based on dimer fatty acid.
- a polyamide resin based on long-chain branched dicarboxylic acids in particular based on dimer fatty acid.
- Such polyamide resins are obtained by known processes by condensation of polyfunctional dicarboxylic acids with polyfunctional amino compounds, if desired in the presence of aminocarboxylic acids or monocarboxylic acids.
- Preferred are polyamide resins in which the dimer fatty acid makes up a substantial proportion, ie more than a third, of the total acid components. High dimer fatty acid levels have a favorable effect on the material fatigue strength.
- the commercially available dimerization products are here under dimer fatty acid understood by unsaturated fatty acids. These are mixtures which can contain mono-, di- and tricarboxylic acids, the dicarboxylic acid fraction being greater than 80% by weight,
- dimer fatty acids which have been obtained by dimerizing C1 und fatty acids and contain predominantly 36 carbon atoms.
- shorter-chain or longer-chain dimer fatty acids can also be used, if available.
- the polyamide resins according to the invention can contain aliphatic dicarboxylic acids having 6 to 22 carbon atoms as a further acid component.
- adipic acid, heptanedicarboxylic acid, octanedicarboxylic acid, azelaic acid, nonandicarboxylic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and / or brassylic acid and their higher homologs are particularly suitable.
- dicarboxylic acids are selected from polyamide resins with a low melting point. If polyamide resins with a low melting point are desired, the person skilled in the art will not use aliphatic dicarboxylic acids having 6 to 22 carbon atoms or only small amounts of such acids. If high melting points are required, larger proportions of such dicarboxylic acids are used within the specified molar amount, in particular the shorter-chain, such as adipic acid.
- the polyamide resins used according to the invention can be aliphatic, aromatic and / or cyclic diamines with 2 to 36 carbon atoms from the class of di-primary diamines, the diamines containing secondary amino groups with alkyl substituents with no more than 25 carbon atoms on the nitrogen atom and / or the heterocyclic diamines capable of double amide formation.
- Diamines with 2 to 20 carbon atoms in particular lower straight or branched chain, aliphatic or monocyclic, di-primary diamines or monocyclic, heterocyclic diamines are preferred.
- the diamines in question can be divided into different groups.
- the di-primary aliphatic diamines with terminal amino groups are of great importance.
- amines are preferred which correspond in their carbon structure to the aforementioned dicarboxylic acids, including dimer fatty acids, and the shorter-chain homologues of such diamines.
- Important diamines in particular are therefore ethylenediamine, propylenediamine, hexamethylenediamine and their homologues, and dimer fatty diamine (which can be prepared by converting dimer fatty acids into the dinitriles and then hydrogenating the two nitrile groups).
- Another group of diamines are aromatic diamines.
- Aromatic diamines derived from benzene, toluene or other substituted aromatics, for example 2,6-toluenediamine, 4,4'-diphenylmethane diamine and / or xylylenediamine, can be used.
- the analog cyclohexane derivatives can also be used.
- Such diamines are derived from the di-primary aliphatic diamines mentioned above and have a short-chain alkyl substituent on the N atom, in particular methyl, ethyl or propyl.
- Another group of diamines which can be used in the polyamide resins according to the invention are the heterocyclic diamines capable of double amide formation. These are preferably aliphatic heterocycles. The most important representative of this group is piperazine.
- the polyamide resins used according to the invention may have at least one side of N-alkyl-substituted aliphatic diamines with 2 to 10 C atoms and 10 to 25 C atoms in the straight-chain or branched N-alkyl radical which are capable of double amide formation.
- the basic body of these amines can be derived from the aliphatic di-primary diamines mentioned above.
- the main body is preferably unbranched, that is to say it is in particular ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine or their higher homologs which have an alkyl radical with 10 to 25 C atoms on at least one of the N atoms.
- the alkyl radical on at least one of the N atoms contains 10 to 25 C atoms; it can be linear, branched or cyclic, although straight-chain radicals are preferred. Among the straight-chain residues, in turn, those with an even number of carbon atoms are preferred.
- the aliphatic diamines which are capable of forming two amides and are at least one-sided N-alkyl-substituted can be used as a defined substance. However, it is preferred to use mixtures here. Products are preferred whose N-alkyl radical has a chain length and chain length distribution of a hydrogenated fatty acid mixture. Particularly preferred N-alkyl-substituted aliphatic diamines have N-alkyl substituents whose chain length corresponds to that of a hydrogenated tallow fatty acid or a hydrogenated tall oil fatty acid.
- the polyamide resins used according to the invention can contain polyether diamines. These are compounds with two terminal primary amino groups and an intermediate polyether chain of at least one ether bond in the chain.
- Typical representatives of the polyether diamines are bis- (3-aminopropyl) -polyoxypropylenes and bis- (2-aminopropyl) -polytetrahydrofurans, which have a molecular weight between about 500 and 5,000.
- the representatives particularly mentioned here are preferred because of their easy availability.
- polyethers with 2 terminal amino groups made from polymeric, optionally branched-chain butanediols, pentanediols and hexanediols. Mixed ethers with two terminal amino groups could also be used.
- non-polymeric ether diamines i.e. those that contain only one or only a few ether groups.
- the polyamide resins used according to the invention can also contain aminocarboxylic acids. Products with a terminal amino group and a terminal carboxyl group, connected by an unbranched carbon chain with 3 to 13 carbon atoms, are preferred here. In addition, amino alcohols may be present in addition to or instead of the diamines in the polyamide resins used in the invention.
- the polyamide resins used according to the invention can contain acid components and amine components (which also include amino alcohols) in stoichiometric amounts.
- acid components which also include amino alcohols
- amine components which also include amino alcohols
- Base terminated resins have amine numbers up to about 50, preferably from 2 to 20 and in particular from 2 to 15.
- Acid-terminated resins should have an acid number in the range up to about 20, preferably from 2 to 10.
- the polyamide resins used according to the invention have a molecular weight (number average) in the range from 5,000 to 40,000, preferably from 8,000 to 12,000.
- the person skilled in the art will use acid and base components in amounts which are as equivalent as possible to achieve high molecular weights, whereas excesses of one component can be used to achieve low molecular weights.
- Another possibility for lowering the molecular weight is the addition of chain terminators such as monofunctional fatty acids or monofunctional amines.
- the molecular weight can be increased by a certain proportion of trifunctional components, such as trimer fatty acid.
- copolymers with carboxylic acids or carboxylic anhydride groups used in the resin solutions used according to the invention are copolymers of polymerizable olefins with polymerizable carboxylic acids and / or carboxylic acid anhydrides and or the polymerizable esters of carboxylic acids.
- copolymers of ethylene with a proportionate use of propylene can be used together with the esters of acrylic acid and / or methacrylic acid and / or maleic anhydride.
- a class of preferred copolymers consist mainly of ethylene, and part of the ethylene can also be replaced by propylene. Based on ethylene, up to 15% propylene can be present.
- Suitable copolymers have a composition in the following range: 50 to 90% by weight of ethylene, 5 to 30 wt .-% (meth) acrylic acid ester of primary, aliphatic linear or branched alcohols with 1 to 18 carbon atoms and 2 to 30% by weight of the internal anhydride of a polymerizable carboxylic acid.
- Cyclic anhydrides such as maleic anhydride, itaconic anhydride and the like are preferred here.
- Maleic anhydride is of particular importance.
- esters of (meth) acrylic acid are of particular importance the methyl, ethyl, propyl, butyl, 2-ethylhexyl ester and esters with so-called fatty alcohols with 12 to 18 carbon atoms, which can also be unsaturated.
- some of the (meth) acrylic acid esters can also be replaced by esters of vinyl alcohol, for example by vinyl acetate or by vinyl esters of C3- to C18-carboxylic acids.
- copolymers which contain 80 to 90% by weight of ethylene, 5 to 15% by weight of the aforementioned esters of (meth) acrylic acid and 2 to 5% by weight of the unsaturated anhydride, preferably have maleic anhydride.
- the copolymers preferably have a weight average molecular weight of about 50,000 to 250,000. In general, smaller amounts are used to prepare the polymers to be used according to the invention in the case of a longer-chain alcohol residue of the acrylic ester and the methacrylic ester.
- the resin solutions used according to the invention may also contain other auxiliaries.
- Stabilizers in the broadest sense, i.e. UV stabilizers or Anti-aging agents in question.
- Other auxiliaries are, for example, dyes or processing aids.
- the total solids content of the resin solutions used according to the invention is 0.5 to 40% by weight, preferably 5 to 15% by weight.
- Suitable solvents are the solvents which are customary for polyamides based on dimer fatty acid.
- a particularly favorable solvent system consists of isopropanol and toluene, for example in a weight ratio of 9: 1.
- Coated polyamide fibers can be produced according to the invention.
- Particularly important coated fibers are fibers made from polyamides, based on aromatic and / or aliphatic basic building blocks. Coated fibers made from aromatic polyamides are of particular importance.
- Aromatic polyamide fibers are generally fibers (continuous fibers, fiber short cuts, fiber composites, yarns, pulp, mixed fibers, fibers with a special surface structure and the like or textile fabrics) made from aromatic polyamides with a fibrous structure viewed.
- Aromatic polyamides are understood to mean those polymers which partially, predominantly or exclusively consist of aromatic rings which are connected to one another by carbonamide bridges and optionally also by other bridge members.
- the structure of such aromatic polyamides can be illustrated in part by the following general formula: (-CO-NH A1-NH-CO-A2) n , in which A1 and A2 represent aromatic and / or heterocyclic rings, which can also be substituted.
- An important class of surface-treated fibers according to the invention is derived from fully aromatic copolyamides.
- aromatic polyamides examples include: poly-m-phenylene-isophthalamide, trade name Nomex (R) (US-A-3,287,324); Poly-p-phenylene terephthalamide, trade name Keylar (R) (DE-A-22 19 703). Also suitable are polyamides of this structure in which at least one of the phenyl radicals carries one or more substituents, for example lower alkyl groups, alkoxy groups or halogen atoms. Other aromatic polyamides at least partially contain building blocks which are derived from 3- or 4-amino-benzoic acid.
- Also suitable for coating with the surface treatment agents according to the invention are those fully aromatic polyamide fibers which, according to DE-A-22 19 646, have been drawn at a temperature above 150 ° C. in a nitrogen atmosphere.
- aromatic polyamides in which the aromatic rings are partly replaced by heterocycles or the heterocycles as substituents or chain links are also suitable also have, and fibers according to US-A-4,075,172, which are offered under the trade name Technora (R) .
- the surface treatment agents according to the invention can be used at various points in fiber production.
- the surface treatment agents can be applied to moist fibers which have never been dried (on line) or they can be applied to the dried fibers (off line). It is preferred to apply the surface treatment agents after drying and, if desired, after stretching. This applies in particular to aramid fibers.
- the usual applicators can be used. These are, for example, metering application systems, roller application systems or baths.
- Ultrasound treatment, electrostatic treatment or plasma treatment of the fiber or yarn can also be carried out before, during or after the application. In some cases this will be preferred to improve the penetration of the treatment agent. In any case, the devices customary here for use with solvent-containing preparations can be used.
- the quantity applied to the fiber is 0.01 to 12% by weight, based on fiber weights.
- the fiber can be dried before or after the coating and possibly can also be coated in several layers, ie after a first coating step is dried and then coated again in a further bath.
- the drying process can be carried out using convection (for example hot air), heat conduction (for example contact drying), radiation (for example infrared) or the like.
- the heat treatment of the fiber usually takes place in a range from 80 to 220 ° C, the higher temperature ranges only at thermally stable fibers can be used, for example with aramid fibers.
- the fiber treated with the resin solution is preferably dried and / or aftertreated at temperatures above 100.degree.
- the drying time can vary between a few seconds and several minutes depending on the degree of drying to be achieved and the further use of the fiber.
- the running speed of the fibers or yarns in the coating device can be chosen between a few meters per minute and a few hundred meters per minute depending on the desired product intake quantity.
- a lower limit of the drying time is about 5 seconds
- an upper limit of the running speed is about 825 m / min.
- the surface-coated fibers according to the invention can be used in a variety of ways. For example, they show better substrate adhesion in cold adhesive processes, but can also be embedded in plastics or vulcanized in rubber, the fibers then having improved binding ability to polar and apolar types of rubber.
- the starting point was a polyamide resin with the following composition: Table 1 polyamide A polymeric fatty acid (mono 1%, dim. 95%; trim. 4%) FSI 265.0 Stearic acid 19.9 Diaminoethane 27.7 Bis (3-aminopropyl) polytetrahydrofuran (MW 1 100) 41.2 Piperazine - Bis (2-aminopropyl) polypropylene oxide (MW 2,000) - Amine number 1.0 Acid number 7.6 and a terpolymer of the following composition: Ethylene content 91% by weight Acrylic acid ethyl ester 6% by weight Maleic anhydride 3% by weight Molar weight (M w ) 45,000 - 50,000 viscosity 87,000 mPa.s / 190 ° C Softening range 80 - 100 ° C and a copolymer of ethylene and an organic acid with an acid number of 60 and a melt index of 35 (product Nucrel (R) 535 from Du Pont).
- An aramid continuous fiber of the p-phenylenediamine-terephthalamide type in the dried (off line) state was drawn through a bath with the surface treatment agent according to the invention described above and then dried at about 120 ° C.
- the yarn had a pretension of 0.6 daN. It was an untwisted 1670 dtex yarn.
- the yarn passed through the immersion bath at a speed of about 30 m / min.
- the solids uptake from the treatment bath was 2 to 3% by weight (after drying).
- the coefficient of friction of treated yarns compared to untreated yarns was determined in preliminary tests. The measurement was carried out in a friction measuring device (Rothschild) according to standard conditions. The coefficient of friction yarn to metal was 0.40 for the treated yarn and 0.54 for the untreated yarn.
- Aramid yarns (Kevlar (R) ) were knitted on an ELHA (R) circular knitting machine (model RRU). The test lasted 4 hours. The machine speed was 670 min ⁇ 1, the knitting speed 15 m / min. In contrast to untreated fibers, no wear was observed. The image of the knitwear was uniform. Furthermore, no deposits were formed in the knitting machine. This means that the surface treatment agents according to the invention significantly improve the interchangeability of aramid yarns.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3912523 | 1989-04-14 | ||
DE3912523A DE3912523A1 (de) | 1989-04-14 | 1989-04-14 | Verwendung von harzloesungen oder dispersionen von harzen zur oberflaechenbehandlung von polymerfasern |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0392476A2 EP0392476A2 (de) | 1990-10-17 |
EP0392476A3 EP0392476A3 (de) | 1992-04-22 |
EP0392476B1 true EP0392476B1 (de) | 1994-07-06 |
Family
ID=6378817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90106889A Expired - Lifetime EP0392476B1 (de) | 1989-04-14 | 1990-04-10 | Verwendung von Harzlösungen oder Dispersionen von Harzen zur Oberflächenbehandlung von Polyamidfasern |
Country Status (8)
Country | Link |
---|---|
US (1) | US5817416A (ja) |
EP (1) | EP0392476B1 (ja) |
JP (1) | JPH03874A (ja) |
KR (1) | KR900016542A (ja) |
AT (1) | ATE108231T1 (ja) |
BR (1) | BR9001725A (ja) |
CA (1) | CA2014093A1 (ja) |
DE (2) | DE3912523A1 (ja) |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1109163A (en) * | 1964-05-12 | 1968-04-10 | Ici Ltd | Surface-modifying treatment of shaped articles made from synthetic polyamides |
JPS5812311B2 (ja) * | 1972-09-25 | 1983-03-07 | レイケム コ−ポレ−シヨン | ホツトメルトガタセツチヤクザイ |
JPS5824556B2 (ja) * | 1974-08-07 | 1983-05-21 | 住友化学工業株式会社 | 繊維または紙の処理方法 |
US4173680A (en) * | 1975-07-18 | 1979-11-06 | Eastman Kodak Company | Hot melt sizing compositions and fibrous articles sized therewith |
DE2923651A1 (de) * | 1979-06-11 | 1980-12-18 | Henkel Kgaa | Bindemittel auf basis waessriger dispersionen zum aufvulkanisieren von kautschuk |
JPS55165952A (en) * | 1979-06-14 | 1980-12-24 | Unitika Ltd | Polyamide composition |
EP0107887B2 (en) * | 1982-11-02 | 1994-08-17 | Akzo Nobel N.V. | Adhesive-coated multifilament yarn of an aromatic polyamide and a method for the manufacture thereof |
US4483962A (en) * | 1983-07-22 | 1984-11-20 | Lord Corporation | Aqueous adhesive systems |
DE3400851A1 (de) * | 1984-01-12 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | Waessriger vulkanisationskleber |
US4720398A (en) * | 1984-03-19 | 1988-01-19 | Akzo Nv | Process for the improvement of the adhesion to rubber or a thermoplastic elastomer of synthetic yarns, cords or fabrics made therefrom |
DE3504804A1 (de) * | 1985-02-13 | 1986-08-14 | Henkel KGaA, 4000 Düsseldorf | Schmelzkleber |
US4764291A (en) * | 1985-05-16 | 1988-08-16 | Colgate-Palmolive Company | Process for treating laundry with multiamide antistatic agents |
JPS62149980A (ja) * | 1985-12-20 | 1987-07-03 | 帝人株式会社 | 被覆全芳香族ポリアミド繊維及びそれを用いた繊維強化樹脂複合体 |
CA1290878C (en) * | 1986-02-15 | 1991-10-15 | Kentaro Mashita | Thermoplastic resin composition |
JPH0715057B2 (ja) * | 1987-02-16 | 1995-02-22 | 住友化学工業株式会社 | 熱可塑性樹脂組成物 |
DE3803524A1 (de) * | 1988-02-05 | 1989-08-17 | Henkel Kgaa | Waessrige dispersionen auf basis von thermoplastischen polyamiden und emulgatoren sowie ihre verwendung als klebstoffe |
DE3804392A1 (de) * | 1988-02-12 | 1989-08-24 | Basf Ag | Fuellstoffhaltige polyamid-formmassen mit verbesserter oberflaeche und lackierbarkeit |
DE3912626A1 (de) * | 1988-10-29 | 1990-10-25 | Henkel Kgaa | Verwendung eines haftvermittlers als oberflaechenbehandlungsmittel, insbesondere fuer fasern |
-
1989
- 1989-04-14 DE DE3912523A patent/DE3912523A1/de not_active Withdrawn
-
1990
- 1990-04-06 CA CA002014093A patent/CA2014093A1/en not_active Abandoned
- 1990-04-10 DE DE59006335T patent/DE59006335D1/de not_active Expired - Fee Related
- 1990-04-10 EP EP90106889A patent/EP0392476B1/de not_active Expired - Lifetime
- 1990-04-10 AT AT90106889T patent/ATE108231T1/de not_active IP Right Cessation
- 1990-04-11 BR BR909001725A patent/BR9001725A/pt not_active IP Right Cessation
- 1990-04-13 KR KR1019900005114A patent/KR900016542A/ko not_active Application Discontinuation
- 1990-04-13 JP JP2096640A patent/JPH03874A/ja active Pending
-
1992
- 1992-11-19 US US07/979,388 patent/US5817416A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
BR9001725A (pt) | 1991-05-21 |
US5817416A (en) | 1998-10-06 |
JPH03874A (ja) | 1991-01-07 |
EP0392476A3 (de) | 1992-04-22 |
KR900016542A (ko) | 1990-11-13 |
CA2014093A1 (en) | 1990-10-14 |
ATE108231T1 (de) | 1994-07-15 |
EP0392476A2 (de) | 1990-10-17 |
DE59006335D1 (de) | 1994-08-11 |
DE3912523A1 (de) | 1990-10-18 |
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