EP0392477B1 - Fibre en polyamide enduite - Google Patents

Fibre en polyamide enduite Download PDF

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Publication number
EP0392477B1
EP0392477B1 EP90106890A EP90106890A EP0392477B1 EP 0392477 B1 EP0392477 B1 EP 0392477B1 EP 90106890 A EP90106890 A EP 90106890A EP 90106890 A EP90106890 A EP 90106890A EP 0392477 B1 EP0392477 B1 EP 0392477B1
Authority
EP
European Patent Office
Prior art keywords
polyamide
amino groups
fiber
fiber according
fibers
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.)
Expired - Lifetime
Application number
EP90106890A
Other languages
German (de)
English (en)
Other versions
EP0392477A2 (fr
EP0392477A3 (fr
Inventor
Jürgen Dr. Wichelhaus
Serge Dr. Rebouillat
Johannes Andres
Werner Dr. Gruber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
Henkel AG and Co KGaA
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA, EI Du Pont de Nemours and Co filed Critical Henkel AG and Co KGaA
Priority to AT90106890T priority Critical patent/ATE100156T1/de
Publication of EP0392477A2 publication Critical patent/EP0392477A2/fr
Publication of EP0392477A3 publication Critical patent/EP0392477A3/fr
Application granted granted Critical
Publication of EP0392477B1 publication Critical patent/EP0392477B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D06M13/11—Compounds containing epoxy groups or precursors 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
    • 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
    • D06M15/55—Epoxy resins

Definitions

  • the invention relates to a polyamide fiber which is coated with a special reaction product consisting of a multifunctional epoxy component and a polyamide resin.
  • the invention further relates to a method for coating polyamide fibers with such agents.
  • fibers are understood to mean both continuous fibers and also fiber cuts, fiber composites, yarns, cords, textile fabrics or pulps.
  • Preferred polyamide fibers are aromatic polyamide fibers.
  • fibers coated in this way show a relatively high water absorption. This is not desirable for numerous subsequent processing steps.
  • Canadian Patent 651,745 describes a process for the preparation of polyaminoamides by the condensation of fatty acids with alkylene polyamines.
  • polyaminoamides are known as hardeners for epoxy resins, there is no indication in the specialist literature that they can be used advantageously for the surface treatment of fibers, in particular aramid fibers.
  • the invention thus relates to a polyamide fiber coated with the reaction products of a multifunctional epoxy compound and a polyamine, characterized in that a polyamide resin with amino groups, in particular amino end groups, is used as the polyamine.
  • Another object of the invention is the use of the above-mentioned reaction product of polyfunctional epoxides and polyamide resins as an adhesive and lubricity-imparting coating on a polyamide fiber.
  • a polyfunctional amine which also has amide groups as the reaction component for the polyfunctional epoxy compound.
  • polyamide resins with amino end groups are those polyamide resins in which one or all of the acid components are branched dicarboxylic acids and in particular dimer fatty acids, or in which at least one of the difunctional amino components is the corresponding dimer fatty acid diamine.
  • Dimer fatty acids are understood here to mean the dimerization products of unsaturated fatty acids. These are mixtures of substances with a high proportion of branched dicarboxylic acids of chain length C3 die, but which also contain monofunctional fatty acids and trimers.
  • polyamide resins with amino end groups the reaction products of such dimer fatty acids with an excess of at least difunctional primary or secondary amines, which may also contain tertiary amino groups, are suitable.
  • Polyamide resins based on dimer fatty acids as dicarboxylic acid and alkylenediamines, dialkylenetriamines and / or their higher homologs as amino components are particularly suitable.
  • polyaminoamide resins which are formed by reacting fatty acids and / or dimer fatty acid, but preferably unsaturated fatty acids with ethylenediamine and / or diethylenetriamine at higher temperatures and / or in the presence of catalysts, and which contain nitrogen-containing heterocycles (generally imidazoline rings) as parts of the molecule.
  • nitrogen-containing heterocycles generally imidazoline rings
  • products are preferred in which the number of nitrogen atoms in rings is 20-90%, preferably 20-60%, based on all nitrogen atoms.
  • the dimer fatty acids can furthermore be partially, i.e. up to about 50% by weight can be replaced by dicarboxylic acids having 3 to 20 carbon atoms. It is also possible to chain extend the polyaminoamides by reaction with e.g. Undergo lactams. Suitable lactams are caprolactam and / or lauryl lactam.
  • the polyaminoamides used according to the invention can also be used in admixture with other mono- or polyfunctional amines will.
  • the amount of monofunctional amines should be limited to about 10 mol%, based on amino groups.
  • the amount of the other multifunctional amines should not be more than 80 mol% of the total amount of amines. However, it is preferred to use such amines only in minor amounts.
  • Suitable here are di- and trifunctional amines, as are usually used as curing agents for epoxides, for example ethylenediamine, diethylenetriamine, aliphatic or cycloaliphatic diprimary amines and the like.
  • amine number should be more than 70, an upper limit being given by the molecular weight and being approximately 700, preferably 100.
  • a large number of multifunctional epoxy compounds can be combined with the polyamide resins mentioned. Attention should be paid to the functionality of the epoxy component from 2 to 4. Preference is given to semi-volatile polyfunctional epoxy compounds, especially those with ring structures, e.g. contain aromatic ring structures as a base.
  • Preferred epoxy compounds are N-glycidyl compounds and / or O-glycidyl compounds, in particular N-glycidyl compounds with functionality 3 to 4.
  • a particularly suitable multifunctional epoxy compound is tetraglycidyldiaminodiphenylmethane.
  • a ratio of amine hydrogens to epoxy rings between 2: 1 and 1: 2, in particular with an excess of either amine component or epoxy component.
  • Higher amounts of amine can also be used, for example between 2 and 4 amine hydrogens per epoxy group. In this case there are amino end groups in the middle, otherwise epoxy end groups.
  • Another object of the invention is a method for modifying polyamide fibers with the reaction products of polyfunctional epoxides and polyamide resins, in which the polyamide resin and the polyfunctional epoxy compound are applied to the fibers simultaneously or in succession as a solution, dispersion or melt and then cured if desired at elevated temperature leaves.
  • the epoxy compounds and the polyamide resin may be preferred to dissolve or disperse the epoxy compounds and the polyamide resin separately, and then to coat the fiber either in a mixture of the solutions / dispersions or in succession in the individual solutions / dispersions.
  • Usual concentrations of the coating solutions are between 1 and 20% by weight.
  • polyfunctional epoxy component can be used in solutions with a solids content of 2 to 10% by weight and the polyamide resin component in solutions with a solids content of 10 to 20% or in dispersions and then applied. It can also be applied from the melt.
  • 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.
  • the coating compositions of the invention may also contain other additives.
  • dyes, anti-aging agents and the like may be present.
  • Catalysts for the reaction of amines with epoxy groups can also be used.
  • catalysts for this are, for example, tertiary amines.
  • coated fibers can be 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, pulps, fiber composites, yarns or textile fabrics) made of aromatic polyamides with a fibrous structure.
  • 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 3,287,324); Poly-p-phenylene terephthalamide, trade name Kevlar (R) (DE 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 22 19 646, have been stretched in a nitrogen atmosphere at a temperature above 150 ° C.
  • aromatic polyamides are also suitable, in which the aromatic rings are partly replaced by heterocycles or which also have heterocycles as substituents or chain links, and fibers according to US Pat. No. 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, roll application systems, serpentine 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 first coating is preferably carried out with epoxy resin solutions, the second coating with the polyaminoamide solution.
  • 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 range can only be used with thermally stable fibers, for example with aramid fibers.
  • 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 750 m / min.
  • the surface-coated fibers according to the invention can be used in a variety of ways.
  • the fibers show reduced water absorption and reduced coefficients of friction, which is important during processing. 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 good binding ability to polar and non-polar types of rubber. Furthermore, the polyamide fibers coated in this way show reduced friction against one another.
  • a polyaminoamide with an amine number between 80 and 95 based on fatty acid and diethylenetriamine analogous to Example 2 of CA 651.745 was dissolved in isopropanol while hot.
  • the solids content of the solution was 12% by weight.
  • the epoxy resin solution and the amine resin solution were then diluted so that the solids content epoxy to amine ratio was 2: 3.
  • an aromatic polyamide fiber Kevlar (R) ) was first drawn through the epoxy resin solution, dried with hot air at 200 ° C and pulled through the polyamide resin solution in the second step, after which a further drying step was carried out at 200 ° C in a counter-air flow.
  • the adhesive characteristics were measured before and after fatigue by pulling the yarns out of the rubber block.
  • treated aramid yarns (Kevlar (R) 1670 dtex, 80 T / M) were introduced into different rubber mixtures and vulcanized at 160 ° C. for a period of 20 minutes.
  • the rubber mixtures with the yarns were pressed between two plates of an electrically heated hydraulic press (18 t).
  • 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 approximately 120.degree.
  • the yarn had a pretension of 0.6 daN. It was an untwisted 1670 dtex yarn.
  • a dried polyamide fiber (Kevlar (R) 29) was first drawn through the epoxy resin solution (2% by weight solid), then dried with hot air at 200 ° C and in the second step through the polyamide resin solution (3% by weight ) each in polyol / isopropanol, then dried at 200 ° C in a counter air stream.
  • 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. The Friction coefficient fiber to fiber was 0.055 for the treated yarn compared to 0.11 for the standard product Kevlar (R) 29)
  • 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, none The image of the knitted fabric was uniform, and there were no deposits in the knitting machine, which means that the surface treatment agents according to the invention markedly improve the knitting properties of aramid yarns.

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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)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Claims (14)

  1. Fibre en polyamide enduite avec les produits de réaction à base d'un composé époxydique plurifonctionnel et d'un polyamide, caractérisée en ce que comme polyamine on met en oeuvre une résine de polyamide ayant des groupes amine.
  2. Fibre en polyamide selon la revendication 1, caractérisée en ce que la résine de polyamide possède un nombre d'amines allant de 20 à 600, de préférence de 70 à 100.
  3. Fibre en polyamide selon l'une des revendications 1 ou 2, caractérisée en ce que comme résine de polyamide ayant des groupes amino, on met en oeuvre un produit de réaction d'acides gras dimérique avec un excès d'amines primaires et/ou secondaires au moins difonctionnelles qui peuvent également renfermer des groupes amino tertiaires.
  4. Fibre de polyamide selon l'une des revendications 1 à 3, caractérisée en ce que comme résine de polyamide ayant des groupes amino, on met en oeuvre un produit de réaction d'acides gras dimérique avec un excès d'amines primaires et/ou secondaires qui peut également renfermer des groupes amino tertiaires, amines qui contiennent de 20 à 90 - en particulier de 20 à 60 % des atomes d'azote sous forme de composés cycliques, de cycles imidazoliniques.
  5. Fibre de polyamide selon l'une des revendications précédentes, caractérisée en ce que comme résine de polyamide, on met en oeuvre un produit de réaction d'acides gras et/ou d'acides gras dimérique avec des alcoylènediamines, des dialcoylènetriamines et/ou leurs homologues supérieurs.
  6. Fibre en polyamide selon l'une des revendications précédentes, caractérisée en ce que le composé époxyde plurifonctionnel possède une fonction comprise entre 2 et 4.
  7. Fibre en polyamide selon l'une des revendications précédentes, caractérisée en ce que le composé époxyde plurifonctionnel possède 3 ou 4 groupes N-glycidyle et/ou des groupes O-glycidyle.
  8. Fibre en polyamide selon l'une des revendications précédentes, caractérisée en ce que le composé époxyde plurifonctionnel est le tétraglycidyldiaminodiphénylméthane.
  9. Fibre en polyamide selon l'une des revendications précédentes, caractérisée en ce que les produits de réaction durcis entre le composé de résine époxyde plurifonctionnel et la résine polyamide possèdent en moyenne des groupes terminaux aminés ou des groupes époxydes.
  10. Fibre de polyamide selon l'une des revendications précédentes, caractérisée en ce qu'il s'agit de libres sans fin, de tranches de fibres, de composites renforcés par des fibres, de fils, de cordons ou de écheveaux textiles en polyamides au moins, d'une manière prépondérante, aromatiques.
  11. Utilisation du produit de réaction à partir d'époxydes plurifonctionnels et de résines polyamides selon les revendications précédentes en tant que revêtement qui facilite l'adhérence et l'action de glissement sur une fibre de polyamide.
  12. Procédé pour modifier des fibres de polyamides avec les produits de réaction entre des époxydes plurifonctionnels et des résines de polyamide dans lequel on applique la résine de polyamide ayant des groupes amino et le composé époxyde plurifonctionnel simultanément ou l'un après l'autre sous forme de solution, de dispersion ou de produit de fusion, sur les fibres et ensuite si désiré on lait durcir à température plus élevée.
  13. Procédé selon la revendication 12, caractérisé en ce que l'on fait traverser les fibres en premier lieu par une solution ou une suspension du composant de résine époxyde et ensuite si désiré après séchage intermédiaire, par une solution ou une suspension de résine de polyamide ayant des groupes amine et ensuite si désiré on sèche et on durcit.
  14. Procédé selon la revendication 12 ou 13, caractérisé en ce que l'on applique sur la fibre le produit de réaction avant ou après le premier séchage.
EP90106890A 1989-04-14 1990-04-10 Fibre en polyamide enduite Expired - Lifetime EP0392477B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90106890T ATE100156T1 (de) 1989-04-14 1990-04-10 Beschichtete polyamidfaser.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3912521 1989-04-14
DE3912521A DE3912521A1 (de) 1989-04-14 1989-04-14 Beschichtete polyamidfaser

Publications (3)

Publication Number Publication Date
EP0392477A2 EP0392477A2 (fr) 1990-10-17
EP0392477A3 EP0392477A3 (fr) 1991-03-06
EP0392477B1 true EP0392477B1 (fr) 1994-01-12

Family

ID=6378816

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90106890A Expired - Lifetime EP0392477B1 (fr) 1989-04-14 1990-04-10 Fibre en polyamide enduite

Country Status (7)

Country Link
EP (1) EP0392477B1 (fr)
JP (1) JP2979483B2 (fr)
KR (1) KR900016541A (fr)
AT (1) ATE100156T1 (fr)
BR (1) BR9001724A (fr)
CA (1) CA2014092A1 (fr)
DE (2) DE3912521A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19622216A1 (de) * 1996-06-03 1997-12-04 Kunstfaserwerk Erwin Hahl Gmbh Monofile mit verbesserter Chemikalienbeständigkeit und höherem E-Modul (Steifheit) sowie Verfahren zu ihrer Herstellung
JP4969425B2 (ja) * 2007-12-04 2012-07-04 旭化成イーマテリアルズ株式会社 アラミド繊維織物、並びに該織物を用いたプリプレグ及び積層板
JP6997499B2 (ja) * 2017-03-31 2022-02-10 東レ・デュポン株式会社 建造物補強用繊維シート

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287324A (en) * 1965-05-07 1966-11-22 Du Pont Poly-meta-phenylene isophthalamides
JPS57205582A (en) * 1981-06-08 1982-12-16 Teijin Ltd Fiber reinforced sheet material
EP0107887B2 (fr) * 1982-11-02 1994-08-17 Akzo Nobel N.V. Filé encollé composé de multifilaments en polyamide aromatique ainsi qu'un procédé pour fabriquer ce filé
JPH0621411B2 (ja) * 1984-12-14 1994-03-23 金井 宏之 耐熱性不織布
JPS61204229A (ja) * 1985-03-07 1986-09-10 Kanebo Ltd 繊維強化樹脂複合材料
JPS63165583A (ja) * 1986-12-26 1988-07-08 旭化成株式会社 パラ系アラミド繊維の接着性改良法

Also Published As

Publication number Publication date
CA2014092A1 (fr) 1990-10-14
DE3912521A1 (de) 1990-10-25
ATE100156T1 (de) 1994-01-15
JP2979483B2 (ja) 1999-11-15
KR900016541A (ko) 1990-11-13
EP0392477A2 (fr) 1990-10-17
BR9001724A (pt) 1991-05-21
EP0392477A3 (fr) 1991-03-06
JPH02293475A (ja) 1990-12-04
DE59004180D1 (de) 1994-02-24

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