EP0345455B1 - Composition for the surface treatment of polymer fibres - Google Patents

Composition for the surface treatment of polymer fibres Download PDF

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Publication number
EP0345455B1
EP0345455B1 EP89107754A EP89107754A EP0345455B1 EP 0345455 B1 EP0345455 B1 EP 0345455B1 EP 89107754 A EP89107754 A EP 89107754A EP 89107754 A EP89107754 A EP 89107754A EP 0345455 B1 EP0345455 B1 EP 0345455B1
Authority
EP
European Patent Office
Prior art keywords
surface treatment
weight
treatment agent
agent 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
EP89107754A
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German (de)
French (fr)
Other versions
EP0345455A2 (en
EP0345455A3 (en
Inventor
Hans-Günther Dr. Seltmann
Eugen Scheidt
Serge Dr. Rebouillat
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
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Application filed by Henkel AG and Co KGaA, EI Du Pont de Nemours and Co filed Critical Henkel AG and Co KGaA
Priority to AT89107754T priority Critical patent/ATE96858T1/en
Publication of EP0345455A2 publication Critical patent/EP0345455A2/en
Publication of EP0345455A3 publication Critical patent/EP0345455A3/en
Application granted granted Critical
Publication of EP0345455B1 publication Critical patent/EP0345455B1/en
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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
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon
    • 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 relates to a surface treatment agent for polymer fibers, polymer fibers treated therewith and a method for coating polymer fibers with such an agent.
  • the aqueous surface treatment agent according to the invention improves the compatibility of the fibers with a matrix in which they are embedded.
  • fibers are understood to mean both continuous fibers and fiber cuts, crimped fiber cuts (pulp), fiber composites, yarns and the like, as well as textile fabrics, whether they are woven, knitted, knitted or otherwise connected as non-woven.
  • 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 for many technical applications.
  • 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.
  • German patent application DE-A-34 25 381 describes a terpolymer latex which is obtained by emulsion polymerization of 2,3-dichloro-1,3-butadiene and a mixture of at least two different unsaturated monomers, e.g. 4-vinyl-benzyl chloride, the unsaturated monomers being copolymerizable at least individually with 2,3-dichloro-1,3-butadiene.
  • adhesive systems that are suitable for connecting natural and synthetic elastomers with rigid and non-rigid substrates.
  • the latices contain an aromatic nitroso compound if they are to be used for gluing. Evidence that these latices can be used as raw materials for a surface treatment agent for polymer fibers cannot be found in the documents in the published patent application.
  • German Offenlegungsschrift DE-A-34 00 851 describes a binder for vulcanizing rubber onto substrates which are stable against vulcanization and which contains, among other components, a copolymer of a halogenated conjugated diene, an alkylating monoalkenyl aromatic alkyl halide and, if desired, an unsaturated carboxylic acid.
  • the registration also describes that such binders can be used to bond aramid fibers in rubber.
  • the binder can be used on pretreated fibers, e.g. B. on fibers that have been pretreated with a phenolic resin.
  • the binders according to this application are not surface treatment agents for polymer fibers. They provide brittle films that can flake off when the fiber is bent. This insufficient flexibility is also observed when the binders are used on treated fibers, such as those which have been pretreated with a phenolic resin as a primer.
  • the binders according to DE-A-34 00 851 contain aromatic dinitroso compounds as crosslinkers.
  • aromatic dinitroso compounds as crosslinkers.
  • Another object of the invention is to provide a fibrous polyamide material, particularly a fibrous aromatic polyamide material, which has an improved bondability to other substrates such as rubber, while showing satisfactory softness and workability, 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 before or after stretching.
  • the surface treatment agents according to the invention contain a polar phenolic of the resol type. It is a condensation product of aldehydes, especially formaldehyde and phenols. Suitable phenoplasts can have been produced on the basis of, for example, phenol, cresols, resorcinol, bisphenol-A or xylenols. They are basic condensed products with a batch ratio of 1 to 3 mol aldehyde, in particular formaldehyde, based on the phenol component. Such resol type phenoplasts are known. Products which are so low molecular weight that they are still soluble or at least dispersible in water are preferred according to the invention.
  • phenol formaldehyde resins are preferred. In general, it applies here that shorter-chain products are particularly important.
  • a particularly preferred product in 65% by weight aqueous solution has a viscosity of 0.3 to 1.4 Pas, in particular around 0.7 Pas.
  • the resol type phenoplasts are present in an amount of 1 to 30% by weight.
  • the surface treatment agents according to the invention contain 2 to 40% by weight of a resol-crosslinkable copolymer of a free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compound, this component preferably being in dispersed form.
  • This component is generally a copolymer.
  • the following monomers are particularly suitable as free-radically polymerizable halomethyl compounds: 2-, 3- or 4-vinylbenzyl chloride (VBC), it being possible to use the individual isomers or, preferably, mixtures thereof, 2-, 3- or 4- (1-chloroethyl) - Vinylbenzene, 2-, 3- or 4- (1-chlorobutyl) vinylbenzene or chloromethylvinylnaphthalene isomers.
  • VBC vinylbenzyl chloride
  • these hydroxymethyl compounds are formed from the halomethyl compounds by hydrolysis, e.g. when the monomers or the polymers are heated during the polymerization or during storage.
  • the copolymers then contain small amounts of HCl, which in turn can catalyze the reaction of the resol with the copolymer or with the fiber to be coated.
  • Particularly important monomers for the purposes of the invention are the isomeric vinylbenzyl chlorides (VBC) and the isomeric vinylbenzyl alcohols (VBA).
  • VBC isomeric vinylbenzyl chlorides
  • VBA isomeric vinylbenzyl alcohols
  • VBC isomeric vinylbenzyl chlorides
  • VBA isomeric vinylbenzyl alcohols
  • a mixture of 60 wt .-% meta compound (3 VBC) and 40 wt .-% para compound (4 VBC) and whose hydrolysis products (3 VBA and 4 VBA) are used successfully.
  • the amount of the free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compound, based on the copolymer is generally between 1 and 40% by weight. Amounts between 2 and 10, in particular between 3 and 8% by weight, based in each case on the copolymer, are preferred.
  • the person skilled in the art can choose the degree of conversion of the halogen compound into the alcohol compound (for example VBC to VBA) within wide limits. So 10% of the halomethyl groups, but also 30, 50, 70 or even more than 90% can be saponified, i.e. be converted into hydroxymethyl groups.
  • copolymers incorporated in the surface treatment agents according to the invention also consist of further monomer units.
  • Olefins or diolefins, which can also contain halogen, are particularly suitable as further monomer units.
  • Esters or amides of acrylic or methacrylic acid can also be used.
  • Styrene methylstyrene, butadiene, isoprene, halogenated butadienes, such as e.g. Dichlorobutadiene, especially 2,3-dichloro-1,3-butadiene, halogenated isoprene, vinyl chloride, vinylidene chloride, ethene, propene.
  • halogenated butadienes such as e.g. Dichlorobutadiene, especially 2,3-dichloro-1,3-butadiene, halogenated isoprene, vinyl chloride, vinylidene chloride, ethene, propene.
  • functional acrylates or methacrylates such as, for example, hydroxyethyl acrylate or hydroxymethacrylate, glycidyl acrylate or glycidyl methacrylate, acrylonitrile, acrylamide and substituted acrylic and / or methacrylamides.
  • copolymers of the free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compounds with halogenated diolefins are particularly suitable, and unsaturated carboxylic acids can also be copolymerized.
  • Copolymers of VBA and / or VBC with halogenated diolefins and, if desired, unsaturated carboxylic acids or dicarboxylic acids are therefore particularly suitable.
  • a preferred copolymer consists of VBA and / or VBC, dichlorobutadiene and acrylic acid. It has proven to be particularly advantageous to build copolymers of 80 to 95% by weight dichlorobutadiene, 2 to 10% by weight acrylic acid and 2 to 10% by weight VBA and / or VBC, based on the copolymer.
  • a particularly suitable copolymer of 3 monomer components is described in DE-A-34 25 381.
  • the emulsion copolymers used according to the invention have a pH in the range between 2 and 3 as latex, especially when unsaturated carboxylic acids are present. Since such acidic compositions produce undesirable effects in fiber treatment, it is advisable to adjust the pH set a value in the range between about 5 and 11, preferably 6 and 10, with acid traps or buffers. Zinc oxide, dibasic lead phosphate, sodium acetate and the like can be used as acid scavengers or buffers. Such acid scavengers are used in amounts sufficient to obtain the desired pH.
  • the surface treatment agents according to the invention can also contain further adhesion promoters.
  • Ethylene-unsaturated carboxylic acids in which the carbonyl group is conjugated with the double bond and / or their derivatives have proven to be favorable as adhesion promoters.
  • Corresponding compounds having 3 to 10 carbon atoms in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and their derivatives, are suitable.
  • the anhydrides, the amides, also substituted with a C1 - C5 alkyl group, the esters and the nitriles can be used.
  • Preferred adhesion promoters are, for example, acrylic acid and the half esters of maleic acid, preferably with C1 - C6 alcohols.
  • adhesion promoters are melamine resins. These are condensation products of melamine with aldehydes, especially formaldehyde. Here, low molecular weight water-soluble condensation products and their etherification products with lower alcohols are preferred, for example hexamethylolmelamine, hexamethylolmelamine hexaalkyl ether, in particular hexamethyl ether.
  • the adhesion improvers are used in amounts of up to 5% by weight, based on the surface treatment agent. It has been shown that comparatively small amounts, for example 0.001 to 1% by weight, of the unsaturated carboxylic acids and their derivatives produce favorable effects. Amounts of this order of magnitude are often present as residual monomer content in the polymer latices described above, the person skilled in the art determining the residual monomer content by choosing the Can control polymerization conditions (eg via the amount of initiator and manner of addition).
  • the melamine resins are preferably added in amounts of up to 3% by weight, in particular in amounts of 0.5 to 1.5% by weight.
  • the copolymers used according to the invention are preferably in the form of latex.
  • To produce the surface treatment agents according to the invention it is therefore best to first carry out an emulsion polymerization to produce the copolymer.
  • the resol-type phenoplast can then be added to the polymer latex thus produced, it being preferred to add the resol-type phenoplast as an aqueous solution or dispersion; this also applies to the adhesion improvers.
  • the surface treatment agents according to the invention mostly contain auxiliary substance residues from the production of the polymer dispersions. These are in particular emulsifiers and / or dispersants as well as residues of initiators such as inorganic salts.
  • the surface-active agents used in the emulsion polymerization of the copolymers are of essential importance for the production of the latexes on which the surface treatment agents are based.
  • Anionic surfactants or mixtures thereof with non-ionic surfactants are preferred.
  • the surface-active agents are used in a range between 0.01 and 15% by weight, preferably 1 to 10% by weight, based on a copolymer latex with 40% active substance content.
  • the use of a mixed anionic, non-ionic surfactant system with a ratio of 1.3 to 2.1: 1, preferably 1.3 to 2.0: 1, anionic to non-ionic agent is preferred.
  • anionic agents are carboxylates, such as fatty acid soaps Lauric, stearic and oleic acid as well as acyl derivatives of sarcosine, such as methylglycine; Sulfates such as sodium lauryl sulfate; sulfated natural oils and esters such as Turkish red oil and alkylaryl polyether sulfates; Alkylaryl polyether sulfonates; Isopropylnaphthalenesulfonates and sulfosuccinates and sulfosuccinanates; Phosphate esters, such as partial esters of complex phosphates with short-chain fatty alcohols; and orthophosphate esters of polyethoxylated fatty alcohols.
  • carboxylates such as fatty acid soaps Lauric, stearic and oleic acid as well as acyl derivatives of sarcosine, such as methylglycine
  • Sulfates such as sodium lau
  • non-ionic agents include ethoxylated (ethylene oxide derivatives), mono- and polyhydric alcohols, ethylene oxide / propylene oxide block copolymers; Esters such as glycerol monostearate; Sorbitol dehydration products such as sorbitan monostearate and polyethylene oxide sorbitan monolaurate; and amines such as lauric acid, isopropenyl halide.
  • the surface treatment agents according to the invention can also contain other additives, for example stabilizers.
  • Chlorine acceptors are preferred among the stabilizers. These are compounds that can bind split off HCl, for example triethanolamine or epoxy compounds. Other additives are dyes.
  • Suitable compounds are zirconium aluminates, which are derived from zirconium oxychloride (ZrOCl2 ⁇ 8H2O) and aluminum chlorohydrate (Al2 (OH) 5Cl) and are selective implemented with carboxylic acids.
  • Other suitable compounds are titanates of the general formula YOTi (OX) 3, in which Y is an isopropyl group and X is a long organic radical, for example a stearate group.
  • UV absorbers e.g. UV absorber based on benzotriazole.
  • additives are also pigments, e.g. Pigments that are stable up to temperatures of up to 200 ° C.
  • emulsifiers or plasticizers can also be present in the surface treatment agents according to the invention. However, those skilled in the art will carefully dose these components to prevent the weakening of the bond strength of the fiber treated in this way to form a matrix.
  • Coated polymer fibers of the most varied types can be produced according to the invention.
  • coated fibers of organic polymers specifically of polymers, such as polycondensates
  • Particularly important coated fibers are fibers made from polyamides, polyesters, polyimides, polyethers and / or polyurethanes, based on aromatic and / or aliphatic basic building blocks. Coated fibers made from aromatic polyamides are of particular importance.
  • Coated aromatic polyamide fibers are of particular importance in the context of the invention.
  • aromatic Polyamide fibers are generally considered fibers (continuous fibers, fiber short cuts, fiber composites, yarns or textile fabrics) made from 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 mean aromatic and / or heterocyclic rings, which can also be substituted.
  • An important class of surface-treated fibers according to the invention is derived from 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 Kevlar (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 contain at least some of the building blocks derived from 3- or 4-aminobenzoic 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 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.
  • the surface treatment agents according to the invention can be applied to the fibers in a simple manner. It may be useful to pull the fibers through a bath containing the surface treatment agent and then to dry them. Thereafter, it is often useful to heat-treat the surface treatment agent on the fiber. For this purpose, the coated fibers are briefly exposed to higher temperatures. For example, fibers with a high melting point can be baked for a few seconds to several minutes at temperatures of 140 to 180 ° C., preferably around 160 ° C.
  • the coating of aramid fibers or other polyamide fibers with the surface treatment agents according to the invention can be carried out in a variety of ways, for example in that the fibers (continuous fibers, yarns etc.) are dried before drying, ie in a state that has never been dried (on line) or after drying as a dried fiber (off line) immersed in a bath loaded with the surface treatment agent. If desired, the fiber can also be immersed several times in a surface treatment agent and dried again in a multistage process. Drying can be done by convection (hot air, for example), heat conduction (for example, contact drying), radiation (for example, infrared).
  • convection hot air, for example
  • heat conduction for example, contact drying
  • radiation for example, infrared
  • the heat treatment of the fiber is usually carried out at temperatures between 80 and 220 ° C for a few seconds to several minutes, depending on the requirements of the degree of drying for further applications.
  • the machine speed can vary from a few meters per Minute up to several hundred meters per minute can be selected, with this machine speed usually also regulating the amount of the surface treatment agent.
  • polyamide and especially aramid fibers can be drawn as continuous fibers through a bath containing the surface treatment agent before stretching in the wet state.
  • the surface treatment agent can have a solids content of 17 to 30% by weight. Drying then takes place, if necessary by hot air at, for example, 170 ° C.
  • the surface treatment agents according to the invention can also be applied to yarns or to cord or to textile fabrics after drying.
  • the yarn is sent through a bath which contains the surface treatment agent in a concentration of 8 to 30% by weight.
  • the drying can then be carried out under tension and at temperatures of e.g. 120 ° C take place.
  • 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.
  • a surface treatment agent was prepared which contained 4% by weight of phenolic resin and 12% by weight of copolymer.
  • a surface treatment agent was produced which contained 3% by weight of phenolic resin and 8% of copolymer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Multicomponent Fibers (AREA)

Abstract

Aqueous surface treatment compositions for polymer fibres based on a resin formulation were to be improved in respect of the textile processing properties of the fibres treated therewith and the adhesion of the fibres to a matrix. This was possible by combining . 1 - 30% by weight of a polar phenolic resin of the resol type . 2 - 40% by weight of a resol-crosslinkable copolymer of a free radical polymerisable aromatic hydroxymethyl and/or methylhalogen compound and water to 100% by weight, and also if desired up to 5% by weight of further adhesion promoters.

Description

Die Erfindung betrifft ein Oberflächenbehandlungsmittel für Polymerfasern, damit behandelte Polymerfasern und ein Verfahren zur Beschichtung von Polymerfasern mit einem solchen Mittel. Das erfindungsgemäße wäßrige Oberflächenbehandlungsmittel führt zu einer besseren Verträglichkeit der Fasern mit einer Matrix, in die sie eingebettet werden. Dabei werden unter Fasern im Sinne der Erfindung sowohl Endlosfasern als auch Faserschnitte, gekräuselte Faserschnitte (Pulpe), Faserverbunde, Garne und dergleichen sowie textile Flächengebinde, seien sie gewoben, gestrickt, gewirkt oder in anderer Weise als non-wovens verbunden, verstanden.The invention relates to a surface treatment agent for polymer fibers, polymer fibers treated therewith and a method for coating polymer fibers with such an agent. The aqueous surface treatment agent according to the invention improves the compatibility of the fibers with a matrix in which they are embedded. In the context of the invention, fibers are understood to mean both continuous fibers and fiber cuts, crimped fiber cuts (pulp), fiber composites, yarns and the like, as well as textile fabrics, whether they are woven, knitted, knitted or otherwise connected as non-woven.

Es ist bekannt, Kunststoffe mit organischen oder anorganischen Fasern zu verstärken, um bessere Materialeigenschaften zu erhalten. Die Reißfestigkeit solcher Verbundwerkstoffe oder andere mechanische Eigenschaften erhöhen sich dabei um den Betrag, der von den eingebauten Fasern herrührt. Es hat sich jedoch gezeigt, daß das volle Leistungsvermögen der Fasern in vielen Fällen nicht ausgenutzt werden kann, da beim Zerreißvorgang an der Grenzfläche der Faser zur Matrix Bruch auftritt, und die Fasern sozusagen aus der Matrix herausgezogen werden. Derartige Phänomene werden insbesondere bei sehr reißfesten Fasern, beispielsweise Aramid-Fasern beobachtet.It is known to reinforce plastics with organic or inorganic fibers in order to obtain better material properties. The tensile strength of such composite materials or other mechanical properties increase by the amount that results from the built-in fibers. However, it has been shown that the full performance of the fibers cannot be used in many cases, since breakage occurs at the interface of the fiber with the matrix during the tearing process, and the fibers are pulled out of the matrix, so to speak. Such phenomena will observed especially in the case of very tear-resistant fibers, for example aramid fibers.

Um dies zu verhindern, werden in der Technik Fasern mit Oberflächenbehandlungsmitteln, beispielsweise Epoxidharz-Zubereitungen oder auch mit anderen Harzen überzogen. Dies wird beispielsweise in US-A-4,557,967 und US-A-4,652,488 beschrieben. Für viele technische Anwendungen sind jedoch die damit verbundenen Verbesserungen der Haftfähigkeit der Fasern in der Matrix noch nicht ausreichend. Darüber hinaus führt die Behandlung der Fasern mit Epoxiden teilweise zu einer Versprödung, so daß die so behandelten Fasern bei nachfolgenden textilen Bearbeitungsschritten, wie dem Stricken oder Weben, brechen oder aufspleißen können.In order to prevent this, 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. However, the associated improvements in the adhesion of the fibers in the matrix are not yet sufficient for many technical applications. In addition, 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.

Aus der deutschen Offenlegungsschrift DE-A-34 25 381 ist ein TerpolymerLatex, der durch Emulsionspolymerisation von 2,3-Dichloro-1,3-butadien und einem Gemisch von wenigstens zwei verschiedenen ungesättigten Monomeren, z.B. 4-Vinyl-benzylchlorid, wobei die ungesättigten Monomeren zumindest einzeln mit 2,3-Dichloro-1,3-butadien copolymerisierbar sind, hergestellt wird. Es werden dort ebenfalls Klebstoffsysteme beschrieben, die zum Verbinden von natürlichen und synthetischen Elastomeren mit starren und nichtstarren Substraten geeignet sind. Die Latizes enthalten, wenn sie zum Verkleben verwendet werden sollen, eine aromatische Nitrosoverbindung. Hinweise darauf, daß diese Latizes als Rohstoffe für ein Oberflächenbehandlungsmittel für Polymerfasern eingesetzt werden können, können den Unterlagen der Offenlegunsschrift nicht entnommen werden.German patent application DE-A-34 25 381 describes a terpolymer latex which is obtained by emulsion polymerization of 2,3-dichloro-1,3-butadiene and a mixture of at least two different unsaturated monomers, e.g. 4-vinyl-benzyl chloride, the unsaturated monomers being copolymerizable at least individually with 2,3-dichloro-1,3-butadiene. There are also described adhesive systems that are suitable for connecting natural and synthetic elastomers with rigid and non-rigid substrates. The latices contain an aromatic nitroso compound if they are to be used for gluing. Evidence that these latices can be used as raw materials for a surface treatment agent for polymer fibers cannot be found in the documents in the published patent application.

In der deutschen Offenlegungsschrift DE-A-34 00 851 wird ein Bindemittel zum Aufvulkanisieren von Kautschuk auf vulkanisationsstabile Substrate beschrieben, das neben anderen Bestandteilen ein Copolymeres aus einem halogenierten konjugierten Dien, einem alkylierenden monoalkenyl-aromatischen Alkylhalogenid und gewünschtenfalls einer ungesättigten Carbonsäure enthält. Die Anmeldung beschreibt auch, daß man derartige Bindemittel zum Verkleben von Aramid-Fasern in Gummi verwenden kann. Weiterhin wird offenbart, daß man das Bindemittel auf vorbehandelten Fasern einsetzen kann, so z. B. auf Fasern, die mit einem Phenolharz vorbehandelt worden sind. Die Bindemittel gemäß dieser Anmeldung sind keine Oberflächenbehandlungsmittel für Polymerfasern. Sie liefern spröde Filme, die beim Knicken der Faser abplatzen können. Diese ungenügende Flexibilität wird auch beobachtet, wenn man die Bindemittel auf behandelten Fasern, etwa solchen Fasern, die mit einem Phenolharz als Primer vorbehandelt sind, einsetzt.German Offenlegungsschrift DE-A-34 00 851 describes a binder for vulcanizing rubber onto substrates which are stable against vulcanization and which contains, among other components, a copolymer of a halogenated conjugated diene, an alkylating monoalkenyl aromatic alkyl halide and, if desired, an unsaturated carboxylic acid. The registration also describes that such binders can be used to bond aramid fibers in rubber. Furthermore, it is disclosed that the binder can be used on pretreated fibers, e.g. B. on fibers that have been pretreated with a phenolic resin. The binders according to this application are not surface treatment agents for polymer fibers. They provide brittle films that can flake off when the fiber is bent. This insufficient flexibility is also observed when the binders are used on treated fibers, such as those which have been pretreated with a phenolic resin as a primer.

Selbst wenn man Fasern, beispielsweise Aramid-Fasern, mit den im folgenden beschriebenen in den erfindungsgemäßen Oberflächenbehandlungsmitteln eingesetzten Phenoplasten vom Resoltyp in wäßriger Lösung vorbehandelt und dann mit den Bindemitteln gemäß der DE-A-34 00 851 bestreicht, werden zum einen Abplatzungen (durch Sprödigkeit der Filme) und zum andern nicht voll befriedigende Festigkeiten der Verbunde so behandelter Fasern mit einer Matrix beobachtet.Even if fibers, for example aramid fibers, are pretreated with the resol-type phenoplasts used in the surface treatment compositions according to the invention and then coated with the binders according to DE-A-34 00 851, flaking (due to brittleness of the films) and, on the other hand, not fully satisfactory strengths of the composites of fibers treated in this way with a matrix.

Darüber hinaus enthalten die Bindemittel gemäß der DE-A-34 00 851 als Vernetzer aromatische Dinitrosoverbindungen. Wie zahlreiche Patente und Patentanmeldungen zeigen, hält die Fachwelt diese Verbindungen für unentbehrlich bei der Bindung von vulkanisierbaren Kautschukmischungen an vulkanisationsstabile Substrate. Bei Aramid-Fasern besteht jedoch die Befürchtung, daß aromatische Dinitrosoverbindungen oder ihre Folgeprodukte im Laufe von Alterungsvorgängen die mechanische Stabilität der Faser herabsetzen können.In addition, the binders according to DE-A-34 00 851 contain aromatic dinitroso compounds as crosslinkers. As numerous patents and patent applications show, experts consider these compounds to be indispensable when binding vulcanizable rubber compounds to vulcanization-stable substrates. With aramid fibers, however, there is a fear that aromatic dinitroso compounds or their secondary products can reduce the mechanical stability of the fiber in the course of aging processes.

Es ist daher Aufgabe der Erfindung, ein Oberflächenbehandlungsmittel für Polymerfasern bereitzustellen, das bei textiler Bearbeitung der Fasern (Endlos-Fasern, Faserschnitte, Garne etc.) weder von der Faser abplatzt noch die Faser versprödet, und das beim Einbau der Fasern in eine Polymer-Matrix für hohe Bindungsfestigkeit der Faser zu einer Matrix sorgt.It is therefore an object of the invention to provide a surface treatment agent for polymer fibers, which neither flakes off the fiber nor embrittles the fiber during textile processing of the fibers (continuous fibers, fiber cuts, yarns, etc.), and that when installing the Fibers in a polymer matrix ensures high bond strength of the fiber to a matrix.

In der industriellen Praxis wird es ferner gewünscht, die Flexibilitätseigenschaften der Fasern und die Schmierwirkung von Faserbeschichtungen zu verbessern und die Faser zu Faserreibung zu vermindern. Bei manchen Anwendungen wird gewünscht, die Wasseraufnahme der Faser zu reduzieren. Es ist daher Aufgabe der Erfindung, Oberflächenbehandlungsmittel für Fasern zu finden, die auch die Verarbeitungseigenschaften von Fasern, insbesondere von Aramid-Fasern, verbessern, in dem sie eine bessere Verarbeitbarkeit beim Stricken oder Weben, eine höhere Ermüdungsfestigkeit und einen geringere Wasseraufnahme bewirken.In industrial practice, it is also desired to improve the flexibility properties of the fibers and the lubricating effect of fiber coatings and to reduce the fiber to fiber friction. In some applications it is desired to reduce the water absorption of the fiber. It is therefore an object of the invention to find surface treatment agents for fibers which also improve the processing properties of fibers, in particular aramid fibers, by causing better processability when knitting or weaving, higher fatigue strength and less water absorption.

Eine weitere Aufgabe der Erfindung ist es, ein faserförmiges Polyamidmaterial, insbesondere ein faserförmiges aromatisches Polyamidmaterial bereitzustellen, das eine verbesserte Bindefähigkeit zu anderen Substraten, wie beispielsweise Gummi, aufweist, dabei befriedigende Weichheit und Verarbeitbarkeit zeigt, sowie ausgezeichnete Widerstandsfähigkeit gegen Materialermüdung. Eine weitere Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung derartiger faserförmiger Polyamide herzustellen, bei denen die Beschichtung mit dem Oberflächenbehandlungsmittel vor oder nach dem Verstrecken stattfinden kann.Another object of the invention is to provide a fibrous polyamide material, particularly a fibrous aromatic polyamide material, which has an improved bondability to other substrates such as rubber, while showing satisfactory softness and workability, 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 before or after stretching.

Gegenstand der Erfindung ist somit ein wäßriges Oberflächenbehandlungsmittel für Polymerfasern auf Basis einer Harzzubereitung, dadurch gekennzeichnet, daß es enthält:

  • ⁻ 1 - 30 Gew.-% eines polaren Phenoplasts vom Resoltyp
  • ⁻ 2 - 40 Gew.-% eines mit Resolen vernetzbaren Copolymeren einer radikalisch polymerisierbaren aromatischen Hydroxymethyl- und/oder Methylhalogenverbindung sowie
Wasser zur Ergänzung auf 100 Gew.-%,
wobei gewünschtenfalls bis zu 5 Gew.-% an weiteren Haftverbesserern zugegen sein können.The invention thus relates to an aqueous surface treatment agent for polymer fibers based on a resin preparation, characterized in that it contains:
  • ⁻ 1 - 30 wt .-% of a polar phenolic of the resol type
  • ⁻ 2 - 40 wt .-% of a copolymer which can be crosslinked with resols of a free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compound and
Water to make up to 100% by weight,
if desired, up to 5% by weight of further adhesion promoters can be present.

Weitere Gegenstände der Erfindung sind Fasern, die mit derartigen Oberflächenbehandlungsmitteln vergütet worden sind, ein Behandlungsverfahren von Fasern mit diesen Oberflächenbehandlungsmitteln und die Verwendung der Oberflächenbehandlungsmittel zum Überziehen von Polymerfasern.Further objects of the invention are fibers which have been treated with such surface treatment agents, a method of treating fibers with these surface treatment agents and the use of the surface treatment agents for coating polymer fibers.

Die erfindungsgemäßen Oberflächenbehandlungsmittel enthalten ein polares Phenoplast vom Resoltyp. Es handelt sich hierbei um ein Kondensationsprodukt aus Aldehyden, insbesondere Formaldehyd und Phenolen. Geeignete Phenoplaste können auf Basis von beispielsweise Phenol, Kresolen, Resorcin, Bis-phenol-A oder Xylenolen hergestellt worden sein. Es handelt sich um basisch kondensierte Produkte mit einem Ansatzverhältnis von 1 bis 3 mol Aldehyd, insbesondere Formaldehyd, bezogen auf die Phenolkomponente. Derartige Phenoplaste vom Resoltyp sind bekannt. Erfindungsgemäß bevorzugt sind Produkte, die so niedermolekular sind, daß sie in Wasser noch löslich oder zumindest dispergierbar sind.The surface treatment agents according to the invention contain a polar phenolic of the resol type. It is a condensation product of aldehydes, especially formaldehyde and phenols. Suitable phenoplasts can have been produced on the basis of, for example, phenol, cresols, resorcinol, bisphenol-A or xylenols. They are basic condensed products with a batch ratio of 1 to 3 mol aldehyde, in particular formaldehyde, based on the phenol component. Such resol type phenoplasts are known. Products which are so low molecular weight that they are still soluble or at least dispersible in water are preferred according to the invention.

Unter den Phenoplasten sind Phenolformaldehydharze bevorzugt. Ganz allgemein gilt hier, daß besonders den kürzerkettigen Produkten Bedeutung zukommt. So zeigt ein besonders bevorzugtes Produkt in 65 Gew.-%iger wäßriger Lösung eine Viskosität von 0,3 bis 1,4 Pas, insbesondere um 0,7 Pas.Among the phenoplasts, phenol formaldehyde resins are preferred. In general, it applies here that shorter-chain products are particularly important. A particularly preferred product in 65% by weight aqueous solution has a viscosity of 0.3 to 1.4 Pas, in particular around 0.7 Pas.

Gute Ergebnisse wurden mit Resolen erzielt, die einerseits wasserlöslich sind und andererseits einen Erweichungspunkt zwischen 65 und 70°C aufweisen.Good results have been achieved with resols which are water-soluble on the one hand and have a softening point between 65 and 70 ° C on the other.

In den wäßrigen Oberflächenbehandlungsmitteln sind die Phenoplaste vom Resoltyp in einer Menge von 1 bis 30 Gew.-% vorhanden.In the aqueous surface treatment agents, the resol type phenoplasts are present in an amount of 1 to 30% by weight.

Bevorzugt ist eine Phenoplast-Konzentration zwischen 2 und 10 Gew.-%, insbesondere zwischen 3 und 8 Gew.-%.A phenoplast concentration of between 2 and 10% by weight, in particular between 3 and 8% by weight, is preferred.

Als weitere Komponente enthalten die erfindungsgemäßen Oberflächenbehandlungsmittel 2 bis 40 Gew.-% eines mit Resolen vernetzbaren Copolymeren einer radikalisch polymerisierbaren aromatischen Hydroxymethyl- und/oder Methylhalogenverbindung, wobei diese Komponente vorzugsweise in dispergierter Form vorliegt.As a further component, the surface treatment agents according to the invention contain 2 to 40% by weight of a resol-crosslinkable copolymer of a free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compound, this component preferably being in dispersed form.

Bei dieser Komponente handelt es sich generell um ein Copolymeres. Als radikalisch polymerisierbare Halogenmethylverbindungen sind insbesondere die folgenden Monomeren geeignet: 2-, 3- oder 4-Vinylbenzylchlorid (VBC), wobei die einzelnen Isomeren oder vorzugsweise deren Mischungen eingesetzt werden können, 2-, 3- oder 4-(1-Chlorethyl)-Vinylbenzol, 2-, 3- oder 4-(1-Chlorbutyl)-Vinylbenzol oder Chlormethylvinylnaphthalin-Isomere.This component is generally a copolymer. The following monomers are particularly suitable as free-radically polymerizable halomethyl compounds: 2-, 3- or 4-vinylbenzyl chloride (VBC), it being possible to use the individual isomers or, preferably, mixtures thereof, 2-, 3- or 4- (1-chloroethyl) - Vinylbenzene, 2-, 3- or 4- (1-chlorobutyl) vinylbenzene or chloromethylvinylnaphthalene isomers.

Neben oder anstelle dieser radikalisch polymerisierbaren aromatischen Halogenmethylverbindungen können auch die entsprechenden Hydroxymethylverbindungen eingesetzt werden.In addition to or instead of these radically polymerizable aromatic halomethyl compounds, the corresponding hydroxymethyl compounds can also be used.

Vielfach entstehen diese Hydroxymethylverbindungen aus den Halogenmethylverbindungen bereits durch Hydrolyse, so z.B. bei Erwärmen der Monomeren oder der Polymeren während der Polymerisation oder bei der Lagerung. Die Copolymeren enthalten dann kleine Mengen an HCl, das wiederum die Reaktion des Resols mit dem Copolymeren oder mit der zu beschichteten Faser katalysieren kann.In many cases, these hydroxymethyl compounds are formed from the halomethyl compounds by hydrolysis, e.g. when the monomers or the polymers are heated during the polymerization or during storage. The copolymers then contain small amounts of HCl, which in turn can catalyze the reaction of the resol with the copolymer or with the fiber to be coated.

Besonders wichtige Monomere im Sinne der Erfindung sind die isomeren Vinylbenzylchloride (VBC) und die isomeren Vinylbenzylalkohole (VBA). So kann beispielsweise eine Mischung aus 60 Gew.-% Metaverbindung (3 VBC) und 40 Gew.-% Paraverbindung (4 VBC) und deren Hydrolyseprodukte (3 VBA und 4 VBA) mit Erfolg eingesetzt werden.Particularly important monomers for the purposes of the invention are the isomeric vinylbenzyl chlorides (VBC) and the isomeric vinylbenzyl alcohols (VBA). For example, a mixture of 60 wt .-% meta compound (3 VBC) and 40 wt .-% para compound (4 VBC) and whose hydrolysis products (3 VBA and 4 VBA) are used successfully.

In den erfindungsgemäß eingesetzten Copolymeren beträgt die Menge der radikalisch polymerisierbaren aromatischen Hydroxymethyl- und/oder Methylhalogenverbindung, bezogen auf Copolymer, im allgemeinen zwischen 1 und 40 Gew.-%. Bevorzugt sind hier Mengen zwischen 2 und 10, insbesondere zwischen 3 und 8 Gew.-%, jeweils bezogen auf das Copolymer.In the copolymers used according to the invention, the amount of the free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compound, based on the copolymer, is generally between 1 and 40% by weight. Amounts between 2 and 10, in particular between 3 and 8% by weight, based in each case on the copolymer, are preferred.

Der Fachmann kann den Umwandlungsgrad der Halogenverbindung in die Alkoholverbindung (etwa VBC in VBA) in weiten Grenzen wählen. So können 10 % der Halogenmethylgruppen, aber auch 30, 50, 70 oder sogar mehr als 90 % verseift, d.h. in Hydroxymethylgruppen umgewandelt sein.The person skilled in the art can choose the degree of conversion of the halogen compound into the alcohol compound (for example VBC to VBA) within wide limits. So 10% of the halomethyl groups, but also 30, 50, 70 or even more than 90% can be saponified, i.e. be converted into hydroxymethyl groups.

Die in den erfindungsgemäßen Oberflächenbehandlungsmitteln eingebauten Copolymeren bestehen darüber hinaus noch aus weiteren Monomerbausteinen. Als weitere Monomerbausteine sind hier insbesondere Olefine oder Diolefine geeignet, welche auch Halogen enthalten können. Weiter verwendet werden können auch Ester oder Amide der Acryl- oder Methacrylsäure. Darüber hinaus hat es sich als vorteilhaft erwiesen, ethylenisch ungesättigte Carbonsäuren oder Dicarbonsäuren und/oder deren Salze miteinzupolymerisieren.The copolymers incorporated in the surface treatment agents according to the invention also consist of further monomer units. Olefins or diolefins, which can also contain halogen, are particularly suitable as further monomer units. Esters or amides of acrylic or methacrylic acid can also be used. In addition, it has proven advantageous to co-polymerize ethylenically unsaturated carboxylic acids or dicarboxylic acids and / or their salts.

Ganz allgemein gilt hier das allgemeine Fachwissen der Polymerchemie, d.h. der Fachmann wird bei der Auswahl geeigneter Monomerer die Copolymerisation-Parameter zu beachten haben und danach Reaktionsbedingungen und Auswahl treffen.In general, the general expertise of polymer chemistry applies here, i.e. those skilled in the art will have to consider the copolymerization parameters when selecting suitable monomers and will then make reaction conditions and selection.

Als Beispiele werden hier die folgenden Comonomeren aufgeführt: Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Itaconsäure, Citraconsäure, Crotonsäure.The following comonomers are listed here as examples: acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, crotonic acid.

Styrol, Methylstyrol, Butadien, Isopren, halogenierte Butadiene, wie z.B. Dichlorbutadien, insbesondere 2,3-Dichloro-1,3-butadien, halogenierte Isoprene, Vinylchlorid, Vinylidenchlorid, Ethen, Propen.Styrene, methylstyrene, butadiene, isoprene, halogenated butadienes, such as e.g. Dichlorobutadiene, especially 2,3-dichloro-1,3-butadiene, halogenated isoprene, vinyl chloride, vinylidene chloride, ethene, propene.

Vinylester, Vinylether, Ester der Acryl- oder Methacrylsäure mit primären Alkohlen der Kettenlänge C1-C18, funktionelle Acrylate oder Methacrylate, wie beispielsweise Hydroxyethylacrylat oder Hydroxymethacrylat, Glycidylacrylat oder Glycidylmethacrylat, Acrylnitril, Acrylamid sowie substituierte Acryl- und/oder Methacrylamide.Vinyl esters, vinyl ethers, esters of acrylic or methacrylic acid with primary alcohols of chain length C1-C18, functional acrylates or methacrylates, such as, for example, hydroxyethyl acrylate or hydroxymethacrylate, glycidyl acrylate or glycidyl methacrylate, acrylonitrile, acrylamide and substituted acrylic and / or methacrylamides.

Unter der breiten Auswahl der hier möglichen und geeigneten Copolymeren sind insbesondere Copolymere der genannten radikalisch polymerisierbaren aromatischen Hydroxymethyl- und/oder Methylhalogenverbindungen mit halogenierten Diolefinen geeignet, wobei auch noch ungesättigte Carbonsäuren miteinpolymerisiert werden können. Besonders geeignet sind daher Copolymere aus VBA und/oder VBC mit halogenierten Diolefinen und gewünschtenfalls ungesättigten Carbonsäuren oder Dicarbonsäuren.Among the broad selection of the possible and suitable copolymers, copolymers of the free-radically polymerizable aromatic hydroxymethyl and / or methylhalogen compounds with halogenated diolefins are particularly suitable, and unsaturated carboxylic acids can also be copolymerized. Copolymers of VBA and / or VBC with halogenated diolefins and, if desired, unsaturated carboxylic acids or dicarboxylic acids are therefore particularly suitable.

Ein bevorzugtes Copolymer besteht aus VBA und/oder VBC, Dichlorbutadien und Acrylsäure. Dabei hat es sich insbesondere als vorteilhaft erwiesen, Copolymere aus 80 bis 95 Gew.-% Dichlorbutadien, 2 bis 10 Gew.-% Acrylsäure und 2 bis 10 Gew.-% VBA und/oder VBC, bezogen auf Copolymer, aufzubauen. Ein besonders geeignetes Copolymer aus 3 Monomerbestandteilen wir in der DE-A-34 25 381 beschrieben.A preferred copolymer consists of VBA and / or VBC, dichlorobutadiene and acrylic acid. It has proven to be particularly advantageous to build copolymers of 80 to 95% by weight dichlorobutadiene, 2 to 10% by weight acrylic acid and 2 to 10% by weight VBA and / or VBC, based on the copolymer. A particularly suitable copolymer of 3 monomer components is described in DE-A-34 25 381.

Die erfindungsgemäß eingesetzten Emulsionscopolymeren weisen insbesondere, wenn ungesättigte Carbonsäuren mit zugegen sind, als Latex einen pH-Wert im Bereich zwischen 2 und 3 auf. Da derartige saure Zusammensetzungen bei der Faserbehandlung nicht wünschenswerte Effekte hervorrufen, ist es ratsam, den pH auf einen Wert im Bereich zwischen etwa 5 und 11, vorzugsweise 6 und 10, mit Säurefängen oder Puffern einzustellen. Als Säurefänger oder Puffer können Zinkoxid, dibasisches Bleiphosphat, Natriumacetat und dergleichen eingesetzt werden. Derartige Säurefänger werden in Mengen eingesetzt, die ausreichen, um den gewünschten pH-Wert zu erhalten.The emulsion copolymers used according to the invention have a pH in the range between 2 and 3 as latex, especially when unsaturated carboxylic acids are present. Since such acidic compositions produce undesirable effects in fiber treatment, it is advisable to adjust the pH set a value in the range between about 5 and 11, preferably 6 and 10, with acid traps or buffers. Zinc oxide, dibasic lead phosphate, sodium acetate and the like can be used as acid scavengers or buffers. Such acid scavengers are used in amounts sufficient to obtain the desired pH.

Die erfindungsgemäßen Oberflächenbehandlungsmittel können darüber hinaus noch weitere Haftverbesserer enthalten. Als Haftverbesserer haben sich hier ethylenisch ungesättigte Carbonsäuren, bei denen die Carbonylgruppe in Konjugation mit der Doppelbindung steht und/oder deren Derivate als günstig erwiesen. Geeignet sind entsprechende Verbindungen mit 3 bis 10 C-Atomen, insbesondere Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Citraconsäure und deren Derivate. Unter den Derivaten wiederum sind die Anhydride, die Amide, auch substituiert mit einer C₁ - C₅-Alkylgruppe, die Ester und die Nitrile einsetzbar. Bevorzugte Haftvermittler sind beispielsweise Acrylsäure und die Halbester der Maleinsäure, vorzugsweise mit C₁ - C₆-Alkoholen.The surface treatment agents according to the invention can also contain further adhesion promoters. Ethylene-unsaturated carboxylic acids in which the carbonyl group is conjugated with the double bond and / or their derivatives have proven to be favorable as adhesion promoters. Corresponding compounds having 3 to 10 carbon atoms, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and their derivatives, are suitable. Among the derivatives in turn, the anhydrides, the amides, also substituted with a C₁ - C₅ alkyl group, the esters and the nitriles can be used. Preferred adhesion promoters are, for example, acrylic acid and the half esters of maleic acid, preferably with C₁ - C₆ alcohols.

Eine andere Klasse von Haftvermittlern sind Melaminharze. Es sind dies Kondensationsprodukte von Melamin mit Aldehyden, insbesondere Formaldehyd. Hier sind niedermolekulare wasserlösliche Kondensationsprodukte und deren Veretherungsprodukte mit niederen Alkoholen bevorzugt, also beispielsweise Hexamethylolmelamin, Hexamethylolmelamin-hexaalkylether, insbesondere - hexamethylether. Die Haftverbesserer werden in Mengen bis zu 5 Gew.-%, bezogen auf das Oberflächenbehandlungsmittel, eingesetzt. Dabei hat es sich gezeigt, daß bei den ungesättigten Carbonsäuren und ihren Derivaten schon vergleichsweise geringe Mengen, nämlich z.B. 0,001 bis 1 Gew.-%, günstige Wirkungen hervorrufen. Mengen dieser Größenordnung sind oftmals als Restmonomergehalt in den zuvor beschriebenen Polymerlatices vorhanden, wobei der Fachmann den Gehalt an Restmonomeren durch Wahl der Polymerisationsbedingungen (z.B. über die Initiatormenge und Zugabeweise) steuern kann.Another class of adhesion promoters are melamine resins. These are condensation products of melamine with aldehydes, especially formaldehyde. Here, low molecular weight water-soluble condensation products and their etherification products with lower alcohols are preferred, for example hexamethylolmelamine, hexamethylolmelamine hexaalkyl ether, in particular hexamethyl ether. The adhesion improvers are used in amounts of up to 5% by weight, based on the surface treatment agent. It has been shown that comparatively small amounts, for example 0.001 to 1% by weight, of the unsaturated carboxylic acids and their derivatives produce favorable effects. Amounts of this order of magnitude are often present as residual monomer content in the polymer latices described above, the person skilled in the art determining the residual monomer content by choosing the Can control polymerization conditions (eg via the amount of initiator and manner of addition).

Die Melaminharze werden bevorzugt in Mengen bis 3 Gew.-%, insbesondere in Mengen von 0,5 bis 1,5 Gew.-%, zugesetzt.The melamine resins are preferably added in amounts of up to 3% by weight, in particular in amounts of 0.5 to 1.5% by weight.

Die erfindungsgemäß eingesetzten Copolymeren liegen vorzugsweise als Latex vor. Zur Herstellung der Oberflächenbehandlungsmittel gemäß Erfindung führt man daher am besten zunächst eine Emulsionspolymerisation zur Herstellung des Copolymeren durch. Zu dem so hergestellten Polymerlatex kann dann der Phenoplast vom Resoltyp zugegeben werden, wobei es bevorzugt ist, den Phenoplast vom Resoltyp als wäßrige Lösung oder Dispersion zuzugeben, dies gilt auch für die Haftverbesserer.The copolymers used according to the invention are preferably in the form of latex. To produce the surface treatment agents according to the invention, it is therefore best to first carry out an emulsion polymerization to produce the copolymer. The resol-type phenoplast can then be added to the polymer latex thus produced, it being preferred to add the resol-type phenoplast as an aqueous solution or dispersion; this also applies to the adhesion improvers.

Die erfindungsgemäßen Oberflächenbehandlungsmittel enthalten meist von der Herstellung der Polymerdispersionen noch Hilfsstoffreste. Es sind dies insbesondere Emulgatoren und/oder Dispergatoren sowie Reste von Initiatoren etwa anorganische Salze.The surface treatment agents according to the invention mostly contain auxiliary substance residues from the production of the polymer dispersions. These are in particular emulsifiers and / or dispersants as well as residues of initiators such as inorganic salts.

Von wesentlicher Bedeutung für die Herstellung der den Oberflächenbehandlungsmitteln zugrunde liegenden Latizes sind die bei der Emulsionspolymerisation der Copolymeren eingesetzten oberflächenaktiven Mittel. Es werden hier anionische oberflächenaktive Mittel oder deren Mischungen mit nicht-ionischen oberflächenaktiven Mitteln bevorzugt. Die oberflächenaktiven Mitteln werden in einem Bereich zwischen 0,01 und 15 Gew.-%, vorzugsweise 1 bis 10 Gew.-%, bezogen auf einen Copolymer-Latex mit 40 % Aktivsubstanzgehalt, eingesetzt. Die Verwendung eines gemischten anionischen, nicht-ionischen oberflächenaktiven Systems mit einem Verhältnis von 1,3 bis 2,1 : 1, vorzugsweise 1,3 bis 2,0 : 1 anionisches zu nicht-ionischem Mittel wird bevorzugt. Repräsentative anionische Mittel sind Carboxylate, wie Fettsäureseifen aus Laurin-, Stearin- und Oleinsäure- sowie Acyl-Derivaten von Sarcosin, wie Methylglycin; Sulfate, wie Natriumlaurylsulfat; sulfatierte natürliche Öle und Ester, wie Türkisch-Rotöl und Alkylaryl-polyethersulfate; Alkylaryl-polyethersulfonate; Isopropylnaphthalinsulfonate und Sulfosuccinate sowie Sulfosuccinanate; Phosphatester, wie partielle Ester komplexer Phosphate mit kurzkettigen Fettalkoholen; und Orthophosphatester von polyethoxylierten Fettalkoholen. Repräsentative nicht-ionische Mittel umfassen ethoxylierte (Ethylenoxid-Derivate), ein- und mehrwertige Alkohole, Ethylenoxid/Propylenoxid-Blockcopolymere; Ester, wie Glycerin-monostearat; Produkte der Dehydratisierung von Sorbitol, wie Sorbitan-monostearat und Polyethylenoxid-sorbitanmonolaurat; und Amine, wie Laurinsäure, Isopropenylhalogenid. Gegenwärtig wird ein 1,8 : 1-Gemisch von Natriumdodecyldiphenylether-disulfonat als anionischem oberflächenaktivem Mittel und Nonylphenylpolyethylenglykol als nichtionischem oberflächenaktivem Mittel bevorzugt. Anionische und anionisch-nichtionische oberflächenaktive Systeme, die erfindungsgemäß verwendet werden müssen, sind im einzelnen beschrieben in "Emulsions: Theory and Practice", von Paul Becher, Kapitel 6, Reinhold Publishing Corporation, New York, 1965, sowie in McCutcheon's "Detergents and Emulsifiers, 1972 Annual".The surface-active agents used in the emulsion polymerization of the copolymers are of essential importance for the production of the latexes on which the surface treatment agents are based. Anionic surfactants or mixtures thereof with non-ionic surfactants are preferred. The surface-active agents are used in a range between 0.01 and 15% by weight, preferably 1 to 10% by weight, based on a copolymer latex with 40% active substance content. The use of a mixed anionic, non-ionic surfactant system with a ratio of 1.3 to 2.1: 1, preferably 1.3 to 2.0: 1, anionic to non-ionic agent is preferred. Representative anionic agents are carboxylates, such as fatty acid soaps Lauric, stearic and oleic acid as well as acyl derivatives of sarcosine, such as methylglycine; Sulfates such as sodium lauryl sulfate; sulfated natural oils and esters such as Turkish red oil and alkylaryl polyether sulfates; Alkylaryl polyether sulfonates; Isopropylnaphthalenesulfonates and sulfosuccinates and sulfosuccinanates; Phosphate esters, such as partial esters of complex phosphates with short-chain fatty alcohols; and orthophosphate esters of polyethoxylated fatty alcohols. Representative non-ionic agents include ethoxylated (ethylene oxide derivatives), mono- and polyhydric alcohols, ethylene oxide / propylene oxide block copolymers; Esters such as glycerol monostearate; Sorbitol dehydration products such as sorbitan monostearate and polyethylene oxide sorbitan monolaurate; and amines such as lauric acid, isopropenyl halide. A 1.8: 1 mixture of sodium dodecyl diphenyl ether disulfonate as an anionic surfactant and nonylphenyl polyethylene glycol as a nonionic surfactant is currently preferred. Anionic and anionic nonionic surfactant systems that must be used in accordance with the invention are described in detail in "Emulsions: Theory and Practice," by Paul Becher, Chapter 6, Reinhold Publishing Corporation, New York, 1965, and in McCutcheon's, "Detergents and Emulsifiers." , 1972 Annual ".

Darüber hinaus können die erfindungsgemäßen Oberflächenbehandlungsmittel auch noch weitere Zusatzstoffe enthalten, so beispielsweise Stabilisatoren. Unter den Stabilisatoren sind Chlorakzeptoren bevorzugt. Es sind dies Verbindungen, die abgespaltenes HCl binden können, beispielsweise Triethanolamin oder Epoxidverbindungen. Weitere Zusatzstoffe sind Farbstoffe.In addition, the surface treatment agents according to the invention can also contain other additives, for example stabilizers. Chlorine acceptors are preferred among the stabilizers. These are compounds that can bind split off HCl, for example triethanolamine or epoxy compounds. Other additives are dyes.

Als weitere Zusatzstoffe können Verbindungsstoffe eingesetzt werden. Geeignete Verbindungsstoffe sind beispielsweise Zirkonaluminate, die sich von Zirkoniumoxychlorid (ZrOCl₂·8H₂O) und von Aluminiumchlorohydrat (Al₂(OH)₅Cl) ableiten und selektiv mit Carbonsäuren umgesetzt eingesetzt werden. Weitere Verbindungsstoffe sind beispielsweise Aminosilane der allgemeinen Formel Y(CH₂)nSiX₃, in der n = 0 bis 3, X eine hydrolisierbare Gruppe, beispielsweise eine Alkoxygruppe oder ein Halogenatom und Y eine organofunktionelle Gruppe darstellen. Beispiele sind 4-Aminopropyltriethoxysilan und andere Verbindungen, wie sie üblicherweise als Silanprimer im Handel sind. Weitere geeignete Verbindungsstoffe sind Titanate der allgemeinen Formel YOTi(OX)₃, in der Y eine Isopropylgruppe und X einen langen organischen Rest, beispielsweise eine Stearatgruppe, darstellen.Connecting substances can be used as further additives. Suitable compounds are zirconium aluminates, which are derived from zirconium oxychloride (ZrOCl₂ · 8H₂O) and aluminum chlorohydrate (Al₂ (OH) ₅Cl) and are selective implemented with carboxylic acids. Further compounds are, for example, aminosilanes of the general formula Y (CH₂) n SiX₃, in which n = 0 to 3, X is a hydrolyzable group, for example an alkoxy group or a halogen atom, and Y is an organofunctional group. Examples are 4-aminopropyltriethoxysilane and other compounds which are usually commercially available as silane primers. Other suitable compounds are titanates of the general formula YOTi (OX) ₃, in which Y is an isopropyl group and X is a long organic radical, for example a stearate group.

Weitere Zusatzstoffe sind beispielsweise UV-Absorber, so z.B. UV-Absorber auf Benzotriazolbasis.Other additives are, for example, UV absorbers, e.g. UV absorber based on benzotriazole.

Weitere Zusatzstoffe sind auch Pigmente, z.B. Pigmente, die bis zu Temperaturen bis 200°C Hitze stabil sind. Gewünschtenfalls können auch Emulgatoren oder Weichmacher in den erfindungsgemäßen Oberflächenbehandlungsmitteln vorhanden sein. Der Fachmann wird jedoch diese Komponenten vorsichtig dosieren, um ein Nachlassen der Bindungsstärke der so behandelten Faser zu einer Matrix zu verhindern.Other additives are also pigments, e.g. Pigments that are stable up to temperatures of up to 200 ° C. If desired, emulsifiers or plasticizers can also be present in the surface treatment agents according to the invention. However, those skilled in the art will carefully dose these components to prevent the weakening of the bond strength of the fiber treated in this way to form a matrix.

Gemäß Erfindung können beschichtete Polymerfasern unterschiedlichster Art hergestellt werden. So können insbesondere beschichtete Fasern organischer Polymerer und zwar von Polymerisaten, wie von Polykondensaten, hergestellt werden. Besonders wichtige beschichtete Fasern sind Fasern aus Polyamiden, Polyestern, Polyimiden, Polyethern und/oder Polyurethanen und zwar auf Basis aromatischer und/oder aliphatischer Grundbausteine. Von besonderer Bedeutung sind beschichtete Fasern aus aromatischen Polyamiden.Coated polymer fibers of the most varied types can be produced according to the invention. In particular, coated fibers of organic polymers, specifically of polymers, such as polycondensates, can be produced. Particularly important coated fibers are fibers made from polyamides, polyesters, polyimides, polyethers and / or polyurethanes, based on aromatic and / or aliphatic basic building blocks. Coated fibers made from aromatic polyamides are of particular importance.

Im Rahmen der Erfindung kommt beschichteten aromatischen Polyamidfasern besondere Bedeutung zu. Unter aromatischen Polyamidfasern werden hier ganz allgemein Fasern, (Endlos-Fasern, Faserkurzschnitte, Faserverbunde, Garne oder textile Flächengebilde) aus aromatischen Polyamiden mit faseriger Struktur angesehen. Dabei werden unter aromatischen Polyamiden solche Polymeren verstanden, die teilweise, überwiegend oder ausschließlich aus aromatischen Ringen bestehen, die durch Carbonamidbrücken und ggf. auch zusätzlich durch andere Brückenglieder miteinander verbunden sind. Die Struktur solcher aromatischen Polyamide läßt sich zum Teil durch die folgende allgemeine Formel verdeutlichen: (-CO-NH A₁-NH-CO-A₂)n, in der A₁ und A₂ aromatische und/oder heterocylische Ringe bedeuten, die auch substituiert sein können. Eine wichtige Klasse von oberflächenvergüteten Fasern gemäß Erfindung leitet sich von soll aromatischen Copolyamiden ab.Coated aromatic polyamide fibers are of particular importance in the context of the invention. Among aromatic Polyamide fibers are generally considered fibers (continuous fibers, fiber short cuts, fiber composites, yarns or textile fabrics) made from 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 mean aromatic and / or heterocyclic rings, which can also be substituted. An important class of surface-treated fibers according to the invention is derived from aromatic copolyamides.

Beispiele für derartige aromatische Polyamide sind: Poly-m-phenylen-isophthalamid, Handelsname Nomex(R) (US-A-3,287,324); Poly-p-phenylen-terephthalamid, Handelsname Kevlar(R) (DE-A-22 19 703). Geeignet sind weiterhin Polyamide dieser Struktur, bei denen zumindest einer der Phenylreste ein oder mehrere Substituenten, z.B. niedrige Alkylgruppen, Alkoxygruppen oder Halogenatome trägt. Weitere aromatische Polyamide enthalten zumindest teilweise Bausteine, die sich von der 3- bzw. 4-Aminobenzoesäure ableiten.Examples of such aromatic polyamides are: poly-m-phenylene-isophthalamide, trade name Nomex (R) (US-A-3,287,324); Poly-p-phenylene terephthalamide, trade name Kevlar (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 contain at least some of the building blocks derived from 3- or 4-aminobenzoic acid.

Weiter geeignet für die Vergütung mit den erfindungsgemäßen Oberflächenbehandlungsmitteln sind solche voll aromatischen Polyamidfasern, die nach der DE-A-22 19 646 in Stickstoffatmosphäre bei einer Temperatur über 150°C verstreckt worden sind.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 in a nitrogen atmosphere at a temperature above 150 ° C.

Weiterhin sind auch aromatische Polyamide geeignet, die Diaminodiphenylengruppen enthalten, bei denen zwei Phenylreste, die je eine Amino- oder Carbonsäuregruppe tragen, über ein Brückenglied, z.B. ein Heteroatom (O, S, SO₂, NR, N₂ oder eine Gruppe CR₂ (mit R = H oder Alkylgruppen) oder eine Gruppe CO miteinander verbunden sind. Geeignet sind schließlich auch aromatische Polyamide, bei denen die aromatischen Ringe zum Teil durch Heterocyclen ersetzt sind oder die Heterocyclen als Substituenten oder Kettenglieder mitaufweisen, sowie Fasern gemäß US-PS 4,075,172.Aromatic polyamides are also suitable which contain diaminodiphenylene groups in which two phenyl radicals, each carrying an amino or carboxylic acid group, via a bridge member, for example a heteroatom (O, S, SO₂, NR, N₂ or a group CR₂ (with R = H or alkyl groups) or a group CO are connected to one another. Finally, 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.

Die erfindungsgemäßen Oberflächenbehandlungsmittel können in einfacher Weise auf die Fasern aufgebracht werden. So kann es zweckmäßig sein, die Fasern durch ein Bad, das das Oberflächenbehandlungsmittel enthält, zu ziehen und anschließend zu trocknen. Hernach ist es oftmals zweckdienlich, das Oberflächenbehandlungsmittel auf der Faser durch Wärmebehandlung zu härten. Dazu werden die beschichteten Fasern kurzzeitig höherer Temperatur ausgesetzt. So können beispielsweise Fasern mit hohem Schmelzpunkt einige Sekunden bis mehrere Minuten bei Temperaturen von 140 bis 180°C, vorzugsweise um 160°C, eingebrannt werden.The surface treatment agents according to the invention can be applied to the fibers in a simple manner. It may be useful to pull the fibers through a bath containing the surface treatment agent and then to dry them. Thereafter, it is often useful to heat-treat the surface treatment agent on the fiber. For this purpose, the coated fibers are briefly exposed to higher temperatures. For example, fibers with a high melting point can be baked for a few seconds to several minutes at temperatures of 140 to 180 ° C., preferably around 160 ° C.

Die Beschichtung von Aramid-Fasern oder anderen Polyamidfasern mit den erfindungsgemäßen Oberflächenbehandlungsmitteln kann in unterschiedlichster Weise erfolgen, so beispielsweise in dem man die Fasern (Endlos-Fasern, Garne etc.) vor dem Trocknen, d.h. in noch nie getrocknetem Zustand (on line) oder nach dem Trocknen als getrocknetes Faser (off line) in ein mit dem Oberflächenbehandlungsmittel beschicktes Bad taucht. Gewünschtenfalls kann bei einem vielstufigen Prozeß die Faser auch mehrmals in ein Oberflächenbehandlungsmittel getaucht werden und wieder getrocknet werden. Das Trocknen kann durch Konvektion (heiße Luft z.B.), Wärmeleitung (z.B. Kontakttrocknung), Strahlung (z.B. Infra-Rot) erfolgen. Die Wärmebehandlung der Faser wird üblicherweise bei Temperaturen zwischen 80 und 220°C für einige Sekunden bis zu mehreren Minuten durchgeführt, in Abhängigkeit von den Erfordernissen des Trocknungsgrades für weitere Anwendungen. Dabei kann die Maschinengeschwindigkeit von einigen wenigen Metern pro Minute bis zu mehreren hundert Metern pro Minute gewählt werden, wobei über diese Maschinengeschwindigkeit in aller Regel auch die Aufnahmemenge des Oberflächenbehandlungsmittels geregelt wird. So können beispielsweise Polyamid und speziell Aramid-Fasern als Endlosfasern vor dem Verstrecken in nassem Zustand durch ein Bad gezogen werden, das das Oberflächenbehandlungsmittel enthält. Dabei kann das Oberflächenbehandlungsmittel einen Feststoffgehalt von 17 bis 30 Gew.-% aufweisen. Trocknung findet dann anschliessend, gewünschtenfalls durch Heißluft bei zum Beispiel 170°C, statt.The coating of aramid fibers or other polyamide fibers with the surface treatment agents according to the invention can be carried out in a variety of ways, for example in that the fibers (continuous fibers, yarns etc.) are dried before drying, ie in a state that has never been dried (on line) or after drying as a dried fiber (off line) immersed in a bath loaded with the surface treatment agent. If desired, the fiber can also be immersed several times in a surface treatment agent and dried again in a multistage process. Drying can be done by convection (hot air, for example), heat conduction (for example, contact drying), radiation (for example, infrared). The heat treatment of the fiber is usually carried out at temperatures between 80 and 220 ° C for a few seconds to several minutes, depending on the requirements of the degree of drying for further applications. The machine speed can vary from a few meters per Minute up to several hundred meters per minute can be selected, with this machine speed usually also regulating the amount of the surface treatment agent. For example, polyamide and especially aramid fibers can be drawn as continuous fibers through a bath containing the surface treatment agent before stretching in the wet state. The surface treatment agent can have a solids content of 17 to 30% by weight. Drying then takes place, if necessary by hot air at, for example, 170 ° C.

Die erfindungsgemäßen Oberflächenbehandlungsmittel können jedoch bei Polyamiden und speziell Aramiden auch auf Garne oder auf Cord oder auf textile Flächengebilde nach dem Trocknen aufgebracht werden. Dazu wird beispielsweise das Garn durch ein Bad geschickt, welches das Oberflächenbehandlungsmittel in einer Konzentration von 8 bis 30 Gew.-% enthält. Die Trocknung kann dann unter Spannung und bei Temperaturen von z.B. 120°C erfolgen.In the case of polyamides and especially aramides, however, the surface treatment agents according to the invention can also be applied to yarns or to cord or to textile fabrics after drying. For this purpose, for example, the yarn is sent through a bath which contains the surface treatment agent in a concentration of 8 to 30% by weight. The drying can then be carried out under tension and at temperatures of e.g. 120 ° C take place.

Die erfindungsgemäß oberflächenvergüteten Fasern sind vielfältig einsetzbar. Sie zeigen beispielsweise bei Kaltklebeverfahren bessere Substrathaftung, können jedoch auch in Kunststoffe eingebettet oder in Gummi einvulkanisiert werden, wobei die Fasern dann zu polaren wie apolaren Gummiarten verbesserte Bindefähigkeit aufweisen.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.

BeispieleExamples Beispiel 1example 1 Vorprodukte / MethodenIntermediate products / methods

  • 1.1 Phenolharzlösung
    Von einem wasserlöslichen Phenolharz mit einem Erweichungspunkt von 70°C wurde eine 65 Gew.-%ige wäßrige Lösung hergestellt.    1.1 Phenolic resin solution
    A 65% by weight aqueous solution was prepared from a water-soluble phenolic resin with a softening point of 70 ° C.
  • 1.2 Copolymerisat
    Durch Emulsionspolymerisation wurde ein ca. 40 Gew.-%iger Latex eines Polymeren aus 90 Gew.-Teilen 2,3-Dichlor-1,3-butadien, 6 Gew.-Teilen Acrylsäure und 4 Gew.-Teilen Vinylbenzylchlorid (Mischung von 3 VBC und 4 VBC) in Gegenwart eines anionischen und eines nichtionischen Emulgators nach dem Beispiel 1 der DE-A-34 25 381 hergestellt.    1.2 copolymer
    An approximately 40% by weight latex of a polymer composed of 90 parts by weight of 2,3-dichloro-1,3-butadiene, 6 parts by weight of acrylic acid and 4 parts by weight of vinylbenzyl chloride (mixture of 3 VBC and 4 VBC) in the presence of an anionic and a nonionic emulsifier according to Example 1 of DE-A-34 25 381.
  • 1.3 Herstellung des Oberflächenbehandlungsmittels
    Phenolharzlösung und Copolymerlatex wurden in verschiedenen Verhältnissen miteinander gemischt und daraus Oberflächenbehandlungsmittel mit einem Feststoffgehalt zwischen 10 und 25 Gew.-% hergestellt. Polyestergewebe (Polyethylenterephthalat) und Polyamidgewebe (6/6) wurden in die Lösungen getaucht und nach dem Trocknen bei Raumtemperatur 2 Minuten bei 160°C behandelt.
    Zur Überprüfung der Eigenschaften der oberflächen- vergüteten Fasern wurden 2,5 cm breite Gewebestreifen geschnitten und diese mit einem handelsüblichen Polyurethanklebstoff (Macroplast(R)UK 8205/5400, Henkel KGaA) zusammengeklebt. Zur Auswertung wurden Schälfestigkeiten der Verbunde gemessen.    1.3 Production of the surface treatment agent
    Phenolic resin solution and copolymer latex were mixed together in different ratios and surface treatment agents with a solids content of between 10 and 25% by weight were produced therefrom. Polyester fabric (polyethylene terephthalate) and polyamide fabric (6/6) were immersed in the solutions and, after drying at room temperature, treated at 160 ° C. for 2 minutes.
    To check the properties of the surface-treated fibers, 2.5 cm wide fabric strips were cut and these were coated with a commercially available polyurethane adhesive (Macroplast (R) UK 8205/5400, Henkel KGaA) glued together. The peel strengths of the composites were measured for evaluation.
Beispiel 2Example 2

Wie in Beispiel 1 beschrieben, wurde ein Oberflächenbehandlungsmittel hergestellt, das 4 Gew.-% Phenolharz und 12 Gew.-% Copolymerisat enthielt.As described in Example 1, a surface treatment agent was prepared which contained 4% by weight of phenolic resin and 12% by weight of copolymer.

Beispiel 3Example 3

Es wurde ein Oberflächenbehandlungsmittel hergestellt, das 3 Gew.-% Phenolharz und 8 % Copolymerisat enthielt.A surface treatment agent was produced which contained 3% by weight of phenolic resin and 8% of copolymer.

Die erhaltenen Schälfestigkeiten sind in der folgenden Tabelle zusammengefaßt.

Figure imgb0001
The peel strengths obtained are summarized in the following table.
Figure imgb0001

Beispiel 4Example 4 Ergebnisse an Aramid-FasernResults on aramid fibers

  • 4.1 Beschichtung vor dem Verstrecken
    Eine Aramid-Endlosfaser vom Typ p-Phenylendiamin-terephthalamid mit einem Wassergehalt von ungefähr 70 Gew.-% wurde durch ein Bad mit dem erfindungsgemäßen Oberflächenbehandlungsmittel (Gesamtfeststoff 17 Gew.-%, davon 12 Gew.-% Latex, 5 Gew.-% Phenolharz) gezogen und danach bei 170°C getrocknet. Die Feststoffaufnahme der Faser betrug etwa 2,7 Gew.-%, bezogen auf Faser. Die getrocknete Faser wurde in üblicher Weise verstreckt.    4.1 Coating before stretching
    An aramid continuous fiber of the p-phenylenediamine-terephthalamide type with a water content of approximately 70% by weight was passed through a bath with the surface treatment agent according to the invention (total solids 17% by weight, thereof 12% by weight latex, 5% by weight Phenolic resin) and then dried at 170 ° C. The solids uptake of the fiber was about 2.7% by weight, based on the fiber. The dried fiber was drawn in the usual way.
  • 4.2 Ein Aramid-Garn von gleichem chemischem Aufbau wurde nach dem Trocknen (off line) durch das gleiche Bad des Oberflächenbehandlungsmittels gezogen und anschließend bei ca. 120°C getrocknet. Das Garn hatte eine Vorspannung von 0,6 daN; es handelte sich um ein unverdrilltes 1670 dtex Garn. Das Garn durchlief das Tauchbad mit einer Geschwindigkeit von etwa 30 m/min. Die Feststoffaufnahme betrug ca. 3 %.4.2 After drying (off line), an aramid yarn with the same chemical structure was drawn through the same bath of the surface treatment agent and then dried at approx. 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 was approx. 3%.
  • 4.3 Die vor dem Trocknen (on line) und nach dem Trocknen (off line) beschichteten Garne wurden einem Klebe- und Ermüdungstest unterzogen (Cofad-Test). Dazu wurde die dynamische Materialermüdung an einem faserverstärkten Gummiblock gemessen, wozu ein Scheibenermüdungstester, der die Gummiblocks zylindrisch preßt und ausdehnt, (siehe dazu US-A-2 559 069) eingesetzt. Die Materialermüdung wurde entweder visuell oder mechanisch ermittelt, indem die Verstärkungsfasern durch Auflösen des Gummis in Toluol freigelegt wurden.
    Die Klebecharakteristik wurde vor und nach Ermüdung gemessen, indem die Garne aus dem Gummiblock gezogen wurden.
    Zur Herstellung der Probekörper wurden nach Verstrecken behandelte Aramid-Garne (Kevlar(R) 1670 dtex, 80 T/M) in unterschiedliche Kautschukmischungen eingebracht und vulkanisiert bei 160°C während einer Zeitdauer von 20 min. Dazu wurden die Kautschukmischungen mit den Garnen zwischen 2 platten einer elektrisch heizbaren hydraulischen Presse gepreßt (18 t).
    Zur Bestimmung der Haftfähigkeit der Garne wurden diese mit einer Zuggeschwindigkeit von 125 mm/min. aus den Gummiblöcken gezogen.
    Für die nach dem Verstrecken mit dem erfindungsgemäßen Mittel behandelten Fasern ergaben sich Zugkräfte von 200 N (Gummimischung ACM); 226 N (Gummimischung CR); 196 N (Gummimischung EPDM) verglichen mit 93/145/100 für unbehandelte Fasern und 173/141/115 für konventionell behandelte Fasern.    4.3 The yarns coated before drying (on line) and after drying (off line) were subjected to an adhesion and fatigue test (Cofad test). For this purpose, the dynamic material fatigue was measured on a fiber-reinforced rubber block, for which purpose a disc fatigue tester, which presses and expands the rubber blocks cylindrically (see US Pat. No. 2,559,069). Material fatigue was determined either visually or mechanically by exposing the reinforcing fibers by dissolving the rubber in toluene.
    The adhesive characteristics were measured before and after fatigue by pulling the yarns out of the rubber block.
    To produce the test specimens, treated aramid yarns (Kevlar (R) 1670 dtex, 80 T / M) were stretched in different rubber mixtures introduced and vulcanized at 160 ° C for a period of 20 min. For this purpose, the rubber mixtures with the yarns were pressed between 2 plates of an electrically heatable hydraulic press (18 t).
    To determine the adhesiveness of the yarns, they were pulled at a speed of 125 mm / min. pulled out of the rubber blocks.
    The tensile forces of the fibers treated with the agent according to the invention after stretching were 200 N (ACM rubber mixture); 226 N (rubber compound CR); 196 N (EPDM rubber compound) compared to 93/145/100 for untreated fibers and 173/141/115 for conventionally treated fibers.
  • 5. Strickversuche mit behandelten Garnen
    Aramid-Garne (Kevlar(R) wurden auf einer ELHA(R) Kreisstrickmaschine (Modell RRU) verstrickt. Der Test dauerte 4 Stunden. Die Maschinengeschwindigkeit war 670 min⁻¹, die Strickgeschwindigkeit 15m/min. Im Gegensatz zu unbehandelten Fasern wurde kein Verschleißen beobachtet. Das Bild der Strickware war einheitlich. Weiterhin bildeten sich keine Ablagerungen in der Strickmaschine. Dies bedeutet, daß die erfindungsgemäßen Oberflächenbehandlungsmittel die Verstrickbarkeit von Aramid-Garnen deutlich verbessern.    5. Knitting tests with treated yarns
    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, there was no wear The image of the knitted fabric was uniform, and no deposits were formed in the knitting machine, which means that the surface treatment agents according to the invention markedly improve the knitability of aramid yarns.

Claims (18)

  1. An aqueous surface treatment agent for polymer fibers based on a resin preparation, characterized in that it contains
    - 1 - 30 percent by weight of a polar phenoplast of the resol type
    - 2 - 40 percent by weight of a copolymer, crosslinkable with resols, of a free radical-polymerizable, aromatic hydroxymethyl and/or methyl halogen compound and
    water to make 100 percent by weight,
    wherein, if desired, up to 5 percent by weight of additional adhesion promoters may be present.
  2. Surface treatment agent according to claim 1, characterized in that the phenoplast is a water soluble product.
  3. Surface treatment agent according to any of claims 1 or 2, characterized in that the phenoplast in a 65 percent by weight aqueous solution exhibits a viscosity of 0.3 to 1.4 Pa·s.
  4. Surface treatment agent according to any of claims 1 to 3, characterized in that the copolymer is present in the dispersed form and contains, incorporated as a reactive component, 3- and/or 4-vinylbenzyl alcohol (VBA) and/or 3-and/or 4-vinylbenzyl chloride (VBC).
  5. Surface treatment agent according to any of claims 1 to 4, characterized in that the sum of VBA and VBC is 1 to 40 percent by weight, relative to the copolymer.
  6. Surface treatment agent according to any of claims 1 to 5, characterized in that the copolymer is based on at least one of the following comonomers in addition to VBA and/or VBC:
    - Ethylenically unsaturated carboxylic acids or dicarboxylic acids that can also be present as salts,
    - olefins or diolefins that can also contain halogen,
    - esters or amides of acrylic or methacrylic acid.
  7. Surface treatment agent according to any of claims 1 to 6, characterized in that the copolymer consists of VBA and/or VBC, halogenated diolefins and unsaturated carboxylic acids.
  8. Surface treatment agent according to any of claims 1 to 7, characterized in that the copolymer consists of VBA and/or VBC, dichlorobutadiene, particularly 2,3-dichloro-1,3-butadiene, and acrylic acid.
  9. Surface treatment agent according to any of claims 1 to 8, characterized in that the copolymer consists of 80 to 95 percent by weight of dichlorobutadiene, particularly 2,3-dichloro-1,3-butadiene, 2 to 10 percent by weight of acrylic acid and 2 to 10 percent by weight of VBA and/or VBC, relative to the copolymer.
  10. Surface treatment agent according to any of claims 1 to 9, characterized in that ethylenically unsaturated carboxylic acids having from 3 to 10 carbon atoms, in which the double bond is conjugated with the acid group, their anhydrides, amides, esters or nitriles are employed as additional adhesion promoters.
  11. Surface treatment agent according to any of claims 1 to 9, characterized in that melamine resins and/or their etherification products with lower alcohols are employed as adhesion promoters.
  12. Surface treatment agent according to any of claims 1 to 11, characterized in that stabilizers, particularly chlorine acceptors and/or UV stabilizers, dyes, pigments, compounds such as the reaction products of zirconia aluminates with carboxylic acids, aminosilanes or titanates are included as further additives.
  13. Polymer fiber, characterized in that it has been coated at least partially with a surface treatment agent according to claims 1 to 12.
  14. Polymer fiber according to claim 13, characterized in that it is made from polyamides, polyesters, polyimides and/or polyurethanes.
  15. Polymer fiber according to any of claims 13 and 14, characterized in that it is made from aromatic polyamides.
  16. Polymer fiber according to any of claims 13 to 15, characterized in that the amount of coating agent is from 0.01 to 5 percent by weight, relative to the fiber weight.
  17. Process for modifying polymer fibers, characterized in that the fiber is treated with a surface treatment agent according to claims 1 to 12 by immersing it before or after drying in a bath containing the surface treatment agent and, if desired, is dried at temperatures above 100 °C for a short time and/or is post-treated.
  18. Use of surface treatment agents according to any of claims 1 to 12 for modifying organic or inorganic polymer fibers, preferably polyamide or polyimide fibers, and particularly aromatic polyimide fibers.
EP89107754A 1988-05-06 1989-04-28 Composition for the surface treatment of polymer fibres Expired - Lifetime EP0345455B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89107754T ATE96858T1 (en) 1988-05-06 1989-04-28 COMPOSITION FOR THE SURFACE TREATMENT OF POLYMER FIBERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3815543 1988-05-06
DE3815543A DE3815543A1 (en) 1988-05-06 1988-05-06 SURFACE TREATMENT FOR POLYMER FIBERS

Publications (3)

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EP0345455A2 EP0345455A2 (en) 1989-12-13
EP0345455A3 EP0345455A3 (en) 1991-11-13
EP0345455B1 true EP0345455B1 (en) 1993-11-03

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US (1) US5118430A (en)
EP (1) EP0345455B1 (en)
JP (1) JP2733546B2 (en)
KR (1) KR960013472B1 (en)
CN (2) CN1040466C (en)
AT (1) ATE96858T1 (en)
AU (1) AU624375B2 (en)
BR (1) BR8902108A (en)
CA (1) CA1332100C (en)
DE (2) DE3815543A1 (en)
DK (1) DK222489A (en)
ES (1) ES2059611T3 (en)
IL (1) IL90174A0 (en)
NO (1) NO891864L (en)
RU (1) RU1838485C (en)
TR (1) TR24730A (en)
ZA (1) ZA893331B (en)

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US5731275A (en) * 1994-04-05 1998-03-24 Universite De Montreal Synergistic detergent and disinfectant combinations for decontaminating biofilm-coated surfaces
EP1124584A1 (en) 1998-11-06 2001-08-22 Universite De Montreal Improved bactericidal and non-bactericidal solutions for removing biofilms
EP1246868B1 (en) 1999-12-30 2005-02-16 Henkel Kommanditgesellschaft auf Aktien Polymer dispersion with a cross-linking resin, a method for producing the same and the use thereof
ATE329073T1 (en) * 2001-02-01 2006-06-15 Teijin Twaron Gmbh METHOD FOR REMOVAL OF A WATER-INSOLUBLE FINISH FROM ARAMID FIBERS
CN1311012C (en) * 2002-03-06 2007-04-18 乐金电子(天津)电器有限公司 Surface treatment agent of acrylonitrile-butadiene-phenylethylene shaping object
AU2007268544B2 (en) * 2006-05-31 2012-10-11 Mitsubishi Gas Chemical Company, Inc. Polyamide resin composition
BRPI0823028A2 (en) * 2008-08-15 2015-07-28 Otis Elevator Co Elongated load bearing element, and method for making a set.
CN101713151A (en) * 2008-10-06 2010-05-26 E.I.内穆尔杜邦公司 Composite reinforcing material, manufacture method and applications thereof
CN102465448B (en) * 2010-11-10 2013-08-07 钦焕宇 Preparation method of pretreatment polyester staple fiber
CN102465449B (en) * 2010-11-10 2013-10-09 钦焕宇 Preparation method for pretreated nylon staple fiber
CN104328661A (en) * 2014-11-28 2015-02-04 何庆堃 Ramie cotton fabric finishing agent with water proof function
US10240012B2 (en) 2015-08-11 2019-03-26 University Of South Carolina Thermoplastic/thermoset grafted composites
CN114940810A (en) * 2022-07-06 2022-08-26 昆山堃烨电子科技有限公司 Special rubber alloy elastomer for sealing element and preparation method thereof
CN115852540A (en) * 2022-11-30 2023-03-28 桐乡市宇翔化纤有限公司 Elasticated CEY composite yarn and production process thereof

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US3597379A (en) * 1968-04-15 1971-08-03 Goodyear Tire & Rubber Adhesive composition of phenol-formaldehyde resin and rubber latices
DE2923651A1 (en) * 1979-06-11 1980-12-18 Henkel Kgaa BINDING AGENT BASED ON AQUEOUS DISPERSIONS FOR FURNISHING RUBBER
DE3369353D1 (en) * 1982-11-02 1987-02-26 Akzo Nv 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
JPS6072930A (en) * 1983-09-30 1985-04-25 Bridgestone Corp Rubber-reinforcing aromatic polyamide fiber material
DE3400851A1 (en) * 1984-01-12 1985-07-25 Henkel KGaA, 4000 Düsseldorf AQUEOUS VOLCANIZATION ADHESIVE
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
CA1264505A (en) * 1986-02-14 1990-01-23 E.I. Du Pont De Nemours And Company Method for producing stain resistant polyamide fibers

Also Published As

Publication number Publication date
IL90174A0 (en) 1989-12-15
TR24730A (en) 1992-03-06
EP0345455A2 (en) 1989-12-13
ATE96858T1 (en) 1993-11-15
DE3815543A1 (en) 1989-11-16
DE58906075D1 (en) 1993-12-09
CN1037750A (en) 1989-12-06
NO891864D0 (en) 1989-05-05
AU624375B2 (en) 1992-06-11
CA1332100C (en) 1994-09-27
JPH0284572A (en) 1990-03-26
RU1838485C (en) 1993-08-30
JP2733546B2 (en) 1998-03-30
DK222489D0 (en) 1989-05-05
DK222489A (en) 1989-11-07
AU3408489A (en) 1989-11-09
CN1040466C (en) 1998-10-28
KR960013472B1 (en) 1996-10-05
KR900000542A (en) 1990-01-30
ES2059611T3 (en) 1994-11-16
CN1203294A (en) 1998-12-30
ZA893331B (en) 1990-01-31
EP0345455A3 (en) 1991-11-13
BR8902108A (en) 1990-09-04
US5118430A (en) 1992-06-02
NO891864L (en) 1989-11-07

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