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.

Landscapes

• 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)
• Multicomponent Fibers (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

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ID=6353844

Family Applications (1)

Country Status (17)

Families Citing this family (14)

Family Cites Families (9)

• 1988
  • 1988-05-06 DE DE3815543A patent/DE3815543A1/de not_active Withdrawn
• 1989
  • 1989-04-28 AT AT89107754T patent/ATE96858T1/de not_active IP Right Cessation
  • 1989-04-28 DE DE89107754T patent/DE58906075D1/de not_active Expired - Lifetime
  • 1989-04-28 ES ES89107754T patent/ES2059611T3/es not_active Expired - Lifetime
  • 1989-04-28 EP EP89107754A patent/EP0345455B1/de not_active Expired - Lifetime
  • 1989-05-03 IL IL90174A patent/IL90174A0/xx unknown
  • 1989-05-03 TR TR89/0374A patent/TR24730A/xx unknown
  • 1989-05-05 RU SU894613963A patent/RU1838485C/ru active
  • 1989-05-05 NO NO89891864A patent/NO891864L/no unknown
  • 1989-05-05 DK DK222489A patent/DK222489A/da not_active Application Discontinuation
  • 1989-05-05 ZA ZA893331A patent/ZA893331B/xx unknown
  • 1989-05-05 US US07/347,906 patent/US5118430A/en not_active Expired - Lifetime
  • 1989-05-05 CA CA000598868A patent/CA1332100C/en not_active Expired - Fee Related
  • 1989-05-05 AU AU34084/89A patent/AU624375B2/en not_active Ceased
  • 1989-05-05 BR BR898902108A patent/BR8902108A/pt not_active IP Right Cessation
  • 1989-05-06 CN CN89103059A patent/CN1040466C/zh not_active Expired - Fee Related
  • 1989-05-06 JP JP1114030A patent/JP2733546B2/ja not_active Expired - Fee Related
  • 1989-05-06 KR KR1019890006053A patent/KR960013472B1/ko not_active IP Right Cessation
• 1998
  • 1998-02-16 CN CN98105201A patent/CN1203294A/zh active Pending

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