EP0301214A2 - Orthopedic casting bandage with a reactive resin - Google Patents

Orthopedic casting bandage with a reactive resin Download PDF

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Publication number
EP0301214A2
EP0301214A2 EP19880109418 EP88109418A EP0301214A2 EP 0301214 A2 EP0301214 A2 EP 0301214A2 EP 19880109418 EP19880109418 EP 19880109418 EP 88109418 A EP88109418 A EP 88109418A EP 0301214 A2 EP0301214 A2 EP 0301214A2
Authority
EP
European Patent Office
Prior art keywords
fibers
extensibility
textile
longitudinal direction
textile fabrics
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.)
Granted
Application number
EP19880109418
Other languages
German (de)
French (fr)
Other versions
EP0301214B1 (en
EP0301214A3 (en
Inventor
Roland Dr. Richter
Wolfram Dr. Mayer
Günter Dr. Langen
Willy Dipl.-Ing. Leyser
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.)
Bayer AG
KOB GmbH
Original Assignee
Karl Otto Braun GmbH and Co KG
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Karl Otto Braun GmbH and Co KG, Bayer AG filed Critical Karl Otto Braun GmbH and Co KG
Priority to AT88109418T priority Critical patent/ATE93909T1/en
Publication of EP0301214A2 publication Critical patent/EP0301214A2/en
Publication of EP0301214A3 publication Critical patent/EP0301214A3/en
Application granted granted Critical
Publication of EP0301214B1 publication Critical patent/EP0301214B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • 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
    • Y10T428/23—Sheet including cover or casing
    • 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
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/237—Noninterengaged fibered material encased [e.g., mat, batt, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31562—Next to polyamide [nylon, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
    • Y10T442/277—Coated or impregnated cellulosic fiber fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2893—Coated or impregnated polyamide fiber fabric

Definitions

  • the invention relates to construction materials, in particular for medical support bandages or technical devices, which in addition to transverse elasticity also have longitudinal elasticity, a method for their production and their use.
  • the construction materials according to the invention generally consist of a carrier layer which is coated and / or impregnated with a reactive resin.
  • construction materials according to the invention can be used for stiffening, shaping and sealing in the medical or technical field.
  • construction materials according to the invention can also be used for the production of containers, filters, pipes, for connecting construction elements, for the production of decorative or artistic articles, for stiffening purposes or as filling or sealing material for joints and cavities.
  • Construction materials which consist of a flexible carrier which is coated or impregnated with a water-hardening reactive resin are already known.
  • DE-A 23 57 931 may be mentioned, in which construction materials made of flexible supports, such as knitted fabrics, woven fabrics or nonwovens, are described, which are coated or impregnated with water-curing reactive resins, such as isocyanates or prepolymers modified by isocyanate groups.
  • water-curing reactive resins such as isocyanates or prepolymers modified by isocyanate groups.
  • carrier materials made of glass fibers were used (US 45 02 479).
  • these known carrier materials are only stretchable in the transverse direction, but are practically rigid in the longitudinal direction in order to achieve greater stability (US 45 02 479, column 3, lines 45 to 47).
  • a disadvantage of the backing materials which are only stretchable in the transverse direction, is the appearance of folds when the material is applied to an uneven surface with conical elevations or variable radii, e.g. a human leg.
  • Construction materials based on glass fibers as described in US 46 09 578, have the disadvantage of poor X-ray transparency. They also form sharp edges at the break points, which lead to injuries. Another disadvantage is the occurrence of glass dust during the manufacture and removal of the construction material.
  • Fibers other than glass fibers have much lower moduli of elasticity, so that no beams with comparable longitudinal and transverse elongation are obtained.
  • textile fabrics which are impregnated and / or coated with a water-hardening reactive resin, characterized in that they consist of organic fibers with a modulus of elasticity of 200 to 2500 daN / mm2 and that they have an extensibility in the longitudinal direction of more than 10% before curing. exhibit.
  • the fabrics according to the invention also have one in the longitudinal direction.
  • the longitudinal direction generally means the processing direction of the textile, for example in the direction of the chain or the wales.
  • Transverse direction generally means perpendicular to the processing direction of the textile, i.e. in the direction of the weft or stitch row.
  • the fabrics according to the invention can be in various geometric shapes. They are preferably in tape form, the long side of the tape corresponding to the processing direction of the textile.
  • Organic fibers for the fabrics according to the invention can be natural fibers or chemical fibers.
  • Natural fibers include, in particular, fibers from plant hair, such as cotton, bast fibers, such as hemp and jute, and hard fibers, such as sisal. Cotton fibers are particularly preferred.
  • fibers made of synthetic polymers may be mentioned as chemical fibers.
  • polymer fibers such as polyethylene, polypropylene, polychloride (e.g. polyvinyl chloride and polyvinylidene chloride), polyacrylic and vinylate fibers, polycondensation fibers such as polyamide, polyester and polyurea fibers, and polyaddition fibers such as spandex or elastane fibers.
  • Preferred synthetic fibers are fibers made of polyesters, polyamides and polyacrylonitriles.
  • Sheets made of polyester and / or polyamide and / or cotton fibers are particularly preferred.
  • the fibers for the fabrics according to the invention are known per se (synthetic fibers, pages 3 to 10 and 153 to 221 (1981), Verlag Chemie, Weinheim).
  • the thread system which is preferably incorporated in the longitudinal direction, enables elastic stretching in the longitudinal direction after a shrinking process.
  • high-twisted yarns or twists made of staple fiber yarns with a twist coefficient ⁇ between 120 and 600 are preferred, so that the high twist gives a high torsional moment and therefore a tendency to curl.
  • the rotation coefficient ⁇ is calculated where T is the number of twists per m of yarn or twine and TEX is the longer thread mass in g per 1000 m of yarn.
  • the threads with an alternating direction of rotation are preferably incorporated in an alternating sequence, for example a thread S - 1 thread Z or 2 threads S - 2 threads Z.
  • Both threads made of natural rubber (elastodia) and synthetic polyurethane elastomer threads (elastane) can be used as permanently elastic threads.
  • Polyfile textured filament yarns made of polyester, polyamide etc. are used as chemical fibers to achieve the elongation.
  • the elastic properties of these yarns are based on the permanent crimping and torsion of the threads obtained in the course of the texturing process, which is achieved by the thermoplastic properties of the materials.
  • All types of texturing threads can be used, e.g. HE yarns (highly elastic crimp yarns), set yarns, HB yarns (high-rise yarns).
  • the thread system incorporated in the longitudinal direction is held together by connecting threads, it being possible to use staple fiber yarns or twists made of natural fibers as well as staple fiber yarns or polyfile filament yarns (plain yarn) made of man-made fibers.
  • the strength of these yarns is characterized by the modulus of elasticity (modulus of elasticity).
  • the fibers for the fabrics according to the invention have a modulus of elasticity (E-module) in the longitudinal direction of 200 to 2500, preferably from 400 to 2000, daN / mm 2.
  • the modulus of elasticity can be determined by methods known per se (synthetic fibers, pages 63 to 68 (1981), Verlag Chemie, Weinheim).
  • the textile fabrics according to the invention generally have an extensibility in the longitudinal direction of more than 10, preferably from 15 to 200%, particularly preferably from 15 to 80%, before the reactive resin cures.
  • Elongation in the longitudinal direction means the change in length compared to the fully relaxed fabric, which is achieved when the fabric is loaded in the longitudinal direction with 10 N per cm of width. Such measurements can be carried out, for example, in accordance with DIN 61 632 (April 1985).
  • the earthen structures according to the invention generally have an extensibility in the transverse direction of 20 to 300%, preferably 40 to 200%, before the reactive resin has hardened.
  • the textile fabrics according to the invention generally have a weight per square meter of 40 to 300 g, preferably 100 to 200 g.
  • textile fabrics made of fibers of synthetic polymers are particularly preferred.
  • mixed textiles are preferred, a fiber made of a synthetic polymer being used in the longitudinal direction and a vegetable fiber being used in the transverse direction.
  • Textiles made of fibers of synthetic polymers or mixed textiles of synthetic polymers in the longitudinal direction and vegetable fibers in the transverse direction, the longitudinal expansion of which has been set by a shrinkage process, are preferred as the flat structures according to the invention.
  • textile fabrics which contain polyfile, textured filament threads made of man-made fibers, such as polyester, polyamide, polyacrylonitrile fibers, which have been thermally shrunk and which are made of natural fibers or man-made fibers with a modulus of elasticity of 400 to 2000 daN / mm2 in the transverse direction consist of fibers made of high-strength polyethylene terephthalates with a modulus of elasticity of 900 to 2000 daN / mm2.
  • man-made fibers such as polyester, polyamide, polyacrylonitrile fibers
  • the processing forms of the textile fabrics according to the invention can be woven, knitted, crocheted or non-woven.
  • Knitted fabrics such as warp knitted fabrics, knitted knitted fabrics and knitted fabrics are mentioned. Raschel knitted fabrics are particularly preferred.
  • Water-curing reactive resins are preferably resins based on polyurethane or polyvinyl resin.
  • Suitable water-curing polyurethanes are all organic polyisocyanates known per se, ie any compounds or mixtures of compounds which have at least two organically bound isocyanate groups per molecule. These include both low molecular weight polyisocyanates with a molecular weight below 400 and modification products of such low molecular weight polyisocyanates with a molecular weight that can be calculated from the functionality and the content of functional groups, for example 400 to 10,000, preferably 600 to 8,000, and in particular 800 to 5,000, molecular weight.
  • Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10, carbon atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10, carbon atoms, an aromatic hydrocarbon radical having 6 to 15, preferably 6 to 13, carbon atoms, or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, carbon atoms, mean.
  • Suitable low molecular weight polyisocyanates of this type are, for example, hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5 trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers,
  • Suitable higher molecular weight polyisocyanates are modification products of simple polyisocyanates of this type, ie polyisocyanates with, for example, isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units, such as those obtained by known processes of the prior art from the exemplified simple polyisocyanates of the above general Formula can be made.
  • modified polyisocyanates the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range 400 to 10,000, preferably 600 to 8,000 and in particular 800 to 5,000 are of particular interest.
  • These compounds are prepared in a manner known per se by reacting excess amounts of simple polyisocyanates of the type mentioned by way of example with organic compounds having at least two groups which are reactive toward isocyanate groups, in particular organic polyhydroxyl compounds.
  • Suitable polyhydroxyl compounds of this type are both simple polyhydric alcohols such as, for example, ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,2-butanediol, but in particular higher molecular weight polyether polyols and / or polyester polyols of the type known per se from polyurethane chemistry with molecular weights of 600 to 8,000, preferably 800 to 4,000, which have at least two, usually 2 to 8, but preferably 2 to 4 primary and / or secondary hydroxyl groups.
  • NCO prepolymers which, for example, consist of low molecular weight polyisocyanates of the type mentioned by way of example and less preferred compounds with isocyanate groups reactive groups such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, hydroxyl-containing polyester amides or hydroxyl-containing copolymers of olefinically unsaturated compounds have been obtained.
  • Compounds suitable for the preparation of the NCO prepolymers and having groups which are reactive toward isocyanate groups, in particular hydroxyl groups are, for example, the compounds disclosed by way of example in US Pat. No. 4,218,543, column 7, line 29 to column 9, line 25.
  • NCO prepolymers In the preparation of the NCO prepolymers, these compounds with groups that are reactive toward isocyanate groups are reacted with simple polyisocyanates of the type mentioned above, while maintaining an NCO / OH equivalent ratio of> 1.
  • the NCO prepolymers generally have an NCO content of 2.5 to 30, preferably 6 to 25% by weight. From this it can already be seen that in the context of the present invention under “NCO prepolymers” or under “prepolymers with terminal isocyanate groups” both the reaction products as such and their mixtures with excess amounts of unreacted starting polyisocyanates, which are often also called “semiprepolymer”. are to be understood.
  • Polyisocyanate components which are particularly preferred according to the invention are the technical polyisocyanates customary in polyurethane chemistry, ie hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, abbreviated: IPDI), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanatodiphenylmethane, its mixtures with the corresponding 2,4'- and 2,2'-isomers, polyisocyanate mixtures of the diphenylemthane series, as can be obtained by phosgenation of aniline / formaldehyde condensates in a manner known per se, the modification products of these technical polyisocyanates and especially NCO prepolymers containing biuret or isocyanurate groups of the type mentioned based on these technical polyisocyanates on the one
  • a polyisocyanate component which is particularly preferred according to the invention is partially carbodiimidized diisocyanatodiphenylmethane which, owing to the addition of monomeric diisocyanate to the carbodiimide structure, also has uretonimine groups.
  • the water-curing polyurethanes can contain catalysts known per se. In particular, this can be tert. Be amines that catalyze the isocyanate / water reaction and not a self-reaction (trimerization, allophanatization) (DE-A 23 57 931). Examples include tert. amine-containing polyethers (DE-A 26 51 089), low molecular weight tert. Amines like or dimorpholine diethyl ether or bis (2,6-dimethylmorpholino) diethyl ether (WO 86/01397. The content of catalyst, based on the tertiary nitrogen, is generally 0.05 to 0.5% by weight, based on the polymer resin.
  • Water-curing polyvinyl resins can be, for example, vinyl compounds which consist of a hydrophilic prepolymer with more than one polymerizable vinyl group in which a solid, insoluble vinyl redox catalyst is incorporated, one component of which is encapsulated by a water-soluble or water-permeable shell.
  • a redox catalyst is, for example, sodium bisulfite / copper (II) sulfate, in which, for example, the copper sulfate is encapsulated with poly-2-hydroxyethyl methyl acrylate.
  • Polyvinyl resins are described, for example, in EP-A 01 36 021. Water-curing polyurethanes are preferred.
  • the water-curing plastic resins can contain additives known per se, such as e.g. Leveling agents, thixotropic agents, defoamers and lubricants.
  • plastic resins can be colored or, if desired, contain UV stabilizers.
  • additives examples include: polydimethylsiloxanes, calcium silicates of the aerosil type, poly waxes (polyethylene glycols), UV stabilizers of the ionol type (DE-A 29 21 163), color pigments such as carbon black, iron oxides, titanium dioxides or phthalocyanines.
  • additives which are particularly suitable for polyurethane prepolymers are described in the Plastics Manual, Volume 7, Polyurethanes, pages 100 to 109 (1983). They are generally added in an amount of 0.5 to 5% (based on the resin).
  • a process for the production of the textile fabrics according to the invention with a water-curing reactive resin was also found, which is characterized in that the textile is produced from organic fibers with a modulus of elasticity in the range from 200 to 2500 daN / mm 2, an extensibility in the longitudinal direction of more than 10%, then impregnated and / or coated with the water-hardening plastic resin.
  • the textile that is to say the woven or knitted fabric, can be produced in a manner known per se.
  • the extensibility in the longitudinal direction can preferably be set by thermal shrinkage or wet treatment.
  • thermal shrinkage is known per se and can be carried out either in a drying oven with warm air and in special ovens with superheated steam.
  • the residence time of the material to be shrunk is generally 0.1 to 60 minutes, preferably 0.5 to 5 minutes, in the heated area.
  • the fabrics according to the invention can be used particularly preferably for support bandages in the medical and veterinary field. They are extremely easy to put on, which is shown by the fact that both human and animal extremities can be wrapped wrinkle-free in difficult areas such as knees, elbows or heels.
  • the fabrics according to the invention Compared to the known bandages made of glass fibers, the fabrics according to the invention, with superior strength, have the advantage of being lighter in weight. In addition, they do not form sharp edges, burn without residue and do not form glass dust when removing them with a saw or when processing them. A particular advantage is the increased X-ray transparency. Compared to bandages made of glass fibers, the flat structures according to the invention do not break even with severe deformation.
  • the textile fabrics according to the invention which are impregnated and / or coated with a water-curing plastic resin, are generally stored in the absence of moisture.
  • the textile backing materials (Example 2) are coated with the resins listed below.
  • the characteristics of the textile backing material used are summarized in Table 1.
  • the carrier material is thermally shrunk to achieve optimal elongation, for example 5 minutes at 110 ° C with steam or 10 minutes at 135 ° C with hot air in a drying cabinet. If necessary, the actual processing step is dried again at 110 ° to 190 ° C in order to completely remove residual moisture.
  • the prepolymers I to IV are coated in a dry cabin, the relative humidity of which is characterized by a water dew point of below -20 ° C.
  • the coating with resin is carried out in such a way that the weight of the desired length of the knitted textile tape is determined (for example 3 m or 4 yards) and then the amount of prepolymer required for adequate bonding is calculated and applied to the knitted tape.
  • This coating can be carried out by dissolving the prepolymer in a suitable inert solvent (for example methylene chloride or acetone), soaking the knitted tape and then removing the solvent in vacuo.
  • a suitable inert solvent for example methylene chloride or acetone
  • the resin can also be applied using suitable roller impregnation units or slide nozzles.
  • Such impregnation devices are described, for example, in US Pat. No. 4,502,479 and US Pat. No. 4,427,002.
  • the level of the resin content depends on the intended use. For use as synthetic support bandages, the resin content is 35 to 65%, while for technical use as insulation or sealing a complete impregnation of all mesh openings may be desirable (application amount of more than 65%) (Order quantity based on total weight).
  • the coated strips cut to length are then rolled up in the relaxed state and sealed in a water vapor-impermeable film.
  • the film bag is opened and the roll is immersed in water.
  • the dripping wet roll is then wound into the desired shaped body in one operation.
  • the processing time of the polyurethane prepolymer preferred according to the invention is approximately 2 to 8 minutes.
  • the elongation of the uncured coated tape is given in Table 1.
  • test specimens are wound, which have an inner diameter of 76 mm and consist of 10 layers, which are arranged flush on top of each other.
  • the test specimens are stored at 40 ° C. for 24 hours and then at 21 ° C. for 3 hours. Then they are crushed in a pressure-stretching machine (type Zwick No. 1484) between two plates in the radial direction (parallel to the cylinder axis), whereby maximum force F and the associated deformation distance are recorded (feed speed 50 mm / min).
  • Results Test specimen from example * F Max [N] Deformation path [mm] 3rd 1300 15 4th 377 18th 12 840 60 11 833 50 13 1310 20th 14 258 16 *) Excess tape is discarded.
  • test specimens are wound, which have an inner diameter of 45 mm and consist of 7 layers, which are arranged flush on top of each other. To determine the breaking strength, they are deformed 20% (9 mm) analogously to Example 19 in a pressure-stretching machine. The required force F is determined. Results: Test specimen from Ex. rated force F [N] at 20% deformation 3rd 1050 4th 180 7 1010 8th 960 9 900 10th 1120
  • test specimens are wound, which have an inner diameter of 76 mm and consist of 8 layers, which are arranged flush on top of each other. To determine the breaking strength, they are deformed analogously to Example 19 in a pressure-stretching machine, with both the force being measured at 20% and 50% deformation. Results: Test specimen from Ex. Measured force F [N] at 20% deformity. at 50% deformity. 3rd 892 1052 4th 185 264 5 236 447 6 404 587 12 370 770
  • Examples 19, 20 and 21 illustrate that elongate textile backing materials which consist of high-strength polyester fibers are at the level of the glass fiber tapes in terms of breaking strength, although they are advantageously about 1/2 to 1/3 in weight and even about 1 in terms of modulus of elasticity / 7 are lower.
  • extensible textile backing materials are quite capable of replacing extensible glass fiber backing materials, because in addition to their good breaking strength properties due to the extensibility, they also have the same good application behavior,
  • disadvantages such as rejected X-ray transparency, sharp edges and the dangerous glass dust do not have.
  • the example shows that the breaking strength is independent of the type of resin (test specimens from Examples 15 and 16). Furthermore, that high-strength polyfile polyester fibers are clearly superior to normal polyester staple fibers (staple yarns) (test specimens from Examples 17 and 18).

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Abstract

Sheet-like textile structures consist of fibres possessing a modulus of elasticity of 200 to 2500 daN/mm<2> and, before curing, have an extensibility in the longitudinal direction of more than 10%. The sheet-like textile structures coated or impregnated with reactive resin can be used as structural materials, in particular as fixed dressings in medicine or for industrial apparatuses.

Description

Die Erfindung betrifft Konstruktionsmaterialien, insbe­sondere für medizinische Stützverbände oder technische Vorrichtungen, die außer einer Querelastizität noch eine Längselastizität aufweisen, ein Verfahren zu ihrer Her­stellung und ihrer Verwendung.The invention relates to construction materials, in particular for medical support bandages or technical devices, which in addition to transverse elasticity also have longitudinal elasticity, a method for their production and their use.

Die erfindungsgemäßen Konstruktionsmaterialien bestehen im allgemeinen aus einer Trägerschicht, die mit einem Reaktivharz beschichtet und/oder imprägniert ist.The construction materials according to the invention generally consist of a carrier layer which is coated and / or impregnated with a reactive resin.

Im allgemeinen können die erfindungsgemäßen Konstruk­tionsmaterialien zur Versteifung, Formgebung und Ab­dichtung im medizinischen oder technischen Bereich verwendet werden.In general, the construction materials according to the invention can be used for stiffening, shaping and sealing in the medical or technical field.

Die erfindungsgemäßen Konstruktionsmaterialien können aber auch zur Herstellung von Behältern, Filtern, von Rohren, zum Verbinden von Konstruktionselementen, zur Fabrikation von dekorativen oder künstlerischen Artikeln, zu Versteifungszwecken oder als Füll- bzw. Dichtungsmaterial für Fugen und Hohlräume eingesetzt werden.However, the construction materials according to the invention can also be used for the production of containers, filters, pipes, for connecting construction elements, for the production of decorative or artistic articles, for stiffening purposes or as filling or sealing material for joints and cavities.

Konstruktionsmaterialien, die aus einem flexiblen Träger bestehen, der mit einem wasserhärtenden Reaktivharz be­schichtet oder getränkt ist, sind bereits bekannt. Bei­spielsweise sei die DE-A 23 57 931 genannt, in der Kon­struktionsmaterialien aus flexiblen Trägern, wie Gewir­ken, Geweben oder Vliesen, beschrieben werden, die mit wasserhärtenden Reaktivharzen, wie Isocyanaten oder durch Isocyanatgruppen modifizierte Präpolymere, be­schichtet oder getränkt sind. Um die Festigkeit dieser Konstruktionsmaterialien zu erhöhen, wurden Trägerma­terialien aus Glasfasern verwendet (US 45 02 479). Diese bekannten Trägermaterialien sind jedoch nur in der Quer­richtung dehnbar, in der Längsrichtung jedoch praktisch starr, um damit eine höhere Stabilität zu erreichen (US 45 02 479, Spalte 3, Zeile 45 bis 47).Construction materials which consist of a flexible carrier which is coated or impregnated with a water-hardening reactive resin are already known. For example, DE-A 23 57 931 may be mentioned, in which construction materials made of flexible supports, such as knitted fabrics, woven fabrics or nonwovens, are described, which are coated or impregnated with water-curing reactive resins, such as isocyanates or prepolymers modified by isocyanate groups. To increase the strength of these construction materials, carrier materials made of glass fibers were used (US 45 02 479). However, these known carrier materials are only stretchable in the transverse direction, but are practically rigid in the longitudinal direction in order to achieve greater stability (US 45 02 479, column 3, lines 45 to 47).

Nachteilig an den nur in Querrichtung dehnbaren Träger­materialien ist das Auftreten von Falten bei der An­bringung des Materials auf einem ungleichmäßigen Unter­grund mit konischen Erhebungen bzw. variablen Radien, z.B. einem menschlichen Bein.A disadvantage of the backing materials, which are only stretchable in the transverse direction, is the appearance of folds when the material is applied to an uneven surface with conical elevations or variable radii, e.g. a human leg.

In der US 46 09 578 werden als Träger für Konstruktions­materialien Raschel- und Trikotgewirke aus Glasfasern genannt, die in einer bestimmten Wirkweise verarbeitet sind. Diese Träger weisen außer der Querdehnung eine Längsdehnung von wenigstens 22 bis 25 % auf. Die Längs­dehnung ist bei diesen Gewirken aufgrund einer be­stimmten Legart bei der Maschenbildung und der hohen Rückstellkräfte der Glasfasern (Elastizitätsmodul 7000 bis 9000 [daN/mm² ]) gegeben.In US 46 09 578, Raschel and tricot fabrics made of glass fibers are mentioned as carriers for construction materials, which are processed in a certain mode of action. In addition to the transverse expansion, these supports have a longitudinal expansion of at least 22 to 25%. The longitudinal elongation is given in these knitted fabrics due to a certain type of stitching and the high restoring forces of the glass fibers (modulus of elasticity 7000 to 9000 [daN / mm²]).

Konstruktionsmaterialien auf Basis von Glasfasern, wie sie in der US 46 09 578 beschrieben werden, haben den Nachteil der schlechten Röntgentransparenz. Auch bilden sie an den Bruchstellen scharfe Kanten aus, die zu Ver­letzungen führen. Nachteilig ist außerdem das Auftreten von Glasstaub bei der Herstellung und dem Abnehmen des Konstruktionsmaterials.Construction materials based on glass fibers, as described in US 46 09 578, have the disadvantage of poor X-ray transparency. They also form sharp edges at the break points, which lead to injuries. Another disadvantage is the occurrence of glass dust during the manufacture and removal of the construction material.

Konstruktionsmaterialien wie sie in der US 46 09 578 be­schrieben werden, lassen sich nicht mit anderen Fasern als Glasfasern herstellen. Andere Fasern als Glasfasern weisen wesentlich geringere Elastizitätsmodule auf, so daß man keine Träger mit vergleichbarer Längs- und Querdehnung erhält.Construction materials as described in US 46 09 578 cannot be produced with fibers other than glass fibers. Fibers other than glass fibers have much lower moduli of elasticity, so that no beams with comparable longitudinal and transverse elongation are obtained.

Es wurden textile Flächengebilde gefunden, welche mit einem wasserhärtenden Reaktivharz imprägniert und/oder beschichtet sind, dadurch gekennzeichnet, daß sie aus organischen Fasern mit einem Elastizitätsmodul von 200 bis 2500 daN/mm² bestehen und vor der Aushärtung eine Dehnbarkeit in Längsrichtung von mehr als 10 % auf­weisen.There have been found textile fabrics which are impregnated and / or coated with a water-hardening reactive resin, characterized in that they consist of organic fibers with a modulus of elasticity of 200 to 2500 daN / mm² and that they have an extensibility in the longitudinal direction of more than 10% before curing. exhibit.

Überraschenderweise weisen die erfindungsgemäßen Flächengebilde außer einer Dehnung in Querrichtung auch eine in Längsrichtung auf.Surprisingly, in addition to stretching in the transverse direction, the fabrics according to the invention also have one in the longitudinal direction.

Die Längsrichtung bedeutet in der Regel die Verarbei­tungsrichtung des Textils, also beispielsweise in Richtung der Kette oder der Maschenstäbe.The longitudinal direction generally means the processing direction of the textile, for example in the direction of the chain or the wales.

Querrichtung bedeutet in der Regel senkrecht zur Verar­beitungsrichtung des Textils, also in Richtung von Schuß­oder Maschenreihe.Transverse direction generally means perpendicular to the processing direction of the textile, i.e. in the direction of the weft or stitch row.

Die erfindungsgemäßen Flächengebilde können in verschie­denen geometrischen Formen vorliegen. Bevorzugt liegen sie in Bandform vor, wobei die lange Seite des Bandes der Verarbeitungsrichtung des Textils entspricht.The fabrics according to the invention can be in various geometric shapes. They are preferably in tape form, the long side of the tape corresponding to the processing direction of the textile.

Organische Fasern für die erfindungsgemäßen Flächenge­bilde können Naturfasern oder Chemiefasern sein.Organic fibers for the fabrics according to the invention can be natural fibers or chemical fibers.

Als Naturfasern seien besonders Fasern von Pflanzen­haaren, wie Baumwolle, Bastfasern, wie Hanf und Jute und Hartfasern, wie Sisal, genannt. Insbesondere bevorzugt werden Baumwollfasern.Natural fibers include, in particular, fibers from plant hair, such as cotton, bast fibers, such as hemp and jute, and hard fibers, such as sisal. Cotton fibers are particularly preferred.

Als Chemiefasern seien besonders Fasern aus syntheti­schen Polymeren genannt. Beispielsweise seien Polymerisatfasern, wie Polyethylen-, Polypropylen-, Polychlorid- (z.B. Polyvinylchlorid und Polyvinyliden­chlorid), Polyacryl- und Vinylat-Fasern, Polykondensatfasern, wie Polyamid-, Polyester- und Polyharnstoffasern, und Polyadditionsfasern, wie Spandex oder Elasthanfasern, genannt.In particular, fibers made of synthetic polymers may be mentioned as chemical fibers. For example, polymer fibers such as polyethylene, polypropylene, polychloride (e.g. polyvinyl chloride and polyvinylidene chloride), polyacrylic and vinylate fibers, polycondensation fibers such as polyamide, polyester and polyurea fibers, and polyaddition fibers such as spandex or elastane fibers.

Es ist auch möglich, Viskosefasern einzusetzen.It is also possible to use viscose fibers.

Es ist auch möglich, Elastodienfäden (Gummifäden) einzu­setzen.It is also possible to use elastode threads (rubber threads).

Bevorzugte Synthesefasern sind Fasern aus Polyestern, Polyamiden und Polyacrylnitrilen.Preferred synthetic fibers are fibers made of polyesters, polyamides and polyacrylonitriles.

Es ist selbstverständlich auch möglich, Flächengebilde aus verschiedenen Fasern einzusetzen.It is of course also possible to use fabrics made of different fibers.

Insbesondere bevorzugt werden Flächengebilde aus Poly­ester- und/oder Polyamid- und/oder Baumwollfasern.Sheets made of polyester and / or polyamide and / or cotton fibers are particularly preferred.

Die Fasern für die erfindungsgemäßen Flächengebilde sind an sich bekannt (Synthesefasern, Seiten 3 bis 10 und 153 bis 221 (1981), Verlag Chemie, Weinheim).The fibers for the fabrics according to the invention are known per se (synthetic fibers, pages 3 to 10 and 153 to 221 (1981), Verlag Chemie, Weinheim).

Das vorzugsweise in Längsrichtung eingearbeitete Faden­system ermöglicht nach einem Schrumfprozeß die elasti­sche Dehnung in Längsrichtung. Im Falle der Verwendung von Fäden aus natürlichen Fasern werden hochgedrehte Garne bzw. Zwirne aus Stapelfasergarnen mit einem Dreh­ungskoeffizienten α zwischen 120 und 600 bevorzugt, so daß durch die hohe Drehung ein großes Torsionsmoment und damit eine Kringelneigung gegeben ist. Der Drehungs­koeffizient α errechnet sich nach

Figure imgb0001
wobei T die Anzahl der Drehungen je m Garn bzw. Zwirn bedeutet und TEX die längerbezogene Garnmasse in g je 1000 m Garn. Um ein unerwünschtes Drehen des textilen Flächengebildes zu vermeiden, werden bevorzugt die Fäden mit wechselnder Drehungsrichtung (im Uhrzeigersinn: S-­Drehung, Gegen-Uhrzeigersinn: Z-Drehung) in alternieren­der Folge, z.B. ein Faden S - 1 Faden Z order 2 Fäden S - 2 Fäden Z, eingearbeitet.The thread system, which is preferably incorporated in the longitudinal direction, enables elastic stretching in the longitudinal direction after a shrinking process. In the case of the use of threads made of natural fibers, high-twisted yarns or twists made of staple fiber yarns with a twist coefficient α between 120 and 600 are preferred, so that the high twist gives a high torsional moment and therefore a tendency to curl. The rotation coefficient α is calculated
Figure imgb0001
 where T is the number of twists per m of yarn or twine and TEX is the longer thread mass in g per 1000 m of yarn. To prevent the textile from rotating To avoid the formation of a flat structure, the threads with an alternating direction of rotation (clockwise: S-rotation, counter-clockwise: Z-rotation) are preferably incorporated in an alternating sequence, for example a thread S - 1 thread Z or 2 threads S - 2 threads Z.

Als dauerelastische Fäden können sowohl Fäden aus Natur­gummi (Elastodien) als auch synthetische Polyurethan-­Elastomerfäden (Elasthan) verwendet werden.Both threads made of natural rubber (elastodia) and synthetic polyurethane elastomer threads (elastane) can be used as permanently elastic threads.

Als Chemiefasern werden zur Erreichung der Längendehn­barkeit polyfile texturierte Filamentgarne aus Poly­ester, Polyamid etc. eingesetzt.Polyfile textured filament yarns made of polyester, polyamide etc. are used as chemical fibers to achieve the elongation.

Die elastischen Eigenschaften dieser Garne beruhen auf der im Verlauf des Texturierprozesses erhaltenen perma­nenten Kräuselung und Torsion der Fäden, die durch die thermoplastischen Eigenschaften der Materialien erreicht wird. Es können alle Typen von Texturierfäden verwendet werden, wie z.B. HE-Garne (hochelastische Kräuselgarne), Set-Garne, HB-Garne (Hochbauschgarne).The elastic properties of these yarns are based on the permanent crimping and torsion of the threads obtained in the course of the texturing process, which is achieved by the thermoplastic properties of the materials. All types of texturing threads can be used, e.g. HE yarns (highly elastic crimp yarns), set yarns, HB yarns (high-rise yarns).

Das in Längsrichtung eingearbeitete Fadensystem wird durch Verbindungsfäden zusammengehalten, wobei sowohl Stapelfasergarne bzw. Zwirne aus natürlichen Fasern als auch Stapelfasergarne bzw. polyfile Filamentgarne (Glattgarn) aus Chemiefasern verwendet werden können. Die Festigkeit dieser Garne wird durch den Elastizitäts­modul (E-Modul) charakterisiert.The thread system incorporated in the longitudinal direction is held together by connecting threads, it being possible to use staple fiber yarns or twists made of natural fibers as well as staple fiber yarns or polyfile filament yarns (plain yarn) made of man-made fibers. The strength of these yarns is characterized by the modulus of elasticity (modulus of elasticity).

Die Fasern für die erfindungsgemäßen Flächengebilde weisen einen Elastizitätsmodul (E-Modul) in Längsrich­tung von 200 bis 2500, bevorzugt von 400 bis 2000, daN/mm² auf. Der Elastizitätsmodul kann nach an sich bekannten Verfahren bestimmt werden (Synthesefasern, Seiten 63 bis 68 (1981), Verlag Chemie, Weinheim).The fibers for the fabrics according to the invention have a modulus of elasticity (E-module) in the longitudinal direction of 200 to 2500, preferably from 400 to 2000, daN / mm 2. The modulus of elasticity can be determined by methods known per se (synthetic fibers, pages 63 to 68 (1981), Verlag Chemie, Weinheim).

Die erfindungsgemäßen textilen Flächengebilde weisen im allgemeinen vor Aushärtung des Reaktivharzes eine Dehn­barkeit in Längsrichtung von mehr als 10, bevorzugt von 15 bis 200 %, insbesondere bevorzugt von 15 bis 80 %, auf. Unter der Dehnbarkeit in Längsrichtung versteht man die Längenveränderung gegenüber dem voll entspannten Flächengebilde, die erreicht wird, wenn das textile Flächengebilde in Längsrichtung pro cm Breite mit 10 N belastet wird. Solche Messungen können beispielsweise nach DIN 61 632 (April 1985) durchgeführt werden.The textile fabrics according to the invention generally have an extensibility in the longitudinal direction of more than 10, preferably from 15 to 200%, particularly preferably from 15 to 80%, before the reactive resin cures. Elongation in the longitudinal direction means the change in length compared to the fully relaxed fabric, which is achieved when the fabric is loaded in the longitudinal direction with 10 N per cm of width. Such measurements can be carried out, for example, in accordance with DIN 61 632 (April 1985).

Die erdfindungsgemäßen Flächengebilde weisem im allge­meinen vor Aushärtung des Reaktivharzes eine Dehnbarkeit in Querrichtung von 20 bis 300 %, bevorzugt von 40 bis 200 %, auf.The earthen structures according to the invention generally have an extensibility in the transverse direction of 20 to 300%, preferably 40 to 200%, before the reactive resin has hardened.

Die erfindungsgemäßen textilen Flächengebilde weisen im allgemeinen ein Gewicht pro Quadratmeter von 40 bis 300 g, bevorzugt von 100 bis 200 g, auf.The textile fabrics according to the invention generally have a weight per square meter of 40 to 300 g, preferably 100 to 200 g.

Erfindungsgemäß werden besonders textile Flächengebilde aus Fasern von synthetischen Polymeren bevorzugt. Im Fall der Verwendung von Pflanzenfasern werden Misch­textilien bevorzugt, wobei man in Längsrichtung eine Faser aus einem synthetischen Polymer und in Querrich­tung eine Pflanzenfaser verwendet.According to the invention, textile fabrics made of fibers of synthetic polymers are particularly preferred. In the case of the use of vegetable fibers, mixed textiles are preferred, a fiber made of a synthetic polymer being used in the longitudinal direction and a vegetable fiber being used in the transverse direction.

Bevorzugt als erfindungsgemäße Flächengebilde werden Textilien aus Fasern von synthetischen Polymeren oder Mischtextilien von synthetischen Polymeren in Längs­richtung und Pflanzenfasern in Querrichtung, deren Längendehnung durch einen Schrumpfungsprozeß eingestellt wurde.Textiles made of fibers of synthetic polymers or mixed textiles of synthetic polymers in the longitudinal direction and vegetable fibers in the transverse direction, the longitudinal expansion of which has been set by a shrinkage process, are preferred as the flat structures according to the invention.

Der Schrumfprozeß setzt nach Aktivierung des textilen Flächengebildes bzw. der darin enthaltenen Garne ein, wobei die Aktivierung z.B. mit Hilfe von folgenden Methoden erreicht werden kann:

  • a) thermische Behandlung mit Heißluft im Temperaturbe­reich 80 - 250°C,
  • b) thermische Behandlung mit Wasserdampf bzw. über­hitztem Wasserdampf im Temperaturbereich 100 - ­180°C,
  • c) Naßbehandlung des textilen Flächengebildes unter Verwendung von geeigneten Flüssigkeitsmedien, z.B. Wasser, Alkohol gegebenenfalls in Gegenwart von Hilfsmitteln (z.B. Tenside).
The shrinking process begins after activation of the textile fabric or the yarns contained therein, whereby the activation can be achieved, for example, using the following methods:
  • a) thermal treatment with hot air in the temperature range 80 - 250 ° C,
  • b) thermal treatment with steam or superheated steam in the temperature range 100-180 ° C,
  • c) Wet treatment of the textile fabric using suitable liquid media, for example water, alcohol, if appropriate in the presence of auxiliaries (for example surfactants).

Insbesondere bevorzugt werden hier textile Flächengebil­de, die in Längsrichtung polyfile, texturierte Filament­fäden aus Chemiefasern wie Polyester-, Polyamid-, Poly­acrylnitrilfasern enthalten, die thermisch geschrumpft wurden und die in Querrichtung aus Naturfasern oder Chemiefasern mit einem Elastizitätsmodul von 400 bis 2000 daN/mm², bevorzugt aus Fasern aus hochfesten Polyethylenterephthalaten mit einem Elastizitätsmodul von 900 bis 2000 daN/mm², bestehen.Particular preference is given here to textile fabrics which contain polyfile, textured filament threads made of man-made fibers, such as polyester, polyamide, polyacrylonitrile fibers, which have been thermally shrunk and which are made of natural fibers or man-made fibers with a modulus of elasticity of 400 to 2000 daN / mm² in the transverse direction consist of fibers made of high-strength polyethylene terephthalates with a modulus of elasticity of 900 to 2000 daN / mm².

Die Verarbeitungsformen der erfindungsgemäßen textilen Flächengebilde können Gewebe, Gewirke, Gestricke oder Vliese sein. Bevorzugt seien Gewirke wie Kettengewirke, Raschelgewirke und Trikotgewirke genannt. Insbesondere bevorzugt werden Raschelgewirke.The processing forms of the textile fabrics according to the invention can be woven, knitted, crocheted or non-woven. Knitted fabrics such as warp knitted fabrics, knitted knitted fabrics and knitted fabrics are mentioned. Raschel knitted fabrics are particularly preferred.

Wasserhärtende Reaktivharze sind bevorzugt Harze auf Polyurethan- oder Polyvinylharz-Basis.Water-curing reactive resins are preferably resins based on polyurethane or polyvinyl resin.

Als wasserhärtende Polyurethane kommen erfindungsgemäß alle an sich bekannten organischen Polyisocyanate in Frage, d.h. beliebige Verbindungen bzw. Gemische von Verbindungen, die pro Molekül mindestens zwei organisch gebundene Isocyanatgruppen aufweisen. Hierzu gehören sowohl niedermolekulare Polyisocyanate mit einem unter 400 liegendem Molekulargewicht als auch Modifizierungs­produkte derartiger niedermolekularer Polyisocyanate mit einem aus der Funktionalität und dem Gehalt an funk­tionellen Gruppen berechenbaren, z.B. 400 bis 10.000, vorzugsweise 600 bis 8.000, und insbesondere 800 bis 5.000, betragenden Molekulargewicht. Geeignete nieder­molekulare Polyisocyante sind beispielsweise solche der Formel
    Q (NCO)n,
in der
n = 2 bis 4, vorzugsweise 2 bis 3,
und
Q      einen aliphatischen Kohlenwasserstoffrest mit 2 bis 18, vorzugsweise 6 bis 10 C-Atomen,
einen cycloaliphatischen Kohlenwasserstoffrest mit 4 bis 15, vorzugsweise 5 bis 10 C-Atomen,
einen aromatischen Kohlenwasserstoffrest mit 6 bis 15, vorzugsweise 6 bis 13 C-Atomen,
oder einen araliphatischen Kohlenwasserstoffrest mit 8 bis 15, vorzugsweise 8 bis 13 C-Atomen,
bedeuten.Suitable water-curing polyurethanes according to the invention are all organic polyisocyanates known per se, ie any compounds or mixtures of compounds which have at least two organically bound isocyanate groups per molecule. These include both low molecular weight polyisocyanates with a molecular weight below 400 and modification products of such low molecular weight polyisocyanates with a molecular weight that can be calculated from the functionality and the content of functional groups, for example 400 to 10,000, preferably 600 to 8,000, and in particular 800 to 5,000, molecular weight. Suitable low molecular weight polyisocyanates are, for example, those of the formula
Q (NCO) n ,
in the
n = 2 to 4, preferably 2 to 3,
and
Q is an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10, carbon atoms,
a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10, carbon atoms,
an aromatic hydrocarbon radical having 6 to 15, preferably 6 to 13, carbon atoms,
or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13, carbon atoms,
mean.

Geeignete derartige niedermolekulare Polyisocyanate sind z.B. Hexamethylendiisocyanat, 1,12-Dodecandiisocyanat, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-­diisocyanat sowie beliebige Gemische dieser Isomeren, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-­cyclohexan, 2,4- und 2,6-Hexahydrotoluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Hexahydro-1,3- ­und/oder -1,4-phenylendiisocyanat, Perhydro-2,4′- ­und/oder -4,4′-diphenylmethan-diisocyanat, 1,3- und 1,4-­Phenylendiisocyanat, 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Diphenyl­methan-2,4′- und/oder -4,4′-diisocyanat, Naphthylen-1,5-­diisocyanat, Triphenylmethan-4,4′,4˝-triisocyanat oder Polyphenyl-polymethylenpolyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung erhalten werden.Suitable low molecular weight polyisocyanates of this type are, for example, hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5 trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4 , 4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4˝-triisocyanate or polyphenyl-polymethylene polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation.

Geeignete höhermolekulare Polyisocyanate sind Modifizie­rungsprodukte derartiger einfacher Polyisocyanate, d.h. Polyisocyanate mit z.B. Isocyanurat-, Carbodiimid-, Allophanat-, Biuret- oder Uretdion-Struktureinheiten, wie sie nach an sich bekannten Verfahren des Standes der Technik aus den beispielhaft genannten einfachen Poly­isocyanaten der oben genannten allgemeinen Formel her­gestellt werden können. Unter den höhermolekularen, modifizierten Polyisocyanaten sind insbesondere die aus der Polyurethanchemie bekannten Prepolymeren mit end­ständigen Isocyanatgruppen des Molekulargewichtsbereichs 400 bis 10.000, vorzugsweise 600 bis 8.000 und insbeson­dere 800 bis 5.000, von Interesse. Diese Verbindungen werden in an sich bekannter Weise durch Umsetzung von überschüssigen Mengen an einfachen Polyisocyanaten der beispielhaft genannten Art mit organischen Verbindungen mit mindestens zwei gegenüber Isocyanatgruppen reak­tionsfähigen Gruppen, insbesondere organischen Poly­hydroxylverbindungen hergestellt. Geeignete derartige Polyhydroxylverbindungen sind sowohl einfache mehr­wertige Alkohole wie z.B. Ethylenglykol, Trimethylol­propan, Propandiol-1,2 oder Butandiol-1,2, insbesondere jedoch höhermolekulare Polyetherpolyole und/oder Poly­esterpolyole der aus der Polyurethanchemie an sich bekannten Art mit Molekulargewichten von 600 biz 8.000, vorzugsweise 800 bis 4.000, die mindestens zwei, in der Regel 2 bis 8, vorzugsweise aber 2 bis 4 primäre und/oder sekundäre Hydroxylgruppen aufweisen. Selbstver­ständlich können auch solche NCO-Prepolymere eingesetzt werden, die beispielsweise aus niedermolekularen Poly­isocyanaten der beispielhaft genannten Art und weniger bevorzugten Verbindungen mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen wie z.B. Polythioetherpolyolen, Hydroxylgruppen aufweisenden Polyacetalen, Polyhydroxy­polycarbonaten, Hydroxylgruppen aufweisenden Polyester­amiden oder Hydroxylgruppen aufweisenden Copolymerisaten olefinisch ungesättigter Verbindungen erhalten worden sind. Zur Herstellung der NCO-Prepolymeren geeignete Verbindungen mit gegenüber Isocyanatgruppen reaktions­fähigen Gruppen, insbesondere Hydroxylgruppen, sind beispielsweise die in US-PS 4 218 543, Kolonne 7, Zeile 29 bis Kolonne 9, Zeile 25 beispielhaft offenbarten Ver­bindungen. Bei der Herstellung der NCO-Prepolymeren werden diese Verbindungen mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen mit einfachen Polyisocyanaten der oben beispielhaft genannten Art unter Einhaltung eines NCO/OH-Äquivalentverhältnisses von >1 zur Um­setzung gebracht. Die NCO-Prepolymeren weisen im allge­meinen einen NCO-Gehalt von 2,5 bis 30, vorzugsweise 6 bis 25 Gew.-% auf. Hieraus geht bereits hervor, daß im Rahmen der vorliegenden Erfindung unter "NCO-Prepoly­meren" bzw. unter "Prepolymeren mit endständigen Iso­cyantgruppen" sowohl die Umsetzungsprodukte als solche als auch ihre Gemische mit überschüssigen Mengen an nicht umgesetzten Ausgangspolyisocyanaten, die oft auch als "Semiprepolymer" bezeichnet werden, zu verstehen sind.Suitable higher molecular weight polyisocyanates are modification products of simple polyisocyanates of this type, ie polyisocyanates with, for example, isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units, such as those obtained by known processes of the prior art from the exemplified simple polyisocyanates of the above general Formula can be made. Of the higher molecular weight, modified polyisocyanates, the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range 400 to 10,000, preferably 600 to 8,000 and in particular 800 to 5,000 are of particular interest. These compounds are prepared in a manner known per se by reacting excess amounts of simple polyisocyanates of the type mentioned by way of example with organic compounds having at least two groups which are reactive toward isocyanate groups, in particular organic polyhydroxyl compounds. Suitable polyhydroxyl compounds of this type are both simple polyhydric alcohols such as, for example, ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,2-butanediol, but in particular higher molecular weight polyether polyols and / or polyester polyols of the type known per se from polyurethane chemistry with molecular weights of 600 to 8,000, preferably 800 to 4,000, which have at least two, usually 2 to 8, but preferably 2 to 4 primary and / or secondary hydroxyl groups. Of course, it is also possible to use those NCO prepolymers which, for example, consist of low molecular weight polyisocyanates of the type mentioned by way of example and less preferred compounds with isocyanate groups reactive groups such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, hydroxyl-containing polyester amides or hydroxyl-containing copolymers of olefinically unsaturated compounds have been obtained. Compounds suitable for the preparation of the NCO prepolymers and having groups which are reactive toward isocyanate groups, in particular hydroxyl groups, are, for example, the compounds disclosed by way of example in US Pat. No. 4,218,543, column 7, line 29 to column 9, line 25. In the preparation of the NCO prepolymers, these compounds with groups that are reactive toward isocyanate groups are reacted with simple polyisocyanates of the type mentioned above, while maintaining an NCO / OH equivalent ratio of> 1. The NCO prepolymers generally have an NCO content of 2.5 to 30, preferably 6 to 25% by weight. From this it can already be seen that in the context of the present invention under “NCO prepolymers” or under “prepolymers with terminal isocyanate groups” both the reaction products as such and their mixtures with excess amounts of unreacted starting polyisocyanates, which are often also called “semiprepolymer”. are to be understood.

Erfindungsgemäß besonders bevorzugte Polyisocyanatkompo­nenten sind die in der Polyurethanchemie üblichen tech­nischen Polyisocyanate, d.h. Hexamethylendiisocyanat, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclo­hexan (Isophorondiisocyanat, abgekürzt: IPDI), 4,4′-­Diisocyanato-dicyclohexylmethan, 4,4′-Diisocyanatodi­phenylmethan, dessen Gemische mit den entsprechenden 2,4′- und 2,2′-Isomeren, Polyisocyanatgemische der Di­phenylemthanreihe wie sie durch Phosgenierung von Anilin/Formaldehyd-Kondensaten in an sich bekannter Weise gewonnen werden können, die Biuret- oder Iso­cyanuratgruppen aufweisenden Modifizierungsprodukte dieser technischen Polyisocyanate und insbesondere NCO-­Prepolymere der genannten Art auf Basis dieser techni­schen Polyisocyanate einerseits und der beispielhaft genannten einfachen Polyolen und/oder Polyetherpolyolen und/oder Polyesterpolyolen andererseits, sowie beliebige Gemische derartiger Polyisocyanate. Isocyanate mit aromatisch gebundenen NCO-Gruppen sind erfindungsgemäß bevorzugt. Eine erfindungsgemäß besonders bevorzugte Polyisocyanat-Komponente stellt teilweise carbodiimidi­siertes Diisocyanatodiphenylmethan dar, welches infolge Anlagerung von monomerem Diisocyanat an die Carbodiimid-­Struktur auch Uretonimingruppen aufweist.Polyisocyanate components which are particularly preferred according to the invention are the technical polyisocyanates customary in polyurethane chemistry, ie hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, abbreviated: IPDI), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanatodiphenylmethane, its mixtures with the corresponding 2,4'- and 2,2'-isomers, polyisocyanate mixtures of the diphenylemthane series, as can be obtained by phosgenation of aniline / formaldehyde condensates in a manner known per se, the modification products of these technical polyisocyanates and especially NCO prepolymers containing biuret or isocyanurate groups of the type mentioned based on these technical polyisocyanates on the one hand and the simple polyols and / or polyether polyols and / or polyester polyols mentioned as examples and any mixtures of such polyisocyanates. Isocyanates with aromatically bound NCO groups are preferred according to the invention. A polyisocyanate component which is particularly preferred according to the invention is partially carbodiimidized diisocyanatodiphenylmethane which, owing to the addition of monomeric diisocyanate to the carbodiimide structure, also has uretonimine groups.

Die wasserhärtenden Polyurethane können an sich bekannte Katalysatoren enthalten. Insbesondere können dies tert. Amine sein, die die Isocyanat/Wasser-Reaktion und nicht eine Selbstreaktion (Trimerisierung, Allophanatisierung) katalysieren (DE-A 23 57 931). Als Beispiele seien genannt tert. aminhaltige Polyether (DE-A 26 51 089), niedermolekulare tert. Amine, wie

Figure imgb0002
oder Dimorpholindiethylether oder Bis-(2,6-dimethylmorpholino)-diethylether (WO 86/01397. Der Gehalt an Katalysator bezogen auf den tert.-Stickstoff beträgt im allgemeinen 0,05 bis 0,5 Gew.-% bezogen auf das Polymerharz.The water-curing polyurethanes can contain catalysts known per se. In particular, this can be tert. Be amines that catalyze the isocyanate / water reaction and not a self-reaction (trimerization, allophanatization) (DE-A 23 57 931). Examples include tert. amine-containing polyethers (DE-A 26 51 089), low molecular weight tert. Amines like
Figure imgb0002
 or dimorpholine diethyl ether or bis (2,6-dimethylmorpholino) diethyl ether (WO 86/01397. The content of catalyst, based on the tertiary nitrogen, is generally 0.05 to 0.5% by weight, based on the polymer resin.

Wasserhärtende Polyvinylharze können biespielsweise Vinylverbindungen sein, die aus einem hydrophilen Pre­polymer mit mehr als einer polymerisierbaren Vinylgruppe bestehen, in der ein fester, unlöslicher Vinyl-Redox Katalysator eingelagert ist, dessen einer Bestandteil von einer wasserlöslichen bzw. wasserdurchlässigen Hülle umkapselt ist. Ein solcher Redox Katalysator ist bei­spielsweise Natriumhydrogensulfit/Kupfer(II)sulfat, bei dem beispielsweise das Kupfersulfat mit Poly-2-hydroxy­ethylmethylacrylat verkapselt ist.Water-curing polyvinyl resins can be, for example, vinyl compounds which consist of a hydrophilic prepolymer with more than one polymerizable vinyl group in which a solid, insoluble vinyl redox catalyst is incorporated, one component of which is encapsulated by a water-soluble or water-permeable shell. Such a redox catalyst is, for example, sodium bisulfite / copper (II) sulfate, in which, for example, the copper sulfate is encapsulated with poly-2-hydroxyethyl methyl acrylate.

Polyvinylharze werden beispeilsweise in der EP-A 01 36 021 beschrieben.
Bevorzugt werden wasserhärtende Polyurethane.Polyvinyl resins are described, for example, in EP-A 01 36 021.
Water-curing polyurethanes are preferred.

Die wasserhärtenden Kunststoffharze können an sich be­kannte Zusatzmittel enthalten, wie z.B. Verlaufshilfs­mittel, Thixotropiermittel, Entschäumer und Gleit­mittel.The water-curing plastic resins can contain additives known per se, such as e.g. Leveling agents, thixotropic agents, defoamers and lubricants.

Weiterhin können die Kunststoffharze eingefärbt sein oder, falls erwünscht, UV-Stabilisatoren enthalten.Furthermore, the plastic resins can be colored or, if desired, contain UV stabilizers.

Als Zusatzmittel seien beispielsweise genannt: Polydi­methylsiloxane, Calciumsilikate vom Aerosil-Typ, Poly­wachse (Polyethylenglykole), UV-Stabilisatoren vom Ionol-Type (DE-A 29 21 163), Farbpigmente, wie Ruß, Eisenoxide, Titandioxide oder Phthalocyanine.Examples of additives which may be mentioned are: polydimethylsiloxanes, calcium silicates of the aerosil type, poly waxes (polyethylene glycols), UV stabilizers of the ionol type (DE-A 29 21 163), color pigments such as carbon black, iron oxides, titanium dioxides or phthalocyanines.

Die insbesondere für Polyurethan-Prepolymere geeigneten Zusatzmittel sind im Kunststoff-Handbuch, Band 7, Poly­urethane, Seiten 100 bis 109 (1983) beschrieben. Sie werden im allgemeinen in einer Menge von 0,5 bis 5% (bezogen auf das Harz) zugesetzt.The additives which are particularly suitable for polyurethane prepolymers are described in the Plastics Manual, Volume 7, Polyurethanes, pages 100 to 109 (1983). they are generally added in an amount of 0.5 to 5% (based on the resin).

Es wurde auch ein Verfahren zur Herstellung der erfin­dungsgemäßen textilen Flächengebilde mit einem wasser­härtenden Reaktivharz gefunden, das durch gekenn­zeichnet ist, daß man aus organischen Fasern mit einem Elastizitätsmodul im Bereich von 200 bis 2500 daN/mm² das Textil herstellt, eine Dehnbarkeit in Längsrichtung von mehr als 10 % einstellt, dann mit dem wasserhärten­den Kunststoffharz imprägniert und/oder beschichtet.A process for the production of the textile fabrics according to the invention with a water-curing reactive resin was also found, which is characterized in that the textile is produced from organic fibers with a modulus of elasticity in the range from 200 to 2500 daN / mm 2, an extensibility in the longitudinal direction of more than 10%, then impregnated and / or coated with the water-hardening plastic resin.

Die Herstellung des Textils, also des Gewebes oder des Gewirkes, kann in an sich bekannter Weise erfolgen.The textile, that is to say the woven or knitted fabric, can be produced in a manner known per se.

Die Einstellung der Dehnbarkeit in Längsrichtung kann bevorzugt durch eine thermische Schrumpfung oder eine Naßbehandlung erfolgen. Die Durchführung der thermischen Schrumpfung ist an sich bekannt und kann entweder im Trockenofen mit Warmluft und in Spezialöfen mit über­hitztem Wasserdampf durchgeführt werden. Die Verweil­dauer des zu schrumpfenden Materials beträgt im all­gemeinen 0,1 bis 60 Minuten, bevorzugt 0,5 bis 5 Mi­nuten, in dem erwärmten Bereich.The extensibility in the longitudinal direction can preferably be set by thermal shrinkage or wet treatment. The implementation of thermal shrinkage is known per se and can be carried out either in a drying oven with warm air and in special ovens with superheated steam. The residence time of the material to be shrunk is generally 0.1 to 60 minutes, preferably 0.5 to 5 minutes, in the heated area.

Die erfindungsgemäßen Flächengebilde können besonders bevorzugt für Stützverbände im medizinischen und veterinärmedizinischen Bereich, verwendet werden. Sie weisen einen hervorragenden Anlegekomfort auf, was sich darin zeigt, daß sowohl menschliche wie tierische Extremitäten an schwierigen Stellen wie Knie, Ellenbogen oder Ferse faltenfrei umwickelt werden können.The fabrics according to the invention can be used particularly preferably for support bandages in the medical and veterinary field. They are extremely easy to put on, which is shown by the fact that both human and animal extremities can be wrapped wrinkle-free in difficult areas such as knees, elbows or heels.

Ähnliches gilt für andere Anwendungsbereiche bei denen man Formteile, die gebogen oder verwinkelt sind, falten­frei umwickeln kann.The same applies to other areas of application in which molded parts that are bent or angled can be wrapped wrinkle-free.

Gegenüber den bekannten Bandagen aus Glasfasern haben die erfindungsgemäßen Flächengebilde bei überlegener Festigkeit, den Vorteil eines leichteren Gewichtes. Hinzu kommt das sie keine scharfen Kanten ausbilden, rückstandfrei verbrennen und bei der Abnahme mit einer Säge und bei der Verarbeitung keinen Glasstaub bilden. Ein besonderer Vorteil ist die erhöhte Röntgentranspa­renz. Im Vergleich zu Bandagen aus Glasfasern brechen die erfindungsgemäßen Flächengebilde selbst bei starker Deformation nicht.Compared to the known bandages made of glass fibers, the fabrics according to the invention, with superior strength, have the advantage of being lighter in weight. In addition, they do not form sharp edges, burn without residue and do not form glass dust when removing them with a saw or when processing them. A particular advantage is the increased X-ray transparency. Compared to bandages made of glass fibers, the flat structures according to the invention do not break even with severe deformation.

Die erfindungsgemäßen textilen Flächengebilde, die mit einem wasserhärtenden Kunststoffharz imprägniert und/oder beschichtet sind, werden im allgemeinen unter Ausschluß von Feuchtigkeit gelagert.The textile fabrics according to the invention, which are impregnated and / or coated with a water-curing plastic resin, are generally stored in the absence of moisture.

Beispiel 1 (wasserhärtende Kunststoffharze) Example 1 (water-curing plastic resins)

Die textilen Trägermaterialien (Beispiel 2) werden mit nachstehend aufgeführten Harzen beschichtet.The textile backing materials (Example 2) are coated with the resins listed below.

Prepolymer IPrepolymer I

100 Tle. eines technischen Polyphenyl-polymethylen-poly­isocyanates, erhalten durch Phosgenierung eines Anilin-­Formaldehyd-Kondensates (η25°C = 200 mPa.s; NCO-Gehalt = 31 %), (Roh-MDI), werden mit 32,2 Teilen propoxylier­tem Triethanolamin (OH-Zahl = 150 mg KOH/g) zu einem Prepolymer mit 20,0 % NCO-Gehalt und einer Viskosität von η25°C = 20.000 mPa.s umgesetzt. Katalysatorgehalt = 0,30 % tert. Aminstickstoff.100 parts of a technical polyphenyl-polymethylene polyisocyanate, obtained by phosgenation of an aniline-formaldehyde condensate (η25 ° C = 200 mPa.s; NCO content = 31%), (crude MDI), with 32.2 parts propoxylated triethanolamine (OH number = 150 mg KOH / g) to a prepolymer with 20.0% NCO content and a viscosity of η25 ° C = 20,000 mPa.s implemented. Catalyst content = 0.30% tert. Amine nitrogen.

Prepolymer IIPrepolymer II

660,0 Tle. Bis-(4-isocyanatophenyl)-methan, welches carbodiimidisierte Anteile enthält (NCO-Gehalt = 29 %), werden mit 3400 Tlen. propoxyliertem Triethanolamin (OH-­Zahl = 150 mg KOH/g) zu einem Prepolymer umgesetzt. Ferner werden zugesetzt 1 Teil eines Polydimethyl­siloxans mit einer Viskosität η25°C von 11,24 mPa.s und 15 Tle. eines handelsüblichen UV-Stabilisators (ein Cyanalkylindolderivat). Das Prepolymer hat nach der Abreaktion eine Viskosität η25°C von 23 000 mPa.s und einen Isocyanatgehalt von 13,5 %; es enthält 0,45 % tert. Stickstoff.660.0 parts of bis (4-isocyanatophenyl) methane, which contains carbodiimidized components (NCO content = 29%), are mixed with 3400 parts. propoxylated triethanolamine (OH number = 150 mg KOH / g) converted to a prepolymer. 1 part of a polydimethylsiloxane with a viscosity η25 ° C. of 11.24 mPa.s and 15 parts of a commercially available UV stabilizer (a cyanalkylindole derivative) are also added. After the reaction, the prepolymer has a viscosity η25 ° C of 23,000 mPa.s and an isocyanate content of 13.5%; it contains 0.45% tert. Nitrogen.

Prepolymer IIIPrepolymer III

In einen Rührkessel werden 6,48 kg Isocyanat (Bis(4-iso­cyanatophenyl)-methan, welches carbodiimidisierte An­teile enthält, vorgelegt. Dann werden 7,8 g eines Poly­dimethylsiloxans mit η25°C = 30 000 g/mol und 4,9 g Benzoylchlorid sowie danach 1,93 kg eines durch Propoxy­lierung von Propylenglykol hergestellten Polyethers (OH-­Zahl 112 mg KOH/g), 1.29 kg eines durfch Propoxylierung von Glycerin hergestellten Polyesters (OH-Zahl 250 mg KOH/g) und 190 g Dimorpholinodiethylether zugegeben. Nach 30 Minuten erreicht die Reaktionstemperatur 45°C, nach 1 Stunde ist das Temperaturmaximum von 48°C er­reicht. 500 g eines Polydimethylsiloxans mit η25°C = 100 mPa.s werden zugesetzt und untergerührt. Die Vis­kosität des fertigen Prepolymers η25°C beträgt 15 700 mPa.s, der Isocyanatgehalt 12,9 %.6.48 kg of isocyanate (bis (4-isocyanatophenyl) methane, which contains carbodiimidized components, are placed in a stirred kettle. Then 7.8 g of a polydimethylsiloxane with η25 ° C. = 30,000 g / mol and 4.9 g of benzoyl chloride are introduced and then 1.93 kg of a polyether produced by propoxylation of propylene glycol (OH number 112 mg KOH / g), 1.29 kg of a polyester produced by propoxylation of glycerol (OH number 250 mg KOH / g) and 190 g of dimorpholinodiethyl ether The reaction temperature reached 45 ° C. for 30 minutes, and after 1 hour the maximum temperature reached 48 ° C. 500 g of a polydimethylsiloxane with η25 ° C. = 100 mPa.s were added and the mixture was stirred in. The viscosity of the finished prepolymer η25 ° C. was 15,700 mPa.s, the isocyanate content 12.9%.

Prepolymer IVPrepolymer IV

100 Tle. eines technischen Polyphenyl-polymethylen­polyisocyanats, erhalten durch Phosgenierung eines Anilin-Formaldehyd-Kondensates (η25°C: 200 mPa.s; NCO-­Gehalt: 31 % (Roh-MDI) werden mit 32,2 Teilen ethoxyliertem Triethanolamin (OH-Zahl = 149 mg KOH/g) zu einem Prepolymer mit 18,9 % NCO-Gehalt und einer Viskosität von η25°C: 28000 mPa.s umgesetzt. Kataly­satorgehalt: 0,3 % tert. Aminstickstoff.100 parts of a technical polyphenyl-polymethylene polyisocyanate obtained by phosgenation of an aniline-formaldehyde condensate (η25 ° C: 200 mPa.s; NCO content: 31% (raw MDI) are mixed with 32.2 parts of ethoxylated triethanolamine (OH- Number = 149 mg KOH / g) converted into a prepolymer with 18.9% NCO content and a viscosity of η25 ° C: 28000 mPa.s Catalyst content: 0.3% tertiary amine nitrogen.

Beispiel 2 (Trägermaterialien) Example 2 (carrier materials)

Die Kenndaten des verwendeten textilen Trägermaterials sind in Tabelle 1 zusammengestellt. Tabelle 1 Textile Trägermaterialien Trägermaterial Zusammensetzung* Gesamttyp/% Breite cm Längendehnung % g/m² Querdehnung % Maschenreihe 10 cm Maschenstäbe 10 cm A PES-TEX/PES-HF 27:73 8,6 37,5 % 115 80 56 49 B PES-TEXS/PES-HF 45:55 7,5 35,0 % 155 68 54 44 C PES-TEXS/PES-GL 59:41 7,6 13 % 142 80 60 59 D PES-TEXS/PES-NS 38:62 7,5 24 % 244 74 50 59 E PES-TEXS/PES-HF 49:51 7,5 25 % 193 70 50 59 F PES-TEXS/PES-HF 42:58 7,5 25 % 230 48 50 59 G PES-TEX/BW 51:49 7,7 53 % 102 84 72 57 H PA1/PES-MF 31:69 7,9 18 % 172 60 55 57 I PES-TEX/PES-MF 19:81 9,0 16 % 170 45 50 59 K PA2/BW 46:54 7,9 26 % 79 74 53 58 L PES-TEX/PES-HF 31:69 11,0 62 % 118 90 51 49 M PES-TEXS/PES-ST 55:45 10,8 47 % 140 64 58 78 V1 (Vergleich) Glasfaser (US-PS 46 09 578) 7,5 19 % 291 66 56 51 V2 (Vergleich) BW (EP-PS 90 289) 7,5 0 64 310 35 60 *) Bemerkung: Die genaue Charakterisierung der Garntypen ergibt sich aus Tabelle 2. Sämtliche Angaben beziehen sich auf das Rohmaterial. Tabelle 2 Charakterisierung der Garntypen PES-TEXS: 167 dtex, f 30 x 2, polyfines texturiertes Polyesterfilamentgarn HE-Garn, K = 62 %) PES-TEX: 167 dtex, f 30 x 1, polyfiles texturiertes Polyesterfilamentgarn (HE-Garn, K = 60%) PES-HF: 550 dtex, f 96 VZ 60, polyfiles, hochfestes Polyesterfilamentgarn normal schrumpfend, E = 1650 daN/mm² PES-GL: 167 dtex, f 32 x 2, polyfiles Polyesterfilamentgarn PES-NS: 830 dtex, f 200, polyfiles, hochfestes Polyesterfilamentgarn, normal schrumpfend E = 1170 daN/mm² PES-MF: 550 dtex, f 96, polyfiles, hochfestes Polyesterfilamentgarn, schrumpfarm, E = 980 daN/mm² PES-ST: 45 tex x 1, normales Polyester Spinnfasergarn (Stapelfaser) PA 1: 110 dtex, f 34 x 2, polyfiles texturierte Polyamidfilamentgarn (HE-Garn, K = 61%). PA 2: 78 dtex, f 17 x 2, polyfiles texturiertes Polyamidfilamentgarn (HE-Garn, K = 66%). K: Kennkräuselung (DIN 53 840) E: Elastizitätsmodul The characteristics of the textile backing material used are summarized in Table 1. Table 1 Textile backing materials Backing material Composition * total type /% Width cm Elongation% g / m² Transverse elongation% Row of stitches 10 cm Meshes 10 cm A PES-TEX / PES-HF 27:73 8.6 37.5% 115 80 56 49 B PES-TEXS / PES-HF 45:55 7.5 35.0% 155 68 54 44 C. PES-TEXS / PES-GL 59:41 7.6 13% 142 80 60 59 D PES-TEXS / PES-NS 38:62 7.5 24% 244 74 50 59 E PES-TEXS / PES-HF 49:51 7.5 25% 193 70 50 59 F PES-TEXS / PES-HF 42:58 7.5 25% 230 48 50 59 G PES-TEX / BW 51:49 7.7 53% 102 84 72 57 H PA1 / PES-MF 31:69 7.9 18% 172 60 55 57 I. PES-TEX / PES-MF 19:81 9.0 16% 170 45 50 59 K PA2 / BW 46:54 7.9 26% 79 74 53 58 L PES-TEX / PES-HF 31:69 11.0 62% 118 90 51 49 M PES-TEXS / PES-ST 55:45 10.8 47% 140 64 58 78 V1 (comparison) Glass fiber (US-PS 46 09 578) 7.5 19% 291 66 56 51 V2 (comparison) BW (EP-PS 90 289) 7.5 0 64 310 35 60 *) Note: The exact characterization of the yarn types is shown in Table 2. All information relates to the raw material. Characterization of yarn types PES-TEXS: 167 dtex, f 30 x 2, polyfine textured polyester filament yarn HE yarn, K = 62%) PES-TEX: 167 dtex, f 30 x 1, polyfiles textured polyester filament yarn (HE yarn, K = 60%) PES-HF: 550 dtex, f 96 VZ 60, polyfiles, high strength polyester filament yarn normal shrinking, E = 1650 daN / mm² PES-GL: 167 dtex, f 32 x 2, polyfiles polyester filament yarn PES-NS: 830 dtex, f 200, polyfiles, high tenacity polyester filament yarn, normal shrinking E = 1170 daN / mm² PES-MF: 550 dtex, f 96, polyfiles, high tenacity polyester filament yarn, low shrinkage, E = 980 daN / mm² PES-ST: 45 tex x 1, normal polyester spun yarn (staple fiber) PA 1: 110 dtex, f 34 x 2, polyfiles textured polyamide filament yarn (HE yarn, K = 61%). PA 2: 78 dtex, f 17 x 2, polyfiles textured polyamide filament yarn (HE yarn, K = 66%). K: characteristic crimp (DIN 53 840) E: modulus of elasticity

Das Trägermaterial wird zur Erzielung einer optimalen Längendehnung thermisch geschrumpft, z.B. 5 Minuten bei 110°C mit Wasserdampf oder 10 Minuten bei 135°C mit Heißluft im Trockenschrank. Falls erforderlich wird zu dem eigentlichen Verarbeitungsschritt nochmals bei 110° bis 190°C getrocknet, um Reste von Feuchtigkeit voll­ständig zu entfernen. Die Beschichtung mit den Prepoly­meren I bis IV erfolgt in einer trockenen Kabine, deren relative Feuchte durch einen Taupunkt des Wassers von unterhalb -20°C gekennzeichnet ist. Die Beschichtung mit Harz wird so durchgeführt, daß man das Gewicht der ge­wünschten Länge des Textilen Gewirkebandes ermittelt (z.B. 3 m oder 4 yard) und dann die für eine ausrei­chende Verklebung erforderliche Menge des Prepolymers berechnet und auf das Gewirkeband aufbringt. Diese Be­schichtung kann in der Weise erfolgen, daß das Prepoly­mer in einem geeigneten inerten Lösungsmittel (bei­speilsweise Methylenchlorid oder Aceton) aufgelöst wird, das Gewirkeband damit getränkt und das Lösungsmittel anschließend im Vakuum entfernt wird. Weiterhin kann das Harz aber auch über geeignete Walzenimprägnierwerke oder Schlitsdüsen aufgebracht werden. Solche Imprägnierein­richtung sind z.B. in der US-PS 4 502 479 und der US-­PS 4 427 002 beschrieben. Die Höhe des Harzgehaltes richtet sich nach dem jeweiligen Verwendungszweck. Für den Einsatz als synthetische Stützverbände beträgt die Höhe des Harzgehaltes 35 bis 65 %, während für technische Verwendung als Isolierung oder Abdichtung eine vollständige Tränkung aller Maschenöffnungen erwünscht sein kann (Auftragsmenge von mehr als 65 %) (Auftragsmenge bezogen auf Gesamtgewicht). Die auf Länge geschnittenen beschichteten Bänder werden dann im entspannten Zustand aufgerollt und in einer wasserdampf­undurchlässigen Folie versiegelt. Zur Herstellung der in den nachfolgenden Beispielen aufgeführten Probekör­per, wird der Folienbeutel geöffnet und die Rolle in Wasser getaucht. Danach wird die tropfnasse Rolle in einem Arbeitsgang zu dem gewünschten Formkörper ge­wickelt. Die Verarbeitungszeit des erfindungsgemäß be­vorzugten Polyurethan-Prepolymeren beträgt ca. 2 bis 8 Minuten. Die Längendehnung des nicht gehärteten be­schichteten Bandes ist in der Tabelle 1 angegebenen.The carrier material is thermally shrunk to achieve optimal elongation, for example 5 minutes at 110 ° C with steam or 10 minutes at 135 ° C with hot air in a drying cabinet. If necessary, the actual processing step is dried again at 110 ° to 190 ° C in order to completely remove residual moisture. The prepolymers I to IV are coated in a dry cabin, the relative humidity of which is characterized by a water dew point of below -20 ° C. The coating with resin is carried out in such a way that the weight of the desired length of the knitted textile tape is determined (for example 3 m or 4 yards) and then the amount of prepolymer required for adequate bonding is calculated and applied to the knitted tape. This coating can be carried out by dissolving the prepolymer in a suitable inert solvent (for example methylene chloride or acetone), soaking the knitted tape and then removing the solvent in vacuo. Furthermore, the resin can also be applied using suitable roller impregnation units or slide nozzles. Such impregnation devices are described, for example, in US Pat. No. 4,502,479 and US Pat. No. 4,427,002. The level of the resin content depends on the intended use. For use as synthetic support bandages, the resin content is 35 to 65%, while for technical use as insulation or sealing a complete impregnation of all mesh openings may be desirable (application amount of more than 65%) (Order quantity based on total weight). The coated strips cut to length are then rolled up in the relaxed state and sealed in a water vapor-impermeable film. To produce the test specimens listed in the examples below, the film bag is opened and the roll is immersed in water. The dripping wet roll is then wound into the desired shaped body in one operation. The processing time of the polyurethane prepolymer preferred according to the invention is approximately 2 to 8 minutes. The elongation of the uncured coated tape is given in Table 1.

Beispiel 3 (Vergleichsbeispiel) Example 3 (comparative example )

3,66 m des Vergleichsmaterials V1 mit einem Gewicht von 79,9 g werden mit 51,1 g Prepolymer II in der oben ange­gebenen Art beschichtet, aufgerollt und verpackt.3.66 m of the comparative material V1 with a weight of 79.9 g are coated with 51.1 g of prepolymer II in the manner indicated above, rolled up and packaged.

Beispiel 4 (Vergleichsbeispiel) Example 4 (comparative example )

3,00 m des Vergleichsmaterials V2 mit einem Gewicht von 14,4 g werden mit 22,3 g Prepolymer I in der oben ange­gebenen Art beschichtet, aufgerollt und verpackt. Beispiele 5 bis 18 Analog zu 1 und 2 werden folgende Bänder hergestellt und verpackt Bsp. Trägermaterial Länge des Bandes Gewicht des Bandes Prepolymer Gewicht des Prepolymeren 5 A 3,00 m 24,6 g II 34,4 g 6 B 3,00 m 35,7 g II 42,8 g 7 C 3,00 m 39,7 g II 55,6 g 8 D 3,00 m 56,0 g II 56,0 g 9 E 3,00 m 44,2 g II 53,0 g 10 F 3,00 m 52,0 g II 57,2 g 11 G 3,00 m 23,3 g I 34,9 g 12 H 3,66 m 47,2 g II 42,4 g 13 I 3,00 m 48,4 g II 53,2 g 14 K 3,00 m 15,6 g I 23,7 g 15 A 3,66 m 32,6 g III 48,9 g 16 A 3,66 m 31,8 g IV 44,5 g 17 L 3,66 m 43,9 g III 65,9 g 18 M 3,66 m 54,8 g III 82,2 g 3.00 m of the comparative material V2 with a weight of 14.4 g are coated with 22.3 g of prepolymer I in the manner indicated above, rolled up and packaged. Examples 5 to 18 The following tapes are produced and packaged analogously to 1 and 2 E.g. Backing material Length of the band Weight of the band Prepolymer Weight of the prepolymer 5 A 3.00 m 24.6 g II 34.4 g 6 B 3.00 m 35.7 g II 42.8 g 7 C. 3.00 m 39.7 g II 55.6 g 8th D 3.00 m 56.0 g II 56.0 g 9 E 3.00 m 44.2 g II 53.0 g 10th F 3.00 m 52.0 g II 57.2 g 11 G 3.00 m 23.3 g I. 34.9 g 12 H 3.66 m 47.2 g II 42.4 g 13 I. 3.00 m 48.4 g II 53.2 g 14 K 3.00 m 15.6 g I. 23.7 g 15 A 3.66 m 32.6 g III 48.9 g 16 A 3.66 m 31.8 g IV 44.5 g 17th L 3.66 m 43.9 g III 65.9 g 18th M 3.66 m 54.8 g III 82.2 g

Beispiel 19Example 19

Es werden 6 Probekörper gewickelt, die einen Innendurch­messer von 76 mm besitzen und aus 10 Lagen bestehen, die bündig übereinander angeordnet sind. Zur Bestimmung der Bruchfestigkeit werden die Probekörper 24 Stunden bei 40°C und danach 3 Stunden bei 21°C aufbewahrt. Danach werden sie in einer Druck-Dehnungs-Maschine (Typ Zwick Nr. 1484) zwischen zwei Platten in radialer Richtung (parallel zur Zylinderachse) zerdrückt, wobei maximale Kraft F und die dazugehörige Deformationsstrecke festge­halten werden (Vorschubgeschwindigkeit 50 mm/Min). Ergebnisse: Probekörper aus Beispiel* FMax [N] Deformationsweg [mm] 3 1300 15 4 377 18 12 840 60 11 833 50 13 1310 20 14 258 16 *) überschüssiges Band wird verworfen. 6 test specimens are wound, which have an inner diameter of 76 mm and consist of 10 layers, which are arranged flush on top of each other. To determine the breaking strength, the test specimens are stored at 40 ° C. for 24 hours and then at 21 ° C. for 3 hours. Then they are crushed in a pressure-stretching machine (type Zwick No. 1484) between two plates in the radial direction (parallel to the cylinder axis), whereby maximum force F and the associated deformation distance are recorded (feed speed 50 mm / min). Results: Test specimen from example * F Max [N] Deformation path [mm] 3rd 1300 15 4th 377 18th 12 840 60 11 833 50 13 1310 20th 14 258 16 *) Excess tape is discarded.

Beispiel 20Example 20

Es werden 6 Probekörper gewickelt, die einen Innendurch­messer von 45 mm besitzen und aus 7 Lagen bestehen, die bündig übereinander angeordnet sind. Zur Bestimmung der Bruchfestigkeit werden sie analog zu Beispiel 19 in einer Druck-Dehnungs-Maschine zu 20 % deformiert (9 mm). Die erforderliche Kraft F wird festgestellt. Ergebnisse: Probekörper aus Bsp. bemessene Kraft F [N] bei 20% Deformation 3 1050 4 180 7 1010 8 960 9 900 10 1120 6 test specimens are wound, which have an inner diameter of 45 mm and consist of 7 layers, which are arranged flush on top of each other. To determine the breaking strength, they are deformed 20% (9 mm) analogously to Example 19 in a pressure-stretching machine. The required force F is determined. Results: Test specimen from Ex. rated force F [N] at 20% deformation 3rd 1050 4th 180 7 1010 8th 960 9 900 10th 1120

Beispiel 21Example 21

Es werden 5 Prüfkörper gewickelt, die einen Innendurch­messer von 76 mm besitzen und aus 8 Lagen bestehen, die bündig übereinander angeordnet sind. Zur Bestimmung der Bruchfestigkeit werden sie analog zu Beispiel 19 in einer Druck-Dehnungs-Maschine deformiert, wobei hier sowohl die Kraft bei 20 % und 50 % Deformation gemessen wurde. Ergebnisse: Probekörper aus Bsp. Gemessene Kraft F [N] bei 20% Deform. bei 50% Deform. 3 892 1052 4 185 264 5 236 447 6 404 587 12 370 770 5 test specimens are wound, which have an inner diameter of 76 mm and consist of 8 layers, which are arranged flush on top of each other. To determine the breaking strength, they are deformed analogously to Example 19 in a pressure-stretching machine, with both the force being measured at 20% and 50% deformation. Results: Test specimen from Ex. Measured force F [N] at 20% deformity. at 50% deformity. 3rd 892 1052 4th 185 264 5 236 447 6 404 587 12 370 770

Beispiele 19, 20 und 21 verdeutlichen, daß längendehn­bare textile Trägermaterialien die aus hochfesten Poly­esterfasern bestehen bezüglich der Bruchfestigkeit auf dem Niveau der Glasfaserbänder liegen, obwohl sie vorteilhafterweise gewichtsmäßig ca. 1/2 bis 1/3 und bezüglich des E-Moduls sogar ca. 1/7 tiefer liegen.Examples 19, 20 and 21 illustrate that elongate textile backing materials which consist of high-strength polyester fibers are at the level of the glass fiber tapes in terms of breaking strength, although they are advantageously about 1/2 to 1/3 in weight and even about 1 in terms of modulus of elasticity / 7 are lower.

Somit sind längendehnbare textile Trägermaterialien durchaus in der Lage, längendehnbare Glasfaser-Träger­materialien zu ersetzen, da sie neben ihren guten Bruch­festigkeitseigenschaften bedingt durch die Längendehn­barkeit auch eine gleich gutes Anlegeverhalten besitzen, jedoch Nachteile wie schlehte Röntgentransparenz, Scharfkantigkeit und den gefährlichen Glasstaub nicht aufweisen.Thus, extensible textile backing materials are quite capable of replacing extensible glass fiber backing materials, because in addition to their good breaking strength properties due to the extensibility, they also have the same good application behavior, However, disadvantages such as rejected X-ray transparency, sharp edges and the dangerous glass dust do not have.

Beispiel 22Example 22

Analog zu Beispiel 19 werden 2 Prüfkörper gewickelt und die Bruchfestigkeit bei 20 % und 50 % Deformation be­stimmt. Ergebnisse: Probekörper aus Bsp. Gemessene Kraft F [N] bei 20% Deform. bei 50% Deform. 15 220 349 16 223 376 17 280 435 18 163 175 (gebrochen) Analogously to Example 19, 2 test specimens are wound and the breaking strength at 20% and 50% deformation is determined. Results: Test specimen from Ex. Measured force F [N] at 20% deformity. at 50% deformity. 15 220 349 16 223 376 17th 280 435 18th 163 175 (broken)

Das Beispiel zeigt, daß die Bruchfestigkeit unabhängig vom Harztyp ist (Probekörper aus Bsp. 15 und 16). Weiterhin, daß hochfeste polyfile Polyesterfasern den normalen Polyester-Spinnfasern (Stapelgarnen) deutlich überlegen sind (Probekörper aus Bsp. 17 und 18).The example shows that the breaking strength is independent of the type of resin (test specimens from Examples 15 and 16). Furthermore, that high-strength polyfile polyester fibers are clearly superior to normal polyester staple fibers (staple yarns) (test specimens from Examples 17 and 18).

Claims (16)

1. Textile Flächengebilde, welche mit einem wasser­härtenden Kunststoffharz imprägniert und/oder be­schichtet sind, dadurch gekennzeichnet, daß sie aus organischen Fasern mit einem Elastizitätsmodul von 200 bis 2500 daN/mm² bestehen und vor der Aushär­tung eine Dehnbarkeit in Längsrichtung von mehr als 10 % aufweisen.1. Textile fabrics which are impregnated and / or coated with a water-curing plastic resin, characterized in that they consist of organic fibers with a modulus of elasticity of 200 to 2500 daN / mm² and have an extensibility in the longitudinal direction of more than 10% before curing . 2. Textile Flächengebilde nach den Anspruch 1, dadurch gekennzeichnet, daß sie aus Fasern mit einen Ela­stizitätsmodul im Bereich von 400 bis 2000 daN/mm² bestehen.2. Textile fabrics according to claim 1, characterized in that they consist of fibers with a modulus of elasticity in the range of 400 to 2000 daN / mm². 3. Textile Flächengebilde nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie vor der Aushärtung eine Dehnbarkeit in Längsrichtung von 15 bis 200 % aufweisen.3. Textile fabrics according to claims 1 and 2, characterized in that they have an extensibility in the longitudinal direction of 15 to 200% before curing. 4. Textile Flächengebilde nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß sie vor der Aus­härtung eine Dehnbarkeit in Längsrichtung von 15 bis 80 % aufweisen.4. Textile fabrics according to claims 1 to 3, characterized in that they have an extensibility in the longitudinal direction of 15 to 80% before curing. 5. Textiles Flächengebilde nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß sie eine Dehnbarkeit in Querrichtung von 20 bis 300 % aufweisen.5. Textile fabric according to claims 1 to 4, characterized in that they have an extensibility in the transverse direction of 20 to 300%. 6. Textile Flächengebilde nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie ein Quadrat­metergewicht von 40 bis 300 g aufweisen.6. Textile fabrics according to claims 1 to 5, characterized in that they have a weight per square meter of 40 to 300 g. 7. Textile Flächengebilde nach Anspruch 1, dadurch ge­kennzeichnet, daß sie aus Polyester- und/oder Poly­amid- und/oder Baumwollfasern besteht.7. Textile fabrics according to claim 1, characterized in that it consists of polyester and / or polyamide and / or cotton fibers. 8. Textile Flächengebilde nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß als wasserhärtendes Kunststoffharz ein Polyurethan- oder ein Polyvinyl­harz eingesetzt wird.8. Textile fabrics according to claims 1 to 7, characterized in that a polyurethane or a polyvinyl resin is used as the water-curing plastic resin. 9. Verfahren zur Herstellung von textilen Flächenge­bilden mit einem wasserhärtenden Reaktivharz, dadurch gekennzeichnet, daß man aus organischen Fasern mit einem Elastizitätsmodul im Bereich von 200 bis 2500 daN/mm² das Textil herstellt, eine Dehnbarkeit in Längsrichtung von mehr als 10 % einstellt, dann mit dem wasserhärtenden Kunststoff­harz imprägniert und/oder beschichtet.9. A process for the production of textile fabrics with a water-curing reactive resin, characterized in that the textile is made from organic fibers with a modulus of elasticity in the range from 200 to 2500 daN / mm², an extensibility in the longitudinal direction of more than 10% is set, then with impregnated and / or coated with the water-hardening plastic resin. 10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man die Dehnbarkeit des Textils in Längsrich­tung durch thermische Schrumpfung und/oder Naß­schrumpfung einstellt.10. The method according to claim 9, characterized in that one adjusts the extensibility of the textile in the longitudinal direction by thermal shrinkage and / or wet shrinkage. 11. Verfahren nach den Ansprüchen 9 und 10, dadurch ge­kennzeichnet, daß man die thermische Schrumpfung im Temperaturbereich von 80 bis 250°C durchführt.11. The method according to claims 9 and 10, characterized in that one carries out the thermal shrinkage in the temperature range from 80 to 250 ° C. 12. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man eine Naßschrumpfung durch Eintauchen und/oder Imprägnierung des Flächengebildes in ein flüssiges Medium gegebenenfalls in Gegenwart von Hilfsmitteln durchführt.12. The method according to claim 9, characterized in that one carries out a wet shrinking by immersing and / or impregnating the fabric in a liquid medium, optionally in the presence of auxiliaries. 13. Verwendung von textilen Flächengebilden, welche mit einem wasserhärtenden Kunststoffharz imprägniert und/oder beschichtet sind, die aus organischen Fasern mit einem Elastizitätsmodul von 200 bis 2500 daN/mm² bestehen und vor der Aushärtung eine Dehn­barkeit in Längsrichtung von mehr als 10 % aufwei­sen als Konstruktionsmaterial.13. Use of textile fabrics, which are impregnated and / or coated with a water-hardening plastic resin, which consist of organic fibers with a modulus of elasticity of 200 to 2500 daN / mm² and, before curing, have an extensibility in the longitudinal direction of more than 10% as construction material . 14. Verwendung nach Anspruch 13 als orthopädische Stützverbände.14. Use according to claim 13 as orthopedic support bandages. 15. Verwendung nach Anspruch 13 als Formungsmaterial für technische Vorrichtungen.15. Use according to claim 13 as a molding material for technical devices. 16. Verwendung nach Anspruch 13 als Isoliermaterial.16. Use according to claim 13 as an insulating material.
EP19880109418 1987-06-24 1988-06-14 Orthopedic casting bandage with a reactive resin Expired - Lifetime EP0301214B1 (en)

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DE19873726268 DE3726268A1 (en) 1987-06-24 1987-08-07 TEXTILE AREA WITH REACTIVE RESIN
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EP0301214B1 (en) 1993-09-01
CN1031081C (en) 1996-02-21
US4940047A (en) 1990-07-10
ATE93909T1 (en) 1993-09-15
KR890000240A (en) 1989-03-13
DE3726268A1 (en) 1989-01-05
NO882524D0 (en) 1988-06-08
NO882524L (en) 1988-12-27
FI95934B (en) 1995-12-29
ES2042650T3 (en) 1993-12-16
DK174216B1 (en) 2002-09-30
BR8803090A (en) 1989-01-31
IL86817A (en) 1991-08-16
CN1030269A (en) 1989-01-11
NO176615B (en) 1995-01-23
IE881917L (en) 1988-12-24
FI95934C (en) 1996-04-10
PH26348A (en) 1992-04-29
DK345788D0 (en) 1988-06-23
JPS6414377A (en) 1989-01-18
DE3883660D1 (en) 1993-10-07
NO176615C (en) 1995-05-03
IL86817A0 (en) 1988-11-30
IE61729B1 (en) 1994-11-30
KR960009086B1 (en) 1996-07-10
HU212119B (en) 1996-02-28
AU1836988A (en) 1989-01-05
CA1330917C (en) 1994-07-26
FI883007A (en) 1988-12-25
HUT50231A (en) 1989-12-28
PT87787B (en) 1994-03-31
AU608622B2 (en) 1991-04-11
EP0301214A3 (en) 1991-07-31
PT87787A (en) 1989-05-31
FI883007A0 (en) 1988-06-22
DK345788A (en) 1988-12-25
SU1600623A3 (en) 1990-10-15

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