EP0301214B1 - Orthopedic casting bandage with a reactive resin - Google Patents

Orthopedic casting bandage with a reactive resin Download PDF

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Publication number
EP0301214B1
EP0301214B1 EP19880109418 EP88109418A EP0301214B1 EP 0301214 B1 EP0301214 B1 EP 0301214B1 EP 19880109418 EP19880109418 EP 19880109418 EP 88109418 A EP88109418 A EP 88109418A EP 0301214 B1 EP0301214 B1 EP 0301214B1
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EP
European Patent Office
Prior art keywords
longitudinal direction
water
fibers
coated
dan
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19880109418
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German (de)
French (fr)
Other versions
EP0301214A2 (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
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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 for medical support bandages, 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 field.
  • EP-A-0021004 describes i.a. orthopedic support bandages, which are only stretchable in the transverse direction. As a result, wrinkle-free donning, particularly with angled limbs, is hardly possible.
  • the teaching of US-A-4688563 can only partially overcome this disadvantage, since it teaches the production of orthopedic support bandages which also have a longitudinal extension, but the bandages described there are produced on the basis of glass fibers, as a result of which the disadvantages associated with glass fibers are produced how bad X-ray transparency and strong tendency to dust when removing the dressing etc. have to be accepted.
  • 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.
  • glass fiber substrates have been used (US-A-45 02 479).
  • these known carrier materials are only stretchable in the transverse direction, but practically rigid in the longitudinal direction in order to achieve greater stability (US-A-45 02 479, column 3, lines 45 to 47).
  • a disadvantage of the carrier materials, which can only be stretched in the transverse direction, is the occurrence 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-A-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.
  • Orthopedic support bandages have been found 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 900 to 2000 daN / mm2 and, prior to curing, an extensibility in the longitudinal direction of 15-200% exhibit.
  • the support bandages according to the invention have not only an elongation in the transverse direction but also an elongation 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 course.
  • the support bandages 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 support bandages according to the invention are polyester fibers.
  • the fibers for the support bandages 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.
  • Polyfile textured polyester filament yarns are used to achieve 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, both staple fiber yarns and polyfile filament yarns (plain yarn) made of polyester can be used.
  • the strength of these yarns is characterized by the modulus of elasticity (modulus of elasticity).
  • the orthopedic support bandages according to the invention generally have an extensibility in the longitudinal direction of 15 to 200%, preferably 15 to 80%, before the reactive resin cures. Elongation in the longitudinal direction means the change in length compared to the fully relaxed support bandage, which is achieved when the orthopedic support bandage is loaded with 10 N per cm width in the longitudinal direction. Such measurements can be carried out, for example, in accordance with DIN 61 632 (April 1985).
  • the support bandages 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 cured.
  • the orthopedic support bandages according to the invention generally have a weight per square meter of 40 to 300 g, preferably 100 to 200 g.
  • Textiles made of fibers are used as the support bandages according to the invention, the elongation of which has been adjusted by a shrinking process.
  • the orthopedic support bandages according to the invention consist in the longitudinal direction of polyfilen, textured polyester filament threads and in the transverse direction of fibers of high-strength polyester fibers, preferably polyethylene terephthalates, with an elastic modulus of 900 to 2000 daN / mm2.
  • the modulus of elasticity can be determined by methods known per se (synthetic fibers, pages 63 to 68 (1981), Verlag Chemie, Weinheim).
  • the processing forms of the orthopedic support bandages according to the invention can be woven, knitted, knitted 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 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-isocyanatomethylcyclohexane, 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, di
  • Suitable higher molecular weight polyisocyanates are modification products of such simple polyisocyanates, ie polyisocyanates with e.g. Isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units, such as can be prepared from the simple polyisocyanates of the above-mentioned general formula mentioned by way of example by methods known in the art.
  • 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 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.
  • 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 diphenylmethane 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 biochemical groups and isocyanurate groups and in particular NCO prepolymers of the type mentioned based on these technical polyisocyanates on the one hand
  • 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 also has uretonimine groups as a result of the addition of monomeric diisocyanate to the carbodiimide structure.
  • 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 catalyst content, 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, polywaxes (polyethylene glycols), UV stabilizers of the ionol type (DE-A 29 21 163), color pigments such as carbon black, iron oxides, titanium dioxide 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 orthopedic support bandages according to the invention with a water-curing reactive resin has also been found, which is characterized in that the textile is produced from the polyester fibers described, an extensibility in the longitudinal direction of 15 to 200% and in the transverse direction of 20-300% is set and then impregnated and / or coated with the water-curing 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 support associations according to the invention can be used for support associations 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 support bandages according to the invention Compared to the known bandages made of glass fibers, the support bandages 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 support bandages according to the invention do not break even with severe deformation.
  • the orthopedic support bandages according to the invention which are impregnated and / or coated with a water-hardening plastic resin, are generally stored in the absence of moisture.
  • the textile backing materials (Example 2) are coated with the resins listed below.
  • 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 in such a way that the prepolymer is dissolved in a suitable inert solvent (for example methylene chloride or acetone), the knitted tape is soaked with it and the solvent is then removed in vacuo.
  • a suitable inert solvent for example methylene chloride or acetone
  • the resin can also be applied using suitable roller impregnation units or slot nozzles.
  • Such impregnation devices are described, for example, in US-A-4,502,479 and US-A-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 applications 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 specimen has an inside diameter of 76 mm and consists 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).
  • Test specimen from example * F Max [N] Deformation path [mm] 3rd 1300 15 4th 377 18th 12th 840 60 13 1310 20th *) 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 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 Measured force F [N] E.g. at 20% deformity. at 50% deformity. 3rd 892 1052 4th 185 264 5 236 447 6 404 587
  • 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 poor X-ray transparency, sharp edges and the dangerous glass dust do not have.
  • Test specimen Measured force F [N] E.g. at 20% deformity. at 50% deformity. 15 220 349 16 223 376 17th 280 435 18th 163 175 (broken)
  • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

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 für medizinische Stützverbände, die außer einer Querelastizität noch eine Längselastizität aufweisen, ein Verfahren zu ihrer Herstellung und ihrer Verwendung.The invention relates to construction materials for medical support bandages, 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 Bereich verwendet werden.In general, the construction materials according to the invention can be used for stiffening, shaping and sealing in the medical field.

Aus der LU-A-0043631 ist ein Verfahren zur Herstellung von Geweben mit Dauerelastizität in Querrichtung bekannt geworden, welches insbesondere die Herstellung von Geweben mit verbesserten Dehnungscharakteristiken für Anwendungen betrifft, bei denen die Elastizität des Gewebes in einer Richtung eine bedeutende Größe für den Anwender ist.From LU-A-0043631 a process for the production of fabrics with permanent elasticity in the transverse direction has become known, which relates in particular to the fabrication of fabrics with improved elongation characteristics for applications in which the elasticity of the fabric in one direction is a significant parameter for the user .

Die EP-A-0021004 beschreibt u.a. orthopädische Stützverbände, die jedoch lediglich in Querrichtung dehnbar sind. Hierdurch ist ein faltenfreies Anlegen, insbesondere bei angewinkelten Gliedmaßen, kaum möglich. Diesen Nachteil kann auch die Lehre der US-A-4688563 nur unvollständig überwinden, denn diese lehrt zwar die Herstellung von orthopädischen Stützverbänden, die auch eine Längsdehnung aufweisen, die dort beschriebenen Verbände werden jedoch auf Basis von Glasfasern hergestellt, wodurch die mit Glasfasern verbundenen Nachteile, wie schlechte Röntgentransparenz und starke Staubneigung bei Entfernung des Verbandes etc. in Kauf genommen werden müssen. Dieses Dokument lehrt auch die Verwendung von Hochmodulfasern wie Polyararmiden, wodurch jedoch auch keine grundlegenden anwendungstechnischen Verbesserungen erreicht werden können, da zwar die Röntgentransparenz und die Staubneigung günstiger im Vergleich zu Glasfasern enthaltenden Stützverbänden bewertet werden kann, die Entfernung derartiger Verbände ist jedoch wegen der enthaltenen Hochmodulfasern problematisch.EP-A-0021004 describes i.a. orthopedic support bandages, which are only stretchable in the transverse direction. As a result, wrinkle-free donning, particularly with angled limbs, is hardly possible. The teaching of US-A-4688563 can only partially overcome this disadvantage, since it teaches the production of orthopedic support bandages which also have a longitudinal extension, but the bandages described there are produced on the basis of glass fibers, as a result of which the disadvantages associated with glass fibers are produced how bad X-ray transparency and strong tendency to dust when removing the dressing etc. have to be accepted. This document also teaches the use of high-modulus fibers such as polyararmides, but this also does not result in any fundamental improvements in application technology, since the X-ray transparency and the tendency to dust can be assessed more cheaply in comparison to support dressings containing glass fibers, but the removal of such dressings is due to the high-modulus fibers contained problematic.

Aus der DE-A-1958368 ist es bekannt, wie durch Schrumpfprozesse die Dehnbarkeit von Fasern in Längs- und Querrichtung beeinflußt werden kann.From DE-A-1958368 it is known how the extensibility of fibers in the longitudinal and transverse directions can be influenced by shrinking processes.

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-A-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-A-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, glass fiber substrates have been used (US-A-45 02 479). However, these known carrier materials are only stretchable in the transverse direction, but practically rigid in the longitudinal direction in order to achieve greater stability (US-A-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 carrier materials, which can only be stretched in the transverse direction, is the occurrence 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-A-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-A-46 09 578 Raschel and tricot knits 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-A-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-A-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-A-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-A-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 orthopädische Stütsverbände gefunden, welche mit einem wasserhärtenden Reaktivharz imprägniert und/oder beschichtet sind, dadurch gekennzeichnet, daß sie aus organischen Fasern mit einem Elastizitätsmodul von 900 bis 2000 daN/mm² bestehen und vor der Aushärtung eine Dehnbarkeit in Längsrichtung von 15 - 200 % aufweisen.Orthopedic support bandages have been found 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 900 to 2000 daN / mm² and, prior to curing, an extensibility in the longitudinal direction of 15-200% exhibit.

Überraschenderweise weisen die erfindungsgemäßen Stützverbände außer einer Dehnung in Querrichtung auch eine in Längsrichtung auf.Surprisingly, the support bandages according to the invention have not only an elongation in the transverse direction but also an elongation 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 Schuß oder Maschenreihe.Transverse direction generally means perpendicular to the processing direction of the textile, i.e. in the direction of the weft or course.

Die erfindungsgemäßen Stützverbände können in verschiedenen geometrischen Formen vorliegen. Bevorzugt liegen sie in Bandform vor, wobei die lange Seite des Bandes der Verarbeitungsrichtung des Textils entspricht.The support bandages 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 Stützverbände sind Polyesterfasern.Organic fibers for the support bandages according to the invention are polyester fibers.

Die Fasern für die erfindungsgemäßen Stützverbände sind an sich bekannt (Synthesefasern, Seiten 3 bis 10 und 153 bis 221 (1981), Verlag Chemie, Weinheim).The fibers for the support bandages 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 Schrumpfprozeß die elastische Dehnung in Längsrichtung.The thread system, which is preferably incorporated in the longitudinal direction, enables elastic stretching in the longitudinal direction after a shrinking process.

Zur Erreichung der Längendehnbarkeit werden polyfile texturierte Filamentgarne aus Polyester eingesetzt.Polyfile textured polyester filament yarns are used to achieve 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 als auch polyfile Filamentgarne (Glattgarn) aus Polyester 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, both staple fiber yarns and polyfile filament yarns (plain yarn) made of polyester can be used. The strength of these yarns is characterized by the modulus of elasticity (modulus of elasticity).

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

Die erfindungsgemäßen Stützverbände weisem im allgemeinen vor Aushärtung des Reaktivharzes eine Dehnbarkeit in Querrichtung von 20 bis 300 %, bevorzugt von 40 bis 200 %, auf.The support bandages 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 cured.

Die erfindungsgemäßen orthopädischen Stützverbände weisen im allgemeinen ein Gewicht pro Quadratmeter von 40 bis 300 g, bevorzugt von 100 bis 200 g, auf.The orthopedic support bandages according to the invention generally have a weight per square meter of 40 to 300 g, preferably 100 to 200 g.

Als erfindungsgemäße Stützverbände werden Textilien aus Fasern eingesetzt, deren Längendehnung durch einen Schrumpfungsprozeß eingestellt wurde.Textiles made of fibers are used as the support bandages according to the invention, the elongation of which has been adjusted by a shrinking process.

Der Schrumpfprozeß 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, 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).

Die erfindungsgemäßen orthopädischen Stützverbände bestehen in Längsrichtung aus polyfilen, texturierten Polyester-Filamentfäden und in Querrichtung aus Fasern aus hochfesten Polyesterfasern, bevorzugt Polyethylenterephthalaten, mit einem Elastizitätsmodul von 900 bis 2000 daN/mm².
Der Elastizitätsmodul kann nach an sich bekannten Verfahren bestimmt werden (Synthesefasern, Seiten 63 bis 68 (1981), Verlag Chemie, Weinheim).The orthopedic support bandages according to the invention consist in the longitudinal direction of polyfilen, textured polyester filament threads and in the transverse direction of fibers of high-strength polyester fibers, preferably polyethylene terephthalates, with an elastic modulus of 900 to 2000 daN / mm².
The modulus of elasticity can be determined by methods known per se (synthetic fibers, pages 63 to 68 (1981), Verlag Chemie, Weinheim).

Die Verarbeitungsformen der erfindungsgemäßen orthopädischen Stützverbände 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 orthopedic support bandages according to the invention can be woven, knitted, knitted 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 Polyisocyanate 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 functionality and content of functional groups that can be calculated, e.g. 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
an aliphatic hydrocarbon radical with 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 Polyisocyänate 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-isocyanatomethylcyclohexan, 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-isocyanatomethylcyclohexane, 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 bis 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-A-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 Isocyanatgruppen" 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 such simple polyisocyanates, ie polyisocyanates with e.g. Isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units, such as can be prepared from the simple polyisocyanates of the above-mentioned general formula mentioned by way of example by methods known in the art. 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 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 Diphenylmethanreihe 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 den 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 CarbodiimidStruktur 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 diphenylmethane 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 biochemical groups and isocyanurate groups and in particular NCO prepolymers 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 on the other hand, 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 also has uretonimine groups as a result of the addition of monomeric diisocyanate to the carbodiimide structure.

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 imgb0001

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 imgb0001
or dimorpholine diethyl ether or bis (2,6-dimethylmorpholino) diethyl ether (WO 86/01397). The catalyst content, based on the tertiary nitrogen, is generally 0.05 to 0.5% by weight, based on the polymer resin.

Wasserhärtende Polyvinylharze können beispielsweise 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 beispielsweise 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-Typ (DE-A 29 21 163), Farbpigmente, wie Ruß, Eisenoxide, Titandioxid oder Phthalocyanine.Examples of additives which may be mentioned are: polydimethylsiloxanes, calcium silicates of the aerosil type, polywaxes (polyethylene glycols), UV stabilizers of the ionol type (DE-A 29 21 163), color pigments such as carbon black, iron oxides, titanium dioxide 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 orthopädischen Stützverbände mit einem wasserhärtenden Reaktivharz gefunden, das dadurch gekennzeichnet ist, daß man aus den beschriebenen Polyesterfasern das Textil hergestellt, eine Dehnbarkeit in Längsrichtung von 15 bis 200 % und in Querrichtung von 20 - 300 % einstellt und dann mit dem wasserhärtenden Kunststoffharz imprägniert und/oder beschichtet.A process for the production of the orthopedic support bandages according to the invention with a water-curing reactive resin has also been found, which is characterized in that the textile is produced from the polyester fibers described, an extensibility in the longitudinal direction of 15 to 200% and in the transverse direction of 20-300% is set and then impregnated and / or coated with the water-curing 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 über-hitztem 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. 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 Stützverbände können 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 worden können.The support associations according to the invention can be used for support associations 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 Stützverbände 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 Stützverbände selbst bei starker Deformation nicht.Compared to the known bandages made of glass fibers, the support bandages 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 support bandages according to the invention do not break even with severe deformation.

Die erfindungsgemäßen orthopädischen Stützverbände, die mit einem wasserhärtenden Kunststoffharz imprägniert und/oder beschichtet sind, werden im allgemeinen unter Ausschluß von Feuchtigkeit gelagert.The orthopedic support bandages according to the invention, which are impregnated and / or coated with a water-hardening 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 AnilinFormaldehyd-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) are mixed with 32.2 parts of 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, weiches 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 durch 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 After 30 minutes the reaction temperature reaches 45 ° C. After 1 hour the maximum temperature has reached 48 ° C. 500 g of a polydimethylsiloxane with η25 ° C. = 100 mPa.s are added and stirred in. The viscosity of the finished prepolymer η25 ° C. is 15 700 mPa.s, the isocyanate content 12.9%.

Prepolymer IVPrepolymer IV

100 Tle. eines technischen Polyphenyl-polymethylen-polyisocyanats, erhalten durch Phosgenierung eines Anilin-Formaldehyd-Kondensates (η25°C: 200 mPa.s; NCO-Gehalt: 31 % (Roh-MDI) werden mit 32,2 Teilen ethoxyiiertem 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 ethoxyated 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.

Figure imgb0002
Tabelle 2 Charakterisierung der Garntypen PES-TEXS: 167 dtex, f 30 x 2, polyfines texturiertes Polyesterfilamentgarn HE-Garn, K = 62 %) E = 450 daN/mm² PES-TEX: 167 dtex, f 30 x 1, polyfiles texturiertes Polyesterfilamentgarn (HE-Garn, K = 60%) E = 420 daN/mm² PES-HF: 550 dtex, f 96 VZ 60, polyfiles, hochfestes Polyesterfilamentgarn normal schrumpfend, E = 1650 daN/mm² 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), E = 320 daN/mm² K: Kennkräuselung (DIN 53 840)
E: Elastizitätsmodul The characteristics of the textile backing material used are summarized in Table 1.
Figure imgb0002
 Table 2 Characterization of yarn types PES-TEXS: 167 dtex, f 30 x 2, polyfine textured polyester filament yarn HE yarn, K = 62%) E = 450 daN / mm² PES-TEX: 167 dtex, f 30 x 1, polyfiles textured polyester filament yarn (HE yarn, K = 60%) E = 420 daN / mm² PES-HF: 550 dtex, f 96 VZ 60, polyfiles, high strength polyester filament yarn normal shrinking, E = 1650 daN / mm² 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), E = 320 daN / mm² 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 (beispielsweise 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 Schlitzdüsen aufgebracht werden. Solche Imprägniereinrichtungen sind z.B. in der US-A-4 502 479 und der US-A-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 Verwendungen 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 in such a way that the prepolymer is dissolved in a suitable inert solvent (for example methylene chloride or acetone), the knitted tape is soaked with it and the solvent is then removed in vacuo. Furthermore, the resin can also be applied using suitable roller impregnation units or slot nozzles. Such impregnation devices are described, for example, in US-A-4,502,479 and US-A-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 applications 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.werden 4 Probekörper gewickelt, die

Figure imgb0003
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. 4 test specimens are wound, the
Figure imgb0003

Beispiel 19Example 19

Es 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 13 1310 20 *) überschüssiges Band wird verworfen. It has an inside diameter of 76 mm and consists 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 12th 840 60 13 1310 20th *) Excess tape is discarded.

Beispiel 20Example 20

Es werden 5 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 8 960 9 900 10 1120 5 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 8th 960 9 900 10th 1120

Beispiel 21Example 21

Es werden 4 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 Gemessene Kraft F [N] Bsp. bei 20 % Deform. bei 50 % Deform. 3 892 1052 4 185 264 5 236 447 6 404 587 4 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 Measured force F [N] E.g. at 20% deformity. at 50% deformity. 3rd 892 1052 4th 185 264 5 236 447 6 404 587

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 ein gleich gutes Anlegeverhalten besitzen, jedoch Nachteile wie schlechte 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 poor X-ray transparency, sharp edges and the dangerous glass dust do not have.

Beispiel 22Example 22

Analog zu Beispiel 19 werden 4 Prüfkörper gewickelt und die Bruchfestigkeit bei 20 % und 50 % Deformation bestimmt. Ergebnisse: Probekörper aus Gemessene Kraft F [N] Bsp. bei 20 % Deform. bei 50 % Deform. 15 220 349 16 223 376 17 280 435 18 163 175 (gebrochen) Analogously to Example 19, 4 test specimens are wound and the breaking strength at 20% and 50% deformation is determined. Results: Test specimen Measured force F [N] E.g. 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 (6)

  1. Process for the preparation of orthopaedic support dressings comprising a textile carrier impregnated and/or coated with water-hardening synthetic resins, which comprises polyfilament texturised polyester filament threads in the longitudinal direction and high-strength polyester threads having an elasticity modulus of 900-2000 daN/mm² in the transverse direction and has an extensibility of 15-200 % in the longitudinal direction and of 20-300 % in the transverse direction before hardening, characterised in that the textile carrier is first prepared from shrinkable polyfilament polyester filament threads in the longitudinal direction and from high-strength polyester threads having an elasticity modulus of 900-2000 daN/mm² in the transverse direction, an extensibility of the textile carrier of 15-200 % in the longitudinal direction is then established by thermal shrinkage in the temperature range from 80 to 200°C and/or by wet shrinkage by immersion and/or impregnation of the textile carrier in a liquid medium, if appropriate in the presence of auxiliaries, and the carrier is then impregnated and/or coated with the water-hardening synthetic resin.
EP19880109418 1987-06-24 1988-06-14 Orthopedic casting bandage with a reactive resin Expired - Lifetime EP0301214B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88109418T ATE93909T1 (en) 1987-06-24 1988-06-14 ORTHOPEDIC SUPPORTS WITH REACTIVE RESIN.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3720762 1987-06-24
DE3720762 1987-06-24
DE3726268 1987-08-07
DE19873726268 DE3726268A1 (en) 1987-06-24 1987-08-07 TEXTILE AREA WITH REACTIVE RESIN

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EP0301214A2 EP0301214A2 (en) 1989-02-01
EP0301214A3 EP0301214A3 (en) 1991-07-31
EP0301214B1 true EP0301214B1 (en) 1993-09-01

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EP (1) EP0301214B1 (en)
JP (1) JPS6414377A (en)
KR (1) KR960009086B1 (en)
CN (1) CN1031081C (en)
AT (1) ATE93909T1 (en)
AU (1) AU608622B2 (en)
BR (1) BR8803090A (en)
CA (1) CA1330917C (en)
DE (2) DE3726268A1 (en)
DK (1) DK174216B1 (en)
ES (1) ES2042650T3 (en)
FI (1) FI95934C (en)
HU (1) HU212119B (en)
IE (1) IE61729B1 (en)
IL (1) IL86817A (en)
NO (1) NO176615C (en)
PH (1) PH26348A (en)
PT (1) PT87787B (en)
SU (1) SU1600623A3 (en)

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Also Published As

Publication number Publication date
PT87787A (en) 1989-05-31
IL86817A0 (en) 1988-11-30
IE61729B1 (en) 1994-11-30
PH26348A (en) 1992-04-29
ES2042650T3 (en) 1993-12-16
AU608622B2 (en) 1991-04-11
NO882524D0 (en) 1988-06-08
SU1600623A3 (en) 1990-10-15
FI95934C (en) 1996-04-10
US4940047A (en) 1990-07-10
HU212119B (en) 1996-02-28
EP0301214A2 (en) 1989-02-01
IE881917L (en) 1988-12-24
EP0301214A3 (en) 1991-07-31
CN1031081C (en) 1996-02-21
CN1030269A (en) 1989-01-11
DE3726268A1 (en) 1989-01-05
FI883007A (en) 1988-12-25
DK174216B1 (en) 2002-09-30
DK345788A (en) 1988-12-25
NO176615B (en) 1995-01-23
DE3883660D1 (en) 1993-10-07
KR890000240A (en) 1989-03-13
ATE93909T1 (en) 1993-09-15
DK345788D0 (en) 1988-06-23
FI883007A0 (en) 1988-06-22
PT87787B (en) 1994-03-31
AU1836988A (en) 1989-01-05
JPS6414377A (en) 1989-01-18
NO882524L (en) 1988-12-27
FI95934B (en) 1995-12-29
CA1330917C (en) 1994-07-26
NO176615C (en) 1995-05-03
BR8803090A (en) 1989-01-31
IL86817A (en) 1991-08-16
KR960009086B1 (en) 1996-07-10
HUT50231A (en) 1989-12-28

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