WO2001019420A1 - Materiau de support orthopedique contenant une substance a changement de phase absorbant la chaleur - Google Patents

Materiau de support orthopedique contenant une substance a changement de phase absorbant la chaleur Download PDF

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Publication number
WO2001019420A1
WO2001019420A1 PCT/US2000/001828 US0001828W WO0119420A1 WO 2001019420 A1 WO2001019420 A1 WO 2001019420A1 US 0001828 W US0001828 W US 0001828W WO 0119420 A1 WO0119420 A1 WO 0119420A1
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Prior art keywords
orthopedic support
support material
phase change
exothermic
hardenable composition
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PCT/US2000/001828
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English (en)
Inventor
Kurt Allenberg
Matt T. Scholz
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3M Innovative Properties Company
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Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to AU24174/00A priority Critical patent/AU2417400A/en
Publication of WO2001019420A1 publication Critical patent/WO2001019420A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07—Stiffening bandages
    • A61L15/14—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07—Stiffening bandages
    • A61L15/10—Stiffening bandages containing organic materials

Definitions

  • the present invention relates to orthopedic support materials that include an exothermic hardenable composition in contact with a phase change material.
  • the invention also relates to methods of making the orthopedic support materials and immobilizing body parts with the support materials.
  • plaster of Paris bandages consisting of mesh fabric (e.g., cotton gauze) with plaster (e.g., calcium sulfate hemihydrate) incorporated into the openings and onto the surface of the mesh fabric.
  • plaster of Paris casts have a number of attendant disadvantages, including, for example, a low strength-to-weight ratio, which results in a finished cast that is very heavy and bulky.
  • plaster of Paris casts develop their strength over a relatively long period of time. This makes it necessary to avoid weight bearing situations for up to 48 hours.
  • plaster of Paris casts typically disintegrate in water. This makes it necessary to avoid bathing, showering, or other activities involving contact with water.
  • Another disadvantage of plaster of Paris is the significant exotherm that can occur during hardening, which can in turn lead to uncomfortably high levels of cast heat to the patient.
  • Orthopedic casting tapes have been produced using resins coated or impregnated onto a substrate.
  • the casting tape is stored as a roll in a water-impermeable storage pouch until needed for use.
  • the roll of tape is removed from the pouch and contacted with water, as by dipping the tape in 23°C water with squeezing, for example.
  • the casting tape includes a water-curable resin.
  • the resin will begin to cure and the tape harden. The medical practitioner applies the casting tape to a patient immediately after it has been soaked with water.
  • resin materials are chosen that begin to cure immediately after being dipped in water, and that will set (i.e., harden) sufficiently to resist passive motion in a joint (e.g., a wrist or ankle) in about 3 minutes to about 5 minutes, and to be weight bearing within a period of about 20 minutes to several hours.
  • Typical resin coatings utilized in conventional orthopedic casting systems include isocyanate-functional urethane prepolymers.
  • Other known systems include non-isocyanate alkoxysilane-terminated urea and/or urethane prepolymers.
  • Such resin coatings also include catalysts to facilitate reaction with water.
  • Lubricants may also be used, e.g., to facilitate unrolling, application, and molding.
  • Filler materials may be added to the resins to increase the strength of the hardened casts.
  • defoaming agents may be used to maintain porosity while carbon dioxide is evolved during the curing process.
  • Typical substrates upon which the above resin coatings are applied to produce an orthopedic casting tape are fabrics prepared from glass and/or synthetic fibers.
  • Fiberglass or other high modulus fibers contribute significant strength to the cured resin substrate composite as well as provide a reservoir for the resin during storage and end-use application of the casting tape.
  • Non-glass low modulus substrates generally provide for a lower weight and more radiolucent cast. With most non-glass substrates the strength is limited by the amount of resin that can be held by the substrate.
  • High resin loading with materials known to date must generally be avoided, however, to prevent excessive heat build-up in the cast while it is in its early stages of cure, e.g., during hardening, as a result of the exotherm produced in the resins. Such heat build-up could potentially cause harm to the patient.
  • a substrate e.g., a fiberglass substrate or a nonglass low modulus substrate
  • the present invention provides a hardenable material capable of immobilizing and/or supporting, for example, a body part.
  • This hardenable material can be used in tape, sheet, film, slab, or tubular form to prepare orthopedic casts, splints, braces, supports, protective shields, orthotics, and other orthopedic support materials. Additionally, other constructions in prefabricated shapes can be used.
  • the hardenable material (e.g., orthopedic support material) of the present invention includes an exothermic hardenable composition (e.g., a composition that produces heat upon hardening) in contact with a phase change material, preferably, a heat- absorbing phase change material.
  • a phase change material can be hydrophilic, preferably, it is hydrophobic.
  • a hardenable orthopedic support material is composed of a substrate coated or impregnated with an exothermic hardenable composition in contact with a heat-absorbing phase change material.
  • the hardenable composition preferably hardens or sets at an initial temperature of about room temperature (i.e., about 18°C to about 27°C upon initiation of the hardening process).
  • it at least partially hardens in less than about 10 minutes to form a structure that is set (e.g., resists passive motion such as that which typically occurs in an ankle or wrist joint).
  • the exothermic hardenable composition hardens and releases heat (i.e., exotherms).
  • this heat i.e., thermal energy
  • the phase change material and hence is preferably referred to herein as heat-absorbing phase change material.
  • this phase change material reduces the peak temperature of the exotherm and allows for a more comfortable application of the orthopedic support material to the patient.
  • the exothermic hardenable composition can be a wide variety of compositions.
  • the exothermic hardenable composition is a one-part system that requires only the addition of water.
  • a "one-part" system can include one component or a mixture of components (e.g., premix), but does not include two-part exothermic hardenable compositions that require mixing of reactive components, other than water, immediately prior to application, since this is generally not practical for orthopedic casting tape applications.
  • the exothermic hardenable composition is preferably in the form of a liquid at room temperature (preferably, having a viscosity of less than about 150,000 centipoise), but may be in the form of a solid paniculate material (such as plaster of Paris), which can be in a paste, slurry, gel, dispersion, or solution.
  • a solid paniculate material such as plaster of Paris
  • the exothermic hardenable composition hardens, preferably, on a substrate, thereby releasing heat to form a hardened material.
  • the phase change material is one that is preferably solid at room temperature. It may be hydrophilic, but preferably it is hydrophobic. It can be mixed with the exothermic hardenable composition.
  • phase change material preferably has an endotherm as seen using Differential Scanning Calorimetry within a temperature range of about 18°C to the peak temperature reached during the hardening process. It is believed that this endotherm occurs as a result of melting and that at least a portion of at least one phase change material melts during the hardening process, although this is not a necessary requirement as long as there is an endothermic process occurring.
  • suitable substrates for use in the present invention include knit, woven, and nonwoven fabrics as well as foams and other porous materials.
  • the substrate is preferably coated or impregnated with the hardenable composition in an amount of about 0.4 time to about 20 times the weight of the substrate.
  • the hardenable composition is typically within some of the spaces in the substrate such that it at least partially impregnates the substrate.
  • the hardenable composition may become bonded to the substrate through the use of coupling agents, for example, silane coupling agents.
  • the hardenable composition may simply encapsulate the substrate prior to forming a hardened composite material.
  • the present invention also provides a method of preparing an orthopedic support material.
  • the method includes: providing a substrate; and applying an exothermic hardenable composition and a phase change material (preferably, a hydrophobic, heat-absorbing phase change material) to the substrate, such that the phase change material is in contact with the exothermic hardenable composition.
  • the present invention also provides a method of immobilizing a body part.
  • the method includes: providing an orthopedic support material including an exothermic hardenable composition in contact with a phase change material; applying water to the orthopedic support material; applying the orthopedic support material to a body part; and allowing the hardenable composition to harden.
  • the step of applying water can occur either before or after the step of applying the orthopedic support material to a body part. Definitions
  • orthopedic support material or “orthopedic casting material” are used to encompass a wide variety of dressings comprising a hardenable composition designed to facilitate healing of an injured body part, e.g., a broken, fractured, or sprained limb; "cast” or “support” are used to include a wide variety of hardened orthopedic support structures that are designed to immobilize a body part, and include both casts and splints; "an effective amount” of an adjuvant means an amount sufficient to provide one or more of the benefits of such an adjuvant, as described herein; "phase change material” is one that absorbs heat given off by an exothermic hardenable composition during the exothermic hardening process; “hydrophobic phase change material” is one that is insoluble in water such that solid material when added to water can be seen as a separate phase by the naked eye, or if the solid is in the form of uniformly distributed particles, the dispersion has a Klett value lower than about 250 under the conditions
  • Fig. 1 is a schematic representation of a casting material 20 of the present invention shown wrapped in position for hardening.
  • Fig. 2 is a schematic representation of a casting material of the present invention shown applied as a splint 30.
  • An optional underpadding 32 and an optional overwrap 34 are also depicted.
  • Suitable hardenable compositions for use in the orthopedic support materials (e.g., casting tapes and splints) of the present invention preferably have one or more of the following properties: substantial storage life; low toxicity; a sufficiently slow hardening rate such that there is a reasonable period of time in which to mold the material to the limb; a sufficiently fast hardening rate such that the composition hardens to form a weight-bearing cast within a period of about 20 minutes to several hours; hardenable to a relatively strong, tough, and long lasting cast such that the cast is sufficiently strong (whether flexible, semi-rigid, or rigid) to support a fractured limb; hardenable to a substantially water resistant cast (e.g., a cast that will not soften to the extent that the cast breaks down during
  • Orthopedic support materials of the present invention include an exothermic hardenable composition in contact with a phase change material.
  • the orthopedic support materials include a substrate coated or impregnated with an exothermic hardenable composition in contact with a phase change material.
  • Hardenable compositions for use in orthopedic support materials of the present invention preferably include exothermic hardenable compositions that are hardenable upon exposure to water at an initial set temperature of about room temperature (e.g., about 18°C to about 27°C).
  • the exothermic hardenable composition can include one or more parts, each of which can include one or more components, although preferably, it is a one-part system that is hardened by exposure to water.
  • the hardenable compositions can include one or more optional adjuvants.
  • Suitable exothermic hardenable compositions can be a wide variety of compositions that are conventionally used in orthopedic support materials, as well as those that may not be conventionally used (because of an extreme exotherm, for example). Such compositions are preferably capable of hardening upon initial exposure to water (e.g., as by dipping in water or exposing to moist air), preferably with the water temperature of about 10°C to about 40°C, more preferably, about 15°C to about 30°C, and most preferably, about 18°C to about 27°C.
  • the exothermic hardenable compositions may be hardened by some other mechanism, for example, by exposure to ultraviolet light, visible light, or ultrasound.
  • Preferred exothermic hardenable compositions are those that satisfy the functional characteristics of an orthopedic support material, which are described above. For example, it is desirable that such compositions should cure sufficiently rapidly but not so rapidly that they do not allow sufficient working time to apply and shape the orthopedic support material. Further, it is desirable that they not give off toxic vapors during curing in amounts that could be harmful to the patient or the person applying the orthopedic support material.
  • a suitable exothermic hardenable composition is preferably in the form of liquid at room temperature (preferably, having a viscosity of less than about 150,000 centipoise measured on a Brookfield Viscometer Model RVT with a #6 Spindle at 10 revolutions per minute and a temperature of 25°C), but may be in the form of a solid particulate material, which can be in a paste, slurry, gel, dispersion, or solution.
  • Preferred exothermic hardenable compositions are described, for example, in U.S. Pat. Nos. 5,716,661 (Scholz et al.) and 4,667,661 (Scholz et al.).
  • the exothermic hardenable composition is a one-part system that requires only the addition of water.
  • a "one-part" system can include one component or a mixture of components (e.g., premix including fillers, lubricants, etc.), but does not include two-part exothermic hardenable compositions that require mixing of reactive components, other than water, immediately prior to application.
  • exothermic hardenable compositions at least partially harden in at least about 1 minute, more preferably, at least about 1.5 minutes, and most preferably, at least about 3 minutes. Preferably, they at least partially harden in no more than about 15 minutes, more preferably, no more than about 7 minutes, and most preferably, no more than about 5 minutes.
  • exothermic hardenable compositions include, but are not limited to, isocyanate-functional urethane prepolymers, alkoxysilane-terminated polyurea and/or polyurethane prepolymers, cyanoacrylate esters, epoxy resins, polyalkoxysilane and/or polyhalosilane prepolymers, and vinyl compounds.
  • Suitable such resins are disclosed, for example, in U.S. Pat. Nos. 4,667,661 (Scholz et al.), 4,774,937 (Scholz et al.), 5,716,661 (Scholz et al.), 5,474,522 (Scholz et al.), and 4,672,956 (Potter).
  • exothermic hardenable compositions examples include plaster of Paris and water-soluble silicates, wherein at least about 1 part of the water-soluble silicate is soluble in about 6 parts water at 25°C, such as those of the formula SiO 2 /M 2 O wherein M is Li, Na, K, or NR 4 , each R is independently hydrogen or a (Cj-C ⁇ o)organic group, which are disclosed in U.S. Patent Application Serial No. 08/969,208, filed on November 12, 1997.
  • Preferred exothermic hardenable compositions include isocyanate-functional urethane prepolymers (i.e., polyisocyanate prepolymer) formed by the reaction of an isocyanate and a polyol.
  • a water-curable isocyanate-functional urethane prepolymer as used herein means a prepolymer derived from polyisocyanate, preferably aromatic, and a reactive hydrogen compound or oligomer.
  • the prepolymer has sufficient isocyanate-functionality to cure upon exposure to water, e.g., moisture vapor, or preferably liquid water.
  • Suitable isocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixture of these isomers, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, mixtures of these isomers together with possible small quantities of 2,2'-diphenylmethane diisocyanate (typical of commercially available diphenylmethane diisocyanate), and aromatic polyisocyanates and their mixtures such as are derived from phosgenation of the condensation product of aniline and formaldehyde.
  • MDI diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • Suitable isocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixture of these isomers, 4,4'-diphenylmethane diisocyanate, 2,4
  • Typical polyols for use in the prepolymer system include polypropylene ether glycols (available from Lyondell Chemical, Newton Square, PA, under the trade name ARCOL PPG and from BASF Wyandotte, Parsippany, NJ, under the trade name PLURACOL), polyoxypropylene polyols (available from Lyondell Chemical), Newton Square, PA, under the trade names ARCOL LG and ARCOL LHT), polytetramethylene ether glycols (available from DuPont, Wilmington, DE, under the trade name TERATHANE), polycaprolactone diols (available from Union Carbide, Danbury, CT, under the trade name TONE series of polyols), and polyester polyols (hydroxyl terminated polyesters obtained from esterification of dicarboxylic acids and diols such as the FOMREZ polyols available from Witco. Melrose Park, IL).
  • polypropylene ether glycols available from Lyondell Chemical, Newton Square, PA, under the trade name AR
  • An example of a resin useful in the orthopedic support material of the invention uses an isocyanate available from the Dow Chemical Company, Midland, MI, under the trade name ISONATE 2143L (a mixture of di- and tri-isocyanates containing about 73% of MDI) and polypropylene oxide polyols available from Lyondell Chemical under the trade name ARCOL LG-650, PPG 2025, and ARCOL 24-32.
  • ISONATE 2143L a mixture of di- and tri-isocyanates containing about 73% of MDI
  • polypropylene oxide polyols available from Lyondell Chemical under the trade name ARCOL LG-650, PPG 2025, and ARCOL 24-32.
  • benzoyl chloride or another suitable stabilizer such as acid chlorides, sulfonyl chlorides, or sulfonic acid.
  • the reactivity of the resin once it is exposed to water can be controlled by the use of a proper catalyst.
  • the reactivity must not be so great that: (1) a hard film quickly forms on the resin surface preventing further penetration of the water into the bulk of the resin; or (2) the cast becomes rigid before the application and shaping is complete.
  • Good results have been achieved using 4-[2-[l-methyl-2-(4-mo holinyl)ethoxy]ethyl]-morpholine (MEMPE) prepared as described in U.S. Pat. No. 4,705,840 (Buckanin), or 2,2'-dimorpholinodiethyl ether (DMDEE) available from Huntsman Chemical, Austin, TX.
  • MEMPE 4-[2-[l-methyl-2-(4-mo holinyl)ethoxy]ethyl]-morpholine
  • DMDEE 2,2'-dimorpholinodiethyl ether
  • such catalyst is used at a concentration of about 0.05 percent to about 5
  • the exothermic hardenable composition of the present invention is used in an amount of at least about 25 percent by weight (wt-%), more preferably, at least about 30 wt-%, and most preferably, at least about 35 wt-%, based on the total weight of the orthopedic support material (which may or may not include a substrate).
  • the exothermic hardenable composition is used in the compositions of the present invention in an amount of no greater than about 98 wt-%, more preferably, no greater than about 95 wt-%, and most preferably, no greater than about 90 wt-%, based upon the total weight of the orthopedic support material.
  • the exothermic hardenable compositions of the present invention advantageously are in contact with, and preferably include, one or more phase change materials (preferably, heat-absorbing, phase change materials).
  • phase change materials preferably, heat-absorbing, phase change materials.
  • phase change materials are in the form of low melting organic compounds, which are solids at room temperature. Such solids are typically crystalline, semicrystalline, or waxy solids.
  • such compounds have an endotherm as determined by Differential Scanning Calorimetry (DSC) within a temperature range about 18°C up to the peak temperature reached during the hardening process of the exothermic hardenable composition. More preferably, they have an endotherm within a temperature range of about 26°C to about 50°C.
  • DSC Differential Scanning Calorimetry
  • Such endotherm for the phase change material can be readily determined by one of skill in the art using DSC.
  • such endotherm temperatures are slightly to moderately above room temperature and within the temperature ranges for hardening of the exothermic hardenable compositions, which allows for effective removal of heat through a change of phase when the exotherm begins as a result of hardening.
  • phase change material may react with a component of the hardenable composition (e.g., an isocyanate); however, this should not hinder its ability to absorb the heat produced as a result of hardening of the hardenable composition.
  • a component of the hardenable composition e.g., an isocyanate
  • the phase change material is that which is added to the hardenable composition or initially brought into contact with the hardenable composition.
  • phase change materials include, but are not limited to, relatively low melting hydrophobic compounds of the following classes: straight or branched chain alkyl or alkenyl hydrocarbons such as octadecane, eicosane, docosane
  • hydrophobic classes may include alkyl or alkenyl polyglucosides, polyglycerol esters, quaternary amines, protonated salts of tertiary amines, amine oxides, zwitterionics, and alkyl and alkenyl amides.
  • Suitable phase change materials include relatively low melting hydrophilic compounds of the following classes: ethers of polyethoxylated alcohols such as polyoxyethylene-2-stearyl ether, polyoxyethylene-21-stearyl ether, and polyoxyethylene-100-stearyl ether available as BRIJ 72, BRIJ 721 and BRIJ 700 from ICI, Wilmington, DE, polyethylene glycol distearates available as PEG DS 400, PEG DS 600 and PEG DS 6000 from PPG, Gurnee, IL, and sorbitan fatty acid esters such as sorbitan monopalmitate available from Aldrich, Milwaukee, WI.
  • ethers of polyethoxylated alcohols such as polyoxyethylene-2-stearyl ether, polyoxyethylene-21-stearyl ether, and polyoxyethylene-100-stearyl ether available as BRIJ 72, BRIJ 721 and BRIJ 700 from ICI, Wilmington, DE
  • polyethylene glycol distearates available as PEG DS 400, P
  • hydrophilic classes include polyoxypropylene/polyoxyethylene copolymers such as PLURONIC PI 05 available from BASF, Mount Olive, NJ, and ethers of long chain alcohols such as oleoyl ether available as HETOXOL OL-40 from Heterene, Newark, NJ.
  • phase change materials are solids at room temperature. There are several factors that can affect whether a particular phase change material will, in fact, be a solid in a curable resin. Certain phase change materials may have reactive functional groups which would cause them to become covalently bound to the resin. This chemical reaction may alter the endotherm temperature of the phase change material; however, it should still function as a phase change material to absorb heat produced during the hardening process. Preferred phase change materials that react into the resin produce a reaction product that still forms a solid phase in the resin with an endotherm above room temperature. Also, certain phase change materials may be solubilized in a curable exothermic resin composition depending on how the phase change material is processed.
  • the phase change material is added as a finely divided solid into the resin at a temperature below the melting point of the phase change material so that it remains solid.
  • the phase change material may be added at a temperature above its melting point and allowed to crystallize out on cooling. Chilling the resin below room temperature may be required to induce crystallization. This is especially true for many hydrophilic phase change materials but may be beneficial for hydrophobic phase change materials as well.
  • One or more phase change materials can be used in the present invention.
  • a phase change material is used in an amount effective to reduce the peak exotherm of the hardenable composition by at least about 2°C, and preferably, by at least about 3°C, compared to the same hardenable composition used in the same amount of hardenable components, but without the phase change material.
  • the phase change materials are used in the orthopedic support materials of the present invention in an amount such that the percent by weight (wt-%) of phase change material based on the amount of exothermic hardenable composition (absent any fillers) is at least about 0.5 wt-%, more preferably, at least about 1.0 wt-%, and most preferably, at least about 2.0 wt-%.
  • the phase change materials are used in the compositions of the present invention in an amount such that the wt-% of phase change material based on the amount of filler- free exothermic hardenable composition is no greater than about 35 wt-%, more preferably, no greater than about 25 wt-%, and most preferably, no greater than about 20 wt-%.
  • the phase change material is preferably physically mixed with the exothermic hardenable composition.
  • the phase change material can be encapsulated or microencapsulated within a relatively inert microcapsule shellwall, for example, a polyurea or polyamide shellwall.
  • the microcapsules can range in size from about 0.5 micron to 1000 microns and can be prepared according to conventional methods well known to those skilled in the art.
  • the phase change material can be in or on an underlying stockinet and/or cast padding, as described below.
  • the exothermic hardenable composition can also include effective amounts of adjuvants such as catalysts, fillers, polymeric toughening agents, drying agents, binding agents, antifoaming agents, lubricants, slip agents, stabilizers, tackifiers, plasticizers, pigments, dyes, and fragrances.
  • adjuvants such as catalysts, fillers, polymeric toughening agents, drying agents, binding agents, antifoaming agents, lubricants, slip agents, stabilizers, tackifiers, plasticizers, pigments, dyes, and fragrances.
  • These adjuvants may be soluble or insoluble in the composition.
  • One or more of these adjuvants may be incorporated into the compositions of the present invention. They are each used in "an effective amount," i.e., an amount sufficient to provide one or more of the benefits of such an adjuvant, as described herein. This amount can range, for example, from about 0.01 weight percent to about 80 weight percent, based on the total weight of the composition
  • Suitable catalysts for use in the hardenable compositions of the present invention include compounds, which, when present in sufficient quantity, will initiate and/or facilitate the hardening of the composition.
  • the catalysts are those compounds that initiate and/or facilitate hardening of the orthopedic support material but permit sufficient working time for the person applying the dressing before it hardens into a cast.
  • Foaming of the exothermic hardenable composition is preferably minimized since it reduces the porosity of the cast and its overall strength. For example, foaming can occur because carbon dioxide is released when water reacts with isocyanate groups.
  • Foam suppressors such as silicone Antifoam A (Dow Corning) or Antifoam 1400 silicone fluid (Dow Corning) can be used to reduce foaming. It is especially preferred to use a silicone liquid such as Dow Corning Antifoam 1400 at a concentration of about 0.05 percent to about 1.0 percent by weight, when an isocyanate-functional prepolymer is used in the exothermic hardenable composition.
  • Fillers may be used in the exothermic hardenable compositions to increase the strength and/or toughness of the cast obtained and/or reduce cost.
  • a filler is a water insoluble solid organic or inorganic material that is added to the exothermic hardenable composition but does not change phases during the hardening process, i.e., it remains solid.
  • Fillers can also be used to modify the appearance and handling characteristics of a substrate coated or impregnated with the hardenable composition.
  • Useful fillers include, but are not limited to, particulate, spherical, fibrous, microfibrous, flake, or platelet forms.
  • the fillers may have solid, porous, or hollow structures. They may be organic or inorganic materials.
  • Fillers may be surface treated using silanes, zirconates, titanates, etc.
  • suitable fillers include, but are not limited to, calcium metasilicate particles and fibers (such as calcium metasilicate, also referred to as wollastonite, microfibers available under the trade designation NYAD-G from NYCO Minerals, Willsboro, NY), calcium carbonate, calcium sulfate, kaolin, mica, talc, feldspar, barium sulfate, barium ferrite, titanium dioxide, fumed or precipitated silicas (such as those available under the trade designations CABOSJL TS-720 from Cabot Corp., Boyertown, PA, or AEROSILS from Degussa Corp., Ridgefield Park, NJ), insoluble amorphous and crystalline silica, ground glass, glass bubbles (such as sodium borosilicate glass bubbles, i.e., hollow glass beads, available under the trade designation K-46 from the 3M Company, St.
  • the orthopedic support material generally preferably includes a substrate or scrim impregnated or coated with the exothermic hardenable composition.
  • Suitable substrates include knit, woven, and nonwoven fabrics as well as foams, such as those described in U.S. Pat. Nos. 5,195,945 (Sandvig et al), 5,002,047 (Sandvig et al), 5,512,354 (Scholz et al.), 4,841,958 (Ersfeld et al.), and 4,888,225 (Sandvig et al), and other porous materials made of natural or synthetic fibers, such as those disclosed, for example, in U.S. Pat. No. 5,716,661 (Scholz et al.).
  • preferred fiber materials that form the substrate include, but are not limited to, fiberglass, silane-treated fiberglass, nylon, polyolefins, polyamides, polyesters, cotton, rayon, and mixtures thereof.
  • Other usable materials include knits, wovens, and nonwovens, any of which may contain elastic yarns or fibers of natural rubber, synthetic rubber, or polyurethane.
  • Preferred fabrics obtain extensibility through mechanical compaction such as microcreping or through the use of heat shrinkable highly twisted texturized yarns. Fabrics such as these are disclosed in U.S. Pat. No. 5,512,354 (Scholz et al.).
  • the substrates may be dyed or pigmented in a solid or patterned manner, as discussed in U.S. Pat. No. 5,342,291 (Scholz et al.).
  • Fiberglass is a high modulus fiber that contributes significant strength to the hardened orthopedic supports of the present invention.
  • the combination hardens to a very hard, lightweight, strong, weight-bearing cast.
  • Fiberglass woven or knitted substrates suitable for use in support materials according to the present invention include those used in the knitted substrate of SCOTCHCAST Plus casting tape, which tape is available from the 3M Company (St. Paul, MN).
  • Other preferred fiberglass fabrics are those discussed in U.S. Pat. No. 4,668,563 (Buese et al.).
  • the substrate be constructed from a fabric or substrate which is relatively extensible and flexible, e.g., which has a lengthwise extensibility of at least about 20%. preferably about 40% to about 60%, once coated with the hardenable composition. This will facilitate fitting the support material around contoured portions of the body, such as the heel, knee, or elbow.
  • the substrate be constructed from a porous or mesh fabric (e.g., a fabric having apertures of sufficient size to enable water to permeate the roll of casting tape during water activation and cause the composition to harden after application to a body part or other structure).
  • a porous fabric is desired to allow air and moisture vapor to move through the material after cure, thereby promoting patient comfort and avoiding skin breakdown caused by excessive moisture build-up under the cured material.
  • Suitable aperture sizes are about 0.3 mm 2 to about 16 mm 2 , preferably about 1.2 mm 2 to about 9 mm 2 .
  • the aperture size is defined by the intersection of chain or wale stitches with the in-lay stitch.
  • Non-fiberglass and low modulus substrates generally provide lower strength to the hardened orthopedic support materials.
  • Preferred non-fiberglass substrates include cheese cloth gauzes and lightweight polyester knit fabrics.
  • Other preferred non-fiberglass fabrics are disclosed in U.S. Pat. Nos. 4,841,958 (Ersfeld et al.) and 4,940,047 (Richter et al.).
  • various chemical treatments and/or coupling agents such as silane, titanate, or zirconate treatment of the scrim may also be included.
  • a substrate can be coated or impregnated with the hardenable composition and the phase change material by any of a variety of means well known in the art, depending on whether the composition is in the form of a dry solid, moist solid, solution, dispersion, slurry, paste, gel, or the like.
  • low viscosity compositions can be sprayed onto a substrate
  • high viscosity compositions can be applied to a substrate as a putty
  • moderate viscosity compositions can be applied to a substrate by brush, knife coating, curtain coating, or with a roll coater.
  • simple absorption of the hardenable composition into the substrate may be used.
  • Compositions of the present invention may be applied at room temperature or at elevated temperature (generally less than about 100°C).
  • the hardenable compositions can also be applied from a solvent that preferably is removed at a later time.
  • the amount of the hardenable composition applied to a substrate can vary.
  • a substrate is coated or impregnated with a hardenable composition in an amount of about 0.4 time to about 20 times the weight of the substrate.
  • a variety of conventional techniques can be utilized to store the substrate coated or impregnated with the hardenable composition, prior to use to form a cast or a splint.
  • a cast roll or splint slab of the coated or impregnated substrate of various widths, generally about 2 centimeters (cm) to about 20 cm in width, and an appropriate length will be prepared.
  • the roll or slab is preferably packaged within a substantially water-impermeable container such as an aluminum foil plastic laminate pouch.
  • the exothermic hardenable compositions of the present invention can be combined with a phase change material to provide orthopedic support materials without the use of a separate substrate.
  • the hardenable composition also comprises a filler, such as described in U.S. Patent No. 5,716,661 (Scholz et al.) to provide materials with sufficient strength to be used as orthopedic support materials.
  • Hardening of the coated substrate of the present invention is preferably accomplished by contacting the exothermic hardenable composition with water.
  • the composition can be hardened upon exposure to water under a variety of conditions of temperature and pressure. For example, it can harden at an initial temperature of the composition of about 10°C to about 100°C, and preferably, about 20°C to about 50°C.
  • extreme temperatures are not required. That is, the composition of the present invention advantageously can harden at an initial temperature of the composition of about 20°C to about 40°C.
  • Orthopedic support materials, involving the hardenable compositions of the present invention may be applied to humans or various animals in the same fashion as other known orthopedic support materials.
  • the body part to be immobilized is preferably covered with a conventional stockinet and/or cast padding for protection.
  • the stockinet is a protective sleeve of an air-permeable fabric such that air may pass in through the sleeve and the cast to the surface of the skin, and moisture vapor may pass out.
  • this sleeve does not appreciably absorb water and permits the escape of perspiration.
  • An example of such a substrate is a knitted or woven polypropylene material.
  • the sleeve and/or cast padding associated with the orthopedic support material may contain the phase change material to reduce the amount of heat resulting from hardening of the exothermic hardenable composition.
  • the hardenable composition may be activated, for example, by dipping the orthopedic support material in water. Excess water may then be squeezed out of the orthopedic support material, and the material wrapped or otherwise positioned around the body part so as to properly conform thereto. Preferably, the material is then molded and smoothed to form the best fit possible and to properly immobilize the body part in the desired position.
  • the orthopedic support material may be held in place during hardening by wrapping an elastic bandage or other securing means around the hardening orthopedic support material.
  • the body part is properly immobilized within the formed orthopedic cast or splint.
  • the orthopedic support material has a working time sufficient to allow the bandage to be positioned and a set time sufficient for the cast, for example, to be molded to take the shape of the body part (but short enough that the applier does not waste time). It has a hardening time sufficient for the cast to become weight-bearing. Suitable working (hardening or set) times are about 1 minute to about 15 minutes, preferably, about 1.5 minutes to about 7 minutes, and more preferably, about 3 minutes to about 5 minutes. Suitable times to weight-bearing (e.g., the time from initial activation until the cast is sufficiently strong to allow weight to be applied) are less than about 24 hours, preferably, less than about 7 hours, and more preferably, less than about 1 hour.
  • the maximum or peak temperature, as determined according to the procedure of Example 2, reached beneath the support material is less than about 50°C, more preferably, less than about 42°C, and most preferably, less than about 38°C.
  • the orthopedic material preferably is shelf stable for at least 1 year, preferably at least 2 years, and most preferably at least 3 years.
  • This example describes the preparation and evaluation of hardenable composition (resin) samples containing either a hydrophobic heat-absorbing phase change material (PCM), as previously defined, or a non-PCM.
  • PCM phase change material
  • a liquid polyurethane prepolymer (Resin- 1) was prepared by combining the ingredients listed in Table la.
  • the temperature of the mass was measured over time using a Portable Hybrid Recorder Model 3087 (Yokogawa Electric Corporation, Shenandoah, GA) and the peak temperature and time to peak temperature were recorded. Results are provided in Table lc as means and standard deviations (SD) of 4-6 replications (n) with an asterisk (*) indicating a statistical difference from Control at a 95% level in a one-way Analysis of Variance (ANOVA).
  • This example describes the preparation and evaluation of orthopedic casting articles comprising hydrophobic PCM-containing water-hardenable resins coated on a fabric backing.
  • a liquid isocyanate-functional polyurethane prepolymer (Resin-2) was prepared by combining the ingredients listed in Table 2a and heating to 65°C for 90 minutes with mixing.
  • a variety of different hydrophobic PCMs were separately added to the pre-made Resin-2 at the concentrations shown in Table 2b.
  • the microencapsulated PCM was pre-dried in a NAPCO Vacuum Oven Model 5851 for 24 hours and added to Resin-2 as a powder. All other PCMs were heated above their respective melting points and added to Resin-2 as liquids. All mixing procedures were conducted under a blanket of nitrogen to minimize access to ambient moisture.
  • the fabric used as an orthopedic casting article backing was a three-bar knit of the following construction:
  • Sample orthopedic casting tapes were made by separately coating the Resin-2 plus PCM Samples (Table 2b) onto the microcreped polyester fabric.
  • In-process coating weight percents were determined by weighing stretched samples before and after coating. Target coating weight percents of plus/minus 1.5% were accepted.
  • a Control sample was prepared in an identical manner except that no PCM was added to the resin.
  • Coating Weight Percent was accurately determined by extracting the resin from a sample using a tetrahydrofuran/methanol (50/50 weight ratio) solution. Samples were immersed in three consecutive extraction baths (1.9-liter solution) at room temperature for 2 minutes each, were air dried for 30 minutes minimum, and were weighed before and after extraction with the difference in weights assumed to be the amount of resin originally present in the sample. The weight percent of resin present in each sample was calculated and the resulting coating weight percents are provided in Table 2c.
  • Twenty-four hour dry ring strength was determined according to the following test method. Resin-coated backing was removed from its storage foil pouch and immersed completely in 25°C water for 30 seconds. The roll of material was then removed from the water and was wrapped around a 5.1 -cm diameter mandrel under controlled tension and speed using an automated ring maker. The roll (or cylinder) consisting of six complete uniform layers was removed from the mandrel after 30 minutes and allowed to cure for 24 hours in a controlled atmosphere of 23°C +/- 2°C and 55% +/- 5% relative humidity. After 24 hours, the cylinder was placed in an Instron instrument fixture for testing. The cylinder was subjected to a compression load applied along the exterior of the cylinder and parallel to its axis.
  • Crushing speed was set at 5 cm/min.
  • the maximum or peak force necessary to crush the sample cylinder was recorded as the dry strength expressed in terms of force per unit length (N/cm) of the cylinder.
  • N/cm force per unit length
  • Eicosane/Docosane and HYDROKOTE M PCMs had somewhat decreased ring strengths compared to the Control, a result consistent with the fact that these hydrocarbon materials can act as plasticizers.
  • This example describes the preparation and DSC evaluations of hardenable composition (resin) samples containing two different hydrophobic PCM additives.
  • a liquid isocyanate-functional polyurethane prepolymer resin was prepared according to Example 2 (Resin-2), except that no PLURONIC F-108 was added.
  • a sample (100 g) of this resin was added to a 275-ml glass jar and heated to 55°C.
  • a sample of LANETTE 14 - Myristyl Alcohol was heated to 50°C and added under nitrogen to the heated resin at a concentration of 7% by weight. The resulting mixture was then allowed to cool overnight to room temperature while being mixed by rolling the sealed jar at 55 revolutions/minute (laboratory roller manufactured by U.S. Stoneware, Mahwah, NJ).
  • CAPTEX 1000 added as a solid to Resin-1 at room temperature as described in Example 1 did show a statistically significant reduction in peak temperature effect (Table lc). It can be concluded that, for these examples, the CAPTEX 1000 added as a heated liquid did not crystallize out of the prepolymer resin upon cooling.
  • shelf stability of the resins and the orthopedic casting articles containing such resins may be affected by the addition of a PCM. This effect may be positive or negative depending on the PCM selected.
  • a liquid isocyanate-functional polyurethane prepolymer (Resin-3) was prepared as described in Example 2, except that the DMDEE catalyst level was increased from 1.25% to 2.00%.
  • the HYDROKOTE M PCM was added to Resin-3 as described in Example 2 at a level of 10% by weight.
  • Sample orthopedic casting tapes were made by separately coating the Resin-3 (or Resin-2) plus HYDROKOTE M PCM samples onto the microcreped polyester fabric as described in Example 2. The rolls of tape were evaluated according to the test methods described in Example 2 and results comparing the two levels of catalyst are provided in Table 4, with an asterisk (*) indicating a statistical difference at a 95% level in a one-way ANOVA.
  • This example describes the preparation and evaluation of an orthopedic casting resin containing various heat-absorbing hydrophilic PCMs.
  • hydrophilic PCM additives were separately added to Resin-1 as described in Example 1 and are listed in Table 5a. Also provided in Table 5 a are the melting point ranges and the heat of fusion (H f ) values for the various additives as determined on a DSC2920 Differential Photocalorimeter (TA Instruments, New Castle, DE).
  • EXAMPLE 7 Orthopedic Casting Article Containing Hydrophilic Heat-Absorbing PCM This example describes the preparation and evaluation of an orthopedic casting article comprising a hydrophilic PCM-containing water-hardenable resin coated on a fabric backing.
  • the hydrophilic PCM additive PEG Distearate 400 was added to the premade Resin-2 at a level of 10 weight percent and the resulting composition was then coated onto the microcreped polyester fabric to provide a coated fabric sheet as described in Example 2.
  • a Control sample was prepared in an identical manner except that no PCM was added to the resin. Coating weight percent, ring strength, peak temperature, and time to peak temperature were determined as described in Example 2 and the results are provided in Table 6.
  • An asterisk (*) indicates a statistical difference from the control value at 95% level in a one-way ANOVA.
  • This example describes the preparation and DSC evaluations of hardenable composition (resin) samples containing two different hydrophilic PCM additives.
  • the first experiment of Example 3 with LANETTE 14) was repeated, except that PEG DS 400 was used in place of the LANETTE 14.
  • the results for the PEG DS 400 samples showed a positive-negative heat flow cycle in the temperature range of -30°C to 0°C (assumed to be a cold crystallization effect), but no negative heat flow was observed above 0°C. No differences were observed between the room temperature cooled sample and the refrigerated sample.
  • These DSC results are in contrast to the statistically significant reduction in peak temperature effect observed with PEG DS 400 added as a solid to Resin- 1 as described in Example 6 (Table 5b).
  • a sample (0.5 g) of the PCM additive was added to deionized, room-temperature water (99.5 g) in a 118-ml glass jar equipped with a magnetic stirring rod and placed on a Fisher Electronic Stirrer 2008 (Fisher Scientific, Pittsburgh, PA). After stirring (300 revolutions/minute) for 1 hour at room temperature, a sample (9 ml) was drawn from the liquid phase (solution or mixture) using a 7-ml disposable polyethylene transfer pipette (VWR Scientific, Media, PA) and transferred into a 10-ml glass culture tube (VWR Scientific).
  • VWR Scientific disposable polyethylene transfer pipette
  • the sample was then measured for turbidity at 640-700 nm using a Klett-Summerson Photoelectric Colorimeter, Model 800-3 (Klett Manufacturing, New York, NY).
  • the measuring unit was an arbitrary Klett unit that expressed the degree of light scattering, i.e., the higher the Klett unit reading, the cloudier the solution.
  • the Klett readings combined with the visual evaluation of the sample provided a basis for the following classification of PCM additives:
  • PCM additives described in these examples were evaluated for hydrophobicity/hydrophilicity according to the above procedure and classified as either hydrophobic or hydrophilic PCM additives. The results are provided in Table 7.

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  • Animal Behavior & Ethology (AREA)
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Abstract

L'invention se rapporte à un matériau de support orthopédique comportant une composition exothermique susceptible de durcir qui est en contact avec une substance à changement de phase, absorbant la chaleur et hydrophobe.
PCT/US2000/001828 1999-09-16 2000-01-24 Materiau de support orthopedique contenant une substance a changement de phase absorbant la chaleur WO2001019420A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077428A2 (fr) * 2004-02-18 2005-08-25 Vigh Kristof Structure de contention assurant le maintien d'une surface de peau recouvrant des muscles et des articulations, preparation permettant de former une telle structure de contention et utilisation de celle-ci
WO2012159987A1 (fr) * 2011-05-20 2012-11-29 Universitätsklinikum Der Rwth Aachen Matière d'adhésion amovible
WO2014209524A1 (fr) * 2013-06-28 2014-12-31 Bsn Medical, Inc. Plâtre orthopédique et bandages d'attelle avec support de durcissement encapsulé et procédé

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1492038A (en) * 1975-12-17 1977-11-16 Smith & Nephew Res Water-hardenable powder material particularly for use in an orthopaedic bandage
EP0279612A1 (fr) * 1987-02-18 1988-08-24 Minnesota Mining And Manufacturing Company Eclissages orthopédiques et leurs procédés
WO1994023768A1 (fr) * 1993-04-13 1994-10-27 Minnesota Mining And Manufacturing Company Nouvelles bandes et resines pour appareils platres, et procedes
US5716661A (en) * 1993-04-16 1998-02-10 Minnesota Mining And Manufacturing Company Method of making a light weight orthopedic casting tape

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1492038A (en) * 1975-12-17 1977-11-16 Smith & Nephew Res Water-hardenable powder material particularly for use in an orthopaedic bandage
EP0279612A1 (fr) * 1987-02-18 1988-08-24 Minnesota Mining And Manufacturing Company Eclissages orthopédiques et leurs procédés
WO1994023768A1 (fr) * 1993-04-13 1994-10-27 Minnesota Mining And Manufacturing Company Nouvelles bandes et resines pour appareils platres, et procedes
US5716661A (en) * 1993-04-16 1998-02-10 Minnesota Mining And Manufacturing Company Method of making a light weight orthopedic casting tape

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077428A2 (fr) * 2004-02-18 2005-08-25 Vigh Kristof Structure de contention assurant le maintien d'une surface de peau recouvrant des muscles et des articulations, preparation permettant de former une telle structure de contention et utilisation de celle-ci
WO2005077428A3 (fr) * 2004-02-18 2005-10-13 Kristof Vigh Structure de contention assurant le maintien d'une surface de peau recouvrant des muscles et des articulations, preparation permettant de former une telle structure de contention et utilisation de celle-ci
WO2012159987A1 (fr) * 2011-05-20 2012-11-29 Universitätsklinikum Der Rwth Aachen Matière d'adhésion amovible
US9211235B2 (en) 2011-05-20 2015-12-15 Rheinisch-Westfaelische Technisch Hochschule Aachen Removable adhesion material
US9795540B2 (en) 2011-05-20 2017-10-24 Rheinisch-Westfalische Technische Hochschule Aachen Removable adhesion material
WO2014209524A1 (fr) * 2013-06-28 2014-12-31 Bsn Medical, Inc. Plâtre orthopédique et bandages d'attelle avec support de durcissement encapsulé et procédé
JP2016530909A (ja) * 2013-06-28 2016-10-06 ビーエスエヌ メディカル，インク． 被包性硬化型媒質が封入された整形外科用ギブスおよび副木の包帯と方法
US10159593B2 (en) 2013-06-28 2018-12-25 Bsn Medical, Inc. Orthopedic cast and splint bandages with encapsulated hardening medium and method

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