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EP1904574A2 - Compositions formant un film copolymere applique par atomisation et visant a proteger les tissus - Google Patents

Compositions formant un film copolymere applique par atomisation et visant a proteger les tissus

Info

Publication number
EP1904574A2
EP1904574A2 EP05770860A EP05770860A EP1904574A2 EP 1904574 A2 EP1904574 A2 EP 1904574A2 EP 05770860 A EP05770860 A EP 05770860A EP 05770860 A EP05770860 A EP 05770860A EP 1904574 A2 EP1904574 A2 EP 1904574A2
Authority
EP
European Patent Office
Prior art keywords
spray
film
composition
water
methacrylate
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.)
Withdrawn
Application number
EP05770860A
Other languages
German (de)
English (en)
Inventor
Shalaby W. Shalaby
James M. Lindsey, Iii
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.)
Poly Med Inc
Original Assignee
Poly Med Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/175,636 external-priority patent/US7842749B2/en
Application filed by Poly Med Inc filed Critical Poly Med Inc
Publication of EP1904574A2 publication Critical patent/EP1904574A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/0066—Medicaments; Biocides
    • 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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/0076—Sprayable compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/202—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with halogen atoms, e.g. triclosan, povidone-iodine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/402—Anaestetics, analgesics, e.g. lidocaine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/442—Colorants, dyes
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow

Definitions

  • This invention deals with amphiphilic, copolymeric, sprayable, organic solvent-borne compositions so designed to provide a means to yield a medicated or unmedicated elastomeric, thin film on intact or compromised vertebrate animal tissue to protect against damaging environmental elements, aid in healing, and/or deliver needed medicaments.
  • the physical and biomechanical properties of these compositions are due to special chain design of the constituent copolymers wherein said chains comprise highly hydrophilic as well as highly hydrophobic segments or blocks.
  • Background of the Invention Protecting compromised tissues, as in the case of lacerated skin or mucous membrane, has been of interest to clinicians for decades.
  • Opsite Flexigrid ® marketed by Smith & Nephew
  • the Opsite Flexigrid ® consists of a thin polyurethane membrane coated with a layer of an acrylic adhesive.
  • the dressing which is permeable to both water vapor and oxygen, is impermeable to micro-organisms. Once in position, the film provides an effective barrier to external contamination, while producing a moist environment at the surface of the wound by reducing water vapor loss from the exposed tissue.
  • Naturally occurring and derivatized naturally occurring polymers have been tested as liquid adhesive coatings for bandage applications and, in some cases, utilized commercially.
  • Typical examples are nitrocellulose in various solvents (e.g., New Skin-Medtech Laboratories, Inc., Cody, Wyoming), agar in water and diethylene glycol (U.S. Patent No. 4,291,025), carrageenan and hydroxypropylmethyl cellulose in water ( U.S. Patent No. 4,318,746), and alginate in glycerin (U.S. Patent No. 4,393,048). All of these natural polymers can support microbial growth, hence requiring the addition of a preservative or antimicrobial agent to the product.
  • liquid bandages based on water, diethylene glycol, glycerin, etc. are not only susceptible to microbial growth, but are often also slow drying due to high heats of vaporization; and are often water sensitive, which can result in problems when used on areas of the body exposed to water.
  • One commercial product, New Skin does dry rapidly and is not water sensitive, but can cause stinging and further irritation of the skin upon appl ication.
  • a few synthetic polymers have been patented for use as liquid adhesive coatings for bandage applications, most notably polymers containing 2-hydroxyethyl methacrylate (U.S. Patent No. 4,303,066).
  • traditional wound and surgical bandages such as Band-Aids (Johnson & Johnson, New Brunswick, New Jersey), comprised of film backings with adhesive, may contain silicones as part of either the adhesive or the backing (e.g., U.S. Patent No.
  • 4,987,893 was noted to consist essentially of a silo?cane-containing polymer and a solvent system comprising a polar solvent in small amount and a volatile liquid which is non-stinging to a user but provides bulk and formability to the liquid.
  • the polymer is present from 1 to 40% by weight, the volatile liquid from 59.9 to 98.9% by weight and the polar solvent from 0.1 to 10% by weight.
  • the volatile liquid can be in amounts of 60 to 99%.
  • the solvent is minimized to obtain flowability desired at the lowest solvent level feasible which minimizes stinging.
  • the material forms a coating or bandage in the form of a dried film when applied to a surface or the skin of a user.
  • Patent No. 4,987,893 claims that combinations of alky siloxy siloxane-containing polymers admixed with liquid polydimethylsiloxanes are excellent non- stinging, non-irritating liquid coating material for forming films which act as conformable bandages adhering to and protecting nails, skin, and mucous membrane wounds from abrasion, contamination, and desiccation, while stopping pain from exposed nerve ends and allowing body fluid evaporation.
  • 4,987,893 are (1) expected to result in low tear strength films because of being made of polysiloxane-based chains; (2) not expected to form, in a timely manner, a solid film at the application site because of the low volatility of their major constituents; (3) expected to yield hydrophobic films that have low or no tendency to adhere to moist tissue for sufficient periods of time — these films offer no advantage over regular bandages; and (4) not expected to yield thin film on diff ⁇ cult-to-reach areas.
  • the dressing is transparent, permits easy follow-up of healing in the donor site, protects the wound against infection, and does not inconvenience trie patient.
  • the treatment is simple, economical, and does not require special skills.
  • the dressing peels off spontaneously after epidermal regeneration of the wound is completed. No complications or allergic reaction were observed with this treatment.
  • a commercial spray bandage sold under the trade name Curad ® Spray Bandage (Beiersdorf, Inc., Winton, Connecticut) was described to have the following ingredients: poly(methyl acrylate-isobutene-mono-isopropyl maleate), ethyl acetate, menthol, pentane, and carbon dioxide. It was noted to yield a transparent, breatheable film that seals applications site from water, dirt, and germs for maximum protection.
  • a second bandage spray that is water-soluble is commercialized by Swift First Aid as Swift Bandage Spray. It is advertised to provide an invisible coat for protection from dire, dust, and bacteria. It has been recommended for minor injuries, irritations, and insect bites.
  • the inactive ingredients of the spray-on are ethyl alcohol, isobutane, n-butane, propane, a water-soluble copolymer of N-vinyl pyrrolidone, and vinyl acetate.
  • the spray-on also contains benzethonium cliloride (0.2% w/w) and benzocaine (5% w/w) as active ingredients.
  • benzethonium cliloride (0.2% w/w
  • benzocaine 5% w/w
  • This invention deals generally with a tissue protecting, spray-on film composition
  • a tissue protecting, spray-on film composition comprising an amphiphilic film-forming, segmented/block copolymer derived from at least one water-soluble monomer and at least another water-insoluble monomer, wherein said respective film can be formed from a water soluble organic solvent such as 2-propaxiol, acetone, and ethyl acetate.
  • the film can contain a bioactive agent including those to have antimicrobial, anesthetic, anti-inflammatory, and wound-healing activities.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein (1) the said solvent may contain water at more than 0.1 percent of its volume; (2) the segmented/block copolymer may be derived from n-hexyl methacrylate and N-vinyl pyrrolidone; and (3) the segmented/block copolymer may be prepared by the controlled incremental addition of either or both monomers (comono
  • An alternative method for preparing the segmented/block copolymer subject of this invention comprises solution or bulk polymerization through controlled/living radical polymerization (CLRP) using NiBr 2 (PPh 3 ) 2 as a catalyst and ethyl 2-bromobutyrate as an initiator.
  • CLRP controlled/living radical polymerization
  • a specific aspect of this invention deals with a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer, having a molecular weight of at least 15 kDa, derived from n-hexyl methacrylate and one or more monomer selected from the group represented by N-vinyl pyrrolidone and 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acrylamide.
  • a general aspect of this invention addresses a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacryla_te wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein the said copolymer is made following a tellurium mediated living radical polymerization (TeRP) using one or more organotellurium compound selected from the group represented by Ph(CH 3 )CH-Te-CH 3 , PHCH 2 -TeMe, Ph-CH(CH
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said copolymer comprises an A-B diblock chain structure wherein the A-block is derived from n-hexyl methacrylate and the B-block is derived from a monomer selected from the group represented by N-vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-
  • the copolymer may be based on an A-B-A triblock chain structure wherein the A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-methyl acrylamide and the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate or structural isomers thereof.
  • A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-methyl acrylamide
  • the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate or structural isomers thereof.
  • the copolymer may be based on a B-A-B triblock chain structure wherein the A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acryla ⁇ mide and the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate, or structural isomers thereof.
  • A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acryla ⁇ mide
  • the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate, or structural isomers thereof.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer, having a molecular weight of at least 15 kDa, in the form of a breatheable, adhering film for protecting compromised skin, wherein said film displays higher oxygen permeability and lower water vapor transmission compared with a Nylon 6 film control at 25°C and 37 0 C, respectively.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said film functions as a protective barrier for tissues of the buccal cavity, mandibular tissue, and dental varnish.
  • an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of
  • a key aspect of this invention deals with a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IcDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said composition comprises an antimicrobial agent selected from the group represented by miconazole and ketoconazole for use in treating athletes' foot and nail infection, and/or a biocompatible dye.
  • a specific aspect of this invention pertains to a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein the said composition is used as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation.
  • a disinfectant spray bandage composition comprising an alcoholic solution of at least 5 percent w/v of at least one amphiphilic, essentially water-insoluble, segmented/block copolymer having a molecular weight of at least 15 kDa, wherein the alcoholic solution comprises a copolymer of an N-vinyl lactam and an alkyl methacrylate in 2-propanol, and preferably the N-vinyl lactam is N-vinyl pyrrolidone and the alkyl methacrylate is n-hexyl methacrylate, and more preferably the copolymer is based on at least 10 mole-percent of N-vinyl pyrrolidone-derived repeat units.
  • Such disinfectant spray bandage composition can be a part of a gas pressurized delivery device capable of in situ forming of an adherent film on viable tissue, such as skin, of a vertebrate animal, wherein the film displays at least 100 percent ultimate elongation, 10 percent reversible elongation, 1.0 MPa maximum stress, and Young's Modulus of less than 100 MPa. And the resulting adherent film exhibits the following properties: (1) an oxygen gas permeability of at least 0.5 cc/100 In 2 /24 hours at 25 0 C; and (2) water-vapor transmission of less than 20 g./100 In 2 /24 hours @ 37°C.
  • a specific aspect of this invention deals with a disinfectant spray bandage composition
  • a disinfectant spray bandage composition comprising an alcoholic solution of at least 5 percent w/v of at least one amphiphilic, essentially water-insoluble, segmented/block copolymer of N-vinyl pyrrolidone and n-hexyl methacrylate, having a molecular weight of at least 15 kDa, wherein the alcoholic solution comprises (1) a hemostatic agent; (2) one pain relieving agent, such as benzocain; (3) a bioactive agent selected from the group represented by antimicrobial, antiseptic, anesthetic, analgesic, wound healing, anti-inflammatory, and antiviral agents; and/or (4) a compatible dye, such as D&C Violet No. 2.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said composition is designed as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation, wherein said copolymer is based on at least 10 mole percent of N-vinyl pyrrolidone, acrylamide,
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, whereas said composition is designed as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation, wherein the alcoholic composition contains trichlosan sodium to yield a clear film comprising at least
  • This invention deals in general with amphiphilic, segmented/block copolymeric compositions based on at least one water-soluble monomer (or comonomer) and at least one water-insoluble monomer (comonomer).
  • volatile organic solvent that can be sprayed on compromised or intact tissues to provide a compliant, resilient, stretchable film that is non- water soluble.
  • the spray-on composition and hence, the resulting film may contain active compounds that (1) are capable of reducing pain, as in the case of local anesthetic agents which may include benzocaine (at 0.1 to 5% w/w) and benzethonium chloride (at 0.01 to 0.5% w/w); (2) are antiseptic, such as iodine which may be complexed with the hydrophilic component of the segmented/block copolymer, as is the case with the poly-N-vinyl pyrrolidone segment or block; (3) have bacteriostatic properties, such as trichlosan (or trichlosan sodium); (4) bacteriostatic/ bacteriocidal/antitumor agent, such as dequalinium chloride; (5) have bacteriocidal properties, such as gentamicin; (6) have fungicidal properties, such as miconazole and ketoconazole; (7) are capable of promoting wound healing, such as growth promoters including epidermal growth factor and its peptid
  • Another general aspect of this invention deals with a spray-on composition that results in thin films with modulated oxygen permeability and water-vapor transmission rate. This can be achieved by varying the film thickness and the ratio of the hydrophiphilic to hydrophobic component of the copolymer chain. Accordingly, these films can be used in two considerably different applications, such as a (1) wound dressing as preferred alternatives to commercially available, preformed, adhering barrier films, as for example the Opsite Flexigrid ® described earlier in tine Background of this Invention section; and (2) temporary dressing for split-thickness skin graft donor sites.
  • the amphiphilic film provides a moist healing environment for many types of wounds, including abrasions, blisters, carpet burns, lacerations, poison ivy rash, road rash, and superficial burns.
  • the amphiphilic tissue protecting film can be applied to cuts, burns, blisters, lacerations, or rashes to prevent or minimize scab formation. This will not obstruct the flow of cell migration freely and allow the wound to heal more naturally.
  • a spray-on amphiphilic bandage can provide a highly conformable, thin film cover to compromised skin and presents a preferred alternative to regular bandages that get wet and fall off easily.
  • the spray-on compositions of the present invention can form a clear cover that protects cuts, scrapes, and blisters and helps prevent the formation of calluses.
  • This clear cover is also a compliant and flexible waterproof film that allows the retention of sufficient moisture at the application site and inward diffusion of oxygen, which in turn permit the tissue, as in skin, to breathe and prevent contamination with dirt and germs.
  • the spray-on film for skin application is tougher and more flexible than a regular bandage. It can be applied to large areas, like legs and arms, or hard-to-reach areas. Additionally, the barrier film dressing is permeable to both water vapor and oxygen, but is impermeable to micro- organisms.
  • the film subject of this invention may be used in the treatment of scalds, first-or second-degree burns, donor sites, post-operative wounds, minor injuries (including abrasions and lacerations), and for the prevention and treatment of superficial pressure areas.
  • the barrier film dressing may be used also as a temporary dressing for split-thickaess, skin graft donor sites.
  • a strongly bacteriocidal and fungicidal agent such as tetramethylthiuram disulfide
  • a strongly bacteriocidal and fungicidal agent such as tetramethylthiuram disulfide
  • the spray-on formulation is considered as a disinfectant one, without adding any antimicrobial agent.
  • the medicated and unmedicated spray-on film may be used as an incise drape.
  • a medicated or unmedicated spray-on film can be used as a (1) hemostatic film in periodontal surgery; (2) protective barrier during periodontal surgical procedures; and (3) protective sealant of dentine, which may also serve as a depot for the controlled delivery of bioactive agents.
  • a specific aspect of this invention deals with a spray-on composition to yield a conformable, solid, adherent coating (without need to add an adhesive) on biological sites which are (1) of irregular or have acute geometries; (2) difficult to reach; and (3) difficult-to- adhere to tissues, such as wet mucous membranes.
  • This invention deals generally with a tissue protecting, spray-on film composition comprising an amphiphilic film-forming, segmented/block copolymer derived form at least one water-soluble monomer and at least another water-insoluble monomer wherein said respective film can be formed from a water soluble organic solvent such as 2-propanol, acetone, and ethyl acetate.
  • the film can contain a bioactive agent including those to have antimicrobial, anesthetic, anti-inflammatory, and wound-healing activities.
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydro>xyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein (1) the said solvent may contain water at more than 0.1 percent of its volume; (2) the segmented/block copolymer may be derived from n-hexyl methacrylate and N-viny
  • An alternative method for preparing the segmented/block copolymer subject of this invention comprises solution or bulk polymerization through controlled/living radical polymerization (CLRP) using NiBr 2 (PPh 3 ) 2 as a catalyst and ethyl 2-bromobutyrate as an initiator.
  • CLRP controlled/living radical polymerization
  • NiBr 2 (PPh 3 ) 2 as a catalyst
  • ethyl 2-bromobutyrate ethyl 2-bromobutyrate
  • a specific aspect of this invention deals with a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer, having a molecular weight of at least 15 kDa, derived from n-hexyl metriacrylate and one or more monomer selected from the group represented by N-vinyl pyrrolidone and 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acrylamide.
  • a general aspect of this invention addresses a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IdDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxy ethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein the said copolymer is made following a tellurium mediated living radical polymerization (TeRP) using one or more organotellurium compound selected from the group represented by Ph(CH 3 )CH-Te-CHj , PHCH 2 -TeMe, Ph-CH(CH 3
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said copolymer comprises an A-B diblock chain structure wherein the A-block is derived from n-hexyl methacrylate and the B-block is derived from a monomer selected from the group represented by N-vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-
  • the copolymer may be based on an A-B-A triblock chain structure wherein the A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-methyl acrylamide and the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate or structural isomers thereof.
  • A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxyl ethyl methacrylate, acrylamide, and N-methyl acrylamide
  • the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate or structural isomers thereof.
  • the copolymer may be based on a B-A-B triblock chain structure wherein the A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acrylamide and the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate, or structural isomers thereof.
  • A-block is derived from a monomer selected from the group represented by N- vinyl pyrrolidone, 2-hydroxy ethyl methacrylate, acrylamide, and N-methyl acrylamide
  • the B-block is derived from one or more alkyl methacrylate monomer selected from the group represented by n-hexyl and n-butyl methacrylate, or structural isomers thereof.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer, having a molecular weight of at least 15 kDa in the form of a breatheable, adhering film for protecting compromised skin, wherein said film displays higher oxygen permeabi lity and lower water vapor transmission compared with a Nylon 6 film control at 25°C and 37°C, respectively.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IcDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said film functions as a protective barrier for tissues of the buccal cavity, mandibular tissue, and dental varnish.
  • an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IcDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said composition comprises a UVB light-absorbing sunscreen compound for use as a protective film on skin.
  • an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl
  • a key aspect of this invention deals with a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IcDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said composition comprises an antimicrobial agent selected from the group represented by miconazole and ketoconazole for use in treating athletes' foot and nail infection, and/or a biocompatible dye.
  • a specific aspect of this invention pertains to a tissue protecting spray-on film composition
  • a tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 IcDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein the said composition is used as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation.
  • a disinfectant spray bandage composition comprising an alcoholic solution of at least 5 percent w/v of at least one amphiphilic, essentially water-insoluble segmented/block copolymer having a molecular weight of at least 15 IcDa, wherein the alcoholic solution comprises a copolymer of an N-vinyl lactam and an alkyl methacrylate in 2-propanol, and preferably the N-vinyl lactam is N-vinyl pyrrolidone and the alkyl methacrylate is n-hexyl methacrylate, and more preferably the copolymer is based on at least 10 mole-percent of N-vinyl pyrrolidone-derived repeat units.
  • Such disinfectant spray bandage composition can be a part of a gas pressurized delivery device capable of in situ forming of an adherent film on viable tissue, such as skin of a vertebrate animal, wherein the film displays at least 100 percent ultimate elongation, 10 percent reversible elongation, 1.0 MPa maximum stress, and Young's Modulus of less than 100 MPa. And the resulting adherent film exhibits the following properties: (1) an oxygen gas permeability of at least 0.5 cc/100 In 2 /24 hours at 25°C; and (2) water-vapor transmission of less than 20 g./100 In 2 /24 hours @ 37°C.
  • a specific aspect of this invention deals with a disinfectant spray bandage composition
  • a disinfectant spray bandage composition comprising an alcoholic solution of at least 5 percent w/v of at least one amphiphilic, essentially water-insoluble, segmented/block copolymer of N-vinyl pyrrolidone and n-hexyl methacrylate, having a molecular weight of at least 15 kDa, wherein the alcoholic solution comprises (1) a hemostatic agent; (2) one pain relieving agent, such as benzocain; (3) a bioactive agent selected from the group represented by antimicrobial, antiseptic, anesthetic, analgesic, wound healing, anti-inflammatory, and antiviral agents; and/or (4) a compatible dye, such as D&C Violet No. 2.
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, wherein said composition is designed as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation, wherein said copolymer is based on at least 10 mole percent of N-vinyl pyrrolidone, acrylamide,
  • tissue protecting spray-on film composition comprising an amphiphilic, film-forming, segmented/block copolymer having a molecular weight of at least 15 kDa derived from at least one water-insoluble alkyl methacrylate and at least one water-soluble monomer selected from the group consisting of N-vinyl pyrrolidone, acrylamide, N-methyl acrylamide, 2-hydroxyethyl methacrylate wherein said copolymer is soluble in one or more water soluble solvent selected from the group represented by ethyl acetate, ethanol, 2-propanol, and acetone, whereas said composition is designed as a disinfectant spray bandage for depositing a flexible-barrier, solid microfilm onto living tissue as in intact or compromised skin, ulcers, or burns, through the combined processes of gas-propelled spray atomization and solvent evaporation, wherein the alcoholic composition contains trichlosan sodium to yield a clear film comprising at least
  • Example 1 General Method of Preparation and Characterization of Segmented/Block Copolymers of Alkyl Methacrylate/N-Vinyl Pyrrolidone Copolymer Using Classical Free-radical Conditions
  • the copolymerization was carried out in two steps.
  • N-vinyl pyrrolidone, a small amount of an alkyl methacrylate, and a catalytic amount of a free- radical initiator were mixed under an oxygen-free environment in a mechanically stirred reaction flask.
  • the mixture was heated for about 30 minutes at 65°C-85°C to allow partial polymerization of the comonomers.
  • the second step commenced by adding a solution of alkyl methacrylate and an additional amount of the free-radical initiator over a long period of time. After completing the addition of the second charge, the reaction was continued for an additional 30 minutes.
  • the purified copolymer was characterized for molecular weight (GPC), identify (IR), and composition (NMR and elemental nitrogen analysis).
  • the polymer was precipitated in ice water in a blender, filtered using a filter fmnnel, blended in -6O 0 C methanol, filtered and dried under reduced pressure at room temperature. It was dissolved as a 20-weight-percent solution in chloroform, precipitated in -60 0 C methanol, filtered, dissolved in chloroform, poured onto a Teflon tray and dried to constant weight under reduced pressure at 45°C.
  • the infrared (IR) and NMR data were consistent with the elemental analysis data.
  • the polymer was precipitated in ice water in a blender, filtered using a filter funnel, blended in -60 0 C methanol, filtered and dried under reduced pressure at room temperature. It was dissolved as a 20-weight-percent solution in chloroform, precipitated in -60 0 C methanol, poured onto a Teflon tray, and dried to constant weight.
  • the IR and NMR data were consistent with the elemental analysis data.
  • Example 4 Copolymerization of 35/65 N-vinyl Pyrrolidone (NVPVn-Hexyl Methacrylate (HMA) to Produce Segmented/Block Copolymer SC-III
  • NDPVn-Hexyl Methacrylate (HMA) 35/65 N-vinyl Pyrrolidone
  • HMA N-vinyl Methacrylate
  • the first charge was based on an N-vinyl-2-pyrrolidone (NVP)-rich comonomer mixture.
  • NVP N-vinyl-2-pyrrolidone
  • HMA n-hexyl methacrylate
  • 1,4-dioxane 47 mL
  • 2-2' Azo-bis-isobutyronitrile 2.20 mmole
  • the polymer was precipitated in ice water in a blender, filtered using a filter funnel, blended in -60 0 C methanol, filtered and dried under reduced pressure at room temperature. It was dissolved as a 20-weight-percent solution in chloroform, precipitated in -6O 0 C methanol, poured onto a Teflon tray, and dried to constant weight. This precipitation was repeated once more to give an "extra pure" polymer.
  • the IR and NMR data were consistent with the elemental analysis data.
  • the desired amount of SC-I, SC-II, or SC-III, from Examples 2, 3 or 4 was dissolved in 2-propanol to yield a solution having a solid content between 10 and 25 percent (w/v), depending on the desired film thickness.
  • the polymer solution was cast on a flat Teflon sheet and thickness was then adjusted with a horizontally rolling draw rod.
  • the film was allowed to dry in a laminar flow hood.
  • the drying time was predetermined in a pilot experiment to insure that the drying process resulted in a constant film weight.

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Abstract

Cette invention concerne une composition formant un film par atomisation visant à protéger les tissus et comprenant un copolymère segmenté/bloc filmogène, amphiphile, dérivé d'au moins un monomère soluble dans l'eau et d'au moins un autre monomère insoluble dans l'eau. Le film peut être formé à partir d'un solvant organique soluble dans l'eau tel que 2-propanol, l'acétone et l'acétate d'éthyle. Le film peut contenir un agent bioactif comprenant ces solvants de façon à avoir des activités antimicrobiennes, anesthésiques, anti-inflammatoires et cicatrisantes.
EP05770860A 2005-07-05 2005-07-08 Compositions formant un film copolymere applique par atomisation et visant a proteger les tissus Withdrawn EP1904574A2 (fr)

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US11/175,636 US7842749B2 (en) 2004-08-02 2005-07-05 Tissue protecting spray-on copolymeric film composition
PCT/US2005/024120 WO2007005029A2 (fr) 2005-07-05 2005-07-08 Compositions formant un film copolymere applique par atomisation et visant a proteger les tissus

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US3577516A (en) * 1969-12-02 1971-05-04 Nat Patent Dev Corp Preparation of spray on bandage
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