US20050215727A1 - Water-absorbent adhesive compositions and associated methods of manufacture and use - Google Patents

Water-absorbent adhesive compositions and associated methods of manufacture and use Download PDF

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US20050215727A1
US20050215727A1 US11/028,702 US2870205A US2005215727A1 US 20050215727 A1 US20050215727 A1 US 20050215727A1 US 2870205 A US2870205 A US 2870205A US 2005215727 A1 US2005215727 A1 US 2005215727A1
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Prior art keywords
poly
composition
polymer
eudragit
film
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US11/028,702
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Inventor
Mikhail Feldstein
Danir Bairamov
Mikhail Novikov
Valery Kulichikhin
Nicolai Plate
Gary Cleary
Parminder Singh
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AV Topchiev Institute of Petrochemical Synthesis
Corium LLC
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AV Topchiev Institute of Petrochemical Synthesis
Corium International Inc
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Priority claimed from US10/137,664 external-priority patent/US8728445B2/en
Priority claimed from US10/359,548 external-priority patent/US8840918B2/en
Priority claimed from US10/936,887 external-priority patent/US20050113510A1/en
Priority to US11/028,702 priority Critical patent/US20050215727A1/en
Application filed by AV Topchiev Institute of Petrochemical Synthesis, Corium International Inc filed Critical AV Topchiev Institute of Petrochemical Synthesis
Assigned to CORIUM INTERNATIONAL reassignment CORIUM INTERNATIONAL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CLEARY, GARY W., SINGH, PARMINDER
Assigned to A.V. TOPCHIEV INSTITUTE OF PETROCHEMICAL SYNTHESIS, RUSSIAN ACADEMY OF SCIENCES reassignment A.V. TOPCHIEV INSTITUTE OF PETROCHEMICAL SYNTHESIS, RUSSIAN ACADEMY OF SCIENCES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PLATE, NICOLAI A., BAIRAMOV, DANIR R., KULICHIKHIN, VALERY G., NOVIKOV, MIKHAIL BORISOVICH, FELDSTEIN, MIKHAIL M.
Publication of US20050215727A1 publication Critical patent/US20050215727A1/en
Priority to ES06717322.9T priority patent/ES2607785T3/es
Priority to PCT/US2006/000098 priority patent/WO2006074173A2/fr
Priority to RU2007129752A priority patent/RU2416433C2/ru
Priority to CA 2594183 priority patent/CA2594183C/fr
Priority to EP06717322.9A priority patent/EP1838358B1/fr
Priority to AU2006204127A priority patent/AU2006204127B2/en
Assigned to SILICON VALLEY BANK reassignment SILICON VALLEY BANK SECURITY AGREEMENT Assignors: CORIUM INTERNATIONAL, INC.
Priority to US12/834,645 priority patent/US20100278757A1/en
Priority to US13/269,465 priority patent/US8273405B2/en
Assigned to OXFORD FINANCE LLC, AS COLLATERAL AGENT reassignment OXFORD FINANCE LLC, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: CORIUM INTERNATIONAL, INC.
Priority to US13/594,746 priority patent/US8617647B2/en
Assigned to CORIUM INTERNATIONAL, INC. reassignment CORIUM INTERNATIONAL, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: OXFORD FINANCE LLC
Priority to US14/139,530 priority patent/US9127140B2/en
Assigned to CORIUM INTERNATIONAL, INC. reassignment CORIUM INTERNATIONAL, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SILICON VALLEY BANK
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—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
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • A61L15/585—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties
    • A61K2800/262—Transparent; Translucent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • This invention relates generally to adhesive compositions, and more particularly relates to water-absorbent adhesive compositions composed of polymer blends.
  • the invention additionally relates to methods for formulating such compositions, including methods for selecting components for inclusion in the compositions, to methods for using the compositions, and to products manufactured with the compositions.
  • the invention finds utility in any context requiring an adhesive composition that adheres to a moist surface and neither dissolves nor loses tack upon absorption of water.
  • Hydrophilic adhesives particularly hydrophilic pressure-sensitive adhesives (“PSAs”)
  • PSAs hydrophilic pressure-sensitive adhesives
  • a general distinctive feature of hydrophilic PSAs is that they typically adhere to wet substrates, while conventional hydrophobic (rubber-based) PSAs typically lose their adhesive properties when moistened.
  • the skin contact adhesive layer of a transdermal drug delivery system should provide for immediate adhesion following application of the patch to the skin and continued adhesion during an extended drug delivery period.
  • delivery systems for application to wet surfaces e.g., the buccal mucosa or the teeth, do not need to adhere to dry surfaces but should become tacky when applied to a hydrated or moistened surface.
  • adhesive compositions used in wound dressings must become substantially nontacky following absorption of wound exudates to avoid tissue damage upon removal.
  • the method is based on new insights into the molecular mechanisms underlying adhesive properties. See, for example, Feldstein et al. (1999) Polym. Mater. Sci. Eng., 81:465-466; Feldstein et al., General approach to the molecular design of hydrophilic pressure - sensitive adhesives , Proceed. 25 th Annual Meeting Adhesion Soc. and 2 nd World Congress on Adhesion and Relative Phenomena, February 2002, Orlando, Fla., vol. 1 (Oral Presentations), p. 292-294; and Chalykh et al. (2002) J. Adhesion 78(8):667-694.
  • pressure-sensitive adhesion results from the coupling of two apparently incompatible types of molecular structures, and there is a fine balance between strong cohesive interaction energy and enhanced “free volume.”
  • the molecular structures of the components dictate the cohesion energy and free volume, and thereby define the adhesive properties of the composition as a whole.
  • strong cohesive interaction energy is a result of hydrophobic attraction between alkyl groups in side chains
  • large free volume results from either electrostatic repulsion of negatively charged carboxyl groups or a significant number of isoalkyl radicals in the side chains.
  • synthetic rubbers large free volume is obtained by adding high volume, low density tackifying resins.
  • hydrophilic adhesives when a high molecular weight polyvinyl lactam, e.g., poly(N-vinyl-2-pyrrolidone) (“PVP”) or polyvinyl caprolactone (“PVCap”), is blended with a polyethylene glycol (“PEG”) oligomer, as described in U.S. Pat. No. 6,576,712, high cohesive strength results from the hydrogen bonding interaction between the oxo ( ⁇ O) moieties of the pyrrolidone or caprolactone ring and the terminal hydroxyl groups of the PEG oligomer, while enhanced free volume is results from the spacing between polymer chains provided by the PEG bridges and the flexibility of the PEG oligomers.
  • PVP poly(N-vinyl-2-pyrrolidone)
  • PVCap polyvinyl caprolactone
  • the balance between cohesive energy and free volume is in large part responsible for the adhesive properties of polymer materials.
  • the ratio between cohesion energy and free volume dictates the glass transition temperature, T g , and elastic modulus, E, of a polymeric material. That is, a composition with higher cohesion energy and lower free volume will have both a higher T g and a higher E.
  • the adhesive compositions described in U.S. Pat. No. 6,576,712 exhibit relatively low adhesion toward dry surfaces. Adhesion increases, however, when the surface of a substrate is moistened or the adhesive composition absorbs water.
  • the maximum adhesion of the PVP-PEG blends described in the '712 patent is observed when the adhesive contains 5-10 wt. % of absorbed water (i.e., when water represents about 5 wt. % to about 10 wt. % of the moistened adhesive composition). This is usually the case when the adhesive is exposed to an atmosphere having 50% relative humidity (rh). When in direct contact with water, the adhesive dissolves. Therefore, the compositions are not optimal in applications wherein an adhesive composition is likely to undergo a significant degree of hydration during use, absorbing on the order of 15 wt. % water or more.
  • the invention is addressed to the aforementioned need in the art, and provides a water-insoluble adhesive composition that adheres well to moist surfaces even after absorbing a significant amount (e.g., greater than 15 wt. %) water.
  • the invention also provides a method for preparing such a water-soluble adhesive composition.
  • a method for preparing a water-insoluble, water-absorbent adhesive composition comprises combining, under conditions effective to form a substantially homogeneous admixture:
  • the recurring functional groups and the recurring polar groups are ionogenic, and an ionizing agent is incorporated into the admixture so as to ionize up to approximate 30% of the ionogenic groups.
  • a water-insoluble, water-absorbent adhesive composition which comprises a blend of:
  • FIG. 1 is a schematic representation of a “ladder-like” interpolymer complex formed by noncovalent association of PVP and a complementary multifunctional polymer containing a plurality of recurring proton-donating functional groups along the polymer backbone, wherein the noncovalent association involves hydrogen bonding between the proton-donating functional groups and the oxo moieties within the pyrrolidone rings.
  • a “carcass-like” complex (described infra and illustrated in FIG. 2 ) leads to enhanced cohesive strength and free volume
  • the formation of a ladder-like complex as illustrated in this figure is accompanied by a decrease in solubility, an increase in cohesive strength, and a decrease in free volume. For this reason, a polymer blend composed of a ladder-like interpolymer complex provides no adhesion.
  • FIG. 2 is a schematic representation of a “carcass-like” complex formed by noncovalent association of PVP and oligomeric PEG, wherein the bifunctional oligomer provides a bridge between two polymer chains and the noncovalent association involves hydrogen bonding between terminal proton-donating moieties on the PEG and the oxo moieties within the pyrrolidone rings.
  • the complex combines high cohesive toughness (as a result of the hydrogen bonding) with a large free volume (resulting from the length and flexibility of the PEG chains).
  • FIG. 3 schematically illustrates an interpolymer complex combining carcass-like and ladder-like types of crosslinking.
  • FFP represents a film-forming polymer
  • CCL represents a carcass-like crosslinker
  • LLC represents a ladder-like crosslinker.
  • FIG. 4 schematically illustrates the structure of an interpolymer complex composed of a film-forming polymer (FFP) and ladder-like crosslinker (LLC).
  • the complex is mixed with a plasticizer (P) and filled with a tackifier (T).
  • FIG. 6 shows the impact of plasticizer (TEC) concentration on probe tack stress-strain curves of the blends of Eudragit E-100 film forming copolymer and Eudragit L-100-55 ladder-like crosslinker (10:1).
  • TEC concentrations are indicated in the Figure.
  • FIG. 7 exhibits the effect of ladder-like electrostatic crosslinking of film-forming polybase (Eudragit E-100) by polyacid (Eudragit L-100-55) on probe tack stress-strain curves.
  • FIG. 8 compares the effects of plasticizer (TEC) and tackifier (glycerol ester of tall oil rosin) on probe tack stress-strain curves of amphiphilic adhesives based on the ladder-like electrostatic complex of Eudragit E-100 and Eudragit L-100-55 copolymers (10:1).
  • TEC plasticizer
  • tackifier glycol ester of tall oil rosin
  • FIG. 9 shows the impact of tackifier content on the work of adhesive debonding for the blends of Eudragit E-100 with 25 wt. % of ATBC.
  • FIG. 10 compares the effects of two tackifiers—Sylvagum RE 85K rosin and PIB (Oppanol B-15) on probe tack of Eudragit E-100—Eudragit L-100-55 blends (10:1), plasticized with 25 wt. % of TEC.
  • FIG. 11 demonstrates the effect of adipic acid on adhesive properties of Eudragit E-100/L100-55 blends with 25% of TEC at different E100/L100-55ratios
  • FIG. 12 represents the curve of potentiometric titration of 1% aqueous solution of Eudragit E-100 polybase with 0.2 N HCl.
  • the ionization degree, f is plotted along a top axis.
  • FIG. 13 represents the curve of potentiometric titration of 1% aqueous solution of Eudragit L-100-55 polyacid with 0.1 N NaOH.
  • the ionization degree, f is plotted along a top axis.
  • FIG. 14 demonstrates the effect of partial ionization of film-forming polymer (Eudragit E-100) by HCl solution on the tack of amphiphilic adhesive containing 35 wt. % of plasticizer TEC.
  • FIG. 15 compares the effects of partial ionization of film-forming polymer (by HCl) and ladder-like crosslinker (by NaOH) on the probe tack stress-strain curves for amphiphilic Eudragit E-100—Eudragit L-100-55 adhesive containing 25 wt. % of plasticizer TEC.
  • FIG. 16 represents probe tack stress-strain curves for the Eudragit E-100—Eudragit L-100-55 complex containing 35 wt. % of plasticizer TEC under 10% ionization of film-forming polymer and ladder-like crosslinker and for the complex formed between partly ionized polymer components at 10% degree of ionization.
  • FIG. 17 represents the effect of partial ionization of carboxyl groups in the ladder-like crosslinker on the stress-strain curves of the PVP-PEG-Eudragit L-100-55 adhesive hydrogel containing 12 wt. % of sorbed water. The degrees of ionization (%) are shown in the Figure.
  • FIG. 18 compares the adhesive properties of interpolymer complexes of Eudragit E-100 film-forming polymer with the ladder-like crosslinkers of different hydrophilicity: Eudragit L-100-55 (Example 9) and Gantrez S-97.
  • the content of plasticizer TEC in blends is 25 wt. %.
  • FIG. 19 demonstrates the effect of ladder-like crosslinker (Eudragit L-100-55 or Gantrez S-97) on water absorbing capacity, expressed in terms of Swell Ratio, for Eudragit E-100 blends, plasticized with 25% of TEC.
  • ladder-like crosslinker Eudragit L-100-55 or Gantrez S-97
  • FIG. 20 exhibits the impact of the nature of plasticizers (TEC, ATEC, TBC and ATBC) on probe tack properties of Eudragit E-100—Eudragit L-100-55 complexes. Concentration of the plasticizers is 45 wt %.
  • FIG. 21 illustrates the influence of the nature of plasticizer in Eudragit E-100—Eudragit L-100-55 complex on Swell Ratio of relevant blends.
  • FIG. 22 shows the effect of mixing the Eudragit E-100—Eudragit L-100-55 complexes with PVP and with PVP-PEG blend (2:1) on water absorbing capacity expressed in terms of Swell Ratio.
  • FIG. 23 demonstrates the influence of hydrophilization of Eudragit E-100—Eudragit L-100-55 plasticized complex on the work of adhesive debonding (probe tack).
  • FIG. 24 demonstrates peel force traces towards dry and wet human skin for Gelva acrylic PSA, water soluble adhesive based on carcass-like PVP-PEG complex outlined by U.S. Pat. No. 6,576,712, hydrophilic PVP-PEG-Eudragit L-100-55 adhesive and amphiphilic adhesive based on the ladder-like Eudragit E-100—Eudragit L-100-55 complex (Example 1).
  • FIG. 25 represents probe tack stress-strain curves for water soluble PVP-PEG (36%) adhesive outlined by U.S. Pat. No. 6,576,712, amphiphilic adhesives described in Example 9 (35% TEC) and in Example 10 (7% of tackifier, 30% TEC), hydrophilic PVP-PEG-Eudragit L-100-55 adhesive at 17% of absorbed water in comparison with two grades of conventional PSAs: SIS-based DURO-TAK®, 34-4230 and acrylic PSA manufactured by 3M.
  • FIG. 26 represents the kinetics of in vitro release of silver sulfate from three adhesive hydrogel compositions used in wound dressings.
  • FIG. 27 demonstrates in vitro release kinetics of silver phosphate from the matrix of wound dressing based on the ladder-like interpolymer complex Eudragit E-100—Eudragit L-100-55, plasticized with 25 wt. % of TEC.
  • a hydrophilic polymer includes not only a single hydrophilic polymer but also two or more hydrophilic polymers that may or may not be combined in a single composition
  • a plasticizer includes a single plasticizer as well as two or more plasticizers that may or may not be combined in a single composition, and the like.
  • a “hydrophobic” polymer absorbs only up to 1 wt. % water at 100% rh, while “hydrophilic” polymers absorb at least 1 wt. % water at 100% rh.
  • a “water-swellable” polymer is one that is capable of absorbing water in an amount that is at least 50% of its own weight. That is, a water-swellable polymer weighing x grams can absorb at least 0.5 ⁇ grams of water, to provide a hydrated polymer weighing at least 1.5 ⁇ grams and having a polymer to water (weight) ratio of at most 3:1.
  • crosslinked refers to a polymer composition containing intramolecular and/or intermolecular noncovalent bonds.
  • Noncovalent bonding includes hydrogen bonding, electrostatic bonding, and ionic bonding.
  • polymer as used herein includes both linear and branched polymers, and homopolymers as well as copolymers, the latter including all types of copolymer structures (e.g., block copolymers, alternating copolymers, random copolymers, etc.) as well as “higher order” copolymers (e.g., terpolymers).
  • oligomers are polymers having a molecular weight below about 1000 Da, preferably below about 800 Da.
  • water-insoluble is used to refer to a polymer, compound or composition whose aqueous solubility measured at 20° C. is less than 5 wt %, preferably less than 3 wt %, and more preferably less than 1 wt %.
  • insoluble is used to refer to a polymer, compound or composition whose solubility in water, polar organic solvents, and possibly nonpolar organic solvents, measured at 20° C., is less than 5 wt %, preferably less than 3 wt %, and more preferably less than 1 wt %.
  • hydrogel is used in the conventional sense to refer to water-swellable polymeric matrices that can absorb a substantial amount of water to form elastic gels, where the “matrices” are three-dimensional networks of macromolecules held together by covalent or non-covalent crosslinks. Upon placement in an aqueous environment, dry hydrogels swell to the extent allowed by the degree of cross-linking.
  • hydrogel composition refers to a composition that either contains a hydrogel or is entirely composed of a hydrogel.
  • hydrogel compositions encompass not only hydrogels per se but also compositions that comprise a hydrogel and one or more non-hydrogel components or compositions, e.g., hydrocolloids, which contain a hydrophilic component (which may contain or be a hydrogel) distributed in a hydrophobic phase.
  • tack and “tacky” are qualitative. However, the terms “substantially nontacky,” “slightly tacky,” and “tacky,” as used herein, may be quantified using the values obtained in a PKI tack determination, a TRBT tack determination, or a PSA tack determination/Polyken Probe (Solutia, Inc.).
  • substantially nontacky is used to refer to a composition having a tack value less than about 25 g-cm/sec
  • lightly tacky refers to a composition having a tack value in the range of about 25 g-cm/sec to about 100 g-cm/sec
  • tacky refers to a composition having a tack value of at least 100 g-cm/sec.
  • plasticizer is used in the conventional sense of the term to refer to a relatively low molecular weight compound that is miscible with a polymer or polymer blend and decreases the glass transition temperature and elastic modulus thereof.
  • water-insoluble, water-swellable hydrophilic adhesive polymers that are capable to form homogeneous films either upon casting a solution to backing layer followed by drying, or under external pressure or by means of extrusion.
  • the film-forming capability requires that the blend has to be free of covalent crosslinks.
  • Blending the polymers provides a convenient way to obtain composite materials with specifically tailored properties, since the properties of the blend are typically intermediate between those of the unblended components when the components are immiscible or partly miscible.
  • water-insoluble materials are usually mixed with water-soluble materials. When this is done, however, a phase separation can often occur that does not favor adhesion.
  • the insolubility of blend components may hamper the procedure of blend preparation, which often involves the dissolution of all the components in a common solvent, followed by casting the solution and drying.
  • Preparation of polymer composite materials whose properties are new and untypical of parent components requires a high skill of a material designer. This challenge may be resolved if the blend components are capable of a strong favorable interaction to each other. More often, such interaction is hydrogen, electrostatic or ionic bonding. In this instance mixing of two or more soluble polymers can give their ladder-like complex schematically shown in FIG. 1 that is swellable, but insoluble or partly soluble.
  • this invention is directed to a method of obtaining water-insoluble, film-forming compositions by blending soluble polymers, more specifically by blending hydrophilic polymers with complementary macromolecules that are capable of hydrogen bonding, electrostatic or ionic bonding.
  • the adhesive compositions of the invention contain at least film-forming hydrophilic polymer having at least one linear segment with a plurality of recurring polar groups thereon, at least one complementary multifunctional polymer that serves as a “ladder-like” noncovalent crosslinker of the film-forming polymer, and at least one plasticizer compatible with (i.e., miscible with) or at least partially compatible with both the film-forming polymer and the complementary multifunctional polymer.
  • the film-forming polymer is present in a higher concentration than the complementary multifunctional polymer, and it is this higher concentration that determines the film-forming characteristics.
  • polyacids such as acrylate polymers bearing carboxylproton-donating functional groups or polyols bearing hydroxylproton-donating functional groups and proton-accepting polymers such as poly(N-vinyl lactams) or polyamines are suited for use as both the film-forming polymer or as the complementary multifunctional polymer.
  • the acrylate polymer serves as the film-forming polymer and the poly(N-vinyl lactam) or polyamine or another proton-accepting polymer serves as the complementary multifunctional polymer, or ladder-like crosslinker.
  • the poly(N-vinyl lactam) or polyamine serves as the film-forming polymer and the acrylate polymer serves as the ladder-like crosslinker.
  • Maintaining a specified pH value in the blend or in an admixture used to provide the blend provides an additional factor controlling the performance of the blend when one or more ionogenic polymers are present.
  • Ionized groups are capable of ionic, but not electrostatic or hydrogen bonding. Fully or partly ionized polymers are always soluble in water, whereas non-ionized polymers as a rule are insoluble or poorly soluble in water. Consequently, the degree of ionization affects appreciably the solubility and swelling of interpolymer complexes involving ionogenic polymers.
  • the adhesive properties of composite materials can be controlled. Indeed, adhesion is a result of specific balance between cohesive interaction energy and free volume.
  • the adhesion profile of the water-insoluble, film-forming compositions of the invention can be tailored based on materials, the ratio of components in the composition, the degree of ionization and the quantity of water in the blend.
  • the ladder-like crosslinker, its ratio to the amount of film-forming polymer, concentration of a plasticizer and ionization degree are selected so as to provide the desired adhesion profile with respect to hydration.
  • the compositions that are relatively slightly crosslinked through comparatively loose hydrogen bonds and demonstrating a large free volume provide initial tack in dry state.
  • Flexible polymers provide higher cohesion than polymers with rigid chains.
  • PVP poly(vinyl pyrrolidone)
  • the ladder-like crosslinker is a rigid-chain cellulose ester bearing OH groups
  • the composition is generally tacky prior to contact with water (e.g., with a moist surface) but gradually loses tack as the composition absorbs moisture.
  • the ladder-like crosslinker is an acrylate polymer or copolymer with carboxyl groups
  • a composition is provided that is generally substantially nontacky prior to contact with water, but that becomes tacky upon contact with a moist surface.
  • the film-forming hydrophilic polymer and the complementary multifunctional polymer are generally selected from the same classes of polymers and copolymers, but have complementary groups along the backbone that interact to form noncovalent bonds (e.g., hydrogen bonds, electrostatic bonds, or ionic bonds), thereby forming a ladder-like complex that is insoluble in aqueous liquids, polar organic solvents, and many nonpolar organic solvents as well.
  • the polymer that serves as the “film-forming” polymer represents a greater weight fraction in the mixtures and compositions of the invention that does the complementary multifunctional polymer.
  • the film-forming hydrophilic polymer represents approximately 20 wt. % to approximately 95 wt.
  • the film-forming polymer will also have a higher molecular weight than the complementary multifunctional polymer.
  • the molecular weight of the film-forming polymer will usually be in the range of about 20,000 to 3,000,000, preferably in the range of about 100,000 to 2,000,000, and most preferably in the range of about 100,000 to 1,500,000.
  • the recurring polar groups on the film-forming polymer and the recurring functional groups on the complementary multifunctional polymer may comprise backbone heteroatoms, e.g., an oxygen atom in an ether (—O—) or ester (—(CO)—O—) linkage, a nitrogen atom in an amine (—NH—), imine (—N ⁇ ), or amide (—NH(CO)—) linkage, a sulfur atom in a thioether (—S—) linkage, and the like.
  • the recurring polar groups and the recurring functional groups may also comprise pendant groups, for instance:
  • Preferred pendant groups are those present on polymers that are readily synthesized or commercially available, typically including hydroxy, C 1 -C 8 alkoxy, carboxyl, carboxylato, sulfo, sulfonato, amino, di(C 1 -C 8 alkyl)-substituted amino, quaternary ammonium, piperidinyl, pyrrolidinyl, pyrrolidinyl, and phosphono groups.
  • the film-forming polymer have an excess of polar groups relative to the corresponding functional groups on the complementary multifunctional polymer, such that, providing that the polar groups and functional groups are ionogenic, the ladder-like complex can readily ionized in the presence of an ionizing agent, e.g., an acid or base.
  • an ionizing agent e.g., an acid or base.
  • zero to about 30% of the ionogenic groups present on the film-forming polymer are ionized, preferably about 5% to 10%.
  • the degree of ionization may be controlled by addition of a suitable ionizing agent, e.g., an acid or base.
  • Suitable polymers include, but are not limited, to the following:
  • Copolymers of any of the above may also be used herein, as will be appreciated by those of ordinary skill in the art.
  • Suitable plasticizers and softeners include, by way of illustration and not limitation: alkyl and aryl phosphates such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, and triphenyl phosphate; alkyl citrates and citrate esters such as trimethyl citrate, triethyl citrate and acetyl triethyl citrate, tributyl citrate and acetyl tributyl citrate, acetyl triethyl citrate, and trihexyl citrate; alkyl glycerolates; alkyl glycolates; dialkyl adipates such as dioctyl adipate (DOA; also referred to as bis(2-ethylhexyl)adipate), diethyl adipate, di(2-methylethyl)adipate, and dihexyl adipate; dialkyl phthalates, dicycl
  • a preferred plasticizer for use in conjunction with the present invention is a bifunctional oligomer that is “complementary” to the film-forming polymer as described in U.S. Pat. No. 6,576,712 to Feldstein et al., cited earlier herein.
  • the complementary oligomer is terminated with hydroxyl groups, amino or carboxyl groups.
  • the oligomer typically has a glass transition temperature T g in the range of about ⁇ 100° C. to about ⁇ 30° C. and a melting temperature T m lower than about 20° C.
  • the oligomer may be also amorphous.
  • the difference between the T g value of the film-forming polymer and that of the complementary oligomer is preferably greater than about 50° C., more preferably greater than about 100° C., and most preferably in the range of about 150° C. to about 300° C.
  • the oligomer will have a molecular weight in the range from about 45 to about 800, preferably in the range of about 45 to about 600.
  • suitable oligomers include, but are not limited to, low molecular weight polyalcohols (e.g.
  • glycerol oligoalkylene glycols such as ethylene glycol and propylene glycol, ether alcohols (e.g., glycol ethers), alkane diols from butane diol to octane diol, including carboxyl-terminated and amino-terminated derivatives of polyalkylene glycols.
  • ether alcohols e.g., glycol ethers
  • alkane diols from butane diol to octane diol including carboxyl-terminated and amino-terminated derivatives of polyalkylene glycols.
  • Polyalkylene glycols, optionally carboxyl-terminated, are preferred herein, and polyethylene glycol having a molecular weight in the range of about 300 to 600 is an optimal complementary oligomer.
  • compositions of the invention may also include two or more plasticizers in combination, e.g., triethyl citrate and tributyl citrate, triethyl citrate and polyethylene glycol 400, polyethylene glycol 400 and dioctyl phthalate, etc.
  • An illustrative composition includes poly(N-vinyl-2-pyrrolidone) (“PVP”) as the film-forming polymer and polyethylene glycol (“PEG”) as the carcass-like non-covalent crosslinker.
  • PVP poly(N-vinyl-2-pyrrolidone)
  • PEG polyethylene glycol
  • An illustrative composition includes poly(N-vinyl-2-pyrrolidone) (“PVP”) as the film-forming polymer and polyethylene glycol (“PEG”) as the carcass-like non-covalent crosslinker.
  • PVP-PEG adhesive blend with a ladder-like non-covalent crosslinker that is a moderately hydrophilic or water-insoluble polymer results in the decrease of blend hydrophilicity and dissolution rate.
  • the PVP-PEG blend can be mixed with polymers that bear complementary (with respect to PVP) reactive functional groups in their repeating units.
  • suitable ladder-like non-covalent crosslinkers are long chain polymers such as polyvinyl alcohols, polyacrylic acids, polymethacrylic acids, homo- and co-polymers thereof, as well as sulfonic acid and alginic acid.
  • Another illustrative composition uses a copolymer of methacrylic acid and methyl methacrylate as the ladder-like non-covalent crosslinker with the PVP/PEG noted above. This composition is used to facilitate in understanding the principles of the invention.
  • the PVP-PEG complex combines high cohesive toughness (due to PVP-PEG H-bonding) with a large free volume (resulting from considerable length and flexibility of PEG chains).
  • this type of complex structure is defined as a “carcass-like” structure (see FIG. 1 ).
  • the carcass-like structure of the complex results from the location of reactive functional groups at both ends of PEG short chains.
  • the ladder-like non-covalent crosslinker contains reactive functional groups in repeating units of the backbone, the resulting complex has so-called “ladder-like” structure (see FIG. 2 ).
  • the ladder-like type of interpolymeric complex was first described by Kabanov et al.
  • the PVP-PEG blend mixed with a long chain polymer giving the ladder-like complex with PVP provides no or negligible initial tack.
  • the glass transition temperature of the blend shifts toward lower values, which are typical features of pressure-sensitive adhesives, and adhesion arises.
  • the ladder-like crosslinker is preferably a poly(dialkyl aminoalkyl acrylate), poly(dialkyl aminoalkyl methacrylate), polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, poly(hydroxyalkyl acrylate), or poly(hydroxyalkyl methacrylate) such as poly(hydroxyethyl methacrylate).
  • the film-forming polymer is a poly(dialkyl aminoalkyl acrylate), poly(dialkyl aminoalkyl methacrylate), polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl alcohol, polyvinyl phenol, or poly(hydroxyalkyl acrylate) such as poly(hydroxyethyl methacrylate)
  • the ladder-like crosslinker is preferably a poly(dialkyl aminoalkyl acrylate, poly(dialkyl aminoalkyl methacrylate), poly(N-vinyl lactam) such as poly(N-vinyl pyrrolidone) or poly(N-vinyl caprolactam), as well as a copolymer of poly(N-dialkylamino alkyl acrylate) with alkyl acrylate, polyethylene oxide, methacrylate or ethacrylate monomers, or a copolymer of poly(N-dialkylamino alkyl methacrylate) and alkyl acryl
  • a preferred carcass-like crosslinker is an oligomeric alkylene glycol comprising about 1-20 alkylene oxide units in its chain such as polyethylene glycol, carboxyl-terminated oligomeric alkylene glycol such as carboxyl-terminated poly(ethylene glycol), or polyhydric alcohols.
  • PVP-PEG-Eudragit blend was used as a typical example, although the approach is general and can be easily reproduced using other water-soluble, hydrophilic polymers.
  • the adhesive compositions of the invention may also include one or more conventional additive, which may be combined with the polymers and the plasticizer during adhesive formulation or incorporated thereafter.
  • Optional additives include, without limitation, fillers, pH regulating agents, ionizing agents, tackifiers, detackifying agents, electrolytes, antimicrobial agents, antioxidants, preservatives, colorants, flavors, and combinations thereof.
  • the compositions of the invention may also include a pharmacologically active agent or a cosmeceutically active agent.
  • transdermal, transmucosal, and topical delivery systems in which an adhesive composition of the invention serves as a drug reservoir and/or skin contact adhesive layer may be formulated for the delivery of a specific pharmacologically active agent.
  • Cosmeceutical products such as tooth whitening gels and strips may be formulated for the delivery of one or more tooth-whitening agents. Examples of such products are described in pending U.S. patent application Ser. No. 10/936,887 to Feldstein et al. for “Method of Preparing Polymeric Adhesive Compositions Utilizing the Mechanism of Interaction Between The Polymer Components, filed Sep. 8, 2004, and U.S. patent application Ser. No. ______ to Singh et al. for “Sustained Release Tooth Whitening Systems and Formulations,” filed Dec. 21, 2004, the disclosures of which are incorporated by reference herein.
  • Absorbent fillers may be advantageously incorporated to control the degree of hydration when the adhesive is on the skin or other body surface.
  • Such fillers can include microcrystalline cellulose, talc, lactose, kaolin, mannitol, colloidal silica, alumina, zinc oxide, titanium oxide, magnesium silicate, magnesium aluminum silicate, hydrophobic starch, calcium sulfate, calcium stearate, calcium phosphate, calcium phosphate dihydrate, woven and non-woven paper and cotton materials.
  • Other suitable fillers are inert, i.e., substantially non-adsorbent, and include, for example, polyethylenes, polypropylenes, polyurethane polyether amide copolymers, polyesters and polyester copolymers, nylon and rayon.
  • a preferred filler is colloidal silica, e.g., Cab-O-Sil® (Cabot Corporation, Boston Mass.).
  • pH regulators include, but are not limited to, glycerol buffers, citrate buffers, borate buffers, phosphate buffers, and citric acid-phosphate buffers. Buffer systems are useful to ensure, for instance, that the pH of a composition of the invention is compatible with that of an individual's body surface.
  • Ionizing agents are also useful to impart a desired degree of ionization to the interpolymer complex within the adhesive compositions of the invention.
  • Suitable ionizing agents are acids and bases, depending on the group to be ionized.
  • the acids and bases may be inorganic (hydrochloric acid, hydrobromic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, etc.) or organic (acetic acid, maleic acid, triethylamine, ethanolamine, etc.).
  • Tackifiers can also be included to improve the adhesive and tack properties of the compositions of the invention.
  • the mechanism underlying tack improvement results from the large size and hydrophobic character of tackifier molecules.
  • Exemplary tackifying materials include tacky rubbers such as polyisobutylene, polybutadiene, butyl rubber, polystyrene-isoprene copolymers, polystyrene-butadiene copolymers, and neoprene (polychloroprene).
  • suitable tackifiers herein are those that are conventionally used with pressure sensitive adhesives, e.g., rosins, rosin esters, polyterpenes, and hydrogenated aromatic resins.
  • conventional detackifying agents may also be used.
  • Suitable detackifiers include crosslinked poly(vinylpyrrolidone), silica gel, bentonites, and so forth.
  • Preferred thickeners herein are naturally occurring compounds or derivatives thereof, and include, by way of example: collagen; galactomannans; starches; starch derivatives and hydrolysates; cellulose derivatives such as methyl cellulose, hydroxypropylcellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose; colloidal silicic acids; and sugars such as lactose, saccharose, fructose and glucose.
  • Synthetic thickeners such as polyvinyl alcohol, vinylpyrrolidone-vinylacetate-copolymers, polyethylene glycols, and polypropylene glycols may also be used.
  • compositions of the invention can be rendered electrically conductive for use in biomedical electrodes and other electrotherapy contexts, i.e., to attach an electrode or other electrically conductive member to the body surface.
  • the composition may be used to attach a transcutaneous nerve stimulation electrode, an electrosurgical return electrode, or an EKG electrode to a patient's skin or mucosal tissue.
  • Suitable conductive species are ionically conductive electrolytes, particularly those that are normally used in the manufacture of conductive adhesives used for application to the skin or other body surface, and include ionizable inorganic salts, organic compounds, or combinations of both.
  • ionically conductive electrolytes include, but are not limited to, ammonium sulfate, ammonium acetate, monoethanolamine acetate, diethanolamine acetate, sodium lactate, sodium citrate, magnesium acetate, magnesium sulfate, sodium acetate, calcium chloride, magnesium chloride, calcium sulfate, lithium chloride, lithium perchlorate, sodium citrate and potassium chloride, and redox couples such as a mixture of ferric and ferrous salts such as sulfates and gluconates.
  • Preferred salts are potassium chloride, sodium chloride, magnesium sulfate, and magnesium acetate, and potassium chloride is most preferred for EKG applications.
  • any electrolyte present in the adhesive compositions of the invention it is preferable that any electrolyte present be at a concentration in the range of about 0.1 to about 15 wt. % of the hydrogel composition.
  • the procedure described in U.S. Pat. No. 5,846,558 to Nielsen et al. for fabricating biomedical electrodes may be adapted for use with the hydrogel compositions of the invention, and the disclosure of that patent is incorporated by reference with respect to manufacturing details. Other suitable fabrication procedures may be used as well, as will be appreciated by those skilled in the art.
  • Antimicrobial agents may also be added to the compositions of the invention. Antimicrobial agents function by destroying microbes, preventing their pathogenic action, and/or inhibiting their growth. Desirable properties of antimicrobial agents include, but are not limited to: (1) the ability to inactivate bacteria, viruses and fungi, (2) the ability to be effective within minutes of application and long after initial application, (3) cost, (4) compatibility with other components of composition, (5) stability at ambient temperature, and (6) lack of toxicity.
  • Antioxidants may be incorporated into the compositions of the invention in lieu of or in addition to any antimicrobial agent(s).
  • Antioxidants are agents that inhibit oxidation and thus prevent the deterioration of preparations by oxidation.
  • Suitable antioxidants include, by way of example and without limitation, ascorbic acid, ascorbyl palmitate, butylated hydroxyanisole, butylated hydroxytoluene, hypophophorous acid, monothioglycerol, sodium ascorbate, sodium formaldehyde sulfoxylate and sodium metabisulfite and others known to those of ordinary skill in the art.
  • antioxidants include, for example, vitamin C, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), sodium bisulfite, vitamin E and its derivatives, propyl gallate, sulfite derivatives, and others known to those of ordinary skill in the art.
  • preservatives that can be incorporated into the present compositions include, by way of example, p-chloro-m-cresol, phenylethyl alcohol, phenoxyethyl alcohol, chlorobutanol, 4-hydroxybenzoic acid methylester, 4-hydroxybenzoic acid propylester, benzalkonium chloride, cetylpyridinium chloride, chlorohexidine diacetate or gluconate, ethanol, and propylene glycol.
  • the adhesive compositions of the invention are useful in a variety of contexts, the desirability or need for certain additives may differ depending on the intended use.
  • the applications in which the adhesive compositions of the invention are useful include, for example: drug delivery systems; wound dressings; conductive hydrogels; pressure-relieving cushions for application to the skin including heel cushions, elbow pads, knee pads, shin pads, forearm pads, wrist pads, finger pads, corn pads, callus pads, blister pads, bunion pads, and toe pads, all of which can include active agents; intraoral applications such as tooth whitening strips, breath freshening films, and oral care products to treat sore throat, sores within the mouth, gingivitis, periodontal and oral infections, periodontal lesions, or dental caries or decay; adhesives for affixing medical devices, diagnostic systems and other devices to a body surface; sealants for ostomy devices, prostheses, and face masks; sound, vibration, and impact absorbing materials; carriers in cosmetic and cosmeceutical
  • compositions of the invention are readily controlled by adjusting one or more parameters during fabrication.
  • the adhesive strength of the composition can be increased, decreased, or eliminated during manufacture, by varying the type and/or quantity of different components, or by changing the mode of manufacture.
  • compositions prepared using a conventional melt extrusion process generally, although not necessarily, exhibit somewhat different properties relative to compositions prepared using a solution cast technique; for example, melt extrusion is typically more useful for preparing adhesive compositions that having lower tack than corresponding adhesive compositions prepared using solution casting.
  • the composition can be also extruded first, and then be pressed against a backing member or laminated to a backing member.
  • a releasable liner may also be included.
  • the thickness of the resulting film for most purposes, will be in the range of about 0.050 to 0.80 mm, more usually in the range of about 0.37 to 0.47 mm.
  • compositions may be prepared by solution casting, by admixing the components in a suitable solvent, e.g., a volatile solvent such as ethyl acetate, or lower alkanols (e.g., ethanol, isopropyl alcohol, etc.) are particularly preferred, at a concentration typically in the range of about 35 to 60% w/v.
  • a suitable solvent e.g., a volatile solvent such as ethyl acetate, or lower alkanols (e.g., ethanol, isopropyl alcohol, etc.) are particularly preferred, at a concentration typically in the range of about 35 to 60% w/v.
  • a suitable solvent e.g., a volatile solvent such as ethyl acetate, or lower alkanols (e.g., ethanol, isopropyl alcohol, etc.) are particularly preferred, at a concentration typically in the range of about 35 to 60% w/v.
  • the solution is cast onto a substrate, backing member
  • the film-forming hydrophilic polymer is selected first. Then, a complementary multifunctional polymer, with recurring functional groups capable of noncovalent bonding to the recurring polar groups within at least one linear segment of the hydrophilic polymer is selected.
  • the complementary multifunctional polymer serves as a “ladder-like” noncovalent crosslinker in that noncovalent bonding to the film-forming polymer results in the formation of a ladder-like interpolymer complex.
  • the plasticizer is then selected, which, as noted elsewhere herein, is a bifunctional linear oligomer capable of forming a bridge between a polar group on one film-forming polymer chain and a polar group on a second film-forming polymer chain, thereby forming a “carcass-like” crosslinked complex.
  • the amount of the film-forming polymer is greater than the amount of the complementary multifunctional polymer and is also greater than the amount of the bifunctional linear oligomer.
  • Optional additives including pharmacologically active agents and cosmeceutical agents, can be combined with the polymers and oligomer during adhesive preparation. Alternately, an additive can be added after the components are mixed and the composition prepared.
  • One method of loading the composition with an active agent involves providing a layer of the composition on a substrate, coating the layer with a solution of the active agent, placing a release liner on top of the active agent layer, and allowing the active agent to become absorbed by the composition.
  • Eudragit E-100 is used as the film-forming polymer, which is a copolymer of 2-dimethylaminoethyl methacrylate (DMAEMA), butyl methacrylate, and methyl methacrylate (2:1:1).
  • DMAEMA 2-dimethylaminoethyl methacrylate
  • the monomer units of DMAEMA are capable of forming electrostatic bonds with carboxyl groups in the ladder-like crosslinker, Eudragit L 100-55 and Eudragit S-100 (copolymer of methacrylic acid with methyl methacrylate (1:2).
  • these blends represent triple blends of two Eudragit grade polymers (E-100 and L 100-55, or S-100) with appropriate plasticizers of hydrophobic units in Eudragit, such as tributyl citrate (TBC), triethyl citrate (TEC), acetyltributyl citrate (ATBC) and acetyltriethyl citrate (ATEC) (see Scheme in FIG. 4 ).
  • TBC tributyl citrate
  • TEC triethyl citrate
  • ATBC acetyltributyl citrate
  • ATEC acetyltriethyl citrate
  • % Ladder-like Film-forming crosslinker Carcass- Sol Sam- polymer: Eudragit L like Fraction, Swell ple Eudragit E-100 100-55 or S-100 crosslinker % Ratio 1a 68 L 100-55 PEG-400 25.5 2.75 7 25 1b 68 L 100-55 TBC 15.06 2.45 7 25 1c 68 L 100-55 TEC 18.62 2.64 7 25 1d 68 S-100 TEC 19.67 1.15 7 25 1e 62.5 L 100-55 TEC 27.86 3.31 12.5 25 1f 62.5 S-100 TEC 26.88 4.43 12.5 25
  • Characteristics of tensile stress-strain curves make possible the evaluation of cohesive strength in terms of ultimate tensile stress under fracture of adhesive film, whereas free volume may be assessed qualitatively in terms of maximum elongation under rupture.
  • the area under stress-strain curve represents the work of viscoelastic polymer deformation up to break, and this value correlates to the work of adhesive debonding (see Feldstein M. M. “ Molecular Fundamentals of Pressure - Sensitive Adhesion ” in Benedek I. “ Development and Manufacture of Pressure - Sensitive Products ”, Marcel Dekker, N.Y., 2005, Chapter 4, pp. 179-215. As follows from the tensile stress-strain curves in FIG.
  • Adhesive properties of binary Eudragit E-100 and Eudragit L-100-55 blends with appropriate plasticizers were the subjects of U.S. Pat. No. 5,133,970 by Petereit & Roth and U.S. Pat. No. 5,296,512 by Beier et al., respectively.
  • tackifier Sylvagum RE 85K glycerol ester of tall oil rosin
  • plasticizers contribute mainly to the increase of material capability to develop large deformations under detaching stress
  • the tackifier enhances appreciably its cohesive strength by the increase in ⁇ max value.
  • Examples 2h-2i exhibit how dramatic is the gain in adhesion if using the tackifier SYLVAGUM is accompanied with the increase of plasticizer concentration.
  • Examples 2k-2m demonstrate how the adhesion of Eudragit E-100—Eudragit L-100 55 blends (10:1) may be optimized by the combined effect of the plasticizer and the tackifier: Ex. Plasti- W deb , ⁇ max , No.
  • SYLVAGUM Resin is not a single tackifier that is miscible with Eudragit E-100—Eudragit L-100-55 ladder-like electrostatic complex, plasticized with TEC.
  • An alternative tackifier, which is miscible with this blend, is Oppanol B15, a PIB of average molecular weight 75,000 g/mol.
  • Adhesive Compositions Based on the Carcass-Like Complex of Eudragit E-100 Polybase and its Combination with the Ladder-Like Electrostatic Crosslinking
  • the film forming polymer may be converted into the form of pressure sensitive adhesive not only by plasticizing with TEC, but and by adding into this blend higher carboxylic acids having 8 to 20 carbon atoms and dicarboxylic acids having 2 to 8 carbon atoms (U.S. Pat. No. 5,113,970 to Petereit and Roth).
  • carboxylic acids having 8 to 20 carbon atoms
  • dicarboxylic acids having 2 to 8 carbon atoms
  • Table Ex.3 see examples 3a and 3b
  • the blends of Eudragit E-100 with TEC and adipic acid (AA, dicarboxylic acid having 6 carbon atoms) are good skin contact adhesives.
  • the AA acts as the carcass-like crosslinker of trialkylamino groups in Eudragit E-100 polybase. Additional incorporation of AA into the plasticized ladder-like Eudragit E-100—Eudragit L-100-55 complex gives the blends outlined by Ex. 3c-3f ( FIG. 11 ), which are good bioadhesives demonstrating the tack to highly moistened biological substrates such as teeth and oral mucosa. As is evident from the probe tack curves presented in FIG. 11 , the less the content of the LLC (Eudragit L-100-55), the higher the adhesion.
  • FIGS. 12 and 13 illustrate the procedure of partial ionization of the Eudragit E-100 polybase and Eudragit L-100-55 polybase with corresponding amounts of neutralizing agents, HCl and NaOH, respectively.
  • titration curve first must be measured. Taking into account that the jump in pH corresponds to 100% ionization of the polyelectrolyte, the amount of neutralizing agent needed for 20% ionization of the polyelectrolyte constitutes a fifth fraction of total (equivalent) amount of the acid or alkali.
  • FFP LLC Plasticizer pH modifier J/m 2 MPa 4a Eudragit E-100, 61.8 Eudragit L 100-55, 6.2 Triethyl citrate, 25 NaOH 5% ionization 18.5 0.73 4b Eudragit E-100, 61.8 Eudragit L 100-55, 6.2 Triethyl citrate, 25 NaOH 10% ionization 20 0.77 4c Eudragit E-100, 59.1 Eudragit L 100-55, 5.9 Triethyl citrate, 35 NaOH 5% ionization 54 0.83 4d Eudragit E-100, 59.1 Eudragit L 100-55, 5.9 Triethyl citrate, 35 NaOH 10% ionization 57 0.97 4e Eudragit E-100, 61.8 Eudragit L 100-55, 6.2 Triethyl citrate, 25 HCl 5% ionization 23 0.82 4f Eudragit E-100, 61.8 Eudragit L 100-55, 6.2 Triethyl citrate, 25
  • both the film-forming polymer and the ladder-like crosslinker are preliminary ionized by treating respectively with HCl and NaOH solutions, then the ionic bonding between cationic groups of Eudragit E-100 copolymer and anionic groups of Eudragit L-100—55 copolymer contributes to the adhesive behavior of the interpolymer complex along with hydrogen bonds formed between uncharged groups.
  • the adhesive properties of the complex are intermediate between those featured for the complex involving partial ionization of either the film-forming polymer or the ladder-like crosslinker. Effects of macromolecular ionization on the tack of adhesive composites involving polyelectrolytes have never been earlier reported.
  • Partial 10% ionization of the ladder-like crosslinker (Eudragit L-100-55) in interpolymer complex with film-forming Eudragit E-100 polymer does not affect the swelling and dissolution of the adhesive.
  • the 10% ionization of the film-forming polymer with HCl solution results in appreciable increase of swell ratio from 3.5 to 22.5, while the amount of soluble fraction has comparatively insignificant effect on the value of sol fraction.
  • the hydrogen bonded interpolymer complexes combining the ladder-like and carcass-like types of noncovalent crosslinking, shown in schematic form in FIG. 3 share the properties of pressure-sensitive adhesives and bioadhesives (see U.S. patent application Ser. No. 10/936,887 to Feldstein et al. for “Method of Preparing Polymeric Adhesive Compositions Utilizing the Mechanism of Interaction Between The Polymer Components, filed Sep. 8, 2004).
  • the effect of partial ionization of Eudragit L100-55 on adhesive properties of PVP/PEG/Eudragit L100-55 is demonstrated by present example.
  • Eudragit E-100 is a typical and comparatively well-studied but not unique representative of polybases suitable for the formulation of adhesives based on the ladder-like interpolymer complexes with polyacids.
  • Others appropriate polybases include homopolymers and copolymers of vinyl amine or chitosan among polyelectrolytes, and PVP or PNIPAM among non-polyelectrolytes.
  • Table outlines the adhesive properties of the blends of high molecular weight PVP K-90 (film-forming polymer) with Eudragit L-100-55 as ladder-like crosslinker, plasticized with TEC.
  • the inverted composition wherein the Eudragit L-100-55 serves as the film-forming polymer and the PVP as the ladder-like crosslinker was also prepared and characterized. These compositions differ from that described in Examples 1-3 by the lack of carcass-like crosslinker and, consequently, represent others examples of the adhesives based on ladder-like interpolymer complexes shown schematically in FIG. 4 .
  • the compositions were prepared by casting-drying method from ethanol solutions. Ex. W deb , ⁇ max , No.
  • the Eudragit E-100 was selected as film-forming polymer (polybase) and Gantrez S-97 as the ladder-like crosslinker (polyacid).
  • the latter is a copolymer of maleic acid with methylvinyl ether (1:1).
  • TEC was used as plasticizer. Under vigorous stirring the powder of Gantrez S-97 polymer was slowly added into the 30% ethyl alcohol solution of Eudragit E-100, that was previously mixed with TEC (plasticizer), until a homogeneous dispersion was obtained. The semitransparent, homogeneous film was obtained using simple casting and drying procedure of the previously obtained dispersion under ambient temperature.
  • FIG. 18 compares the probe tack stress-strain curves for the Eudragit E-100—Gantrez S-97 ladder-like complex with the curve featured for Eudragit E-100—Eudragit L-100-55 composition plasticized with equivalent amount of TEC.
  • Suitable ladder-like crosslinkers for Eudragit L-100-55 polymer are alginic acids and carboxyl-containing cellulose derivatives such as HPMCP. Their mixing with Eudragit L-100-55 in solutions can be significantly facilitated by partial ionization of relevant polymers.
  • Eudragit E-100 is not unique polybase that can be used as FFP in the blends with Eudragit L-100-55 polybase.
  • Other suitable candidates as FFP in plasticized ladder-like complexes are the Eudragit RS and Eudragit RL.
  • the Eudragit RS is a copolymer of trimethylammonioethylmethacrylate chloride (0.1) with ethylacrylate (1) and methylmethacrylate (2), available from Rohm Pharma Polymers.
  • the Eudragit RL is a copolymer of trimethylammonioethyl methacrylate chloride with ethylacrylate and methylmethacrylate (0.2:1:2), available from Rohm Pharma Polymers as well.
  • both TL and RS polymer contain ionic groups, they are insoluble in water due to high concentration of hydrophobic polymer units.
  • the Eudragit RL and RS polymers are capable to form ionic bonds with polymer units bearing negative charge (carboxylate anions).
  • Appropriate ladder-like crosslinker for such polymers is ionized Eudragit L-100-55.
  • composition of adhesive blend prepared using Eudragit RL and Eudragit RS polymers Composition % wt. Eudragit RL 49.1 Eudragit RS 16.4 TEC 28.0 Eudragit L100-55 6.5 Fully ionized
  • Another appropriate polybase forming the ladder-like complexes with polyacids is chitosan.
  • FIGS. 20 and 21 illustrate the influence of hydrophilicity of plasticizers on the adhesive and water absorption properties of the compositions based on the interpolymer complex between Eudragit E-100 polybase Eudragit L-100-55 polyacid.
  • more hydrophilic plasticizers TEC and ATEC
  • demonstrate more ductile mechanism of deformation under debonding stress developing higher values of maximum elongation compared to more hydrophobic TBC and TBC, which behave like solid adhesives and deform without fibrillation.
  • the adhesion measured in terms of the work of debonding, decreases in a row ATEC ⁇ TEC>ATBC>TBC.
  • the swell ratio of the blends of Eudragit E100—Eudragit L100-55 with plasticizers TEC, ATEC, TBC, ATBC decreases with the decrease in their hydrophilicity in the row TEC>ATEC>TBC>ATBC. It is worthy of note, that the nature of plasticizers affects the water absorbing capacity in a smaller extent than the adhesion.
  • adhesive blends based on plasticized Eudragit E-100—Eudragit L-100-55 complexes are miscible with such hydrophobic plasticizers and tackifiers as PIB (Oppanol B-15) (See FIG. 10 ). Because the monomer units in Eudragit E-100—Eudragit L-100-55 complexes combine polar hydrophilic and non-polar lipophylic entities, these adhesives belong to the class of amphiphilic materials and are also miscible with hydrophilic and even hygroscopic polymers and filers. Hydrophilization of amphiphilic Eudragit E-100—Eudragit L-100-55 adhesives represents an important tool to enhance their water-absorbing capacity and modify the adhesion.
  • the films of Eudragit E100/Eudragit L100-55/TEC blends with PVP K-30 were semitransparent indicating of their heterogeneous structure. These films had poor or no initial tack in contrast to the blends with PVP-PEG carcass-like complex ( FIG. 23 ). These latter films were homogeneous and transparent.
  • Tables 8.2-8.5 illustrate other approaches towards adhesive materials of controlled water-absorbing capacity based on ladder-like interpolymer complexes.
  • the Carbopol serves both as a ladder-like crosslinker and hydrophilizing agent.
  • the Kollidon CLM serves as a ladder-like crosslinker and hydrophilizing agent.
  • Kollidon CLM is physically crosslinked polyvinylpyrrolidone supplied with BASF in the form of finely micronized powder. Under vigorous stirring Solution II was added into Solution I, and the mixture was stirred over 20 min. Polymer films were prepared by solution casting onto a PET backing with following drying at ambient temperature over 3 days. Films of 0.20 ⁇ 0.04 mm thickness were obtained. TABLE Example 8.4 Kollidon Example Eudragit RS Eudragit RL TEC CLM Swell ratio 1 45 15 30 10 2.3 2 41.25 13.75 30 15 3.1 3 45 15 20 20 4.0 4 37.5 12.5 20 30 4.8
  • the Cab-O-Sil M5 serves as a hydrophilizing agent.
  • Cab-O-Sil M5 is synthetic silicone dioxide supplied with Cabot Corporation in the form of finely micronized powder. Under vigorous stirring Solution II was added into Solution I, and the mixture was stirred over 20 min. Polymer films were prepared by solution casting onto a PET backing with following drying at ambient temperature over 3 days. Films of 0.20 ⁇ 0.04 mm thickness were obtained. TABLE Example 8.5 Cab-O-Sil Example Eudragit RS Eudragit RL TEC M5 Swell ratio 1 49.5 16.5 30 4 2.2 2 46.5 15.5 30 8 2.8 3 43.5 14.5 30 12 3.8
  • Swell Ratio featured for parent Eudragit RL/RS—TEC blend is around 2.0.
  • Tables Ex. 8.3-8.5 have shown, the hydrophilization of the blends with crosslinked water absorbents such as Carbopol 974, Kollidon CLM and Cab-O-Sil M5 results only in comparatively insignificant increase in Swell Ratio. This is most likely due to very low water permeability of hydrophobic film based on Eudragit RL/RS polymers.
  • the materials described in the Examples 8-3-8.5 may be useful as a carriers of hydrogen peroxided solution in teeth whitening strips.
  • the hydrophilic filler (Carbopol 974, Kollidon CLM or Cab-O-Sil M5) should be impregnated with the hydrogen peroxide solution before incorporation into the Eudragit RL/RS film. This film provides good tack and adhesion toward hydrated tooth surface.
  • the properties of the triple blend hydrogels of the invention were compared with those of the PVP-PEG binary blends, described in U.S. Pat. No. 6,576,712, and with those of conventional pressure sensitive adhesives (“PSA”; DURO-TAK® 34-4230, National Starch and Chemicals) and classical bioadhesives (covalently crosslinked polyacrylic acid polymers Carbopol® 974P and Noveon® AA1, both from B.F. Goodrich, Co.).
  • PSAs exemplified above by the SIS block-copolymer based DURO-TAK® 34-4230 adhesive, represent a special class of viscoelastic polymers. They are capable of forming a strong adhesive bond with various substrates under application of a slight external pressure over a short time (1-2 seconds). It is noteworthy that the typical PSAs for human use are mainly based on hydrophobic elastomers with low glass transition temperatures, ranging from ⁇ 120 to ⁇ 30° C., which are usually increased by addition of tackifying resins. The common property of the PSAs is a loss of adhesion as the surface of a substrate is moistened.
  • the adhesives of various hydrophilic-hydrophobic balances outlined by present invention and obtained by non-covalent crosslinking of film-forming hydrophilic polymers share the properties of both pressure sensitive adhesives and bioadhesives. Indeed, while their adhesive strength is typical of the PSAs, it has increased adhesion towards moistened substrate like bioadhesives. Varying the hydrogel composition and degree of ionization of ionogenic polymers can easily provide the further control of adhesive, water sorption and mechanical properties of the products based on non-covalently crosslinked hydrogels.
  • FIG. 24 compares the peel adhesion towards dry and moistened human forearm skin in vivo for conventional acrylic PSA and three grades of adhesives based on interpolymer complexes. According to these data, the adhesive properties of polymer composites described in present invention and in U.S. Pat. No. 6,576,712 share the properties of PSAs and bioadhesives by combining high adhesion featured for conventional PSAs with capability to adhere to moistened skin and biological tissues typical of bioadhesives.
  • the tack of adhesives based on interpolymer complexes is comparable with that typical of conventional PSAs.
  • the distinctive feature of the adhesive blends described in this invention is the lower values of maximum elongation that results from non-covalent crosslinking of the chains of film-forming polymer. Because the carcass-like crosslinking is significantly looser than the ladder-like crosslinking, it is no wonder that the water-soluble PVP-PEG adhesive demonstrates higher stretching at probe detachment than the adhesives involving the ladder-like type of crosslinking.
  • the main tools to increase fluidity and maximum elongation of the adhesives provided by the ladder-like crosslinking it is the dilution of network density due to mixing with plasticizers, in the course of swelling in water and also the decrease in concentration of the ladder-like crosslinker.
  • hydrophilic and amphiphilic adhesives described in this invention is typical of covalently crosslinked polymers.
  • the adhesives based on interpolymer complexes can be easily prepared using a simpler blending process, and, furthermore, provide film-forming properties that are unattainable using crosslinked polymers.
  • the adhesive films of the present invention can be also produced by direct mixing the components in dry state followed by extrusion.
  • the mixing was provided using Thermo Haake Mixer, whereas the extrusion was performed with Skania Single-Screw Extruder.
  • the procedures of mixing and extrusion of the major formulations described in this invention are presented below.
  • Wound dressings were prepared from the following ingredients using either a melt extrusion or casting/drying processes: Composition, wt. % Sam- Film-forming Ladder-like Carcass-like Silver salt ple polymer crosslinker crosslinker (1%) 11a Eudragit E-100, Eudragit L 100-55, Triethyl Silver 67.2 6.7 citrate, 25.0 sulfate 11b Eudragit L 100- PVP, 9.9 PEG-400, Silver 55, 49.5 39.6 sulfate 11c Eudragit E-100, Eudragit S-100, 6.7 Triethyl Silver 66.9 citrate, 24.9 sulfate 11d Eudragit E-100, Eudragit L 100-55, Triethyl Silver 67.2 6.7 citrate, 25.0 phosphate
  • sample 11b was initially tacky and maintained a good adhesion toward dry and moderately exudating wounds, but could be removed from the skin without pain by washing with a large amount of water. Samples 11a and 11c possessed a slight initial tack but became nontacky in a swollen state. Accordingly, sample 11b is useful for treatment of pressure, diabetic, arterial and venous ulcers, whereas Samples 6a and 6c are more suited for covering large, wet and infected wounds and burns.
  • Potentiometric method with Ag ion selective electrode was used to study silver release from anti-microbial dressings.
  • Aqueous solutions of silver nitrate in the concentration range 2.5*10 ⁇ 6 -10 ⁇ 3 M were used to calibrate the Ag ion selective electrode.
  • the receptor solution in the beaker over the sample was stirred and silver concentration was measured with the Ag ion selective electrode. After measurement the receptor solution was removed and replaced with 50 ml of distilled water. Cumulative Ag release was calculated and expressed in ⁇ g per cm 2 of the anti-microbial dressing.
  • FIG. 26 demonstrates how the release kinetics of silver sulfate, as the active agent, from the matrices in vitro were affected by the change in matrix composition.
  • All three hydrogel compositions provided different drug release profiles: Sample 11a delivered the highest amount of silver sulfate; Sample 11b provided a fast release of the active agent during the onset period, followed by a rapid decrease of release rate within steady state stage; and Sample 11c provided zero-order release kinetics. Since various silver salts are characterized with different values of solubility product, it would be expected that different salts of silver, being incorporated into the same hydrogel matrix, may demonstrate different release kinetics.
  • FIG. 27 illustrates the effect of silver salts on release profile of Ag ion from the formulation outlined by Example 1d.
  • the matrix based on Eudragit E-100—Eudragit L-100-55 ladder-like complex was loaded with silver phosphate instead of silver sulfate. Since solubility of silver phosphate in the matrix is about three orders of magnitude lower than that of silver sulfate, the adhesive matrix loaded with silver phosphate provides prolonged release kinetics of anti-microbial agent.
  • compositions were prepared by dissolution in ethanol of components listed in the Table presented below, casting the solution and drying at temperature of 50° C.
  • Sample 12a uses two ladder-like crosslinkers, an acrylate polymer (Eudragit L 100—55) and a poly(N-vinyl lactam) (PVP 90), while Sample 12b only includes one ladder-like crosslinker, Eudragit L 100-55.
  • Sample 12a uses two carcass-like crosslinkers, an alkyl citrate (triethyl citrate) and a polyalkylene glycol (PEG 400), while Sample 12b only includes one carcass-like crosslinker, triethyl citrate.
  • Samples 13a-13d represent liquid compositions suitable for application to skin as liquid bandages.
  • Sample 13a is a liquid formulation for tooth whitening which contains the insoluble film-forming polymer (Eudragit RS) and plasticizer for this polymer tributylcitrate (TBC).
  • Eudragit RS is a copolymer of trimethylammonioethylmethacrylate chloride (0.1) with ethylacrylate (1) and methylmethacrylate (2), available from Rohm Pharma Polymers.
  • Samples 13b-13d contain no ladder-like crosslinker for the hydrophilic polymer, Eudragit L 100-55. Actually, the ladder-like crosslinker makes the polymer film insoluble.
  • the ladder-like crosslinker of PVP was not a necessary component, because the blend is not soluble.
  • Sample 13e is a film-forming liquid formulation suitable for the treatment of cold sores and canker sores. It contains Eudragit E-100 as a soluble film-forming polymer instead of PVP. Correspondingly, PEG-400 is omitted from the formulation, because TBC is a good plasticizer for both Eudragit RS and E-100.
  • Liquid bandage and cold sore compositions for skin applications may also contain active agents such as local anesthetics.
  • Suitable local anesthetics include dibucaine hydrochloride; dibucaine; lidocaine hydrochloride; lidocaine; benzocaine; p-butylaminobenzoic acid 2-(diethylamino) ethyl ester hydrochloride; procaine hydrochloride; tetracaine hydrochloride; chloroprocaine hydrochloride; oxyprocaine hydrochloride; mepivacaine; cocaine hydrochloride; and piperocaine hydrochloride.
  • flavorants include wintergreen, peppermint, spearmint, menthol, fruit flavors, vanilla, cinnamon, spices, flavor oils (oil of cloves) and oleoresins, as known in the art, as well as combinations thereof.
  • the amount of flavorant employed is normally a matter of preference, subject to such factors as flavor type, individual flavor, and strength desired.
  • Samples 13c and 13e contain also a skin softening agent such as glycerol monooleate (Peceol, Gattefosse, France). Composition, wt % Insoluble Soluble Ladder-like Carcass-like film-forming Plasticizer film-forming crosslinker crosslinker Sample polymer (A) for (A) polymer (B) for (B) for (B) Additives Solvent 13a Eudragit TBC, PVP K-90, Eudragit L PEG, 3.00 Sodium Ethanol, (Liquid Bandage) RS, 29.00 2.50 3.00 100-55, 2.20 Citrate, 2.50 38.20 13b Eudragit TBC, PVP K-90, — PEG, — Ethanol, (Liquid Bandage) RS, 35.11 11.70 0.36 0.18 52.65 13c Eudragit TBC, PVP K-90, — PEG, 3.00; GMO, Ethanol, (Liquid Bandage)

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US8617647B2 (en) 2013-12-31
RU2007129752A (ru) 2009-02-10
AU2006204127A1 (en) 2006-07-13
CA2594183A1 (fr) 2006-07-13
US8273405B2 (en) 2012-09-25
US20100278757A1 (en) 2010-11-04
US20120321569A1 (en) 2012-12-20
CA2594183C (fr) 2014-05-13
EP1838358B1 (fr) 2016-11-30
RU2416433C2 (ru) 2011-04-20
EP1838358A2 (fr) 2007-10-03
US20140322143A1 (en) 2014-10-30
US20120027695A1 (en) 2012-02-02
AU2006204127B2 (en) 2010-12-23
US9127140B2 (en) 2015-09-08

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