WO1991014733A1 - Composition adhesive a polymere adhesif organique acide et a polymere a substitution amine - Google Patents

Composition adhesive a polymere adhesif organique acide et a polymere a substitution amine Download PDF

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Publication number
WO1991014733A1
WO1991014733A1 PCT/US1991/001553 US9101553W WO9114733A1 WO 1991014733 A1 WO1991014733 A1 WO 1991014733A1 US 9101553 W US9101553 W US 9101553W WO 9114733 A1 WO9114733 A1 WO 9114733A1
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Prior art keywords
adhesive
amine
polymer
water
substituted
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PCT/US1991/001553
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English (en)
Inventor
Steven Daryl Smith
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The Procter & Gamble Company
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Publication of WO1991014733A1 publication Critical patent/WO1991014733A1/fr
Priority to FI924337A priority Critical patent/FI924337A/fi

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    • 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
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A61K6/35—Preparations for stabilising dentures in the mouth
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • This invention relates to improvements in adhesives and, in particular, improved bioadhesives, such as denture adhesives.
  • Dentures Ordinary removable dentures, dental plates, and the like, comprise teeth mounted in a suitable plate or base. Dentures function as a substitute for missing teeth and serve as a replacement for all or a portion of the teeth ordinarily found in the oral cavity. Although dentures generally are skillfully prepared, often they do not fit perfectly. Moreover, no matter how satisfactory at first, after a period of time the fit of the denture becomes loose and imperfect due to natural shrinkage and changes in the gums, mucous tissues, and the like. Loose and imperfectly fitted dentures usually are corrected and stabilized by the use of a denture adhesive. Denture adhesives are used to fill the interstices between the denture and the gums or tissues.
  • a denture adhesive Prior to placement of the denture in the oral cavity, a denture adhesive is applied to the denture-plate surface which, for a perfect fit, should uniformly contact the gums and mucous tissues.
  • the denture adhesive is formulated not only for its adherent properties, but also to provide a cushion or gasket between the denture and the gums or tissues, thereby positioning the denture securely in the oral cavity.
  • Requirements and characteristics for a satisfactory denture adhesive composition are many and are dictated by numerous factors. Desirably, one daily application of such a composition should function as an effective means for insulating, cushioning, and securely positioning the denture.
  • the composition should retain its characteristics and properties in the typical powder and cream forms during storage under various climatic conditions such as high temperature and humidity; be readily and easily capable of application to the denture surface; not be irritating or uncomfortable to the user; have no disagreeable odor or color; have no unpalatable taste; optionally provide antiseptic and germicidal properties for preventing or inhibiting the growth of organisms ordinarily found in the mouth; and function as an agent for prevention of putrefaction or malodorous decomposition of foods or secretions lodging beneath or adjacent to the denture.
  • the adhesive material must be capable of imbibing water and saliva and swelling, so as to fill the interstices between the denture and the gum or mucous tissues.
  • the adhesive should not attack or damage the denture, as by causing a crazing of the denture-plate material. Additionally, the adhesive should be stable to bacteria, molds and enzyme systems found in the oral cavity, and have a pH that is nonirritating to the oral mucosa, generally 5-8.5, preferably a pH around neutrality.
  • the mechanical strength of the adhesive mass, be it gel or colloid, formed by imbibition of water should be great enough to securely maintain the position of the denture under normal use, and not so great as to make denture removal difficult when desired, or as to damage or injure the gums, tissues, or denture upon removal.
  • denture adhesives that will provide the above-described characteristics and, importantly, will both maintain the secure fit of the denture over prolonged periods (10-16 hours) without the need for reapplication and will be easily, removed by the user without the necessity for brushing or scraping substantial amounts of adhesive from the gums or the denture.
  • U.S. Patent 3,868,432 discloses denture adhesive compositions wherein the anionic component is a polymer of maleic acid and a vinyl-lower alkyl-ether (i.e., GantrezTM) and the cationic material is a copolymer of an acrylamide and a vinyl quaternary ammonium salt or a copolymer of an acrylamide with vinyl and alkyl substituted vinyl pyridinium salts. Similar technical disclosures can be found in U.S. Patent 3,868,340 (Keegan et al., issued 2/25/75), U.S.
  • Patent 3,919,357 (Keegan et al., issued 11/11/75) and U.S. Patent 3,833,518 (Rubin et al., issued 9/3/74).
  • U.S. Patents 3,878,135 (Keegan et al., 4/15/75), 3,878,138 (Keegan et al., 4/15/75), 3,926,870 (Keegan et al., 12/16/75), and 4,001,151 (Keegan et al., 1/4/77) disclose anionic cationic denture adhesive compositions comprising: a) copolymers of acrylamide with vinyl quaternary ammonium salts; and b) protein material, peroxymethylcellulose or cellulose sulfate gum, casein or its alkyl metal salts, or certain gums (karaya, arabic, Shiraz, tragacanth, pectin, pectinates, algin, and alginates), respectively, as the anionic components.
  • U.S. Patents 3,868,259 disclose ammonium chloride substituted anhydroglucose polymers with carboxymethylcellulose or cellulose sulfates, natural anionic gum materials (such as gum karaya, gum arabic, gum Shiraz, etc.), protein materials (such as soybean meal, sunflower seed meal, or peanut meal, or combinations thereof, respectively.
  • natural anionic gum materials such as gum karaya, gum arabic, gum Shiraz, etc.
  • protein materials such as soybean meal, sunflower seed meal, or peanut meal, or combinations thereof, respectively.
  • German 2,408,125 (8/28/75) to G. Seeh relates to the use of dental adhesive compositions containing chewing gum.
  • German 2,446,449 (6/6/75) assigned to Hydrophilics Int. Inc., based on U.S. priority serial number 435,283 (1/21/74) relates to hydrophilic copolymer salts of aminomethacrylates and a hydrophobic monomer for use in controlled release of agricultural chemicals and as a spray-on adhesive for dentures.
  • German 2,558,602 (6/30/77) to T. Pantenge relates to denture-fixing compositions comprising polyisobutylene and other thickening agents such as natural gums, starch, and the like.
  • German 2,841,823 (3/27/80) to A. Breuer, relates to denture paste comprising polystyrene, gelatin, polyether resin and hydrogenated hydrocarbon.
  • German 2,901,661 (1/15/79) to A. Breuer relates to compositions for improving the fit of dentures using a paste of polystyrene, gelatin, polyether resin, gum arabic, etc.
  • German 2,932,455 (8/10/79) to L. Frohmuller relates to denture-securing systems comprising a hardenable fluid substance such as silicone rubber.
  • German, 3,228,335 (2/9/84) to E. Hofacker relates to a fixative for dentures comprising an ethanol solution containing untreated polyvinyl-pyrrolidone and densified polyvinyl- pyrrolidone.
  • European Patent Application 140,486 (filed 7/31/84) to A. J. Desmarais, relates to denture adhesive compositions containing a hydrophobically modified water-soluble polymer, alone or admixed with an alkali metal salt of CMC. Hydrophobically modified hydroxyalkyl celluloses and copolymers of ethylene oxide and long chain epoxyalkanes are preferred for use in the compositions.
  • Japanese Patent Document 84/144,708 (8/18/84) to Kureha Chem Ind KK relates to cavity lining material for dentures that comprises fluorine-containing copolymers and fluorine-containing telomers.
  • Seiyaku relates to stabilizers for artificial teeth containing partially saponified vinyl acetate resins, which also can contain water-insoluble inorganic substances such as calcium carbonate, talc or silica.
  • Japanese 86/87,608 (/6/86) to Saotome K, relates to denture fixing compositions containing highly "water absorbing" resins, such as N,N'-methylene bisacrylamide, in combination with sodium CMC and polyethylene glycol.
  • Yakuhin Kako KK relates to a glue for fixing artificial dentures comprising water-soluble high polymers such as gelatin and a binder such as hydroxypropyl cellulose, together with fat-soluble vitamins.
  • Japanese Patent Document 87/129,210 (6/11/87) to Kobayashi Seiyaku relates to a copolymeric resin containing acetyloxy- substituted repeat units which provide tacky adhesion to false teeth.
  • U.S. Patent 3,440,065 (4/22/69) to A. Laurence relates to denture adhesives containing wood flour, microcrystalline cellulose or other natural wood pulp derivatives in a gum-petroleum base.
  • U.S. Patent 3,511,791 (5/12/70) to Puetzer et al relates to denture adherents having an acrylamide polymer as the principal adhesive component, preferably in combination with some natural gum.
  • U.S. Patent 3,575,915 (4/20/71) to Novak et al relates to denture adhesives comprising polyvinyl acetate, a mineral hydrocolloid such as colloidal silicates, and plasticizers.
  • U.S. Patent 3,736,274 (5/29/73) to Schoenholz et al, relates to denture compositions comprising maleic anhydride and/or acid copolymer, polymeric N-vinyl lactam and CMC.
  • U.S. Patent 3,740,361 (6/19/73) to 0. Altwirth, relates to denture adhesive compositions comprising a mixture of alginate and an ethanol solution of a normally solid polyvinyl acetate resin.
  • A. Starace relates to thickening compositions, including denture adhesives, comprising a hydrophilic colloid derived from Xanthomonas, in combination with dextrin.
  • U.S. Patent 4,239,488 (12/16/80) to V. A. Sempler relates to encapsulated denture adhesives.
  • U.S. Patent 4,280,936 (7/28/81) to Dhabhar, Heyd and Schmidt, relates to improved denture adhesives containing a specified ratio of CMC and poly(ethyleneoxide) in a mineral oil base.
  • U.S. Patent 4,318,742 (3/9/82) to 0. Lokken, relates to denture adhesives containing a major amount of gum base and a quantity of hydrophilic polymer to modify the adhesive properties of the gum base.
  • U.S. Patent 4,373,036 (2/8/83) to Chang et al relates to denture fixative compositions containing various cellulose derivatives and polymers such as partially neutralized alkylvinylethermaleic acid or anhydride copolymers, optionally with cross! inking agents. See also U.S. Patent 4,470,814 (9/11/84) to Chang et al.
  • U.S. Patent 4,474,902 (10/2/84) to Dhabhar and Schmidt, relates to improved denture adhesives containing karaya gum in a hydrophilic vehicle.
  • U.S. Patent 4,514,528 (4/30/85) and U.S. Patent 4,518,721 (5/21/85) to these same inventors relating, respectively, to improved denture adhesives containing adhesive polymeric fractions consisting of admixtures of partial salts of lower alkylvinyl ether maleic anhydride-type copolymers with CMC or poly(ethyleneoxide), as well as denture adhesives containing CMC and poly(ethyleneoxide).
  • U.S. Patent 4,522,956 (6/11/85) to Dhabhar and Schmidt relating to improved denture adhesives containing poly(ethyleneoxide) as the sole adhesive component in a hydrophilic vehicle comprising certain polyethylene glycols.
  • U.S. Patent 4,529,748 (7/16/85) to H. G. P. Wienecke relates to dental prosthesis adhesives formed from film-forming substances such as various cellulose derivatives, acrylate polymers, methacrylate polymers, and other film-providing substances.
  • U.S. Patent 4,608,088 (8/26/86) to 0. Lokken relates to dental adherents containing a dental adhesive, an alginate, and a setting agent for the alginate.
  • U.S. Patent 4,664,630 (5/12/87) to 0. Lokken, relates to denture adherents comprising a dental adhesive and a gel-forming mixture of a water-soluble alginate, together with a setting agent for said alginate.
  • the compositions are said to be useful as denture adhesives, and also as a depot formulation for delivery of therapeutic agents to the oral cavity.
  • U.S. Patent 4,504,618 (3/12/85) to Irvine et al, relates to aqueous dispersions of film-forming addition polymers said to be useful as components of adhesives.
  • the present invention encompasses adhesive compositions, comprising an intimate mixture of: (a) from about 10% to about 90%, by weight, of an acidic organic adhesive polymer, preferably selected from the poly(lower alkyl vinyl ether/maleic
  • Adjunct materials can include pharmacologically active compounds for delivery to the oral cavity or skin.
  • the organic adhesive being acidic in character, interacts with the organic amine-substituted polymer in such a way in the presence of water to form a water-insoluble gel.
  • the organic adhesive and amine-substituted polymer are selected such that the gel formed from the components and water is characterized by a Gel Volume (as determined according to the procedure described hereafter) between about 0.5 and about 10.0 g water/g acidic organic adhesive polymer and amine-substituted polymer (combined), preferably between about 0.5 and about 4.0 g/g, more preferably between about 1.0 and about 3.0 g/g.
  • the invention provides improved adhesives which are particularly useful for application as bioadhesives, i.e., for adherence to human and animal tissue.
  • the adhesive compositions hereof can be provided in various forms, including powder, paste, and gel.
  • the bioadhesives are especially useful for denture adhesive compositions.
  • Paste compositions herein can be conveniently packaged in a tube or pump dispenser.
  • the invention also provides adhesive tape comprising an adherent amount of the adhesive composition on a solid backing material.
  • An adherent medical dressing comprises such tape, in combination with an absorbent material to imbibe blood or other body fluids.
  • the adhesive compositions herein also provide a depot which can be used, for example, to deliver pharmacologically active materials to the oral cavity or skin over extended periods.
  • pharmacologically active substances include, for example: fluoride ion (anti caries) ; antimi crobial agents (antipl aque/anti gingivitis); antidepressants; antifungals; antihypertensives; pain remedies, and the like, where gradual, prolonged release is beneficial.
  • organic water soluble polymers used in the present invention comprise water soluble amine-substituted vinyl monomer units.
  • the average molecular weight of the amine-substituted polymer should be at least about 2,000. Typically the number molecular weight will range from about 2,000 to about 1,000,000, preferably average from about 20,000 to about 200,000, more preferably from about 75,000 to about 150,000. Without intending to necessarily limit the invention, it is believed that increasing molecular weight, with other factors being constant, will slow dissolution and increase gel strength.
  • Preferred starting monomers for polymerization to form amine-substituted vinyl polymers include vinyl compounds of the general formula:
  • R 1 is hydrogen or an alkyl, preferably hydrogen or a short chain alkyl, e.g., C 1 -C 5 alkyl; and R 2 is a moiety having an amine functionality.
  • R 2 moieties are:
  • R 2 - C-O-R 3 -N-(R 4 ) 2 ;
  • R 2 - C-NH-R 5 -N-(R 6 ) 2 ;
  • R 3 and R 5 are alkyls, preferably short chain alkyls, more preferably C 2 -C 7 alkyls; and each R 4 and R 6 are, independently, hydrogen or alkyls, preferably short chain alkyls such as C 1 -C 7 alkyls.
  • each of the R 4 or R 6 alkyl moieties can be different chain length alkyls.
  • Suitable starting monomers include dialkylaminoalkyl acryl ate, dialkyl aminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkyl aminoalkyl methacryl amide, wherein the alkyl groups are preferably 1 to 7 carbon alkyls, more preferably 1 to 3 carbon alkyls.
  • the preferred polymers will comprise vinyl monomeric units of the formula:
  • R 1 is as defined above and R 1 is
  • R 3 , R 4 , R 5 , and R 6 are as defined above.
  • Free radical polymerization is preferred. Suitable free radical polymerization processes include solution polymerization.
  • a variety of free radical initiators can be used. e.g., azo compounds, peroxides, persulfates, redox couples, etc.
  • Polymerization of acrylamide monomers for example is discussed in Encyclopedia of Polymer Science and Engineering, Vol. 1, John Wiley & Sons, Inc. (1985) at pages 176-186, incorporated by reference herein. Polymerization of acryl ates can be performed utilizing free radical polymerizaton, although polymerization of the acrylamide or amino-substituted acryl ates is preferred.
  • the amine-substituted monomers can be co-, ter-, etc. polymerized with spacer monomers.
  • the spacer monomer chosen should be of a type and used in an amount such that the polymer is water soluble. Also the spacer monomer used should readily polymerize with the amine-substituted monomer.
  • Exemplary spacer monomers include, but are not limited to, acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, and N-vinyl pyrrol idone.
  • the alkyl and dialkyl substituted monomers preferably have C 1 -C 7 alkyl groups, more preferably C 1 -C 3 alkyl groups.
  • the amine-substituted polymers hereof can be copolymers, terpolymers, etc. which have amine-substituted vinyl monomer units, non-amine-substituted vinyl units, as well as other monomer units.
  • exemplary copolymers include copolymers of the above starting amine-substituted monomers with acrylamides, such as, but not limited to, acrylamide and dimethylacrylamide, and vinyl monomers such as, but not limited to, N-vinylpyrrolidinone.
  • the polymer product will have at least about 25% of the amine-substituted vinyl monomer units on a molar basis, more preferably at least about 50%, most preferably at least about 75%, and can comprise up to and including 100% of the amine-substituted vinyl monomer units. It is believed that reduced levels of substitution results in compositions having lower degrees of cohesion, water insolubility, and in-use periods of effectiveness for bioadhesive applications (e.g., denture adhesives).
  • Suitable methods include free radical polymerization processes such as solution polymerization and are described, for example, in Principles of Polymerization , 2nd edition, George Odian, John Wiley & Sons, Inc. (NY, 1981) pp 179-318 and 423-507, and Encyclopedia of Polymer Science and Engineering, 2nd edition, executive editor Jacqueline Kroschwitz, Volume 13, pp 708-867, "Radical Polymerization", John Wiley & Sons, Inc. (New York, 1988), each of which are incorporated herein by reference.
  • amine-substituted organic polymers useful for the present invention include, but are not necessarily limited to, GAF Corp. (New Jersey, U.S.A.) for their GAF series of copolymers of vinylpyrrolidone and dimethyl aminoethyl methacrylate.
  • amine-substituted polymer Slow dissolution of the amine-substituted polymer may be disadvantageous in certain applications wherein the polymer can be washed away prior to gel formation (e.g., in a powder dentur adhesive composition formul ated for in situ formation of the gel in the mouth of the user). Under circumstances wherein increase gel strength is nevertheless desired, the amine-substitute polymer can be pre-hydrated to facilitate fast dissolution and gel formation.
  • the acidic organic adhesive polymers used in the practice of this invention can be any of the tacky or pressure-adherent gums, resins, polymers, and the like, both synthetic and naturally- occurring, which are well known for their adherent properties.
  • the selection of acceptable adhesives for use in sealing/adhering dentures to oral tissues is readily made by referring to the above-noted patents, or to standard texts.
  • the adhesive will comprise from about 10% to about 90% by weight of the compositions herein.
  • acidic adhesive polymers useful in the practice of the present invention: alkyl vinyl ether-maleic anhydride or -maleic acid copolymers, polyacrylic acid, polymethacrylic acid, salts thereof, and combinations thereof.
  • Suitable salts include, but are not limited to, inorganic salts such as metal salts (e.g., sodium, zinc, calcium, strontium) and ammonium.
  • the salt form of the polymer should remain soluble in the polar solvent to be used.
  • Preferred are alkyl vinyl ether-maleic acid copolymers.
  • a particularly preferred adhesive polymer herein is GANTREZ Resin (TM GAF Corporation, N.J.) which can comprise a poly(lower alkyl vinyl ether/maleic acid and anhydride) material; See GANTREZ AN Tech. Bulletin 7543-017.
  • the acid form of the maleic monomer of the copolymer, and salts thereof, is preferred for use herein for reason of better solubility in polar solvent.
  • the lower alkyl vinyl ether-maleic anhydride and acid (GANTREZ-type) copolymers are readily obtained by copolymerizing a lower alkyl vinyl ether monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether and isobutyl vinyl ether, with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer, which is readily hydrolyzable to an acid copolymer.
  • a lower alkyl vinyl ether monomer such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether and isobutyl vinyl ether
  • maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer, which is readily hydrolyzable to an acid copolymer.
  • Both anhydride and acid forms are also available from commercial suppliers.
  • GANTREZ S Series the polymeric free acid form
  • GANTREZ AN Series the polymeric free acid form
  • GANTREZ S Series the polymeric free acid form
  • GANTREZ AN Series the polymeric free acid form
  • Said acid and anhydride forms of such copolymers have an average molecular weight of from about 50,000 to about 80,000 (as measured by membrane osmometry in
  • the anhydride form which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elevated temperatures may be advantageously employed to enhance the rate of anhydride-to-acid hydrolysis.
  • GANTREZ materials and their use for preparing denture adhesives are described in detail in U.S. Patent 3,003,988 (Oct. 10, 1961) and EPO 0,265,916, filed October 27, 1987, to Shah, Gounaris and Holeva, incorporated herein by reference. Detailed disclosure regarding the use of this adhesive in the manner of the present invention is also provided hereinafter.
  • Mixtures of GANTREZ with other materials, especially carboxymethyl cellulose generally, at a weight ratio GANTREZ:CMC in the range of 5:1 to 1:5) is especially preferred.
  • the salts of GANTREZ can also be used herein. These can be prepared by dissolving the acidic GANTREZ polymer in water and neutralizing it with the appropriate bases.
  • the desired salts in a form suitable for use as denture adhesives advantageously can be prepared by reacting the alkyl vinyl ether and maleic anhydride used to make GANTREZ and the bases in a slurry in a mixture of a lower aliphatic alcohol and water.
  • this process utilizes smaller amounts of liquid medium than other processes and permits separation of the salts by relatively simple procedures. This permits savings. Additionally the improved process avoids the use of excessive amounts of cation materials and consistently produces the desired GANTREZ-type salts with the requisite physical characteristics and properties.
  • a slurry is prepared of a suitable lower alkyl vinyl ether-maleic anhydride copolymer in a lower aliphatic alcohol (i.e., containing less than 5 carbon atoms).
  • Calcium cations preferably in the form of calcium hydroxide (Ca(OH) 2 )
  • An aqueous solution containing the amount of the particular alkali metal cation preferably by solution of the particular hydroxide [e.g., NaOH] in water
  • the particular hydroxide e.g., NaOH
  • the overall alcohol-water ratio after addition of the aqueous alkali cation solution, should be between 60:40 to 80:20 with a 70:30 ratio by volume preferred.
  • the resulting slurry is heated with stirring until the pH levels off near neutrality.
  • the resulting mass is then filtered, dried and ground.
  • the resulting product consists essentially of the particular mixed calcium-alkali partial salt of the partial ester of the copolymer.
  • the alcohol in a preferred embodiment of the process, is isopropyl alcohol and the ratio of alcohol to water is between 60:40 and 80:20 by volume, with the preferred ratio about 70:30.
  • a higher water content causes coagulation of the slurry, while a substantially lower water content provides an adhesive having an apparent bulk density below about 0.5 gram per cubic centimeter.
  • Denture-adhesive characteristics of the mixed salts of the GANTREZ seem to depend on their apparent bulk densities, with the lower apparent bulk densities providing inferior adhesive characteristics. Bulk densities higher than 0.7 gram per cubic centimeter are preferred. A significant decrease in adhesive characteristics is obtained with apparent bulk densities less than 0.5 gram per cubic centimeter.
  • Slurry temperatures should not exceed about 60oC.
  • the preferred and optimum slurry temperature is less than 50o, and is generally from 40o to 50oC. While lower slurry temperatures are operable, an increase in reaction time is required.
  • Cations utilized in the processes for preparation of the partial, mixed salts of the invention may be provided by a number of various materials.
  • the cations are obtained from compounds which contain the particular cations and are at least soluble in part in water, and, more particularly, from the more common salts or hydroxides containing the particular cations.
  • Salts and alkalis which are particularly suitable are those that are completely soluble or soluble to a significant degree in water, or water-alcohol mixtures.
  • Suitable compounds include calcium hydroxide, calcium acetate, calcium halides, calcium lactate, calcium gluconate, sodium hydroxide, sodium acetate, sodium carbonate, sodium halides, sodium potassium carbonate, sodium sulfate, potassium hydroxide, potassium halides, quaternary ammonium hydroxides, etc.
  • the compounds used should be substantially pure to assure obtaining pure, white or colorless, partial, mixed salts. Salts having anions that form toxic or irritating by-products should be avoided, or special precautions and treatment provided to assure the removal and absence of such by-products from the partial, mixed salt product. Some byproducts in various amounts may be tolerated without a detrimental effect on the stabilizing properties and characteristics of the mixed, partial salt.
  • the GANTREZ-type resin is used, in this embodiment, in the form of its mixed calcium/alkali metal salt.
  • These mixed, partial salts have a pH within the range of 5 to 8.5, with those having a pH between 6 and 7 preferred.
  • the mixed, partial salts are frangible so that appropriate particle size and bulk density can be obtained.
  • the particles should be capable of passage through a 150-mesh sieve (U.S.B.S. series) and preferably are less than 0.74 millimeter in their largest dimension.
  • These salts consist of mixed, partial salts containing calcium cations and alkali cations selected from the group consisting of sodium, potassium, and quaternary ammonium cations at an equivalent ratio of calcium cations to the alkali cations in the mixed salts in the range from 2:1 to 10:1 and preferably between 3:1 and 7:1 (on a mole ratio basis, the range of calcium to alkali cations is from 1:1 to 5:1).
  • the sum total of cations in the partial, mixed salt should be sufficient to give a neutralization of from 0.5 to 0.95 and preferably 0.7 to 0.9 of the total initial carboxyl groups in the GANTREZ-type copolymer.
  • the GANTREZ adhesives include mixed salts of the specific copolymers that have less than about one-third of the total initial carboxyl groups esterified.
  • the total initial carboxyl groups neutralized by salt formation, or by salt formation and esterification do not exceed 95% of the total of the initial carboxyl groups of the specific copolymer.
  • the mixed salts of copolymers containing about 5% to 15% of the total initial carboxyl groups as unreacted acid groups, rather than salts or esters thereof, provide particularly superior properties in the practice of this invention.
  • a reaction kettle is charged with 825 parts of anhydrous isopropyl alcohol.
  • 234 parts of a methyl vinyl ether-maleic anhydride copolymer (PVM/MA), naving a specific viscosity of between 2.5 and 3.5, and 66.6 parts of calcium hydroxide are added to the isopropyl alcohol slowly, with good agitation, to form a slurry.
  • PVM/MA methyl vinyl ether-maleic anhydride copolymer
  • naving a specific viscosity of between 2.5 and 3.5
  • 66.6 parts of calcium hydroxide are added to the isopropyl alcohol slowly, with good agitation, to form a slurry.
  • the resulting slurry has an isopropyl alcohol-to-water ratio of from 70:30% by volume.
  • the resulting slurry is heated to a temperature of about 45oC and held at this temperature until the pH of the slurry levels off at about 6.6 (approximately 1-1/2 hours).
  • the slurry is then cooled to room temperature and filtered.
  • the filter cake is dried in an air-circulating oven at
  • a white powder consisting essentially of the calcium-sodium partial salt of an isopropyl partial ester of the methyl vinyl ether-maleic anhydride copolymer with a calcium-to-sodium equivalent ratio of 0.6:0.1 per initial carboxyl group in the copolymer and with the balance of the initial carboxyl groups present as unreacted acid and isopropyl ester groups.
  • the product is an apparent bulk density of 0.80 gram per cubic centimeter and, at a concentration of 1% by weight in water, has a pH of 6.7.
  • cations other than Ca/Na can be used advantageously to prepare the GANTREZ-type adhesive.
  • zinc (preferred) and strontium salts of alkyl vinyl ether (AVE)-maleic acid copolymers(MA) such as GANTREZ can be used. See U.S. Patent 4,758,630; July 19, 1988 to Shah, Gounaris and Holeva.
  • Such polymeric salts are advantageously prepared by the interaction of the AVE/MA copolymer with a cationic zinc or strontium compound, such as, for example, the hydroxide, acetate, halide, lactate, etc., salts, in an aqueous medium.
  • a cationic zinc or strontium compound such as, for example, the hydroxide, acetate, halide, lactate, etc., salts
  • a cationic zinc or strontium compound such as, for example, the hydroxide, acetate, halide, lactate, etc.
  • a cationic zinc or strontium compound such as, for example, the hydroxide, acetate, halide, lactate, etc.
  • strontium compound such as, for example, the hydroxide, acetate, halide, lactate, etc.
  • anions that form toxic, irritating or contaminating by-products should be avoided, or special precautions and treatment provided to assure the removal and absence of such by-products from the polymeric salt end-product.
  • the particular compound used should be substantially pure to assure obtaining a substantially pure, substantially white or off-white polymeric salt end-product.
  • the lower AVE/MA copolymer, or its corresponding anhydride is added to water preheated to about 70-80oC with vigorous stirring to form a homogeneous mixture. If the anhydride precursor is utilized, it is recommended that the aqueous mixture be further heated to about 90oC with stirring to ensure complete hydrolysis of the anhydride to the acid form. Heating is then discontinued although mixing is continued until the batch turns clear with a simultaneous decrease in viscosity (about 65-75oC).
  • An aqueous solution of the cationic zinc or strontium salt forming compound, or, for example, an aqueous dispersion of particulate zinc oxide in the form of a slurry, in an amount sufficient to provide the desired cationic content desired in the end-product, is separately prepared at ambient temperature and slowly added to the hot polymeric acid solution with continuous vigorous mixing so as to prevent localized precipitation of the cationic polymeric salt. After addition is complete, mixing is continued to ensure that all the salt forming compound i s reacted with the copolymer.
  • the sum total of zinc or strontium cations in the resultant unmixed partial salts of AVE/MA copolymers should be sufficient to give a neutralization of from about 10 to about 60% and preferably from about 40 to about 50% of the total initial carboxyl groups in the copolymer.
  • reaction batch is then transferred to shallow drying trays in a convection oven maintained at about 70oC with hot air circulation to evaporate the water content and recover the polymeric salt product in dry form.
  • reaction solution may be treated according to conventional purification methodology to remove or minimize any contaminants occasioned by anionic functions in the aforementioned cationic zinc or strontium salt-forming compound.
  • the resultant product which consists essentially of the particular zinc or strontium unmixed partial salt of the AVE/MA copolymer, is then ground or milled to the desired mesh size for providing the satisfactory denture-adhering properties.
  • Said salts are frangible so that appropriate particle size and bulk density can be obtained.
  • particles should be capable of passage through a 140- to 20-mesh sieve (0.105 to 0.074 mm sieve opening) (U.S.B.S. series) and preferably are less than 0.074 mm in their largest dimension.
  • the zinc and strontium GANTREZ-type AVE/MA copolymer salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materials.
  • the salt in particulate form is preferably characterized by a particle size of at least 140-mesh U.S.B.S. sieve; a bulk density greater than 0.5 gram per cubic centimeter and preferably higher than 0.7 gram per cubic centimeter; and a pH between 3 and 4.7, the pH being determined on a 1% by weight dispersion in water.
  • the resultant solution of the zinc salt of methyl vinyl ether-maleic acid (MVE/MA) copolymer is then transferred to shallow stainless steel drying trays and the trays placed in a hot air convection oven at 70oC for a sufficient time to evaporate the water content (about 16-18 hours).
  • the dried zinc MVE/MA copolymer salt is then ground in a milling apparatus and screened through a 140-mesh sieve and then through a 200-mesh sieve (U.S.B.S. sieve series).
  • the powder has an apparent bulk density of about 0.9-1.1 gram per cubic centimeter, and a pH of 4.6 for a 1% solution in water.
  • the salt has about 50% neutralization (with zinc) of the total initial carboxyl groups in the original copolymeric salt molecule.
  • the adhesive compositions of the present invention comprise, as described above, from about 10% to about 90% of the acidic organic adhesive polymer, from about 10% to about 90% of the organic amine-substituted polymer, and from 0% to about 80% of a pharmaceutically acceptable carrier or adjunct materials.
  • the weight ratio of acidic organic adhesive polymer to amine-substituted polymer should be from about 9:1 to about 1:9, preferably from about 5:1 to about 1:5, more preferably from about 4:1 to about 1:1.
  • the preferred compositions will compris poly(alkyl vinyl ether-maleic acid) copolymer (or salts thereof) as the organic adhesive polymer and an amine-substituted vinyl polymer as in Formula I, or co-, ter-, etc.
  • compositions preferably having a degree of amine substitution of at least about 25%, more preferably at least about 50%, most preferably at least about 75%, and will have a molecular weight of from about 20,000 to about 200,000, preferably about 75,000 to about 150,000.
  • these compositions are characterized by having a Gel Volume (as determined according to the following procedure) of between about 0.5 and about 10.0 g water/g acidic organic adhesive polymer and amine-substituted polymer (combined), preferably from about 0.5 to about 4.0 g/g, more preferably from about 1.0 to about 3.0 g/g.
  • the preferred and more preferred Gel Volumes are especially desirable for bioadhesive applications such as, but not limited to, denture adhesives.
  • the above percentages of acidic organic adhesive polymer, organic amine-substituted polymer, and optional carrier and adjunct material are calculated on a weight basis exclusive of water or other polar solvent.
  • This invention also encompasses the gel compositions comprising the above amine-substituted polymers and acidic organic adhesive polymers, and optional carriers and adjunct materials in the above ranges on a weight basis exclusive of water or other polar solvent, and from about 0.5 g water or other polar solvent/g polymer (combined) to about 10.0 g water or other polar solvent/g polymer (combined), preferably from about 0.5 g/g to about 4.0 g/g, more preferably from about 1.0 g/g to about 3.0 g/g. Water is the preferred polar solvent. Additionally, it is not meant to exclude from the scope of this invention gels made from the amine-substituted and acidic organic adhesive polymers hereof and polar solvents other than water. Other suitable polar solvents include, but are not limited to, methanol, ethanol, and propanol.
  • compositions of this invention can contain pharmaceutically acceptable carriers and adjunct materials.
  • the compositions can be provided to the user in the form of powder, paste, or gel.
  • Powders preferably comprise an intimate mixture of the amine-substituted and acidic adhesive polymers.
  • the powders can be first hydrated with water or otherwise formed into a gel with another polar solvent and then used. Alternately, the powder can be applied directly to a surface, which is to be adhered to tissue, such as a denture, and be subsequently hydrated after being placed into position, such as in the oral cavity, where sufficient water is present to hydrate the composition to form the gel.
  • Gels comprise the polymers, as described above, and water or other polar solvent.
  • Pastes can be formed by including a carrier such as mineral oil, petrolatum, or other paste-forming carriers known in the art.
  • the pastes can be hydrated or otherwise formed into contact with the gel before or after contact with the surface or surfaces to which it is to adhere.
  • Adjunct materials included will depend upon the intended use of the composition, and can include any compatible pharmacologically active compounds for delivery to human or animal tissue, e.g., delivery to the oral cavity or the skin.
  • Such pharmacologically active substances include, for example: fluoride ion (anticaries); antimicrobial, agents (antiplaque/antigingivitis); antidepressants; antifungals; antihypertensives; pain remedies, and the like, where gradual, prolonged release is beneficial.
  • the invention also provides adhesive tape comprising an adherent amount of the adhesive polymer compositions hereof on a solid backing material, such as a textile fabric or thermoplastic film, as are well known in the art.
  • An adherent medical dressing comprises such tape, in combination with an absorbent material to imbibe blood or other body fluids.
  • Gel Volume for the compositions of the present invention is calculated as the ratio of grams of distilled water absorbed per gram of gel-forming polymers (combination of acidic organic adhesive and the amine-substituted polymer, dry weight basis).
  • a known amount of the gel-forming polymers is mixed in a beaker with an excess of distilled water and allowed to swell for a period of 24 hours with gentle stirring.
  • An excess of distilled water will vary dependent upon the Gel Volume of sample, but ten to twelve times the weight of the gel-forming polymers will typically provide an excess of distilled water for the compositions of the present invention.
  • the polymer gel is removed from the excess distilled water.
  • the tea bag utilized should be grade 1234, obtainable from C. H. Dexter Division of the Dexter Corp., Windsor Locks, Connecticut, USA, or equivalent.
  • the sample is then weighed.
  • the polymer gel is then dried to completion under reduced pressure in an environment having no greater than 6.0% relative humidity and again weighed.
  • Gel Volume is calculated by dividing the difference between the polymer gel weight and the dried polymer gel weight by the weight of the dried polymer gel.
  • This example exemplifies production of amine-substituted vinyl polymer which is suitable for use in the adhesive compositions of the present invention.
  • a 250 ml roundbottom flask is charged with 100.0 ml of degassed toluene. 30.0 g of N,N-dimethylaminoethyl methacrylate and 0.3 g of azoisobutylnitrile are also added to the flask and the contents are mixed. The flask is then purged with nitrogen gas, to remove ambient air, and sealed. The contents of the flask are next heated at 65oC for 30 hours. A viscous reaction product containing poly (N,N-dimethylaminoethyl methacrylate) forms. The reaction product is stripped under vacuum to remove the solvent
  • a denture adhesive composition in dry powder form is prepared by admixing the GANTREZ-adhesive (Ca/Na) prepared in the above- described manner with the poly(N,N-dimethylaminoethyl methacrylate) prepared in the above-described manner, at a weight ratio of GANTREZ: amine-substituted polymer (solids) of about 3:1 to about 4:1.
  • the above powder typically 2-10 g
  • a premoistened denture typically 2-10 g
  • the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
  • the powder denture adhesive composition of Example I is modified by blending it with mineral-oil/petrolatum to provide a denture paste.
  • a typical composition is as follows:
  • the paste is placed on a premoistened denture.
  • a denture adhesive is prepared in the manner of Example I, using a 1:1 mixture (solids basis) of a mixed Ca/Na salt of GANTREZ Adhesive (Ca/Na) and organic amine-substituted polymer of
  • Example I Aqueous dispersions of the polymers are then mixed and freeze-dried. Alternately, the mixture can be drum-dried. After freeze-drying, the composition can be used in powder form or, optionally, blended with oleaginous materials to form a paste. The paste can be packaged in a tube or pump, of the type used with dentifrices.
  • the GANTREZ adhesive and amine-substituted polymer can be mixed together and ground, such as with a mortal and pedestal in the laboratory (or, for example, by using pinmills or hammermills on an industrial scale) to form a powder.
  • the powder can then be used directly or formed into a paste, as described above.
  • a denture adhesive comprises a freeze-dried or drum-dried mixture, as follows.
  • An improved denture adhesive comprises the following:
  • An adhesive suitable for use on tapes, envelope flaps, stamps, and the like comprises a 1:1:1 mixture (by weight of solids) of Ca/Na GANTREZ: organic amine-substituted polymer (of Example I):gelatin.
  • the adhesives of the above-disclosed type can be affixed to bandages, catamenials, or other absorbent structures to provide self-adhering medical dressings.
  • the adhesives can also be used to deliver pharmacologically active agents to the oral tissues.
  • the ingredients are dry-blended, then moistened to provide a
  • This example exemplifies production of an amine-substituted vinyl co-polymer having a degree of amine-substitution of about 60 mole percent suitable for use in the adhesive compositions of the present invention.
  • a 250 ml roundbottom flask is charged with 100.0 ml of degassed water.
  • 25.3 g (0.15 moles) of N, N-dimethylaminopropyl methacryl amide, 9.9 g (0.1 moles) of N, N-dimethy ⁇ acryl amide, and 0.35 g of 2,2'-azobis (2-amidinopropane) dihydrochloride (1.0% aqueous solution) are then added to the flask and the contents are mixed.
  • the flask is purged with nitrogen gas, to remove ambient air, and sealed.
  • the contents of the flask are heated at 65°C for 30 hours.
  • a viscous reaction product containing poly (N, N-dimethylaminopropyl methacryl amide- co- N,N-dimethyl acrylamide) forms.
  • the reaction product is dried under vacuum and ground into a fine powder and then admixed with GANTREZ adhesive and formulated as in Examples I through VII.
  • Higher mole percentages of amine-substituted polymer can be obtained by increasing the starting N,N-dimethyl aminopropyl-methacryl amide:N,N-dimethyl - acrylamide molar ratio.
  • the product will typically have about 60 mole % dimethyl aminopropyl methacryl amide monomeric units.
  • Number average molecular weight as determined by Gel Permeation Chromatography (GPC) analyses, will typically be about 150,000.
  • Confirmation of the mole percent N-dimethyl aminopropyl-methacryl- amide monomeric units in the polymer can be obtained by Infra-red (IR) and Nuclear Magnetic Resonance (NMR) analysis.
  • IR Infra-red
  • NMR Nuclear Magnetic Resonance

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  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dental Preparations (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

On utilise un polymère vinylique à substitution amine afin d'améliorer les propriétés de rendement de certains adhésifs. Des adhésifs tels que des acides alkyle vinyle éther/maléique ainsi que divers autres adhésifs polymères présentent des propriétés de maintien améliorées lorsqu'on les combine avec le polymère à substitution amine, notamment en présence d'humidité. L'invention concerne également des bioadhésifs améliorés, par exemple, des adhésifs dentaires.
PCT/US1991/001553 1990-03-29 1991-03-07 Composition adhesive a polymere adhesif organique acide et a polymere a substitution amine WO1991014733A1 (fr)

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FI924337A FI924337A (fi) 1990-03-29 1992-09-28 Smittaemneskomposition med sur, organisk adhesiv polymer och aminsubstituerad polymer

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US501,642 1990-03-29

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CA (1) CA2076389A1 (fr)
FI (1) FI924337A (fr)
IE (1) IE911055A1 (fr)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010988A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Composition servant a stabiliser une denture artificielle
WO1992010986A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Composition servant a la stabilisation d'une denture artificielle et presentant une tenue amelioree
WO1992010987A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Compositions servant a stabiliser une denture artificielle et offrant un gout ameliore
WO1993014737A1 (fr) * 1992-01-27 1993-08-05 The Procter & Gamble Company Compositions de stabilisation destinees a des dentiers
WO1996010976A1 (fr) 1994-10-07 1996-04-18 The Procter & Gamble Company Article hygienique absorbant
WO1997026864A2 (fr) * 1996-01-26 1997-07-31 Brown University Research Foundation Procedes et compositions permettant de renforcer les proprietes bioadhesives de polymeres
US6232250B1 (en) 1993-06-04 2001-05-15 The Procter & Gamble Company Absorbent article
US6368586B1 (en) 1996-01-26 2002-04-09 Brown University Research Foundation Methods and compositions for enhancing the bioadhesive properties of polymers
WO2007012859A2 (fr) * 2005-07-29 2007-02-01 Reckitt Benckiser (Uk) Limited Composition
WO2007012850A2 (fr) * 2005-07-29 2007-02-01 Reckitt Benckiser (Uk) Limited Composition

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US3868260A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868339A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868340A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868432A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US4504618A (en) * 1982-07-12 1985-03-12 Dulux Australia Ltd. Aqueous dispersions

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US4045517A (en) * 1975-11-24 1977-08-30 Rohm And Haas Company Polyacrylic hot melt adhesives
DE3274743D1 (en) * 1981-10-15 1987-01-29 Allied Colloids Ltd Adhesives for prepasted wallcoverings
JPS594666A (ja) * 1982-06-30 1984-01-11 Mitsubishi Petrochem Co Ltd 軟質ポリ塩化ビニル積層物の製造方法

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Publication number Priority date Publication date Assignee Title
US3868260A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868339A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868340A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US3868432A (en) * 1972-04-13 1975-02-25 Warner Lambert Co Denture adhesive preparation
US4504618A (en) * 1982-07-12 1985-03-12 Dulux Australia Ltd. Aqueous dispersions

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See also references of EP0521913A4 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010988A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Composition servant a stabiliser une denture artificielle
WO1992010986A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Composition servant a la stabilisation d'une denture artificielle et presentant une tenue amelioree
WO1992010987A1 (fr) * 1990-12-21 1992-07-09 Richardson-Vicks Inc. Compositions servant a stabiliser une denture artificielle et offrant un gout ameliore
TR25732A (tr) * 1990-12-21 1993-09-01 Richardson Vicks Inc Daha iyi tada sahip, protez dis stabilize edici terkipler
TR28678A (tr) * 1990-12-21 1997-01-17 Richardson Vicks Inc Daha iyi tutma özelligine sahip, protez dis stabilize edici terkipler.
WO1993014737A1 (fr) * 1992-01-27 1993-08-05 The Procter & Gamble Company Compositions de stabilisation destinees a des dentiers
US6232250B1 (en) 1993-06-04 2001-05-15 The Procter & Gamble Company Absorbent article
WO1996010976A1 (fr) 1994-10-07 1996-04-18 The Procter & Gamble Company Article hygienique absorbant
WO1997026864A3 (fr) * 1996-01-26 1997-10-09 Univ Brown Res Found Procedes et compositions permettant de renforcer les proprietes bioadhesives de polymeres
US5985312A (en) * 1996-01-26 1999-11-16 Brown University Research Foundation Methods and compositions for enhancing the bioadhesive properties of polymers
US6123965A (en) * 1996-01-26 2000-09-26 Brown University Research Foundation Methods and compositions for enhancing the bioadhesive properties of polymers
WO1997026864A2 (fr) * 1996-01-26 1997-07-31 Brown University Research Foundation Procedes et compositions permettant de renforcer les proprietes bioadhesives de polymeres
US6368586B1 (en) 1996-01-26 2002-04-09 Brown University Research Foundation Methods and compositions for enhancing the bioadhesive properties of polymers
WO2007012859A2 (fr) * 2005-07-29 2007-02-01 Reckitt Benckiser (Uk) Limited Composition
WO2007012850A2 (fr) * 2005-07-29 2007-02-01 Reckitt Benckiser (Uk) Limited Composition
WO2007012850A3 (fr) * 2005-07-29 2007-03-29 Reckitt Benckiser Uk Ltd Composition
WO2007012859A3 (fr) * 2005-07-29 2007-04-26 Reckitt Benckiser Uk Ltd Composition

Also Published As

Publication number Publication date
AU7469791A (en) 1991-10-21
CA2076389A1 (fr) 1991-09-30
FI924337A0 (fi) 1992-09-28
PT97174A (pt) 1991-11-29
FI924337A (fi) 1992-09-28
EP0521913A1 (fr) 1993-01-13
EP0521913A4 (en) 1993-08-04
IE911055A1 (en) 1991-10-09
NZ237621A (en) 1994-03-25

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