WO1998043595A1 - Compositions de stabilisation pour prothese dentaire - Google Patents

Compositions de stabilisation pour prothese dentaire Download PDF

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Publication number
WO1998043595A1
WO1998043595A1 PCT/IB1998/000443 IB9800443W WO9843595A1 WO 1998043595 A1 WO1998043595 A1 WO 1998043595A1 IB 9800443 W IB9800443 W IB 9800443W WO 9843595 A1 WO9843595 A1 WO 9843595A1
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WIPO (PCT)
Prior art keywords
copolymer
adhesive composition
composition according
denture adhesive
partial salt
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PCT/IB1998/000443
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English (en)
Inventor
Nong Liang
Jayanth Rajaiah
Kimberly Ann Gilday-Weber
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The Procter & Gamble Company
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Publication date
Priority claimed from US08/835,040 external-priority patent/US5872160A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP54133698A priority Critical patent/JP2001517125A/ja
Publication of WO1998043595A1 publication Critical patent/WO1998043595A1/fr

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    • 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

Definitions

  • Denture adhesives or stabilizers are used to provide a cushion or gasket between the denture and the gums or tissues and to fill the interstices between the dentures and the gums or tissues.
  • Lower alkyl vinyl ether-maleic copolymers and salts thereof are known in the art for use in denture adhesive compositions. Such disclosures include: U.S. Patent 3,003,988 to German et al., issued October 10, 1961; U.S. Patent 4,980,391 to Kumar et al., issued December 25, 1990; U.S. Patent 5,073,604 to Holeva et al., issued December 17, 1991; and U.S. Patent 5,525,652 to Clarke, issued June 11, 1996.
  • denture adhesive compositions comprising partial salts of lower alkyl vinyl ether-maleic acid copolymers lightly crosslinked covalently with an organic crosslinker, and optionally a non-adhesive self-supporting layer, provide superior denture stability and retention over a significantly longer period of time versus conventional denture adhesives.
  • the compositions exhibit higher resistance to salivary washout while maintaining the same or better denture hold as conventional denture adhesives. This added resistance to salivary washout translates to longer denture hold and stability.
  • the present invention relates to a denture adhesive composition
  • a denture adhesive composition comprising a partial salt of a lower alkyl vinyl ether-maleic acid copolymer, the partial salt copolymer comprising carboxyl groups, of which from about 50% to about 95% are neutralized by one or more metal cations; wherein the partial salt copolymer is covalently crosslinked with an organic crosslinker and wherein the molar ratio of organic crosslinker to carboxyl groups, prior to neutralization by the metal cations, is from about 0.1% to about 30%.
  • These compositions may optionally comprise at least one non-adhesive self-supporting layer.
  • the denture adhesive compositions of the present invention comprise a partial salt of a lower alkyl vinyl ether-maleic acid copolymer covalently crosslinked with an organic crosslinker.
  • the adhesive compositions may in the form of a powder which is sprinkled on a dental prosthesis, moistened and then inserted into the oral cavity.
  • the compositions may be combined with various conventional delivery vehicles to form liquids or pastes which are applied to a dental prosthesis and inserted into the oral cavity.
  • compositions may also comprise a non-adhesive self-supporting layer.
  • These adhesive compositions are thoroughly moistened and applied to dentures.
  • the attachment of the adhesive component to the non-adhesive self-supporting layer provides a composition which is peeled from the dentures upon their removal.
  • a detailed description of essential and optional components of the present invention is given below. Partial Salt of a Lower Alkyl Vinyl Ether-Maleic Acid Copolymer
  • the lower alkyl vinyl ether-maleic acid (“AVE/MA”) copolymer consists essentially of the repeated structural unit:
  • n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer.
  • n is large enough such that the specific viscosity of the copolymer is larger than 1.2, the specific viscosity being determined in methyl ether ketone at 25°C.
  • Lower alkyl vinyl ether maleic polymers are readily obtained by copolymerizing a lower alkyl vinyl ether monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether, isobutyl vinyl ether and the like, with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer which is readily hydrolyzable to the acid copolymer.
  • the resulting copolymer is a 1:1 copolymer.
  • Both anhydride and acid forms are also available from commercial suppliers. For example, ISP Technologies Inc.
  • the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is formed.
  • 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.
  • the anhydride form of copolymer is particularly useful in this invention.
  • the said covalent crosslinking occurs through opening the anhydride with an organic crosslinker.
  • the acid form of the copolymer can be converted back to the anhydride form at elevated temperature and upon removal of water from the polymer.
  • the lower alkyl vinyl ether-maleic ("AVE/M”) polymers useful in the present invention are partial copolymer salts.
  • the partial salt form of the copolymer comprises at least one type of metal cations which are available for neutralization of the carboxylic acid groups of the copolymer.
  • Suitable metal cations may be monovalent, polyvalent (i.e., divalent and trivalent metal cations) or mixtures thereof.
  • Such metal cations include calcium, sodium, magnesium, potassium, ammonium, zinc, strontium, aluminum, iron, and mixtures thereof.
  • Preferred are zinc, strontium, magnesium, iron, aluminum, calcium, and sodium, and mixtures thereof. Most preferred are zinc, iron and calcium.
  • Partial salts of lower alkyl vinyl ether-maleic acid polymers are also described in U.S. Patent 5,073,604 to Holeva et al., issued 12/17/91; U.S. Patent 4,980,391 to Kumar et al., issued 12/25/90; and U.S. Patent 5,525,652 to Clarke, issued 6/11/96; all of which are incorporated herein by reference.
  • the copolymer salts may be mixed or unmixed or both.
  • unmixed polymer salts refers to salts of lower alkyl vinyl ether-maleic polymers wherein the cations are unmixed with any other ester functions or nonidentical cations on the same polymer, the remaining carboxyl groups being unreacted.
  • mixed polymer salts refers to salts of the lower alkyl vinyl ether-maleic polymers where different cations are mixed on the same polymer with each other or with other ester functions. Preferred are mixed polymer salts containing zinc and calcium cations.
  • the salt form of the subject copolymers can be prepared by the interaction of the AVE/M anhydride polymer with at least one type of metal cation, such as zinc, strontium, calcium, sodium, magnesium, potassium, aluminum, iron, or ammonium compounds having a functional group typical of reactants of a carboxylic acid; such as, for example, the hydroxide, acetate, halide, lactate, etc. in an aqueous medium.
  • the oxide of zinc, the hydroxide of calcium and the sulfate of iron are utilized. Since zinc hydroxide is not commercially available, its use as a reactant is readily and more economically accomplished by employing an aqueous slurry of particular zinc oxide which, although practically insoluble in water, provides hydration to zinc hydroxide on the paniculate surface.
  • the sum total of metal cations in the resultant partial salt of AVE/M copolymers should be sufficient to give a neutralization ranging from about 0.1% to about 75% of the metal cations selected from the group consisting of aluminum, iron, zinc, strontium, calcium, sodium, magnesium, potassium, ammonium, and mixtures thereof.
  • the resulting partial copolymer salts contain free acid in the range of from about 5% to about 50%.
  • Preferred partial copolymer salts comprise zinc from about 10% to about 65%, preferably from about 5% to about 45%, and most preferably from about 10% to about 30%, of the initial carboxyl groups reacted; and calcium from about 10% to about 75%, preferably from about 25% to about 60%, and most preferably from about 40% to about 60%, of the total initial carboxyl groups reacted. Also preferred are partial copolymer salts comprising iron from 0.1% to about 10%, preferably from about 0.5% to about 5%, and most preferably from about 0.5% to about 3%, of the initial carboxyl groups reacted. Copolymer salts comprising sodium from about 1% to about 20%, preferably from about 1% to about 15%, and most preferably from about 1% to about 10%, of the total initial carboxyl groups reacted, are also preferred.
  • Cations 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 off-white copolymeric salt end-product.
  • the partial salt copolymers are utilized in the present composition in an amount of at least 10 percent and more preferably in amount of at least 20 percent, by weight of the adhesive composition.
  • the organic crosslinker is at least partially chemically incorporated by reaction with maleic anhydride moieties of the copolymer so that it is no longer in the free state and acts as a crosslinking group in the adhesive.
  • Suitable organic crosslinkers include polyols, polyamines, and compounds containing at least two mixed functional groups. Each of these classes of compounds has at least two functional group which are available to covalently crosslink with a carboxyl group of the copolymer, e.g. polyols, -hydroxyl; and polyamines, -primary or secondary amines.
  • Polyols suitable herein are organic molecules consisting essentially of carbon, hydrogen and oxygen and have two or more -OH groups. While a wide variety of polyols are useful herein, preferred polyols are diols, especially water-soluble diols. Preferred diols are selected from the group consisting of polyethylene glycol, alkane diols, polyethylene-polypropylene block copolymers, poloxamers, and the like. In more preferred embodiments, the polyol is a polyethylene glycol, (commonly known as "PEG”), which can have varying molecular weight. Polyethylene glycol has the formula HO(CH2CH2 ⁇ ) n H wherein n is greater than or equal to 4.
  • PEG compounds are commercially available under the trade name Carbowax and sold by Union Carbide, Carleston, West Virginia. Preferred embodiments of these materials are found in the commercial PEG series having average molecular weights of from about 200 to about 1000. More preferred are PEG having average molecular weights of from about 200 to about 600. PEG having average molecular weight of about 300 is most preferred for use herein.
  • Polyamine compounds suitable for use herein include primary or secondary polyamines, preferably diamines of C12-C18, such as polyoxyethylenated 1,12- dodecanediamine. Proportions of Components
  • the proportion of organic crosslinker to carboxyl groups of the partial salt copolymer is described herein in terms of the molar ratio of organic crosslinker functional groups to carboxyl groups of the partial copolymer salts. Therefore, when used herein, the percentages for "molar ratio of organic crosslinker” refer to molar ratio of organic crosslinker functional groups, which are available to covalently crosslink with the carboxyl groups of the partial copolymer salts prior to neutralization, the number of such functional groups then divided by two.
  • the molar ratio of organic crosslinker to carboxyl groups is from about 0.1% to about 30%, preferably from about 1% to about 20%, most preferably from about 2% to about 10%. Without being bound by theory, it is believed that the proportion of organic crosslinker to copolymer is very important for controlling the crosslink density in the present adhesive invention. The above-cited ranges take into account that maintaining a relatively constant, low crosslink density is preferred.
  • the low covalent crosslinking density, co-existing non-covalent crosslinking with polyvalent metal cations and moderate chain length of the organic crosslinker provide several physical properties which characterize the present invention.
  • the copolymers are water insoluble and exhibit limited water uptake while maintaining high adhesive tensile strength under washout in a modified commercial adhesive block test.
  • the adhesive copolymers form brittle flakes when dried.
  • the adhesive copolymers have no appreciable cohesive strength, (i.e., they do not form a highly cohesive mass, either in a dried form or after activation by moisture, which is moldable and/or peelable). They are easily ground to a fine powder form which can be activated by moisture and/or combined with conventional denture adhesive delivery vehicles to a desired product form.
  • the adhesive copolymers offer improved spreading and lubricity.
  • the present denture adhesive compositions may comprise at least one non- adhesive self-supporting layer.
  • the non-adhesive self-supporting layer is characterized by its ability to maintain strength and provide integrity for the adhesive composition in the presence of water and/or saliva.
  • the non-adhesive self-supporting layer may include such materials as polyester, polypropylene, nylon, rayon, polyethylene oxide, cellulose acetate, cellulose derivatives, cloth, fibrous fleece, paper, plastic, leather, microcrystaUine wax, synthetic fibers, natural fibers, and mixtures thereof.
  • Preferred are cellulose derivatives, polyester, polypropylene, nylon, rayon, cloth, paper, microcrystaUine wax, and mixtures thereof.
  • Most preferred are polyester, polypropylene, rayon, nylon, cloth and paper.
  • the non-adhesive self-supporting layer may be in any physical form suitable for providing strength and/or integrity to the present adhesive compositions. Such physical forms include non-woven, woven, continuous, chopped, and combinations thereof.
  • the non-adhesive self-supporting layer may be formed by any process commonly known in the art. Such processes include un-bonded, spraybonded, spun-bonded, needle-punched, carded, thermal bonded hydroentangled, meltblown, aperture print bonded, needled, wet-laid, dry-laid, and combinations thereof.
  • Other Adhesive Components include un-bonded, spraybonded, spun-bonded, needle-punched, carded, thermal bonded hydroentangled, meltblown, aperture print bonded, needled, wet-laid, dry-laid, and combinations thereof.
  • compositions may also include other adhesive components. These adhesive components, if present, are used in safe and adhesively effective amounts.
  • safe and adhesively effective amount means an amount sufficient to provide adherence of a dental prosthesis to the palate and ridge of the oral cavity without toxicity to the user, damage to oral tissue, and alteration of the denture material.
  • Suitable adhesive components include a water-soluble hydrophilic colloid or polymer having the property of swelling upon exposure to moisture to form a mucilaginous mass.
  • Such adhesive materials include natural gums, synthetic polymeric gums, adhesive materials commonly employed in denture stabilizing compositions and compatible with the subject AVE/MA copolymers, synthetic polymers, mucoadhesive polymers, hydrophilic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
  • Examples of such materials include karaya gum, guar gum, gelatin, algin, sodium alginate, tragacanth, chitosan, polyethylene glycol, acrylamide polymers, carbopol, polyvinyl alcohol, polyvinyl acetate, polyamines, polyquarternary compounds, polybutenes, silicones, ethylene oxide polymers, polyvinylpyrrolidone, cationic polyacrylamide polymers.
  • the organic crosslinker utilized in the formulation should not be included as an additional adhesive material in the same formulation.
  • cellulose derivatives such as methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose hydroxy- propylmethylcellulose, carboxymethylcellulose. Most preferred are carboxymethylcellulose and sodium carboxymethylcellulose.
  • the other adhesive components may be present at a level of from about 0% to about 70%, preferably from about 10% to about 50%, and most preferably from about 20% to about 40%, by weight of the composition.
  • Plasticizers that may be used in the present compositions include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, glycerin, diethylene glycol, triethylene glycol, Igepal, Gafac, sorbitol, tricresyl phosphate, dimethyl sebacate, ethyl glycolate, ethylphthalyl ethyl glycolate, o- and p-toluene ethyl sulfonamide, and mixtures thereof. Plasticizers may be present at a level of from about 0% to about 70%, preferably from about 0.1% to about 30%, by weight of the compositions.
  • the denture adhesive compositions may also be used as a denture adhesive and/or bioadhesive and comprise one or more therapeutic actives suitable for mucosal or topical administration.
  • suitable for mucosal or topical administration describes agents which are pharmacologically active when absorbed through internal mucosal surfaces of the body such as the oral cavity, or applied to the surfaces of the skin.
  • Therapeutic actives may be present at a level of from about 0% to about 70%, by weight of the composition.
  • Therapeutic actives that are useful in these compositions include antimicrobial agents such as iodine, sulfonamides, bisbiguanides, or phenolics; antibiotics such as tetracycline, neomycin, kanamycin, metronidazole, or clindamycin; anti-inflammatory agents such as aspirin, acetaminophen, naproxen and its salts, ibuprofen, ketorolac, flurbiprofen, indomethacin, cimetidine, eugenol, or hydrocortisone; dentinal desensitizing agents such as potassium nitrate, strontium chloride or sodium fluoride; anesthetic agents such as lidocaine or benzocaine; anti-fungals; aromatics such as camphor, eucalyptus oil, and aldehyde derivatives such as benzaldehyde; insulin; steroids; and anti-neoplasties. It is recognized that in certain
  • the present denture adhesive compositions may also comprise coating which is sticky to dry dentures and, if present, will be placed on one side of the denture adhesive composition comprising at least one non-adhesive self-supporting layer.
  • Compositions suitable for use as the adhesive layer include polybutenes, silicones, rubbers, petrolatum, natural polymers, synthetic polymers, and mixtures thereof.
  • the adhesive layer may be present at a level of from about 0% to about 70%, and preferably from about 0.5% to about 20%, by weight of the composition.
  • colorants include colorants, preservatives such as methyl and propyl parabens; thickeners such as silicon dioxide; and delivery vehicles such as liquid petrolatum, petrolatum, mineral oil and glycerin. Preferred are polyethylene glycol, silicon dioxide, and petrolatum. Colorants, preservatives, thickeners and delivery vehicles may be present at levels of from about 0% to about 20%, by weight of the composition.
  • compositions of the present invention may also include one or more components which provide flavor, fragrance, and/or sensate benefit.
  • Suitable components include natural or artificial sweetening agents, menthol, menthyl lactate, wintergreen oil, peppermint oil, spearmint oil, leaf alcohol, as well as coolants 3-1- menthoxypropane-l,2-diol and paramenthane carboxyamide agents such as N-ethyl- p-menthane-3-carboxamide which is described in U.S. Patent 4,136,163 to Watson et. al., which is incorporated by reference herein in its entirety. These agents may be present at a level of from about 0% to about 50%, by weight of the composition.
  • compositions can be prepared by any of the methods or combination of methods which follow.
  • mixture refers to a solution, slurry, or suspension.
  • the lower alkyl vinyl ether maleic anhydride copolymers can be obtained either from commercial suppliers under the trade names disclosed previously or by copolymerization of a lower alkyl vinyl ether monomer with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer which is readily hydrolyzable to the acid copolymer.
  • Covalent crosslinking of AVE/MA copolymer is achieved though esterification of the maleic anhydride unit of the copolymer.
  • the reaction occurs at elevated temperature.
  • the temperature range of from about 45°C to about 100°C may be used.
  • the temperature is in the range of from about 65°C to about 100°C, and most preferably from about 85°C to about 95°C.
  • the polymer may be neutralized during or after esterification.
  • the polymer may also be crosslinked with polyvalent metal ions in addition to the polyol during or after esterification.
  • the resultant polymer may be dried either in a forced air mechanical convection oven or a drum dryer. After drying, the sticky polymer turns into brittle flakes which can be easily peeled off from the drying surface and further grounded to a fine powder as desired.
  • Covalent crosslinking of AVE/MA copolymer or its partial salts can also be made during curing of a solids mixture of the copolymer or its salts and the organic crosslinker. Curing can be achieved in a conventional heating element or a microwave source. For a conventional heating element, a temperature range of from about 90°C to about 150°C is preferred. Most preferred is a temperature range of from about 110°C to about 130°C. Curing of the copolymers after the solution processes is preferred. Without being bound by theory, it is believed that during the curing process, the anhydride forms from the un-neutralized carboxyl group, therefore, esterification of the anhydride by an adjacent organic crosslinker could occur.
  • the adhesive components may be coated on a non-adhesive self-supporting layer using various methods. These include: (a) wetting the non-adhesive self-supporting layer with water, uniformly sifting the adhesive component powder(s) onto the wet layer and then rewetting the layer with water; (b) dissolving the adhesive component(s) in water and/or other solvent(s) and coating the resulting mixture onto the layer; (c) coating the layer with the mixture produced during Gantrez® processing; (d) incorporating the adhesive component(s) into the layer as the layer is being formed; and (e) dissolving the adhesive component(s) in water and/or other solvent(s), wetting/coating the resulting mixture onto the layer, and uniformly sifting one or more adhesives in powder form onto the wet/coated layer and optionally re-coating/re-
  • Solvents for the AVE/MA polymers include water and/or alcohols such as methanol, propanol, isopropanol, ethanol, butanol, 1,4-butanediol, cyclohexanol, and diethylene glycol; ethers or ether alcohols such as tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dioxane, and ethyl ether; esters such as methyl acetate, ethyl acetate and sec-butyl acetate; aldehydes, ketones or ketone-alcohols such as benzaldehyde, formaldehyde solution, methyl ethyl ketone, diacetone alcohol, acetone, cyclohexanone, mesityl oxide, and methyl isobuty
  • Preferred solvents for the AVE/MA polymers are water, methanol, propanol, isopropanol, tetrahydrofuran, methyl acetate, benzaldehyde, formaldehyde solution, methyl ethyl ketone, diacetone alcohol, N-methyl-2-pyrrolidone, N-vinyl-2- pyrrolidone, dimethyl formamideand mixtures thereof.
  • Compounds commonly used as plasticizers can also be used as solvents for the AVE/MA polymers.
  • plasticizers include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, glycercin, diethylene glycol, triethylene glycol., Igepal® CO-630, Gafac ® RE-610, Sorbitol, tricresyl phosphate, dimethyl sebacate, ethyl glycolate, ethylphthalyl ethyl glycolate, and p-toluene ethyl sulfonamide.
  • Solvents for other adhesives such as carboxymethylcellulose ("CMC") which may be optionally included in the adhesive compositions include mixtures of water and water-miscible solvents such as ethanol and acetone. Solutions of low concentration can be made with up to 40% acetone and/or 50% alcohol. Other solvents which made be used include ethanolamines; ethylene glycol; glycerol; 1,2,6- hexanetriol; mono-, di-, and triacetin; 1,5-pentanediol; polyethylene glycol (molecular weight 600 or less); propylene glycol; and trimethylolpropane.
  • CMC carboxymethylcellulose
  • various embodiments of the process includes: dissolving AVE/MA adhesives in one or more of the solvents for AVE/MA polymers; dissolving an optional adhesive in a suitable solvent and coating the resulting mixture onto the non-adhesive self-supporting layer and then optionally sifting one or more adhesives onto the coated layer. Coating the layer can be achieved by techniques commonly known in the art including extrusion, doctor blading, spraying, dipping, etc. After the adhesive component(s) has been deposited on a layer by one of the means described above, the layer is then dried.
  • the denture adhesive composition is mechanically softened by running it through a ring-roller or micro- cracker or any other suitable means.
  • the composition is then pressed smooth in a hydraulic press or flat-roller or other suitable means.
  • the composition is then die-cut into denture shapes. These shapes may facilitate application of the composition to the dentures.
  • PEG polyethylene glycol
  • MVE/MA poly (methyl vinyl ether / maleic anhydride)
  • the resulting adhesive copolymer yields a 60% neutralized partial calcium salt of MVE/MA copolymer covalently crosslinked with PEG 300.
  • the PEG:COOH molar ratio is 5%.
  • compositions comprising at least one non-adhesive self-supporting layer
  • wet 58" by 20" of the non-adhesive self-supporting layer with water Uniformly coat 150 grams of adhesive components (90g Ca MVE/MA copolymer and 60g carboxymethylcellulose) onto the layer and rewet the layer with water. Dry the layer.
  • Mechanically soften the denture adhesive composition by ring-roller, and then smooth the composition on a hydraulic press. Cut the composition into denture-shaped wafers. Moisten the wafers and apply to the dentures. This wafer is peelable from the denture and forms a sticky seal that holds the dentures in place, does not ooze, and aids in preventing food from sticking between the dentures and gums.
  • Example I Repeat the same drying, curing and milling procedures described in Example I.
  • the resulting adhesive copolymer yields a 60% neutralized partial calcium salt of MVE/MA copolymer covalently crosslinked with PEG 300 (PEG:COOH molar ratio is 5%).
  • the procedures for preparing the non-adhesive self-supporting layer, as described in Example I, may also be repeated.
  • Metal cations and their corresponding percents of initial carboxyl groups of partial salt AVE/MA copolymers reacted, described in Table IV, can be utilized in the processes of Examples I-III to formulate mixed partial salts of MVE/MA copolymers crosslinked with PEG.
  • divalent metal cations the appropriate metal oxide, hydroxide, carbonate or bicarbonate can be used.
  • trivalent metal cations the sulfate salt is preferred.
  • the adhesive copolymers produced in Examples I-IV can be utilized to formulate denture adhesive compositions in powder, cream or liquid forms by combining the adhesive copolymers with conventional denture adhesive delivery vehicles. The compositions are applied to dentures and then the dentures are inserted into the oral cavity. The adhesive copolymers may also be delivered on at least one self-supporting layer by the procedures described in Example I.
  • the adhesive component in Examples V-TX may also include 0.1 to 15 grams of silicon dioxide.
  • Examples V-1X are prepared as follows. Wet 58" by 20" of the non-adhesive self-supporting layer with water. Uniformly coat 150 grams of the adhesive component (90g MVE/MA/PEG partial salt copolymer and 60g CMC) onto the layer and rewet the layer with water. Dry the layer. Mechanically soften the denture adhesive composition by ring-roller, and then smooth the composition on a hydraulic press. Cut the composition into denture-shaped wafers. Moisten the wafers and apply to the dentures. This wafer is peelable from the denture and forms a sticky seal that holds the dentures in place, does not ooze, and aids in preventing food from sticking between the dentures and gums.
  • the adhesive component 90g MVE/MA/PEG partial salt copolymer and 60g CMC
  • EXAMPLE X Denture adhesive compositions in powder form can be made by blending together the following ingredients:
  • EXAMPLE XI Denture adhesive compositions in cream form can be made by blending together the following ingredients:
  • Flavor oil may be incorporated into the composition at 0.1% to 0.5% (w/w) level.
  • EXAMPLE XII Denture adhesive compositions in liquid form can be made by blending together the following ingredients:
  • Flavor oil may be incorporated into the composition at 0.1% to 0.5% (w/w) level.

Abstract

La présente invention concerne une composition adhésive pour prothèse dentaire comprenant un sel partiel d'un copolymère d'éther alkyle vinylique inférieur-acide maléique. Le sel partiel de copolymère comprend des groupes carboxyles, dont 50 % environ à 95 % environ sont neutralisés par au moins un cation métallique, et il est lié par réticulation covalente à un réticulant organique, le rapport molaire entre le réticulant organique et les groupes carboxyles avant la neutralisation par les cations métalliques étant compris entre 0,1 % environ et 30 % environ. Les compositions de la présente invention peuvent également comprendre au moins une couche autoportante non adhésive.
PCT/IB1998/000443 1997-03-27 1998-03-24 Compositions de stabilisation pour prothese dentaire WO1998043595A1 (fr)

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US82508397A 1997-03-27 1997-03-27
US08/825,083 1997-03-27
US08/835,040 1997-03-27
US08/835,040 US5872160A (en) 1997-03-27 1997-03-27 Denture stabilizing compositions

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Cited By (8)

* Cited by examiner, † Cited by third party
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WO2000033792A1 (fr) * 1998-12-08 2000-06-15 Block Drug Company, Inc. Adhesif dentaire
WO2000061070A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions de ciment pour prothese dentaire
WO2000061072A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions de ciments pour prothese dentaire
WO2000061071A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions adhesives pour prothese dentaire
US6617374B1 (en) 1999-04-14 2003-09-09 The Procter & Gamble Company Denture adhesives with mixed salts of alkyl vinyl ether-maleic copolymer or terpolymer
US9365723B2 (en) 2011-04-01 2016-06-14 Omya International Ag Process for preparing self-binding pigment particles
US10723886B2 (en) 2011-08-31 2020-07-28 Omya International Ag Self-binding pigment hybrid
EP3945123A1 (fr) 2020-07-31 2022-02-02 Universitat Politècnica De Catalunya Composition adhésive à base d'un copolymère anhydride maléique / éther de vinyle et des agents de réticulation d'origine naturelle et procédé pour sa préparation

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
JP4542707B2 (ja) * 1998-09-30 2010-09-15 ブロック ドラッグ カンパニー インコーポレイテッド 義歯接着剤組成物
JP4969081B2 (ja) * 2005-09-30 2012-07-04 小林製薬株式会社 義歯安定剤
JP2014200641A (ja) * 2013-04-01 2014-10-27 毅 春名 入れ歯安定剤

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US6166102A (en) * 1998-12-08 2000-12-26 Block Drug Company, Inc. Denture adhesive
WO2000033792A1 (fr) * 1998-12-08 2000-06-15 Block Drug Company, Inc. Adhesif dentaire
AU760182B2 (en) * 1999-04-14 2003-05-08 Procter & Gamble Company, The Denture adhesive compositions
WO2000061071A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions adhesives pour prothese dentaire
WO2000061072A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions de ciments pour prothese dentaire
US6355706B1 (en) 1999-04-14 2002-03-12 The Procter & Gamble Company Denture adhesives with mixed salt copolymers of terpolymers
WO2000061070A1 (fr) * 1999-04-14 2000-10-19 The Procter & Gamble Company Compositions de ciment pour prothese dentaire
US6617374B1 (en) 1999-04-14 2003-09-09 The Procter & Gamble Company Denture adhesives with mixed salts of alkyl vinyl ether-maleic copolymer or terpolymer
AU765154B2 (en) * 1999-04-14 2003-09-11 Procter & Gamble Company, The Denture adhesive compositions
AU765259B2 (en) * 1999-04-14 2003-09-11 Procter & Gamble Company, The Denture adhesive compositions
US9365723B2 (en) 2011-04-01 2016-06-14 Omya International Ag Process for preparing self-binding pigment particles
US10723886B2 (en) 2011-08-31 2020-07-28 Omya International Ag Self-binding pigment hybrid
EP3945123A1 (fr) 2020-07-31 2022-02-02 Universitat Politècnica De Catalunya Composition adhésive à base d'un copolymère anhydride maléique / éther de vinyle et des agents de réticulation d'origine naturelle et procédé pour sa préparation

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