CA2098826C - Denture stabilizing compositions having improved hold - Google Patents
Denture stabilizing compositions having improved holdInfo
- Publication number
- CA2098826C CA2098826C CA002098826A CA2098826A CA2098826C CA 2098826 C CA2098826 C CA 2098826C CA 002098826 A CA002098826 A CA 002098826A CA 2098826 A CA2098826 A CA 2098826A CA 2098826 C CA2098826 C CA 2098826C
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- CA
- Canada
- Prior art keywords
- denture
- copolymer
- zinc
- salt
- cations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
Abstract
Disclosed are stabilizer compositions comprising specific mixed partial salts of a lower alkyl vinyl ether-maleic acid copolymer wherein said partial salts containing from about 15 % to about 40 % free acid, and as the cationic salt function: (a) from about 0.1 % to about 9.9 % zinc or strontium cations; and (b) from about 20 % to about 67 % calcium cations of the total initial carboxyl groups reacted. Also disclosed are denture stabilizing compositions comprising these mixed partial salts, as well as denture stabilizing compositions comprising a safe and adhesively effective amount of two or more denture adhesive components wherein one of said denture adhesive components is the mixed partial salt(s) of the present invention.
Description
2~ 6 TECHNICAL FIELD
~ his invention relates to improvements in adhesives, in particu-lar, improved denture adhesives.
BACKGROUNO OF ~E INVEN~ION
Ordinary removable dentures, dental plates, and the like, com-prise 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. Althougn ~entures generally are skillfully prepared, often they do not fit iS perfectly. Moreover, no matter how sat~factory at first, after a period of time thè 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 stabilizer. Denture stabilizers are used to fill the interstices between the dentures and the gums or tissues. Prior to placement of the denture in the oral cavity, a denture stabilizer is applied to the denture-plate surface which, for a perfect fit, should uniformly contact the gums and mucous tissues.
The denture stabilizer is formulated not only for its adherent proper-ties, but also to provide a cushion or gasket between the denture ancthe gums or tissues, thereby positioning the denture securely in the oral cavity.
Requirements and characteristics for a satisfactory denture stabilizing 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 posi-tioning the denture. The composition should retain its characteris-tics 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; be safe ana ~9~82~
nontoxic; 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 of adjacent to the denture. The stabilizing 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 stabilizer should not attack or damage the denture, as by causing a crazing of iO the denture-plate material. Additionally, the stabilizer 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 S-8.5, preferably a pH around neutrality. ~he mechanical strength of the stabilizing mass, be it gel or colloid, formed by imbibition of lS 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.
There has been a considerable effort made over many years to develop improved denture adhesives. Both synthetic and natural polymers and gums have been used singly, in combination, and in combination with various additives.
European Patent 64,672 to Ohabhar and Schmidt, published November 17, 1982, relates to a hydrophilic denture adhesive containing an adhesive polymeric fraction comprising carboxymethylcellulose (CMC) and polyethylene oxide in a hydrophilic vehicle.
European Patent Application 140,486 to A.J. Desmaris, filed July 31, 1984 relates to denture adhesive compositions containing a hydro-phobically 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 epoxy-alkanes are p~eferred for use in the compositions.
U.S. Patent 4,280,936 to Dhabhar, ~eyd and Schmidt, issued July 28, 1981, relates to improved denture adhesives containing a specified ratio of CMC and polyethylene oxide in a mineral oil base.
U.S. Patent 4,474,902 to Dhabhar and Schmidt, issued October 2~
1984, relates to improved denture adhesives containing karaya gum in a hydrophilic vehicle. See also U.S. Patent 4,514,528, issued April 30.
1985, and U.S. Patent 4,518,721, issued May 21, 1985 to these same inventors, relating, respectively, to improved denture adhesives containing adhesive polymeric fractions consisting of admixtures of partial salts of lower alkyl vinyl ether maleic anhydride-type copolymers with CMC or polyethylene oxide, as well as denture aa-hesives containing CMC and polyethylene oxide. See also U.S. Patent 4,522,956, issued June 11, 1985 to Ohabhar and Schmidt relating to improved denture adhesives containing polyethylene oxide as the sole adhesive component in a hydrophilic vehicle comprising certain poly-ethylene glycols.
Other denture adhesives are described in U.S. Patents 4,530,942.
Ii issued July 23, 1989; 4,542,168, issued September 17, 1985; ana 4,569,955, issued February 11, 1986.
U.S. Patent 4,529,748 to H.G.P. ~ienecke, issued July 16, 1985, relates to dental prosthesis adhesives formed from film-formlng substances such as various cellulose derivatives, acrylate polymers, methacrylate polymers, and other film-providing substances.
U.S. Patent 4,138,47~ to Gaffar, issued February 6, 1979 dis-closes oral compositions to control mouth odor containing zinc-oolymer combinations formed from zinc reacted with an anionic polymer contain-ing carboxylic, sulfonic and/or phosphonic acid radicals.
U.S. Patent 3,003,988, to D.P. Germann et al., issued Octo~er 10, 1961, describes certain water-sensitized, but water-insoluble, materl-als for stabilizing dentures which are synthetic, hydrophilic, col-loidal materials comprising mixed partial salts and esters of lower alkyl (1 to 4 carbons) vinyl ether-maleic anhydride-type copolymers.
said mixed partial salts and esters containing both divalent calcium and monovalent alkali (i.e., sodium, potassium and ammonium) cations.
U.S. Patent 4,758,6~0 to Shah et al., issued July 19. 1~88 relates to zinc and strontium partial salts of lower alkyl (Cl to C"
vinyl ether-maleic acid copolymers, wherein said zinc and strontium cations are "unmixed" with any other cations or ester functions in the 2~98~2S
copolymeric salt, the remaining initial carboxyl groups beinq unreact-ed. These lower alkyl vinyl ether-maleic acid copolymers are referrea to hereinafter by the abbreviated term "AVE/MA copolymer" and the methyl vinyl ether-maleic acid copolymer as "MVE/MA copolymer"
Further, European Patent Application 396,411, to Holeva and Gounaris published November 7, 1990, discloses mixed partial MVE/MA copolymer salts.
It is known, therefore, that combinations of mixed and unmixed partial salts of lower alkyl vinyl ether-maleic anhydride-type co-polymers are useful as denture adhesive compositions.
Yet, the search continues for denture stabilizers that will provide the above-described characteristics and, importantly, will maintain the secure fit of the denture over prolonged periods (10-14 hours) without the need for reapplication.
In accordance with the present invention, improved adhesive and other charactertst1cs are obtained in a denture stabilizing composi-tion by using specific single mixed partial salt(s) of a lower alkyl vinyl ether-maleic acid copolymer. The copolymers have a specific level of zinc (or strontium) cations, i.e., below about 9.g%.
It is an object of the present invention to provide improvea denture stabilizers which are easy to manufacture and that will be stable over prolonged periods in the oral cavity, yet will allow easy removal of the denture on demand.
It is a further object of the present invention to provide denture compositions which provide the user with improved sensory, such a~-flavor, benefits.
It is a further object to provide such stabilizers using toxico-logically-acceptable, palatable materials.
It is another object herein to provide stabilizers that perform well in the presence of moisture, particularly in the presence of body fluids such as saliva, perspiration and blood.
These and other objects are secured by the present invention, in the manner disclosed hereinafter.
209~8%i3 SUMMARY OF THE INVEN~ION
The present invention encompasses stabilizer compositions com-prising: the mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
~R
0~ C~O (I) HO OH
_ J n wherein R represents a Cl , alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl iS ketone at 25-C, said partial salts contaimTng from about 15% to about 40~. free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.gX zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
Also disclosed are denture stabillzing compositions comprising these mixed partial salts, as well as denture stabilizing compositions comprising a safe and adhesively effective amount of two or more denture adhesive components wherein one of said denture adheslve components is the mixed partial salt(s) of the present invention.
Preferably these mixed partial salts are used along with a water-sensitized polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
All percentages and ratios used herein relating to the neutrali-zation of the salts of the present invention are based upon the stoichiometric percent of the cations present in the salt. All other percentages and ratios used herein are by weight, unless otherwlse specified.
WO 92/10986 PCI'/US91/09465 ~-0~98~26 OETAILED OESCRIPTION OF THE INVENTION
The polymeric salts of the present invention are the mixea partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
; OR
----CH~----CH---CH---CH
O~C C~O (I) HO OH
n 10 wherein R represents a C1 , alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25-C, said partial salts containing from about 15X to about 407. free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
R is preferably methyl.
Preferably, these mixed partial salts comprise from about 2% to about 9.9%, more preferably from about 2.1% to about 9.9% and most preferably from about 2.5% to about 9.9% zinc or strontium cations (preferably zinc~, and from about 20% to about 65%, more preferably from about 40% to about 65% calcium cations and from about 25% to about 35% free acid.
The mixed partial salts preferably further comprise from about O.lX to about 25%, and more preferably from about 0.1% to about 20%
sodium cations.
The subject polymeric salts are advantageously prepared by the interaction of the AVE/MA copolymer (I) with cationic calcium, sodium, and either zinc or strontium compounds having a functional group typical of reactants of carboxylic acid, such as, for example, the hydroxide, acetate, carbonate, halide, lactate, etc. in an aqueous medium. In a preferred embodiment, the oxide of zinc and the hy-W O 92/10986 PC~r/US91/09465 ;20~8 B ~:~
droxide of calcium and sodium 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 particu-late zinc oxide which, although practically insoluble in water, provides hydration to zinc hydroxide on the particulate surface.
Calcium and sodium hydroxide as well as strontium hydroxide, on the other hand, are available in either crystalline or powder form and are soluble in about 50 parts water. Aqueous solutions of strontium oxide, however, which form the hydroxide when treated with water (caution: heat evolution), may also be used. Strontium carbonate powder may also be used.
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 substantial-ly pure to assure obtaining a substantially pure, substantially off-white polymeric salt end-product.
The lower alkyl vinyl ether 0aleic acid (AVE/MA) copolymers tI) are readily obtained by copolymerizing a lower alkyl vinyl ether monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl either and isobutyl vinyl ether, with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer which is readily hydrolyzable to the acid copolymer (I).
Both anhydride and acid forms are also available from commercial suppliers. For example, the GAF Corporation, ~ayne, New Jersey, provides both the polymeric free acid form (I) and the corresponding anhydride form under its "GANTREZ~ trademark as the "GANTREZ S Series"
and ~GANTREZ AN Seriesn, respectively. In the former acid series, the GANTREZ 5-97 (M.~.~S0,000) is particularly suitable, and, in the latter anhydride series, the GANTREZ AN-149 (M.~.-50,000), the GANTRE~
AN-169 (M.~.~67,000) and the GANTREZ AN-179 (M.~.~80,000) coDolymers are particularly suitable. Said acid and anhydride forms of AVE/MA
copolymers, having an average molecular weight of from about S0,000 to about 80,000 (as measured by membrane osmometry in 2-butanone 1-10 grams/1000 ml solution), are also characterized by having the previ-2098~26 ously described specific viscosity parameter of more than 1.2. When the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is formea.
Accordingly, the anhydride form, which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elev?ted temperatures may be advantageously employed to enhance the rate of anhydride-to-acid hydrolysis.
In general, the lower alkyl vinyl ether-maleic acid copolymer (I), or its corresponding anhydride, is added to water preheated to about 70-80-C with vigorous stirring to form a homogeneous mixture.
~f the anhydride precursor is utilized, it is recommended that the aqueous mixture be further heated to about 90-C 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 65-75-C).
An aqueous solution of the cationic zinc or strontium salt forming compound, or, for example, an aqueous dispersion of particulate zinc oxide is combined with calcium hydroxide in the form of a slurry, in an amount sufficient to provide the desired zinc and calcium 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 Ot the cationic polymeric salt. After the calcium and zinc have reacted an aqueous solution of sodium hydroxide is added slowly, in the amount sufficient to provide the cation sodium content desired in the end-product. After addition is complete, mixing is continued t~
ensure that all the salt forming compounds are reacted with the CoDo-lymer.
Alternati~ely, an aqueous solution containing the zinc anc calcium source is preheated to 70-80-C with vigorous stirring to for~
a homogeneous slurry. The lower alkyl vinyl ether-maleic acid copolv-mer (I) or its corresponding anhydride is then added to the slurrJ
while further heating to 90'C and stirring to ensure complete hydroly-sis. Alternatively, the AVE/MA copolymer, calcium, and strontium or ~5 zinc oxide powders are slurried in water at 25- and subsequentl~
PC~rlUS9l/09465 2098~ ~
'' '' t '' ~
heated to 80-C - 90-C for reaction to occur. Upon completion of this reaction step an aqueous solution of sodium hydroxide is slowly added.
The sum total of zinc (or strontium), and calcium cations in the resultant mixed partial salt of AVE/MA copolymers should be sufficient to give a neutralization ranging frem about 20% to about 67%, prefera-bly from about 40% to about 65% calcium and from about O.I% to about 9.9%, preferably from about 2% to about 9.g%, more preferably from about 2.1% to about 9.9% and most preferably from about 2.5~. to about 9.97. zinc or strontium, resulting in a salt containing free acid in the range of from about 15% to about 40%, preferably from about 25% to about 35%. Sodium is preferably present at a level of from about 0.1~~o to about 20%.
The reaction batch is then dried such as by shallow drying trays in a convection oven maintained at about 70-C with hot air circulation ;; to evaporate the water content and recover~the polymeric salt product in dry form. Alternatively, the reaction batch is then transferred to drum dryers maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt in the flake form.
The resulting flakes may be subjected to milling and screening to yield the desired physical properties to provide satisfactory denture stabilizing properties.
Said salts are friable so that appropriate particle size and bulk density can be obtained. For best results, drum dried flakes should be milled to a preferred bulk density of about 0.5 to about 1.2 more preferably about 0.6 to about 1.1 and most preferably about 0.7 to about 1.0 grams per cubic centimeter while maintaining a specific surface area of about O.S to about 2.5, more preferably about 0.6 to about 2.0, and most preferably about 0.7 to about 1.5 square meters per gram. Ground particles should be capable of passage through a 140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than 0.3 millimeters in their largest dimension. Bulk densities are measured according to ASTM method B-52 (02.05).
The subject zinc or strontium, and calcium AVE/MA copolymer salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materi-als in denture stabilizing compositions. For such use the salt in ~Og~X6 particulate form is preferably characterized by a particle size of at least minus 140-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram per cubic centimeter and preferably higher then 0.6 gram per cubic centimeter; and a pH between 3 and 8 and preferably between 5 S and 7.5, the pH being determined on a one percent by weight dispersion in water.
Each of the subject copolymer salts may be utilized in effective adhesive amounts, preferably at least 25 percent by weight, as the sole adhesive component or as a co-adhesive in joint usage with other active adhesive components in denture stabilizing compositions.
It is preferred that said copolymer salt be used along with a co-adhesive in denture stabilizing compositions. Preferably, the co-adhesive is a polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof. In general, from about 15 to about 70 percent, based on the total wetght of the compositton, of said mixed calcium/sodium/zinc or strontium salt is present.
Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the particular property of swelling upon exposure to moisture to form a mucilaginous mass. Such adhesive materials include both natural gums and synthetic polymeric gums and, among those commonly employed in denture stabilizing compositions and which are also suitable herein co-adhesive action with the subject mixed AVE/MA copolymer salts, there may be mentioned, for example, karaya gum, gelatin, algin, sodium alginate, tragacanth, methylcellu-lose, acrylamide polymers, ethylene oxide polymers, polyvinylpyrroli-done, cationic polyarylamide polymers and, as the most preferred, sodium carboxymethylcellulose and mixed partial salts of poly(vinyl methylether-maleic acid) copolymer.
wo 92!10986 2 0 9 8 8 2 6 PCr/US91/09465 ._ Accordingly, a preferred aspect of the subject invention provides a denture stabilizing composition having as a stabilizing component an effective adhesive amount of a mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the ; repeated structural unit: -OR
O~C C~O (I) I HO OH
!O L _ n wherein R represents a C, to C, alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enougn to characterize said copolymer is having a specific viscosity larger !S than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25-C, said parttal salts containing from about 15% to about 40% free acid, and as the cat10nic salt functlon:
(a) from about 0.1% to about 9.9X zinc or strontium cations; and (b) from about 20X to about 67X calcium cations 20 of the total initial carboxyl groups reacted.
Another preferred aspect of this invention provides a denture stabilizing composition comprising a safe and adhesively effective amount of at least two denture adhesive components, wherein one of said denture adhesive components is the mixed partial salt of a lower 25 alkyl vinyl ether-maleic acid copolymer described above. Preferabl~
the co-adhesive is as described above.
The co~oostttons of the present invention can optionally include from about O.OlX to about 5% of one or more components which provide the user with sensory, including flavor, benefits. Suitable compo-30 nents include menthol, menthyl lactate, peppermint oil, spearmint oil.
peppermint oil, leaf alcohol, as well as those paramenthane carboxy-amides flavorinq agents available from ~ilkinson-Sword (such as ~S-3) which are described in U.S. Patent 4,136,163 to ~atson et al., issued January Z3, 1979.
The compositions of the present invention are manufactured in an art-recognized manner known to those skilled in the art, such as in a powder, cream, ointment, liquid, paste, water or film. ~he comoo-V 92/10986 2 0 9 & 8 2 6 PC~r/US9l/0946~
sitions of the present invention are pr~ferably manufactured uslng appropriate micronization such as fluid energy or air jet or hammer milling of drum dried mixed partial salts of AVE/~A copolymer.
Suitable examples of such formulations are disclosed in U.S. Patent 4 518 721 issued May 21 1985 and U.S. P-tent 4 514 528 issued April 30 1985 both to Dhabhar et al.
It is to be recoqnized that the adhesive salts of the present invention can be used for a wide variety of general adhesive uses including but not limited to pharmaceuttcal uses (e.g. oral drug aelivery and topical bandages); and a~ueous adhesives (e.g. where adhesiveness in the presence of water is required).
~he following non-limiting examples illustrate embodiments of the subject invention wherein both essential and optional ingredients are combined. It is to be understood that these ex~nples are for illus-trattve purposes only and are not to be construed as limtttng the scope of the invention thereto.
~ ~.
PC~r/US9l/09465 W O 92/10986 2~9882~
-i3-ExamDle I
Into a reaction vessel equipped with a high speed stirrer and containing 84.7 parts (7.6 kg) of purified water heated to 85'C, s slowly added 0.2 parts (18 grams) of zinc oxide and calcium hydroxide ; 0.92 parts (82.7 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 3.9 parts (348 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period. At about 15 minutes the iO resulting adhesive polymeric dispersion is characterized by an in-crease in viscosity, and a decrease and stabilization of the reaction pH which is a dispersion of said material in water, said material consisting of mixed partial calcium zinc salt of methyl vinyl ether-maleic acid copolymer. Temperature and mixing remain constant for 60 :5 ~inutes. Next, 890 grams of a 1% solution of sodium hydroxide is slow~y added o~er a 30 minute period and the reaction is allowed to go to completion as indicated by the stabilization of the reaction pH.
The resultant solution of the calcium zinc sodium 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 70 ~C for a sufficient time to evaporate the water content (about 16-18 hours). The thus obtained dried calcium zinc sodium MVE/MA copolymer salt is then ground in a ~illing apparatus and screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series). The powder would have a bulk density of about 0.6-1.2 gram per cubic centimeter. Analysis of the salt would indicate about 50 percent of the carboxyl groups neutralized with calcium, 9.9 percent neutralized with zinc and 5% neutralized wlth sodium with ~S% carboxyl groups remaining unreacted. This particular salt will be referred to hereinafter by the abbreviated ter~, "5C~.
Ca/9.9% Zn/ 5% Na partial salt of MVE/MA copolymern.
The product, when used in conjunction with conventional denture adhesives and applied to wet dentures with normal usage, provldes denture stabilizing characteristics superior to those obtained b~ the iS particular conventional denture adhesive itself.
W O 92/10986 PC~r/US91/09465 20Y~8~6 ~4 ExamDle II
The procedure of Example I is repeated except that the following amounts of reactants are employed: 3.9 parts (348 grams) of the anhydride copolymer, 94.9 parts (8.5 kg) purified water; and 0.2 parts S (18 grams) of zinc oxide; 0.2 parts (17.8 grams) of sodium hydroxide and 0.83 parts (74.3 g) calcium hydroxide.
The resultant powder would have a bulk density of about 0.6-1.2 grams per cubic centimeter. Analysis of the salt indicates about 45 percent calcium neutralization of the total initial carboxyl groups in the copolymer salt molecule; 9.9 percent neutralization with zinc and 10% neutralization with sodium will be referred to hereinafter by the abbreviated term "45% calcium/9.97. zinc/1~% sodium partial salt of MVE/MA copolymer".
WO 92/10986 PCr/US91/0946~
21~8~
ExamDle III
By following the general procedure of ExamPle I, except that an appropriate amount of zinc oxide is utilized to provide the tabulated zinc substitution, the following calcium/zinc~sodium salts of MVEiMA
copolymer are obtained:
Sodium Calcium Zinc 9.9 Each of the indicated MVE/MA copolymer salts, would have a bulk density for the minus l~0-mesh U.S.B.S. sieve powder greater than O.S
gram per cubic centimeter, and provide markedly beneficial denture stabilizing characteristics. Each of the indicated salts may be abbreviated by the percent of calcium/percent of zinc/percent sodium iS neutralization as done in Examples I and II .
PC~r/US9l/0946 2098~26 -i6-ExamDle IV
The MVE/MA copolymeric anhydride-to-acid hydrolysis procedure outlined in Example I is repeated. To a vessel containing 8.5 Kg of purified water heated to 85~C is added 16.5 grams of strontium carbo-s nate. With vigorous mixing, 99.4 grams of calcium hydroxide is slowlyadded. After addition is complete, the temperature of the slurry is kept constant mixing, 349 grams of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkali dispersion over a 20 minute period. This produces a mixed partial calcium strontium salt of methyl vinyl ether-maleic acid copolymer.
li W O 92tlO986 PC~r/US91/09465 209~S~6 ExamDle V
Denture stabilizing powder compositions are prepared by blending together the following:
~. w/w S A. Karaya gum 53 Sodium carboxymethylcellulose 16 Sodium borate 7 50% Ca/9.9% Zn/5% Na partial salt of PVM/MA copolymer 24 B. Sodium alginate 55 Sodium carboxymethylcellulose 10 Polyvinylpyrrolidone (average M.~.-90,000) 15 45% Ca/9.9% Zn/10% Na partial salt of PVM/MA copolymer ZO
In use, the above po~ders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
20~82 6 -18-ExamDle Vl Liquid-type denture stabilizing compositions are prepared by mixing together the following:
~. w/w A B
Mineral oil, heavy 44.9 43.9 Petrolatum 3.0 5.0 Colloital silica l.S 1.0 Sodium carboxymethylcellulose 35.0 20.0 Menthol 0.1 0.1 60% Ca/5% Zn partial salt of MVE/MA copolymer 15.5 30.0 100.0 100.0 In use, the above liquid compositions (typically 0.1-1 9) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manne~r of denture adhesives well-known in the art.
WO 92/10986 PCr/US91/0946~
2098~26 ExamDle VII
A cream-type denture stabilizing composition is prepared by mixing together the following:
7. w/w A B
Mineral oil, heavy 24.824 24.824 Sodium carboxymethylcellulose 22.000 22.000 Petrolatum 19.016 19.016 Silicon dioxide, colloidal 1.100 1.100 Colorant (oil soluble red color dispersion) 0.060 0.060 50%Ca/9.97,Zn/5% Na partial mixed salt of PVM/MA copolymer 33.000 -----45%Ca/9.9XZn/10% Na partial mixed salt of PVM/MA copolymer ------ 33.000 In use, the above compositions (typically 0.1-2 9) are placed on a premoistened denture, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
WHA~ IS CLAIMED IS:
~ his invention relates to improvements in adhesives, in particu-lar, improved denture adhesives.
BACKGROUNO OF ~E INVEN~ION
Ordinary removable dentures, dental plates, and the like, com-prise 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. Althougn ~entures generally are skillfully prepared, often they do not fit iS perfectly. Moreover, no matter how sat~factory at first, after a period of time thè 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 stabilizer. Denture stabilizers are used to fill the interstices between the dentures and the gums or tissues. Prior to placement of the denture in the oral cavity, a denture stabilizer is applied to the denture-plate surface which, for a perfect fit, should uniformly contact the gums and mucous tissues.
The denture stabilizer is formulated not only for its adherent proper-ties, but also to provide a cushion or gasket between the denture ancthe gums or tissues, thereby positioning the denture securely in the oral cavity.
Requirements and characteristics for a satisfactory denture stabilizing 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 posi-tioning the denture. The composition should retain its characteris-tics 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; be safe ana ~9~82~
nontoxic; 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 of adjacent to the denture. The stabilizing 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 stabilizer should not attack or damage the denture, as by causing a crazing of iO the denture-plate material. Additionally, the stabilizer 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 S-8.5, preferably a pH around neutrality. ~he mechanical strength of the stabilizing mass, be it gel or colloid, formed by imbibition of lS 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.
There has been a considerable effort made over many years to develop improved denture adhesives. Both synthetic and natural polymers and gums have been used singly, in combination, and in combination with various additives.
European Patent 64,672 to Ohabhar and Schmidt, published November 17, 1982, relates to a hydrophilic denture adhesive containing an adhesive polymeric fraction comprising carboxymethylcellulose (CMC) and polyethylene oxide in a hydrophilic vehicle.
European Patent Application 140,486 to A.J. Desmaris, filed July 31, 1984 relates to denture adhesive compositions containing a hydro-phobically 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 epoxy-alkanes are p~eferred for use in the compositions.
U.S. Patent 4,280,936 to Dhabhar, ~eyd and Schmidt, issued July 28, 1981, relates to improved denture adhesives containing a specified ratio of CMC and polyethylene oxide in a mineral oil base.
U.S. Patent 4,474,902 to Dhabhar and Schmidt, issued October 2~
1984, relates to improved denture adhesives containing karaya gum in a hydrophilic vehicle. See also U.S. Patent 4,514,528, issued April 30.
1985, and U.S. Patent 4,518,721, issued May 21, 1985 to these same inventors, relating, respectively, to improved denture adhesives containing adhesive polymeric fractions consisting of admixtures of partial salts of lower alkyl vinyl ether maleic anhydride-type copolymers with CMC or polyethylene oxide, as well as denture aa-hesives containing CMC and polyethylene oxide. See also U.S. Patent 4,522,956, issued June 11, 1985 to Ohabhar and Schmidt relating to improved denture adhesives containing polyethylene oxide as the sole adhesive component in a hydrophilic vehicle comprising certain poly-ethylene glycols.
Other denture adhesives are described in U.S. Patents 4,530,942.
Ii issued July 23, 1989; 4,542,168, issued September 17, 1985; ana 4,569,955, issued February 11, 1986.
U.S. Patent 4,529,748 to H.G.P. ~ienecke, issued July 16, 1985, relates to dental prosthesis adhesives formed from film-formlng substances such as various cellulose derivatives, acrylate polymers, methacrylate polymers, and other film-providing substances.
U.S. Patent 4,138,47~ to Gaffar, issued February 6, 1979 dis-closes oral compositions to control mouth odor containing zinc-oolymer combinations formed from zinc reacted with an anionic polymer contain-ing carboxylic, sulfonic and/or phosphonic acid radicals.
U.S. Patent 3,003,988, to D.P. Germann et al., issued Octo~er 10, 1961, describes certain water-sensitized, but water-insoluble, materl-als for stabilizing dentures which are synthetic, hydrophilic, col-loidal materials comprising mixed partial salts and esters of lower alkyl (1 to 4 carbons) vinyl ether-maleic anhydride-type copolymers.
said mixed partial salts and esters containing both divalent calcium and monovalent alkali (i.e., sodium, potassium and ammonium) cations.
U.S. Patent 4,758,6~0 to Shah et al., issued July 19. 1~88 relates to zinc and strontium partial salts of lower alkyl (Cl to C"
vinyl ether-maleic acid copolymers, wherein said zinc and strontium cations are "unmixed" with any other cations or ester functions in the 2~98~2S
copolymeric salt, the remaining initial carboxyl groups beinq unreact-ed. These lower alkyl vinyl ether-maleic acid copolymers are referrea to hereinafter by the abbreviated term "AVE/MA copolymer" and the methyl vinyl ether-maleic acid copolymer as "MVE/MA copolymer"
Further, European Patent Application 396,411, to Holeva and Gounaris published November 7, 1990, discloses mixed partial MVE/MA copolymer salts.
It is known, therefore, that combinations of mixed and unmixed partial salts of lower alkyl vinyl ether-maleic anhydride-type co-polymers are useful as denture adhesive compositions.
Yet, the search continues for denture stabilizers that will provide the above-described characteristics and, importantly, will maintain the secure fit of the denture over prolonged periods (10-14 hours) without the need for reapplication.
In accordance with the present invention, improved adhesive and other charactertst1cs are obtained in a denture stabilizing composi-tion by using specific single mixed partial salt(s) of a lower alkyl vinyl ether-maleic acid copolymer. The copolymers have a specific level of zinc (or strontium) cations, i.e., below about 9.g%.
It is an object of the present invention to provide improvea denture stabilizers which are easy to manufacture and that will be stable over prolonged periods in the oral cavity, yet will allow easy removal of the denture on demand.
It is a further object of the present invention to provide denture compositions which provide the user with improved sensory, such a~-flavor, benefits.
It is a further object to provide such stabilizers using toxico-logically-acceptable, palatable materials.
It is another object herein to provide stabilizers that perform well in the presence of moisture, particularly in the presence of body fluids such as saliva, perspiration and blood.
These and other objects are secured by the present invention, in the manner disclosed hereinafter.
209~8%i3 SUMMARY OF THE INVEN~ION
The present invention encompasses stabilizer compositions com-prising: the mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
~R
0~ C~O (I) HO OH
_ J n wherein R represents a Cl , alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl iS ketone at 25-C, said partial salts contaimTng from about 15% to about 40~. free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.gX zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
Also disclosed are denture stabillzing compositions comprising these mixed partial salts, as well as denture stabilizing compositions comprising a safe and adhesively effective amount of two or more denture adhesive components wherein one of said denture adheslve components is the mixed partial salt(s) of the present invention.
Preferably these mixed partial salts are used along with a water-sensitized polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
All percentages and ratios used herein relating to the neutrali-zation of the salts of the present invention are based upon the stoichiometric percent of the cations present in the salt. All other percentages and ratios used herein are by weight, unless otherwlse specified.
WO 92/10986 PCI'/US91/09465 ~-0~98~26 OETAILED OESCRIPTION OF THE INVENTION
The polymeric salts of the present invention are the mixea partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
; OR
----CH~----CH---CH---CH
O~C C~O (I) HO OH
n 10 wherein R represents a C1 , alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25-C, said partial salts containing from about 15X to about 407. free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
R is preferably methyl.
Preferably, these mixed partial salts comprise from about 2% to about 9.9%, more preferably from about 2.1% to about 9.9% and most preferably from about 2.5% to about 9.9% zinc or strontium cations (preferably zinc~, and from about 20% to about 65%, more preferably from about 40% to about 65% calcium cations and from about 25% to about 35% free acid.
The mixed partial salts preferably further comprise from about O.lX to about 25%, and more preferably from about 0.1% to about 20%
sodium cations.
The subject polymeric salts are advantageously prepared by the interaction of the AVE/MA copolymer (I) with cationic calcium, sodium, and either zinc or strontium compounds having a functional group typical of reactants of carboxylic acid, such as, for example, the hydroxide, acetate, carbonate, halide, lactate, etc. in an aqueous medium. In a preferred embodiment, the oxide of zinc and the hy-W O 92/10986 PC~r/US91/09465 ;20~8 B ~:~
droxide of calcium and sodium 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 particu-late zinc oxide which, although practically insoluble in water, provides hydration to zinc hydroxide on the particulate surface.
Calcium and sodium hydroxide as well as strontium hydroxide, on the other hand, are available in either crystalline or powder form and are soluble in about 50 parts water. Aqueous solutions of strontium oxide, however, which form the hydroxide when treated with water (caution: heat evolution), may also be used. Strontium carbonate powder may also be used.
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 substantial-ly pure to assure obtaining a substantially pure, substantially off-white polymeric salt end-product.
The lower alkyl vinyl ether 0aleic acid (AVE/MA) copolymers tI) are readily obtained by copolymerizing a lower alkyl vinyl ether monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl either and isobutyl vinyl ether, with maleic anhydride to yield the corresponding lower alkyl vinyl ether-maleic anhydride copolymer which is readily hydrolyzable to the acid copolymer (I).
Both anhydride and acid forms are also available from commercial suppliers. For example, the GAF Corporation, ~ayne, New Jersey, provides both the polymeric free acid form (I) and the corresponding anhydride form under its "GANTREZ~ trademark as the "GANTREZ S Series"
and ~GANTREZ AN Seriesn, respectively. In the former acid series, the GANTREZ 5-97 (M.~.~S0,000) is particularly suitable, and, in the latter anhydride series, the GANTREZ AN-149 (M.~.-50,000), the GANTRE~
AN-169 (M.~.~67,000) and the GANTREZ AN-179 (M.~.~80,000) coDolymers are particularly suitable. Said acid and anhydride forms of AVE/MA
copolymers, having an average molecular weight of from about S0,000 to about 80,000 (as measured by membrane osmometry in 2-butanone 1-10 grams/1000 ml solution), are also characterized by having the previ-2098~26 ously described specific viscosity parameter of more than 1.2. When the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is formea.
Accordingly, the anhydride form, which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elev?ted temperatures may be advantageously employed to enhance the rate of anhydride-to-acid hydrolysis.
In general, the lower alkyl vinyl ether-maleic acid copolymer (I), or its corresponding anhydride, is added to water preheated to about 70-80-C with vigorous stirring to form a homogeneous mixture.
~f the anhydride precursor is utilized, it is recommended that the aqueous mixture be further heated to about 90-C 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 65-75-C).
An aqueous solution of the cationic zinc or strontium salt forming compound, or, for example, an aqueous dispersion of particulate zinc oxide is combined with calcium hydroxide in the form of a slurry, in an amount sufficient to provide the desired zinc and calcium 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 Ot the cationic polymeric salt. After the calcium and zinc have reacted an aqueous solution of sodium hydroxide is added slowly, in the amount sufficient to provide the cation sodium content desired in the end-product. After addition is complete, mixing is continued t~
ensure that all the salt forming compounds are reacted with the CoDo-lymer.
Alternati~ely, an aqueous solution containing the zinc anc calcium source is preheated to 70-80-C with vigorous stirring to for~
a homogeneous slurry. The lower alkyl vinyl ether-maleic acid copolv-mer (I) or its corresponding anhydride is then added to the slurrJ
while further heating to 90'C and stirring to ensure complete hydroly-sis. Alternatively, the AVE/MA copolymer, calcium, and strontium or ~5 zinc oxide powders are slurried in water at 25- and subsequentl~
PC~rlUS9l/09465 2098~ ~
'' '' t '' ~
heated to 80-C - 90-C for reaction to occur. Upon completion of this reaction step an aqueous solution of sodium hydroxide is slowly added.
The sum total of zinc (or strontium), and calcium cations in the resultant mixed partial salt of AVE/MA copolymers should be sufficient to give a neutralization ranging frem about 20% to about 67%, prefera-bly from about 40% to about 65% calcium and from about O.I% to about 9.9%, preferably from about 2% to about 9.g%, more preferably from about 2.1% to about 9.9% and most preferably from about 2.5~. to about 9.97. zinc or strontium, resulting in a salt containing free acid in the range of from about 15% to about 40%, preferably from about 25% to about 35%. Sodium is preferably present at a level of from about 0.1~~o to about 20%.
The reaction batch is then dried such as by shallow drying trays in a convection oven maintained at about 70-C with hot air circulation ;; to evaporate the water content and recover~the polymeric salt product in dry form. Alternatively, the reaction batch is then transferred to drum dryers maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt in the flake form.
The resulting flakes may be subjected to milling and screening to yield the desired physical properties to provide satisfactory denture stabilizing properties.
Said salts are friable so that appropriate particle size and bulk density can be obtained. For best results, drum dried flakes should be milled to a preferred bulk density of about 0.5 to about 1.2 more preferably about 0.6 to about 1.1 and most preferably about 0.7 to about 1.0 grams per cubic centimeter while maintaining a specific surface area of about O.S to about 2.5, more preferably about 0.6 to about 2.0, and most preferably about 0.7 to about 1.5 square meters per gram. Ground particles should be capable of passage through a 140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than 0.3 millimeters in their largest dimension. Bulk densities are measured according to ASTM method B-52 (02.05).
The subject zinc or strontium, and calcium AVE/MA copolymer salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materi-als in denture stabilizing compositions. For such use the salt in ~Og~X6 particulate form is preferably characterized by a particle size of at least minus 140-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram per cubic centimeter and preferably higher then 0.6 gram per cubic centimeter; and a pH between 3 and 8 and preferably between 5 S and 7.5, the pH being determined on a one percent by weight dispersion in water.
Each of the subject copolymer salts may be utilized in effective adhesive amounts, preferably at least 25 percent by weight, as the sole adhesive component or as a co-adhesive in joint usage with other active adhesive components in denture stabilizing compositions.
It is preferred that said copolymer salt be used along with a co-adhesive in denture stabilizing compositions. Preferably, the co-adhesive is a polymeric material selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof. In general, from about 15 to about 70 percent, based on the total wetght of the compositton, of said mixed calcium/sodium/zinc or strontium salt is present.
Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the particular property of swelling upon exposure to moisture to form a mucilaginous mass. Such adhesive materials include both natural gums and synthetic polymeric gums and, among those commonly employed in denture stabilizing compositions and which are also suitable herein co-adhesive action with the subject mixed AVE/MA copolymer salts, there may be mentioned, for example, karaya gum, gelatin, algin, sodium alginate, tragacanth, methylcellu-lose, acrylamide polymers, ethylene oxide polymers, polyvinylpyrroli-done, cationic polyarylamide polymers and, as the most preferred, sodium carboxymethylcellulose and mixed partial salts of poly(vinyl methylether-maleic acid) copolymer.
wo 92!10986 2 0 9 8 8 2 6 PCr/US91/09465 ._ Accordingly, a preferred aspect of the subject invention provides a denture stabilizing composition having as a stabilizing component an effective adhesive amount of a mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the ; repeated structural unit: -OR
O~C C~O (I) I HO OH
!O L _ n wherein R represents a C, to C, alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enougn to characterize said copolymer is having a specific viscosity larger !S than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25-C, said parttal salts containing from about 15% to about 40% free acid, and as the cat10nic salt functlon:
(a) from about 0.1% to about 9.9X zinc or strontium cations; and (b) from about 20X to about 67X calcium cations 20 of the total initial carboxyl groups reacted.
Another preferred aspect of this invention provides a denture stabilizing composition comprising a safe and adhesively effective amount of at least two denture adhesive components, wherein one of said denture adhesive components is the mixed partial salt of a lower 25 alkyl vinyl ether-maleic acid copolymer described above. Preferabl~
the co-adhesive is as described above.
The co~oostttons of the present invention can optionally include from about O.OlX to about 5% of one or more components which provide the user with sensory, including flavor, benefits. Suitable compo-30 nents include menthol, menthyl lactate, peppermint oil, spearmint oil.
peppermint oil, leaf alcohol, as well as those paramenthane carboxy-amides flavorinq agents available from ~ilkinson-Sword (such as ~S-3) which are described in U.S. Patent 4,136,163 to ~atson et al., issued January Z3, 1979.
The compositions of the present invention are manufactured in an art-recognized manner known to those skilled in the art, such as in a powder, cream, ointment, liquid, paste, water or film. ~he comoo-V 92/10986 2 0 9 & 8 2 6 PC~r/US9l/0946~
sitions of the present invention are pr~ferably manufactured uslng appropriate micronization such as fluid energy or air jet or hammer milling of drum dried mixed partial salts of AVE/~A copolymer.
Suitable examples of such formulations are disclosed in U.S. Patent 4 518 721 issued May 21 1985 and U.S. P-tent 4 514 528 issued April 30 1985 both to Dhabhar et al.
It is to be recoqnized that the adhesive salts of the present invention can be used for a wide variety of general adhesive uses including but not limited to pharmaceuttcal uses (e.g. oral drug aelivery and topical bandages); and a~ueous adhesives (e.g. where adhesiveness in the presence of water is required).
~he following non-limiting examples illustrate embodiments of the subject invention wherein both essential and optional ingredients are combined. It is to be understood that these ex~nples are for illus-trattve purposes only and are not to be construed as limtttng the scope of the invention thereto.
~ ~.
PC~r/US9l/09465 W O 92/10986 2~9882~
-i3-ExamDle I
Into a reaction vessel equipped with a high speed stirrer and containing 84.7 parts (7.6 kg) of purified water heated to 85'C, s slowly added 0.2 parts (18 grams) of zinc oxide and calcium hydroxide ; 0.92 parts (82.7 grams). After addition is complete, the temperature of the slurry is kept constant with high speed mixing. While keeping heat and mixing constant add 3.9 parts (348 grams) of methyl vinyl ether-maleic anhydride copolymer to the reaction vessel containing the alkali dispersion over a 15 minute period. At about 15 minutes the iO resulting adhesive polymeric dispersion is characterized by an in-crease in viscosity, and a decrease and stabilization of the reaction pH which is a dispersion of said material in water, said material consisting of mixed partial calcium zinc salt of methyl vinyl ether-maleic acid copolymer. Temperature and mixing remain constant for 60 :5 ~inutes. Next, 890 grams of a 1% solution of sodium hydroxide is slow~y added o~er a 30 minute period and the reaction is allowed to go to completion as indicated by the stabilization of the reaction pH.
The resultant solution of the calcium zinc sodium 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 70 ~C for a sufficient time to evaporate the water content (about 16-18 hours). The thus obtained dried calcium zinc sodium MVE/MA copolymer salt is then ground in a ~illing apparatus and screened through a 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve series). The powder would have a bulk density of about 0.6-1.2 gram per cubic centimeter. Analysis of the salt would indicate about 50 percent of the carboxyl groups neutralized with calcium, 9.9 percent neutralized with zinc and 5% neutralized wlth sodium with ~S% carboxyl groups remaining unreacted. This particular salt will be referred to hereinafter by the abbreviated ter~, "5C~.
Ca/9.9% Zn/ 5% Na partial salt of MVE/MA copolymern.
The product, when used in conjunction with conventional denture adhesives and applied to wet dentures with normal usage, provldes denture stabilizing characteristics superior to those obtained b~ the iS particular conventional denture adhesive itself.
W O 92/10986 PC~r/US91/09465 20Y~8~6 ~4 ExamDle II
The procedure of Example I is repeated except that the following amounts of reactants are employed: 3.9 parts (348 grams) of the anhydride copolymer, 94.9 parts (8.5 kg) purified water; and 0.2 parts S (18 grams) of zinc oxide; 0.2 parts (17.8 grams) of sodium hydroxide and 0.83 parts (74.3 g) calcium hydroxide.
The resultant powder would have a bulk density of about 0.6-1.2 grams per cubic centimeter. Analysis of the salt indicates about 45 percent calcium neutralization of the total initial carboxyl groups in the copolymer salt molecule; 9.9 percent neutralization with zinc and 10% neutralization with sodium will be referred to hereinafter by the abbreviated term "45% calcium/9.97. zinc/1~% sodium partial salt of MVE/MA copolymer".
WO 92/10986 PCr/US91/0946~
21~8~
ExamDle III
By following the general procedure of ExamPle I, except that an appropriate amount of zinc oxide is utilized to provide the tabulated zinc substitution, the following calcium/zinc~sodium salts of MVEiMA
copolymer are obtained:
Sodium Calcium Zinc 9.9 Each of the indicated MVE/MA copolymer salts, would have a bulk density for the minus l~0-mesh U.S.B.S. sieve powder greater than O.S
gram per cubic centimeter, and provide markedly beneficial denture stabilizing characteristics. Each of the indicated salts may be abbreviated by the percent of calcium/percent of zinc/percent sodium iS neutralization as done in Examples I and II .
PC~r/US9l/0946 2098~26 -i6-ExamDle IV
The MVE/MA copolymeric anhydride-to-acid hydrolysis procedure outlined in Example I is repeated. To a vessel containing 8.5 Kg of purified water heated to 85~C is added 16.5 grams of strontium carbo-s nate. With vigorous mixing, 99.4 grams of calcium hydroxide is slowlyadded. After addition is complete, the temperature of the slurry is kept constant mixing, 349 grams of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkali dispersion over a 20 minute period. This produces a mixed partial calcium strontium salt of methyl vinyl ether-maleic acid copolymer.
li W O 92tlO986 PC~r/US91/09465 209~S~6 ExamDle V
Denture stabilizing powder compositions are prepared by blending together the following:
~. w/w S A. Karaya gum 53 Sodium carboxymethylcellulose 16 Sodium borate 7 50% Ca/9.9% Zn/5% Na partial salt of PVM/MA copolymer 24 B. Sodium alginate 55 Sodium carboxymethylcellulose 10 Polyvinylpyrrolidone (average M.~.-90,000) 15 45% Ca/9.9% Zn/10% Na partial salt of PVM/MA copolymer ZO
In use, the above po~ders (typically 0.1-1 g) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
20~82 6 -18-ExamDle Vl Liquid-type denture stabilizing compositions are prepared by mixing together the following:
~. w/w A B
Mineral oil, heavy 44.9 43.9 Petrolatum 3.0 5.0 Colloital silica l.S 1.0 Sodium carboxymethylcellulose 35.0 20.0 Menthol 0.1 0.1 60% Ca/5% Zn partial salt of MVE/MA copolymer 15.5 30.0 100.0 100.0 In use, the above liquid compositions (typically 0.1-1 9) are placed on a premoistened denture, allowed to hydrate briefly, and the denture is inserted in the mouth and pressed into place, all in the manne~r of denture adhesives well-known in the art.
WO 92/10986 PCr/US91/0946~
2098~26 ExamDle VII
A cream-type denture stabilizing composition is prepared by mixing together the following:
7. w/w A B
Mineral oil, heavy 24.824 24.824 Sodium carboxymethylcellulose 22.000 22.000 Petrolatum 19.016 19.016 Silicon dioxide, colloidal 1.100 1.100 Colorant (oil soluble red color dispersion) 0.060 0.060 50%Ca/9.97,Zn/5% Na partial mixed salt of PVM/MA copolymer 33.000 -----45%Ca/9.9XZn/10% Na partial mixed salt of PVM/MA copolymer ------ 33.000 In use, the above compositions (typically 0.1-2 9) are placed on a premoistened denture, and the denture is inserted in the mouth and pressed into place, all in the manner of denture adhesives well-known in the art.
WHA~ IS CLAIMED IS:
Claims (10)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED
AS FOLLOWS:
1. The mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
2. The mixed salt of Claim 1 wherein R is methyl.
3. The mixed salt of Claim 2 wherein said partial salt comprises:
(a) from about 2% to about 9.9% zinc or strontium cations; and (b) from about 40% to about 65% calcium cations of the total initial carboxyl groups reacted and from about 25% to about 35%
free acid.
(a) from about 2% to about 9.9% zinc or strontium cations; and (b) from about 40% to about 65% calcium cations of the total initial carboxyl groups reacted and from about 25% to about 35%
free acid.
4. A denture stabilizing composition comprising a polymeric material and having as a stabilizing component an effective adhesive amount of a mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
5. A denture stabilizing composition comprising a safe and adhesively effective amount of at least two denture adhesive components, wherein one of said denture adhesive components is the mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of said structural unit in a molecule of said copolymer and n is large enough to characterize said copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25°C, said partial salts containing from about 15% to about 40% free acid, and as the cationic salt function:
(a) from about 0.1% to about 9.9% zinc or strontium cations; and (b) from about 20% to about 67% calcium cations of the total initial carboxyl groups reacted.
6. The denture stabilizing composition of Claim 5 wherein R is methyl.
7. The denture stabilizing composition of Claim 6 wherein said partial salt comprises:
(a) from about 2% to about 9.9% zinc or strontium cations; and (b) from about 40% to about 65% calcium cations of the total initial carboxyl groups reacted and from about 25%
to about 35% free acid.
(a) from about 2% to about 9.9% zinc or strontium cations; and (b) from about 40% to about 65% calcium cations of the total initial carboxyl groups reacted and from about 25%
to about 35% free acid.
8. The denture stabilizing composition of Claim 7 wherein (a) is from about 2.5% to about 9.9% zinc cations.
9. The denture stabilizing composition of Claim 4 wherein said polymeric material is selected from the group consisting of natural gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
10. The denture stabilizing composition of Claim 9 which further comprises from about .01% to about 5.0% of menthol, menthyl lactate, spearmint oil, peppermint oil, leaf alcohol, and paramenthane carboxyamides, and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63229290A | 1990-12-21 | 1990-12-21 | |
| US07/632292 | 1990-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2098826A1 CA2098826A1 (en) | 1992-06-22 |
| CA2098826C true CA2098826C (en) | 1997-11-25 |
Family
ID=24534924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002098826A Expired - Lifetime CA2098826C (en) | 1990-12-21 | 1991-12-16 | Denture stabilizing compositions having improved hold |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US5424058A (en) |
| EP (1) | EP0563275B1 (en) |
| JP (1) | JPH06504545A (en) |
| AT (1) | ATE144128T1 (en) |
| AU (1) | AU664981B2 (en) |
| BR (1) | BR9107175A (en) |
| CA (1) | CA2098826C (en) |
| CZ (1) | CZ122093A3 (en) |
| DE (1) | DE69122771T2 (en) |
| ES (1) | ES2093249T3 (en) |
| FI (1) | FI932839A (en) |
| HU (1) | HUT64464A (en) |
| IE (1) | IE914510A1 (en) |
| PL (1) | PL168052B1 (en) |
| PT (1) | PT99914A (en) |
| SK (1) | SK63293A3 (en) |
| TR (1) | TR28678A (en) |
| WO (1) | WO1992010986A1 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369145A (en) * | 1993-06-14 | 1994-11-29 | Block Drug Company | Denture adhesive |
| CA2192322A1 (en) * | 1994-06-09 | 1995-12-14 | Jayanth Rajaiah | Denture stabilizing compositions |
| US5525652A (en) * | 1994-08-10 | 1996-06-11 | Block Drug Company, Inc. | Denture adhesive |
| US5750591A (en) * | 1996-02-29 | 1998-05-12 | The Block Drug Company | Denture adhesive containing partial zirconium, calcium, sodium gantrez salt |
| US6069188A (en) * | 1996-07-08 | 2000-05-30 | The Procter & Gamble Company | Denture stabilizing compositions |
| US5877233A (en) * | 1997-03-27 | 1999-03-02 | The Proctor & Gamble Company | Denture adhesive compositions |
| US5872161A (en) * | 1997-03-27 | 1999-02-16 | The Procter & Gamble Company | Denture adhesive compositions |
| US6281265B1 (en) | 1998-02-19 | 2001-08-28 | Salim A. Nathoo | Curable compositions with antimicrobial properties |
| US6124374A (en) * | 1998-05-29 | 2000-09-26 | Block Drug Company, Inc. | Antimicrobial denture adhesive and cleanser compositions |
| WO2000018356A1 (en) * | 1998-09-30 | 2000-04-06 | Block Drug Company, Inc. | Improved denture adhesive |
| US6110989A (en) * | 1998-09-30 | 2000-08-29 | Block Drug Company, Inc. | Denture adhesive |
| US6918765B1 (en) | 1999-01-25 | 2005-07-19 | Dentsply Research & Development Corp. | Hydrogel dental adhesive composition, product, system, method and dispenser |
| 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 |
| US6355706B1 (en) | 1999-04-14 | 2002-03-12 | The Procter & Gamble Company | Denture adhesives with mixed salt copolymers of terpolymers |
| DE19948508A1 (en) * | 1999-10-05 | 2001-05-23 | Hertz Inst Heinrich | Optical delay network e.g. for microwave antenna, has delay lines with different defined lengths of optical fibre |
| US6475497B1 (en) * | 1999-12-08 | 2002-11-05 | The Procter & Gamble Company | Tartar control denture adhesive compositions |
| US6905672B2 (en) * | 1999-12-08 | 2005-06-14 | The Procter & Gamble Company | Compositions and methods to inhibit tartar and microbes using denture adhesive compositions with colorants |
| US6475498B1 (en) | 1999-12-08 | 2002-11-05 | The Procter & Gamble Company | Method to inhibit tartar and stain using denture adhesive compositions |
| WO2002030317A1 (en) * | 2000-10-10 | 2002-04-18 | Block Drug Company, Inc. | Film extruded denture adhesive liner |
| US20050192376A1 (en) * | 2004-02-26 | 2005-09-01 | Ha Thinh N. | Denture care method and kit |
| EP1948116A1 (en) | 2005-11-09 | 2008-07-30 | The Procter & Gamble Company | Denture adhesive compositions |
| US20070149642A1 (en) * | 2005-12-28 | 2007-06-28 | Sunstar, Inc. | Denture fixative composition |
| US20090104128A1 (en) * | 2007-10-17 | 2009-04-23 | Orahealth Corporation | Denture adhesive compositions with anti-ucler agents |
| WO2017147887A1 (en) * | 2016-03-03 | 2017-09-08 | Boai Nky Pharmaceuticals Ltd. | Fine and uniform methyl vinyl ether-maleic acid inorganic salt copolymers and their use in oral care and pharmaceutical applications |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3003988A (en) * | 1958-10-16 | 1961-10-10 | Clark Cleveland Inc | Stabilizer for dentures |
| US4223109A (en) * | 1979-02-22 | 1980-09-16 | Adria Laboratories Inc. | Calcium salts of divinyl ether--maleic anhydride copolymer |
| US4569955A (en) * | 1983-03-17 | 1986-02-11 | Richardson-Vicks Inc. | Denture adhesive |
| US4758630A (en) * | 1986-10-27 | 1988-07-19 | Richardson-Vicks Inc. | Denture stabilizing zinc and strontium salts of ave/ma copolymer |
| US4980391A (en) * | 1988-10-27 | 1990-12-25 | Warner-Lambert Company | Denture adhesives and methods for preparing same |
| US4910247A (en) * | 1989-03-27 | 1990-03-20 | Gaf Chemicals Corporation | Adhesive composition |
| US5073604A (en) * | 1989-05-04 | 1991-12-17 | Richardson-Vicks, Inc. | Denture stabilizing compositions |
| CA2076389A1 (en) * | 1990-03-29 | 1991-09-30 | Steven Daryl Smith | Adhesive composition with acidic organic adhesive polymer and amine-substituted polymer |
-
1991
- 1991-12-16 DE DE69122771T patent/DE69122771T2/en not_active Expired - Lifetime
- 1991-12-16 CZ CS931220A patent/CZ122093A3/en unknown
- 1991-12-16 EP EP92903414A patent/EP0563275B1/en not_active Expired - Lifetime
- 1991-12-16 PL PL91299659A patent/PL168052B1/en unknown
- 1991-12-16 WO PCT/US1991/009465 patent/WO1992010986A1/en active IP Right Grant
- 1991-12-16 BR BR919107175A patent/BR9107175A/en not_active Application Discontinuation
- 1991-12-16 HU HU9301818A patent/HUT64464A/en unknown
- 1991-12-16 CA CA002098826A patent/CA2098826C/en not_active Expired - Lifetime
- 1991-12-16 ES ES92903414T patent/ES2093249T3/en not_active Expired - Lifetime
- 1991-12-16 AU AU91669/91A patent/AU664981B2/en not_active Expired
- 1991-12-16 AT AT92903414T patent/ATE144128T1/en not_active IP Right Cessation
- 1991-12-16 SK SK632-93A patent/SK63293A3/en unknown
- 1991-12-16 JP JP4503359A patent/JPH06504545A/en active Pending
- 1991-12-19 TR TR01160/91A patent/TR28678A/en unknown
- 1991-12-20 IE IE451091A patent/IE914510A1/en not_active Application Discontinuation
- 1991-12-20 PT PT99914A patent/PT99914A/en not_active Application Discontinuation
-
1993
- 1993-06-18 FI FI932839A patent/FI932839A/en unknown
-
1994
- 1994-04-15 US US08/227,917 patent/US5424058A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69122771T2 (en) | 1997-03-20 |
| BR9107175A (en) | 1994-02-08 |
| TR28678A (en) | 1997-01-17 |
| WO1992010986A1 (en) | 1992-07-09 |
| AU664981B2 (en) | 1995-12-14 |
| IE914510A1 (en) | 1992-07-01 |
| EP0563275A1 (en) | 1993-10-06 |
| ATE144128T1 (en) | 1996-11-15 |
| PT99914A (en) | 1992-12-31 |
| FI932839A0 (en) | 1993-06-18 |
| AU9166991A (en) | 1992-07-22 |
| FI932839A (en) | 1993-06-18 |
| CZ122093A3 (en) | 1994-02-16 |
| ES2093249T3 (en) | 1996-12-16 |
| CA2098826A1 (en) | 1992-06-22 |
| JPH06504545A (en) | 1994-05-26 |
| HU9301818D0 (en) | 1993-09-28 |
| US5424058A (en) | 1995-06-13 |
| EP0563275B1 (en) | 1996-10-16 |
| SK63293A3 (en) | 1994-06-08 |
| DE69122771D1 (en) | 1996-11-21 |
| PL168052B1 (en) | 1995-12-30 |
| HUT64464A (en) | 1994-01-28 |
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