Hydrophilic denture adhesive

Abstract

An improved denture adhesive containing an adhesive polymeric fraction consisting essentially of an admixture of mixed, partial salts of lower alkyl vinyl ether-maleic adhydride-type copolymers with either of sodium carboxymethylcellulose or poly(ethylene oxide) homopolymer or both in a hydrophilic vehicle comprising certain polyethylene glycols and, as an optional component in certain forms of the subject adhesives, glycerin, for enhancing pharmaceutical elegance of the final product.

Description

SUMMARY OF THE INVENTION

A highly effective hydrophilic denture adhesive composition is provided comprising a substantially anhydrous mixture of, as one essential component, an effective adhesive amount of an adhesive polymeric fraction consisting essentially of mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymers in combination with sodium carboxymethylcellulose and/or ethylene oxide homopolymer, and, as another essential component, a hydrophilic vehicle comprising a polyethylene glycol (PEG) fraction with average viscosity of from about 44 to about 25,600 centipoises at about 60.degree. C. Various forms of the subject compositions are available, for example, liquids, creams and powders. Optionally, up to about one-half of the polyethylene glycol fraction may be substituted with glycerin in the non-powder forms of the subject compositions. The denture adhesive composition may also have present colorants, flavoring agents, odorants, sweeteners and other additives in amounts generally employed for their respective intended purposes.

BACKGROUND OF THE INVENTION

Denture adhesive cream formulations have heretofore been comprised mainly of natural or synthetic polymeric adhesives suspended in an anhydrous oleagenous vehicle system generally consisting of mineral oil and/or petrolatum. These hydrophobic formulations have viscosities ranging from moderately thick to very thick making them difficult to squeeze out evenly and fluidly from the generally employed collapsible tubes or containers. However, this thickness range is necessary to prevent syneresis (i.e., phase separation) from occurring due to the solid adhesive particles being only suspended in the hydrophobic vehicle.

More recently, liquid denture adhesives have been reported containing sodium carboxymethylcellulose and ethylene oxide homopolymer as the solid adhesives suspended in mineral oil (e.g. see U.S. Pat. No. 4,280,936). Examples of such hydrophobic denture adhesives are the products commercially available from Block Drug Company, Inc. in the United States under the trademark "Dentrol" and in West Germany under the trademark "Cedenta", which are believed to contain about 41-45% w/w of sodium carboxymethylcellulose and ethylene oxide homopolymer in a mineral oil base. However, upon standing, considerable phase separation occurs thus requiring a "shake well" indication on the container.

Furthermore, whereas such formulations may be effective in securing dentures quickly within the oral cavity, it may be necessary to apply more than one application per day to obtain sufficient adhesion throughout the day, depending on the fit of the denture and the psychological need of the denture wearer. Such multiple applications are inconvenient and at times impractical or impossible and, therefore, these heretofore known denture adhesive liquids are not totally acceptable and in some cases undesirable.

Whereas these conventional types of denture adhesive creams and liquids have provided good stabilizing/hold properties to denture wearers, some organoleptic negatives have also been perceived with these products. Some of these commonly perceived negatives are, for example, unpleasant mouth feel, bad taste, grittiness, oily sensation in the mouth and difficulty of application and removal from dentures. Another disadvantage is that the salivary fluids have to penetrate a hydrophobic vehicle in order to reach and hydrate the adhesive system. This hydrophobic barrier may cause a time lag before the adhesive is hydrated and starts to work. Due to such slowed rate of hydration of adhesive components, there results a lack of immediate denture hold.

It has therefore been desirable to provide a denture adhesive of superior adherent properties over prolonged periods of time. Such is accomplished with the denture adhesive compositions herein described, a unique combination of an adhesive system in a hydrophilic vehicle system which eliminates many of the aforementioned disadvantages found with denture adhesives having conventional oleagenous vehicle systems. For example, the hydrophilicity of this unique combination facilitates the penetration of the saliva to the adhesive system, thereby allowing quicker hydration, and, therefore, quicker hold. Test results hereinafter demonstrate the stronger hold of the subject compositions. Furthermore, they are available in forms with variable consistencies, for example, liquids, creams and powders.

In our copending application Ser. No. 361,631, filed Mar. 26, 1982, entitled "Hydrophilic Denture Adhesive" now abandoned, the use of a polymeric adhesive system comprising sodium carboxymethylcellulose in admixture with an ethylene oxide homopolymer in specified ratios together with a hydrophilic PEG vehicle was described. In contrast, the instant compositions utilize a combination of a mixed, partial salt of lower alkyl vinyl ether-maleic anhydride-type copolymer with said sodium carboxymethylcellulose and/or said ethylene oxide homopolymer as the adhesive component in the hydrophilic PEG vehicle.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a hydrophilic denture adhesive composition which, when in contact with saliva, hydrates within the oral cavity to provide superior adherent properties. The composition comprises two essential components. The first is an adhesive fraction consisting essentially of a mixed, partial salt of lower alkyl vinyl ether-maleic anhydride-type copolymer in combination with either or both of sodium carboxymethylcellulose and ethylene oxide homopolymer. The second is a hydrophilic vehicle comprising a polyethylene glycol fraction with average viscosity of from about 44 to about 25,600 centipoises when measured at about 60.degree. C., generally 60.degree..+-.2.degree. C.

With regard to the adhesive component, the mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymers, the sodium carboxymethylcellulose and the ethylene oxide homopolymer constituents are well known and have been used heretofore to stabilize and secure dentures.

In U.S. Pat. No. 3,003,988, issued to D. P. Germann et al. and entitled "Stabilizer for Dentures", there are described certain water-sensitized, but water-insoluble, materials for stabilizing dentures which are synthetic, hydrophilic, colloidal materials comprising mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymers. It is these very same mixed, partial salts that are utilized as part of the adhesive component of this invention and, accordingly, the written description of said mixed, partial salts and the method and examples of preparing same which is set forth in said U.S. Pat. No. 3,003,988 is incorporated herein and made a part of this specification by reference thereto. Said mixed, partial salts are particularly defined in the claimed composition of claim 1 of said U.S. Pat. No. 3,003,988. as follows:

". . . a water-insoluble water-sensitized polymeric material; said material characterized by a particle size of minus 150-mesh U.S.B.S. sieve, by an apparent bulk density greater than 0.5 gram per cubic centimeter, and by a pH between 5 and 8.5, the pH being determined on a one percent by weight aqueous dispersion of said material in water; said material consisting essentially of a partial mixed salt of a copolymer selected from the group consisting of copolymers and partial lower alkyl esters of these copolymers, said copolymers consisting essentially of the repeated structural unit, ##STR1## wherein X and Y separately each represent a hydroxyl radical and X and Y together represent a bivalent oxygen atom, R represents an alkyl radical of less than 5 carbon atoms, 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.degree. C., said partial lower alkyl esters of said copolymers having less than one-third of the total initial carboxyl groups esterified, said partial mixed salts containing calcium cations and alkali cations, in a mole ratio between 1:1 and 5:1, the alkali cations selected from the group consisting of sodium, potassium, and quaternary ammonium cations, with not more than one third of the total initial carboxyl groups unreacted."

For purposes of convenience, the aforementioned mixed, partial salts will be generically referred to in this specification and claims hereinafter as mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymer and also denoted by the abbreviated term, "mixed, partial salts of AVE/MA copolymer". The preferred mixed, partial salts of AVE/MA copolymer for purposes of this invention are those indicated as preferred or with the preferred specifications denoted in said U.S. Pat. No. 3,003,988.

The most preferred mixed, partial salts of AVE/MA copolymer for use in the adhesive compositions of this invention are the calcium-sodium partial salts of a methyl vinyl ether-maleic anhydride (MVE/MA) copolymer with about 20-36 percent of the total initial carboxyl groups of the copolymer unreacted, a calcium-to-sodium mole ratio of from about 2.5:1 to about 4:1 per initial carboxyl group, an apparent bulk density of about 0.5 gram per cubic centimeter as a minimum and substantially from about 0.7 to about 0.9 gram per cubic centimeter, and a pH of about 6-7.5 for the powder at a concentration of 1 percent by weight in water. For purposes of convenience, these most preferred mixed, partial salts will be referred to hereinafter by the abbreviated term, "Ca/Na partial salts of MVE/MA copolymer".

In Example VI of the aforementioned Germann et al. U.S. Pat. No. 3,003,988, a calcium-sodium partial salt of mixed vinyl ether-maleic anhydride (MVE/MA) copolymer is described with about 30 percent of the total initial groups of the copolymer unreacted, a calcium-to-sodium equivalent ratio of 0.51:0.19 (i.e., about 2.6:1) per initial carboxyl group, an apparent bulk density of 0.88 gram per cubic centimeter, and a pH of 7.5 for the powder at a concentration of 1 percent by weight in water. This particular 2.6:1 Ca:Na partial salt, which is among the preferred, mixed partial salts utilized in this invention, is prepared by reacting aqueous solutions of calcium acetate and sodium hydroxide with the MVE/MA copolymer (Note: in U.S. Pat. No. 3,003,988, said MVE/MA copolymer is denoted as PVM/MA copolymer).

The preparation of another preferred Ca/Na partial salt is shown in Example VII of the '988 patent, wherein the calcium-to-sodium equivalent ratio is 0.5:0.134 (i.e., about 3.75:1), with about 35 percent of the total initial groups of the copolymer unreacted, an apparent bulk density of 0.92 gram per cubic centimeter, and a pH of 6.2 for the powder at a concentration of 1 percent by weight in water. This particular 3.75:1 Ca:Na partial salt is prepared by reacting aqueous solutions of calcium acetate and sodium acetate with the MVE/MA copolymer.

Among the most preferred Ca/Na partial salts of MVE/MA copolymer is the calcium-sodium partial salt with about 20 percent of the total initial carboxyl groups of the copolymer unreacted, a calcium-to-sodium mole ratio of about 3.5:1 per initial carboxyl group, an apparent bulk density of about 0.8-0.95 gram per cubic centimeter, and a pH of about 6.3-7.4 for the powder at a concentration of 1 percent by weight in water. For purposes of convenience, this particular most preferred Ca/Na partial salt will be referred to hereinafter by the abbreviated term, "3.5:1 Ca:Na partial salt of MVE/MA copolymer".

This most preferred Ca/Na partial salt may be obtained by following the procedures of the aforementioned Examples VI and VII of the '988 patent by, for example, utilizing aqueous solutions of sufficient calcium acetate and sodium hydroxide (via Example VI) or calcium acetate and sodium acetate (via Example VII) to yield the desired Ca:Na ratio upon reaction with the appropriate MVE/MA copolymer.

Sodium carboxymethylcellulose is a powder which, when moistened, becomes hydrated and tacky or gummy in consistency with adhesive characteristics. The sodium carboxymethylcellulose "gums" employed in this invention are water soluble, anionic, long chain polymers, derived from cellulose. Properties vary with the average number of carboxy methyl groups that are substituted per anhydroglucose unit in each cellulose molecule. This property is generally referred to as "the degree of substitution", with the maximum substitution possible designated as "3.0" since there are just three hydroxy groups capable of reaction in each anhydroglucose unit. For the practice of this invention, it has been found that one or more such cellulose gums having a degree of substitution of from about 0.4 to about 1.2 is suitable. The viscosity of a 1 percent solution of the gum, measured at 25.degree. C., should be in the range of from about 400 to 4,500, preferably 1,500 to 2,500 centipoises.

Sodium carboxymethylcellulose gums of this type are more fully described in "Chemical and Physical Properties: Cellulose Gum," 1978, published by Hercules, Incorporated, Coatings and Specialty Products Department, 910 Market Street, Wilmington, Del. 19899.

As examples of commercially available sodium carboxymethylcellulose gums suitable for use in this invention there may be mentioned those sold by Hercules, Incorporated, Wilmington, Del., as types 4H1, 7H, 9H4, 7H3S, 7HOF and 7H4. Type 7H3S is preferred for use in this invention.

The ethylene oxide hompolymers employed in the compositions of the invention are water soluble nonionic poly(ethylene oxide) homopolymers having molecular weights of from about 100,000 to about 5,000,000. The polymers have the structure O--CH.sub.2 CH.sub.2n wherein n represents the degree of polymerization and has a value of from about 2,000 to about 100,000. These polymers are white powders, which, when moistened with water, become hydrated to form a gelatinous mass with adhesive characteristics.

Poly(ethylene oxide) homopolymers of this type are more fully described in "Polyox", 1978, published by Union Carbide Corporation, 270 Park Avenue, New York, N.Y. 10017, as Technical Bulletin F-44029B.

As examples of commercially available powdered poly(ethylene oxide) homopolymers suitable for use in this invention there may be mentioned those polymers sold by Union Carbide Corporation under the trademark POLYOX as grades WSR N-10, WSR N-80, WSR N-750, WSR N-3000, WSR -205, WSR -1105 and WSR -301. Preferred for use in this invention is POLYOX WSR -301 homopolymer.

In the compositions of this invention the adhesive component comprises an effective adhesive amount of an admixture of (i) a mixed, partial salt of lower alkyl vinyl ether-maleic anhydride-type copolymer with either of (ii) sodium carboxymethylcellulose or (iii) poly (ethylene oxide) homopolymer or both of said (ii) and (iii).

With the adhesive component consisting essentially of a combination of (i) and (ii), the subject compositions preferably comprise either:

(a) from about 25 to about 50% by weight, based on the total weight of the composition (i.e., "% w/w"), of such adhesive component and from about 50 to about 75% w/w of the PEG fraction with, moreover, the respective weight ratio of (i):(ii) being from about 1:1 to about 1:9; or

(b) from about 40 to about 50% w/w of such adhesive component and from about 50 to about 60% w/w of the PEG fraction with, moreover, the respective weight ratio of (i):(ii) being about 3:2.

With the adhesive component consisting essentially of a combination of (i) and (iii), the subject compositions preferably comprise from about 25 to about 35% w/w of such adhesive component and from about 65 to about 75% w/w of the PEG fraction with, moreover, the respective weight ratio of (i):(iii) being about 1:3.

With the adhesive component consisting essentially of a combination of (i), (ii) and (iii), the subject compositions preferably comprise from about 25 to about 50% w/w of such adhesive component and from about 50 to about 75% w/w of the PEG fraction with, moreover, the respective weight ratio of (i):(ii):(iii) being about 1:1:1.

With regard to the hydrophilic vehicle component, the polyethylene glycols suitable for use in the compositions of the invention are also well known and commercially available, for example, those marketed by Union Carbide Corporation under its trademark "Carbowax".

Polyethylene glycols are polymers of ethylene oxide with the generalized formula HOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.n --CH.sub.2 OH wherein n represents the average number of oxyethylene groups. These polyethylene glycols, which are designated by a number that represents the average molecular weight, range from clear viscous liquids at room temperature (e.g., PEGs 200, 300, 400 and 600) to soft solids (e.g. PEGS 1000 and 1450) to waxy solids available in the form of flakes or powders (e.g. PEGs 3350 and 8000) to granular solids (e.g., PEG 14,000). All these polymers dissolve in water to form clear solutions and this water solubility feature imparts a hydrophilic characteristic to the compositions of this invention.

The polyethylene glycol (PEG) fraction of the subject compositions have an average viscosity when measured at about 60.degree. C. of from about 44 to about 25,600 centipoises (cps), preferably from about 44 to about 2,500 cps, and most preferably from about 44 to about 300 cps, as determined, for example, by an instrument such as the Brookfield RVT Viscometer. Either individual polyethylene glycols or blends of two or more polyethylene glycols within this viscosity range may be utilized. For example, and without being limited thereto, a blend of liquid PEG 400 or PEG 600 and solid PEG 8000 in a respective weight ratio of from about 9:1 to about 33:1, has been found particularly suitable for the lotion-like liquids and soft creams of this invention.

The data presented in following Table 1 illustrate the variety of final product consistencies obtainable according to this invention by varying the make-up of the PEG fraction in a particular formulation. In Example 3, hereafter, a lotion liquid formulation is described which contains 33% w/w adhesives, 10% w/w glycerin and 57% PEGs, the latter made up PEG 400 and PEG 8000 in a ratio of about 24:1, respectively. By substituting an equivalent amount of total PEG but in the indicated varying ratios, the following results are approximated:

TABLE 1______________________________________Vehicle Ratio PEG Fraction(PEG 400: Viscosity** ProductPEG 8000) (cps @ 60.degree. C.) Consistency______________________________________100:0 56 liquid98:2 (49:1) 44 liquid97:3 (32.3:1) 61 liquid lotion94:6 (19:1) 72 liquid lotion92:8 (11.5:1) 94 liquid lotion90:10 (9:1) 94 soft cream80:20 (4:1) 170 cream70:30 (2.3:1) 315 thick cream60:40 (1.5:1) 600 very thick cream0:100 (PEG 8000*) 2,500 powder0:100 (PEG 14000*) 25,600 powder______________________________________ *The 10% w/w glycerin replaced by equal amount of PEG. **Determined on a Brookfield RVT Viscometer.

By blending numbers of the PEG series, different viscosities within the defined range may be obtained, as desired. For example, by utilizing increasing amounts of higher molecular weight PEGs, i.e. more solids than liquids, the resultant viscosity of the polyethylene glycol fraction will also increase (assuming other ingredients in the denture adhesive composition are maintained constant) so that one can readily obtain embodiments of the subject compositions ranging in consistency from viscous liquids to creams and powders. For example, with about 32 percent w/w of the adhesive fraction and 10 percent w/w of glycerin, a polyethylene glycol fraction having a viscosity at about 60.degree. C. of about 44-95 cps affords a final product with a liquid lotion to soft cream consistency; whereas a polyethylene glycol fraction having a viscosity of about 100-300 cps affords a cream type of final product; whereas a polyethylene glycol fraction above 300 cps affords a thick creamy product; and whereas without glycerin a polyethylene glycol fraction having a very high viscosity of about 2500-25,600 cps affords a final product in powder form. This ability to adjust the fluidity of the final product is a particularly advantageous feature of the invention since it affords commercialization of final product forms with consumer acceptable consistencies such as (i) liquids and soft creams, which are readily extrudable from appropriate containers, for example, pump action bottles, squeezable tubes and the like, (ii) thicker creams and (iii) powders, all of which forms are suitable for easy application to dentures.

With regard to the liquid and cream compositions of this invention, one particular ingredient that is preferred and recommended as a substitute for part of the polyethylene glycol fraction is glycerin which has a known soothing effect on oral gum tissue and also affords a pleasant mouth feel and sweetening taste to the finished composition. Due to its humectant character, glycerin also contributes to the hydrophilicity of the finished composition, thereby allowing quicker hydration on contact with moisture or saliva. Thus, although glyerin is not an essential component of the hydrophilic vehicle or of the finished composition, it does enhance the latter's esthetic appearance and acceptability.

It has been found that a significant amount of glycerin can be substituted for the polyethylene glycol fraction, for example, up to about one-half of the latter may be so substituted without any significant detriment to the overall adhesive ability of the finished composition. However, due to the increased cost incurred with high amounts of the relatively expensive glycerin, about 25% w/w of glycerin is recommended as the upper limit with about 5 to about 15 percent w/w being preferred and about 10 percent w/w most preferred.

Any suitable flavoring agent, colorant, odorant, natural or synthetic sweetener, deodorant, antimicrobial agent, tissue healing agent or other optional ingredient generally employed as an additive in denture adhesives may be utilized in the compositions of this invention, if so desired, so long as such addition is not detrimental to the overall adhesive ability of the compositions. Preferably, up to about 1.0% w/w of such additives may be utilized.

Typical of the compositions encompassed in the present invention are the formulations exemplified in Table 2. The symbol "% w/w" indicates the weight of each ingredient based on the total weight of the particular composition.

TABLE 2______________________________________Formulation Examples in % w/w Ex. 1 Ex. 2 Ex. 3______________________________________Ca/Na salt.sup.1 10.0 10.0 11.0Na--CMC.sup.2 30.0 10.0 11.0Polyox.sup.3 10.0 11.0PEG 400 54.7PEG 600 44.59PEG 8000 5.0 70.0 2.3Glycerin 10.0 10.0Colorant 0.01Flavor.sup.4 0.4 100.00 100.0 100.0Form: soft cream powder lotion______________________________________ .sup.1 3.5:1 Ca:Na partial salt of MVE/MA copolymer. .sup.2 Sodium carboxymethylcellulose type 7H3S. .sup.3 Poly(ethylene oxide) homopolymer type WSR301. .sup.4 Premix of mint oils.

The compositions of this invention can be produced by standard compounding techniques. For example, the liquid and cream compositions are readily prepared by heating with stirring the polyethylene glycol fraction to about 65.degree.-70.degree. C. at which temperature any solid or semisolid polyethylene glycols which may be present are liquified and the fraction has a syrupy gel-like consistency. The adhesive component, i.e., the mixed, partial salt of the AVE/MA copolymer, in admixture with sodium carboxymethylcellulose and/or poly(ethylene oxide) homopolymer, is added to the polyethylene glycol fraction, slightly cooled to about 50.degree.-60.degree. C., with constant stirring to obtain a uniform adhesive/vehicle mixture. Any optional additives such as flavor, color and the like may then be incorporated into the adhesive/vehicle mixture. It is recommended, however, that the adhesive/vehicle mixture be cooled to about or slightly below 40.degree. C. before incorporation of any such additives of a volatile character, for example, aromatic flavors, in order to preserve their characteristic essences.

When glycerin is to be included in the final product, it is advantageously added to and mixed into the slightly cooled (about 50.degree.-60.degree. C.) polyethylene glycol fraction prior to admixture with the adhesive component. The glycerin addition step may also be utilized as a way of carrying any compatible optional additive such as a sweetener, colorant and the like into the final product by simply mixing or dissolving the desired additive in the glycerin beforehand.

The powder compositions of this invention are readily obtained by simple admixture of the powder constituents of the adhesive component with the powder PEG fraction of the hydrophilic vehicle component. The preferred polyethylene glycol for making the powder compositions is PEG 8000 alone. It is recommended that granular forms of polyethylene glycol, such as PEG 14,000, be pulverized to a fine powder prior to admixture with the powder adhesive constituent(s).

The denture adhesive compositions of this invention possess superior and unexpected adhesion/cohesion properties as measured by the Texturometer evaluation test. The term Texturometer is a trademark for an instrument manufactured and sold by C. W. Brabender Instruments, Inc. of Hackensack, N.J. which enables a quantitative measurement of textural parameters of products. The instrument mechanically simulates the chewing motions of the human jaws. A plunger is driven through the test sample (approx. 3 ml) held in a sample holder under which there is a strain-gauge hooked up to a high-speed chart recorder. The instrument draws force-time curves which are indicative of the cohesive/adhesive ability of the test sample. The plunger is driven through the test sample at the rate of 12 times per minute and the chart paper speed is 1500 mm per minute.

The test sample is prepared by uniformly mixing the product to be tested with distilled water in a small mortar and pestle at a ratio of one part by weight of product to four parts by weight of water. The areas under the cohesion and adhesion parts of the force-time curves are measured and these areas are a measure of the cohesive/adhesive abilities of the hydrated adhesive formulation, i.e., the larger the areas, the greater such abilities. After the initial measurement, the test sample is kept undisturbed in a tightly covered petri-dish (to prevent evaporation) for 5 hours at 25.degree. C. and then retested. Accordingly, in Table 3 hereafter, the tabulated numbers indicating the observed Texturometric evaluations represent areas under the cohesion/adhesion Texturometric curves. The unexpected superiority of the compositions of the present invention is demonstrated by the Texturometer evaluation data set forth in Table 3 wherein the compositions of Examples 4 through 12 are tested and compared with Example 13, a commercial product available under the brand name "Dentrol" from the Block Drug Company, Inc. This product, which has a mixture of sodium carboxymethylcellulose and ethylene oxide homopolymer as the adhesive constituents, utilizes a hydrophobic mineral oil vehicle rather than the hydrophilic PEG vehicle of this invention. The adhesive/cohesive properties of the tested hydrated products are evaluated initially and again after 5 hours.

TABLE 3__________________________________________________________________________Texturometric Evaluations.sup.1 COHESION ADHESION (sq. mm.) (sq. mm.)Ex. % Weight After AfterNo. Test Prod. w/w.sup.2 Ratio Initial 5 hrs. Initial 5 hrs.__________________________________________________________________________4 Ca/Na Salt.sup.3 + NA--CMC 50 1:9 989 1444 374 5615 " 25 1:9 441 459 182 1786 " 50 1:1 481 922 374 5357 " 25 1:1 241 214 107 2948 " 50 3:2 374 575 227 2279 Ca/Na Salt.sup.3 + Polyox 25 1:3 205 234 168 27810 " 35 1:3 321 642 227 60211 Ca/Na Salt.sup.3 + Na--CMC + Polyox 50 1:1:1 521 1070 374 119012 " 25 1:1:1 166 154 134 8713 Dentrol -- -- 279 568 71 37__________________________________________________________________________ .sup.1 Numbers represent areas under cohesion/adhesion Texturometric curves. .sup.2 Balance of composition is PEG 600. .sup.3 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

The data listed in Table 3 shows clearly the unexpected and superior nature of the cohesion and adhesion parameters obtained with compositions of this invention. Particularly noteworthy is the general increase in both cohesion and adhesion abilities of the subject compositions after 5 hours. In contrast, the measured adhesion of the comparative commercial product decreased significantly, almost 50% after 5 hours. The marked cohesion and adhesion parameters after keeping for 5 hours, characteristic of the subject compositions, is even more surprising since it might be expected that with passing of time the water of hydration, considering the hydrophilicity of the subject compositions, might weaken rather than strengthen the structure of such compositions.

The foregoing in-vitro Texturometric evaluation data illustrate the effectiveness of the denture adhesive compositions of this invention. When in contact with moistened denture plates, gums and saliva, the subject compositions hydrate within the oral cavity to provide superior denture stabilizing properties not possessed by denture adhesives generally having hydrophobic vehicles for the adhesive components rather than hydrophilic vehicles as with the subject compositions.

Claims

1. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) an effective adhesive amount of an adhesive fraction consisting essentially of a mixed, partial salt of AVE/MA copolymer in combination with either or both of sodium carboxymethylcellulose and poly(ethylene oxide) homopolymer; and

(b) a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 25,600 centipoises at about 60.degree. C.

2. The composition of claim 1 wherein (a) is an effective adhesive amount of a mixed, partial salt of AVE/MA copolymer in combination with sodium carboxymethylcellulose.

3. The composition of claim 1 wherein (a) is an effective adhesive amount of a mixed, partial salt of AVE/MA copolymer in combination with poly(ethylene oxide) homopolymer.

4. The composition of claim 1 wherein (a) is an effective adhesive amount of a mixed, partial salt of AVE/MA copolymer in combination with sodium carboxymethylcellulose and poly(ethylene oxide) homopolymer.

5. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of from about 1:1 to about 1:9; and

(b) from about 50 to about 75 percent w/w of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 2500 centipoises at about 60.degree. C.

6. The composition of claim 5 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

7. The composition of claim 5 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

8. The composition of claim 5 wherein up to about one-half of said polyethylene glycol fraction is substituted with glycerin.

9. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 40 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of about 3:2; and

(b) from about 50 to about 60 percent w/w of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 2500 centipoises at about 60.degree. C.

10. The composition of claim 9 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

11. The composition of claim 9 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

12. The composition of claim 9 wherein up to about one-half of said polyethylene glycol fraction is substituted with glycerin.

13. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 35 percent w/w of a mixed partial salt of AVE/MA copolymer and poly(ethylene oxide) homopolymer in a respective weight ratio of about 1:3; and

(b) from about 65 to about 75 percent w/w of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 2500 centipoises at about 60.degree. C.

14. The composition of claim 13 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

15. The composition of claim 13 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

16. The composition of claim 13 wherein up to about one-half of said polyethylene glycol fraction is substituted with glycerin.

17. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer, sodium carboxymethylcellulose and poly(ethylene oxide) homopolymer in a respective weight ratio of about 1:1:1; and

(b) from about 50 to about 75 percent w/w of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 2500 centipoises at about 60.degree. C.

18. The composition of claim 17 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

19. The composition of claim 17 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

20. The composition of claim 17 wherein up to about one-half of said polyethylene glycol fraction is substituted with glycerin.

21. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of from about 1:1 to about 1:9;

(b) up to about 25 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

22. The composition of claim 21 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

23. The composition of claim 21 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

24. The composition of claim 21 wherein (b) comprises from about 5 to about 15 percent w/w of said glycerin.

25. The composition of claim 21 wherein (b) comprises about 10 percent w/w of said glycerin.

26. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 40 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of about 3:2;

(b) up to about 25 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

27. The composition of claim 26 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

28. The composition of claim 26 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

29. The composition of claim 26 wherein (b) comprises about 5 to about 15 percent w/w of said glycerin.

30. The composition of claim 26 wherein (b) comprises about 10 percent w/w of said glycerin.

31. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 35 percent w/w of a mixed, partial salt of AVE/MA copolymer and poly(ethylene oxide) homopolymer in a respective weight ratio of about 1:3;

(b) up to about 25 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

32. The composition of claim 31 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

33. The composition of claim 31 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

34. The composition of claim 31 wherein (b) comprises about 5 to about 15 percent w/w of said glycerin.

35. The composition of claim 31 wherein (b) comprises about 10 percent w/w of said glycerin.

36. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a mixed, partial salt of AVE/MA copolymer, sodium carboxymethylcellulose and poly(ethylene oxide) homopolymer in a respective weight ratio of about 1:1:1;

(b) up to about 25 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

37. The composition of claim 36 wherein said mixed, partial salt is a Ca/Na partial salt of MVE/MA copolymer.

38. The composition of claim 36 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

39. The composition of claim 36 wherein (b) comprises about 5 to about 15 percent w/w of said glycerin.

40. The composition of claim 36 wherein (b) comprises about 10 percent w/w of said glycerin.

41. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a Ca/Na partial salt of MVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of from about 1:1 to about 1:9;

(b) from about 5 to about 15 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

42. The composition of claim 41 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

43. The composition of claim 42 wherein (b) comprises about 10 percent w/w of said glycerin.

44. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 40 to about 50 percent w/w of a Ca/Na partial salt of MVE/MA copolymer and sodium carboxymethylcellulose in a respective weight ratio of about 3:2;

(b) from about 5 to about 15 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

45. The composition of claim 44 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

46. The composition of claim 45 wherein (b) comprises about 10 percent w/w of said glycerin.

47. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 35 percent w/w of a Ca/Na partial salt of MVE/MA copolymer and poly(ethylene oxide) hompolymer in a respective weight ratio of about 1:3;

(b) from about 5 to about 15 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

48. The composition of claim 47 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

49. The composition of claim 48 wherein (b) comprises about 10 percent w/w of said glycerin.

50. A denture adhesive composition comprising a substantially anhydrous mixture of:

(a) from about 25 to about 50 percent w/w of a Ca/Na partial salt of MVE/MA copolymer, sodium carboxymethylcellulose and poly(ethylene oxide) hompolymer in a respective weight ratio of about 1:1:1;

(b) from about 5 to about 15 percent w/w of glycerin; and

(c) substantially the remainder of a polyethylene glycol fraction comprising one or more polyethylene glycols each having an average molecular weight of from about 200 to about 20,000 and said fraction having an average viscosity of from about 44 to about 300 centipoises at about 60.degree. C.

51. The composition of claim 50 wherein said mixed, partial salt is a 3.5:1 Ca:Na partial salt of MVE/MA copolymer.

52. The composition of claim 50 wherein (b) comprises about 10 percent w/w of said glycerin.