SK63393A3 - Denture stabilizing compositions - Google Patents

Abstract

Disclosed are adhesives and stabilizer compositions comprising a lower alkyl vinyl ether-maleic acid copolymer and their salts, said copolymer having a specific viscosity larger than 1.2, the sepcific viscosity being determined in methyl ethyl ketone at 25 DEG C and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.

Description

(57) Denture stabilizing formulations comprise an effective adhesive amount of an alkyl vinyl ether-maleic acid copolymer having a structural unit of formula (I) wherein R is an alkyl having a carbon number of 1 to 4, preferably methyl, and n is an integer greater than one. bulk density 0.3 to 1.2 g / cm ³ and specific surface area 0.5 to 2.5 m ² / g.

DENTAL STABILIZATION PREPARATIONS

Technical field

The present invention relates to improved adhesives, in particular improved denture adhesives.

BACKGROUND OF THE INVENTION

Conventional removable dentures, denture, and the like, include teeth attached to a suitable plate or base. Dental prostheses serve as a substitute for missing teeth and replace; _: Y.še.tky. ^ L eb.Q, l €> n _M .čá.st.zubov, commonly found in the oral cavity. Although dentures are generally made professionally, they often do not fit precisely. Moreover, it does not matter that they adhere initially, but after some time the adhesion deteriorates and is imperfect due to the shrinkage and changes of resin, mucosal tissues and the like. The loss of adherence of dental prostheses and thus their imperfection is corrected and stabilized by means of their stabilization. Dental stabilizing agents are used to fill the gaps between a resin or tissue prosthesis. Before placing the prosthesis in the oral cavity, a denture stabilizer is applied to the surface of the denture so that the resin and mucosal tissues are in perfect contact. Denture stabilizing formulations are processed not only for their adherent properties, but also for the need to form an insert or pad between the replacement and the resin or tissue to ensure proper and reliable placement in the oral cavity.

The requirements and characteristics for satisfactory dentifrice stabilizing compositions are numerous and are determined by many factors. It is desirable that once daily dosing, these formulations function as an effective detachment, soft lining and proper placement of the dentures. These preparations, usually in the form of a powder mixture or cream, should retain their characteristics during storage under various climatic conditions such as high temperature and humidity, they should be readily applicable to the surface of the dentures; they should not be irritating and user-friendly, safe and non-toxic; they should not have an unpleasant odor or color, unpleasant taste; optionally, they should have antiseptic or germicidal properties to prevent or inhibit the growth of organisms commonly found in the mouth. They should act as preventive agents against rotting or odorous decomposition of food or secretions near or close to the denture. The stabilizing agent must soak up the water and saliva and be swellable to fill the gaps between the prosthesis and the resin or mucosal tissue. The stabilizer should not damage or attack the prosthesis, for example by cracks in the prosthesis material. Further, the stabillizer should be stable to bacteria, fungi and enzymatic systems occurring in the oral cavity, having a pH value that is non-irritating to the oral mucosa, generally 5 to 8.5, preferably approximately neutral pH. The mechanical strength of the stabilizing mass in the form of a gel or collide, formed by water soaking, should be sufficient to secure the position of the prosthesis in normal use and should not be so high as to cause problems with the required removal of the prosthesis or Select.

In recent years, considerable efforts have been made to develop improved denture adhesives. Both synthetic and natural polymers and resins were used both singly and in combination and further in combination with various additives.

European Patent 64672, Dhabhar and Schmidt, published November 17, 1982, relates to hydrophilic denture adhesives comprising an adhesive polymer fraction comprising a carboxymethylcellulose (CMC) and polyethylene oxide in a hydrophilic vehicle.

European Patent Application 140486, A.J. Desmaris, filed July 31, 1984, relates to denture adhesive compositions comprising a hydrophobically modified water-soluble polymer, alone or mixed with an alkali metal salt of CMC. For use in these compositions, hydrophobically modified hydroxyalkyl celluloses and copolymers of ethylene oxide and long chain epoxyalkanes are preferred.

U.S. Patent 4,280,936, Dhabhar, Heyd and Schmidt, issued July 28, 1981, relates to improved denture adhesives containing a specific ratio of CMC and polyethylene oxide in a mineral oil base.

US Patent 4474902, Dhabhar, Heyd and Schmidt, issued October 2, 1984, relates to improved denture adhesives containing a Karaya resin in a hydrophilic vehicle. See also U.S. Pat. No. 4,541,428, issued April 30, 1985 by the same inventor, relates to improved denture adhesives containing adhesive polymer fractions including mixtures of partial copolymer salts, lower alkyl vinyl ether-maleic anhydride with CMC or polyethylene oxide as well as adhesives containing CMC and polyethylene. See also U.S. Patent 4,522,956, issued June 11, 1985 to Dhabhar and Schmidt for improved denture adhesives containing polyethylene oxide as the sole adhesive component in a hydrophilic vehicle containing certain polyethylene glycols.

Other denture adhesives are described in U.S. Patent Nos. 4,530,942, issued July 23, 1989, 4,542,168, issued September 18, 1985, and 456,9955, issued February 11, 1986.

U.S. Patent 4,529,748 to H.G.P. Wienecke, issued July 16, 1985, relates to denture adhesives formed from film-forming substances, such as various cellulose derivatives, acrylate polymers, meta-crystalline polymers, and other films providing substances.

U.S. Pat. No. 4,138,477, Gaffar, issued February 6, 1979, discloses oral oral odor compositions comprising zinc-polymer combinations formed from anionic reactive zinc. a polymer containing carboxylic, sulfonic and / or phosphonic acid radicals.

U.S. Patent 3,939,888, DPGermann et al., Issued October 10, 1961, discloses certain water-sensitive but water-insoluble denture stabilizing materials which are synthetic, hydrophilic, colloidal materials containing mixed partial salts and esters of copolymers of the type lower alkyl (C 1-4) vinyl ether-maleic anhydride, wherein said mixed partial salts and esters contain both divalent calcium and monovalent alkali (ie, sodium, potassium and ammonium) cations.

U.S. Patent 4,758,630, Shah et al., Issued July 19, 1988, relates to partial zinc and strontium salts of lower alkyl (C1 to C4) vinyl ether-maleic acid copolymers, wherein said zinc and strontium cations are unmixed with any other cations or ester functions in the copolymer salt, the remaining initial carboxyl groups are unreacted. These lower alkyl vinyl ether-maleic acid copolymers will hereinafter be abbreviated as AVE / MA copolymer and methyl vinyl ether-maleic acid copolymer as MVE / MA copolymer. Further, European Patent Application 396411, Holeva and Gounaris, published November 7, 1990, discloses mixed partial salts of an MVE / MA copolymer.

Thus, it is known that combinations of mixed and non-mixed partial salts of lower alkyl vinyl ether-maleic anhydride copolymers are suitable as adhesive compositions for dental prostheses.

Further research is ongoing on denture stabilizers having the characteristics described above and, importantly, they will provide the denture for a longer period (10-14 hours) without the need for a new application.

. Accordingly, according to the present invention, improved adhesion and other characteristics of denture stabilizing formulations will be obtained using specific acids and lower alkyl vinyl ether-maleic acid partial salt (s) with a specific bulk density and specific surface area.

It is an object of the present invention to provide improved denture stabilizers that are easy to prepare and that will be stable over an extended period of time in the oral cavity while still allowing easy removal of the denture when needed.

Another object is to provide such stabilizers using toxicologically acceptable, climatic materials.

Yet another object is to provide stabilizers that function well in the presence of moisture, particularly in the presence of liquids such as saliva, sweat and blood.

These and other objects are accomplished by the present, described below.

SUMMARY OF THE INVENTION.

The present invention relates to adhesive and stabilizer formulations comprising: a lower alkyl vinyl ether-maleic acid copolymer comprising a substantially repeating unit:

OR

.........-— C H.-C H - C H - C H .......

² ii

0 "Cc = o

HO OH_ structural

H 1 where R represents C 1-6 to C4 alkyl radical, n is an integer greater than one, representing the number of repetitions of said structural unit in the molecule of said copolymer and n being such that it characterizes said copolymer as having a specific viscosity greater than 1.2, wherein the specific viscosity is determined in methylethyl ketone at 25 ^° C and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.

Preferably, the copolymers are partial salts (mixed or unmixed, preferably mixed), wherein the partial salts contain from about 10% to about 40% of the free acid and from about 0.1% to about 85% of the total initial carboxyl groups reacted as cationic salt function. with one or more cationic salt groups selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations and ammonium cations and mixtures thereof and wherein said copolymer has a a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram. Also disclosed are dentifrice stabilizing formulations comprising a safe and adhesive effective amount of two or more denture adhesive components, wherein one of said denture adhesive components is either a copolymer blended partial salt (i) of the present invention. The bulk density is measured according to ASTM method B-52 (02.05).

Preferably, these copolymers or mixed partial salts are used together with a water-sensitive polymeric material selected from the group consisting of:. natural, resins, synthetic polymers, carbohydrate derivatives, cellulose derivatives and mixtures thereof.

All percentages and ratios used to neutralize the salts of the present invention are based on stoichiometric percentages of cations present in the salt. All percentages and ratios are by weight unless otherwise indicated.

The present invention relates to stabilizing compositions comprising a lower alkyl vinyl ether-maleic acid copolymer comprising a substantially repeating structural unit:

OR-CH-CH-CH-CH

2. i i

HO

OH

III wherein R represents C 1-6 to C4 alkyl radical, n is an integer greater than one, indicating the number of repeating structural units in the molecule of said copolymer, and n is large enough to characterize said copolymer as having a specific viscosity greater than 1.2, the specific viscosity being determined in methylethylketone at 25 ^° C and said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.

Preferably, the copolymers are partial salts, wherein the partial salts contain from about 10% to about 40% of the free acid and, as a cationic salt function, from about 0.1% to about 85% of the total initial carboxyl groups reacted. with one or more cationic salt groups selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations, and mixtures thereof, and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.

Preferably, the partial salts (preferably mixed) contain from about 0.1% to about 85% of one or more of the above cationic groups at the following levels: from 0.1% to about 65%, more preferably from about 2% to about 45% and most preferably from about 2.5% to about 30% of zinc or strontium (more preferably zinc) cations, and from about 10% to about 75%, more preferably from about 20% to about 65%, and most preferably from about 40% to about 65% calcium. from about 0.1% to about 25% and more preferably from about 0.1% to about 20% sodium cations and from about 10% to about 40%, most preferably from about 20% to about 35% of the free acid.

Said polymeric salts are preferably prepared by interaction of the AVE / MA copolymer (I) optionally with compounds with calcium, sodium, ammonium and either zinc or strontium cations having functional groups of typical carboxylic acid reactants such as hydroxides, acetates, carbonates, halides, lactates, etc., in an aqueous medium. In a preferred embodiment, zinc oxide and calcium and sodium hydroxide are used. Although zinc hydroxide is not commercially available, its use as a reactant is not difficult and is economical in conjunction with the use of an aqueous suspension of zinc oxide particles which, although practically insoluble in water, provides zinc oxide on the surface of the timers by hydration. Conversely, calcium and sodium hydroxide as well as strontium hydroxide are available in either crystalline or powder form and are soluble in about. 50 parts., Water. Aqueous solutions of strontium oxide which form the hydroxide when treated with water (caution: heat evolution) can also be used. Strontium carbonate may also be used.

Anions that form toxic, irritating or contaminating by-products should be avoided or treated in a special way to ensure the removal and absence of such by-products from polymeric salt by-products. The individual compounds used herein should be substantially pure to provide a substantially pure, substantially white, polymeric salt end product.

Lower alkyl vinyl ether-maleic acid copolymers (I) are readily obtained by copolymerizing a lower alkyl vinyl ether monomer such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether and isobutyl vinyl ether with maleic anhydride to form the corresponding lower alkyl vinyl ether-copolymer which is easily (I). Both anhydride and acid forms are also available from commercial suppliers. For example, GAF Corporation

Wayne, New Jersey provides both the polymeric free acid form (I) and the corresponding anhydride form under the trade name G ANTRES as G ANTRES S SERES and GANTREZ AN SERES. Of the acidic series, G ANTRES S-97 (M.wt. - 50,000) are particularly suitable, and of the above anhydride series, G ANTRES AN-149 (mw = 50,000), G ANTRES AN-169 (m. = 67,000) and G ANTRES AN-179 (wt.% = 80,000) copolymers. Said acid and anhydride forms of AVE / MA copolymers having an average molecular weight of from about 50,000 to about 80,000 (measured by membrane osmometry in 2-butanone, 1-10 grams / 1,000 mL solution) are also characterized in having the above described a specific viscosity parameter greater than 1,2. If the anhydride copolymer is dissolved in water, the anhydride linkage is cleaved to form a highly polar polymer free acid (I). Accordingly, the anhydride form, which is relatively less expensive than the acid form, can be used as a conventional and inexpensive acid precursor. Increased temperature may be advantageously used to increase the rate of hydrolysis of the anhydride to the acid.

Generally, the lower alkyl vinyl ether-maleic acid copolymer (I), or the corresponding anhydride thereof, is added to the water preheated to about 70-80 ° C with vigorous stirring to form a homogeneous mixture. If an anhydride precursor is used, it is recommended to first heat the aqueous mixture to about 90 ° C with stirring to achieve complete hydrolysis of the anhydride to the acid form. The heating is then discontinued and stirring is continued until the batch is clear while the viscosity is reduced (about 65-75 ° C). In a preferred embodiment, the aqueous solution with cationic zinc or strontium salt-forming compounds, or, for example, an aqueous dispersion of particulate zinc oxide, is combined with calcium hydroxide to form a slurry, in an amount sufficient to provide the zinc or calcium cation content desired in the final product. at ambient temperature and slowly added to the hot polymeric acid solution while continuing vigorous stirring to avoid local precipitation of the cationic polymeric salt. After the calcium and zinc have been reacted, a solution of sodium hydroxide is added slowly in an amount sufficient to provide the sodium cation content required in the final product. After the addition was complete, stirring was continued until all of the salt-forming compounds had reacted with the copolymer.

Alternatively for this preferred embodiment, the aqueous solution containing the zinc and calcium source is preheated to 70-80 ° C with vigorous stirring to form a homogeneous slurry. The lower alkyl vinyl ether - maleic acid (I) copolymer or its corresponding anhydride is then added to the slurry and further heated to 90 ° C. C and stirring is continued until complete hydrolysis is achieved. Alternatively, the AVE / MA copolymer, pulverized calcium and zinc oxide, is slurried in water at 25 ° C and then heated to 80-90 ° C to effect the reaction.

The zinc (or strontium), calcium and sodium cations in the resulting mixed partial salt of the AVE / MA copolymer should be sufficient to achieve a neutralization range of up to about 10% to about 75%, preferably from about 20% to about 65%, and most preferably from about 40%. % to about 65% calcium and from about 0.1% to about 65%, preferably from about 2% to about 45%, and most preferably from about 2.5% to about 30% zinc or strontium, and from about 0.1% to about 25%, preferably from 0.1% to about 20% sodium, resulting in a salt containing free acid ranging from about 10% to about 40%, preferably from about 20% to about 35%.

The batch is then dried using a hot tub steam dryer at a pressure of 560 to 700 kPa to evaporate the contained water and obtain a high specific surface area polymer salt in flake form.

The resulting flakes are ground and tested to have the desired physical properties to provide stabilizing properties for dentures, while maintaining the desired high specific surfaces. These specific surfaces may be obtained by any suitable micronization technique, preferably by airborne or roller / disc milling or hammer mills as described in Remington's Pharmaceutical Sciences (16th edition) p. 1535-1539, the disclosure of which is incorporated herein by reference.

Said salts are free-flowing and bulk density can be obtained. For best results, the drum-dried particles should be ground to a preferred bulk density of about 0.3 to about 1.2, more preferably about 0.6 to about 1.2, and most preferably about 0.7 to about 1.2 grams, per cubic by maintaining a specific surface area of about 0.5 to about 2.5, more preferably about 0.6 to about 2.5, and most preferably about 0.7 to about 2.0 square meters per gram. The milled particles should be able to pass through a sieve having a mesh size of 140-200 mesh (U.S.B.S. width) and preferably be less than 0.3 millimeters in their largest dimension.

Said acidic copolymers and their possible salts have an exceptional adhesive quality in contact with water or saliva, making them particularly suitable as denture adhesive materials in stabile denture preparations. For such use, the salt in particulate form is preferably characterized by a particle size of at least below 140 mesh U.S.B.S. a sieve having a bulk density of greater than 0.3 grams per cubic centimeter and preferably greater than 0.6 grams per cubic centimeter and a pH between 3 and 8, preferably between 5 and 7.5 when determining the pH of a one percent dispersion in water.

Each of said copolymer salts can be used in effective adhesive amounts, preferably at least 25% by weight, as an adhesive component alone or as a coadhesive in conjunction with other active adhesive components in dentifrice stabilizing formulations.

Preferably, said copolymer salt is used together with a co-adhesive in dentifrice stabilizing formulations. Preferably, the co-adhesive is a polymeric material selected from the group consisting of natural gums, synthetic polymers, carbohydrate derivatives, cellulose derivatives, and mixtures thereof. Generally, from about 15 to about 70 percent, based on the total weight of the composition, of said mixed calcium / sodium / zinc or strontium salt is present.

Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the property of swelling under the action of moisture to form a mucilaginous mass. Such adhesive materials include both natural gums and synthetic polymeric resins and many are commonly used in dentifrice stabilizing formulations and are also suitable as co-adhesives with mixed AVE / MA copolymer salts and may be, for example, karaya gum, gelatin , algin, sodium alginate, tragacanth, methylcellulose, acrylamide polymers, ethylene oxide polymers, polyvinylpyrrolidone, cationic polyarylamide polymers, and as the most preferred sodium salt of carboxymethylcellulose and a poly (vinylmethyl maleic acid copolymer) mixed salt.

Accordingly, according to the present invention, an advantageous solution provides an adhesive and dentifrice stabilizing compositions having an effective adhesive amount of a lower alkyl vinyl ether-maleic acid copolymer as a stabilizing component, which essentially comprises a repeating structural unit:

H1 wherein R represents up to a C4 alkyl radical, n is an integer greater than one, representing the number of structural unit repetitions in the molecule of said copolymer and n is so high as to characterize said copolymer as having a specific viscosity greater than 1.2, wherein the specific viscosity is determined in methyl ethyl ketone at 25 ° C and wherein said copolymer has a bulk density of from about .3 to about 1.2 grams per cubic centimeter and a specific surface area from about 0.5 to about 2.5 square meters per g.

Preferably, the copolymers are partial salts, wherein the partial salts contain from about 10% to about 40% of the free acid, and as cationic salt function from about 0.1% to about 85% of the total initial carboxyl groups reacted with one or more cationic salt groups, selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations, and mixtures thereof, and wherein said copolymer has a bulk density of from about 0.3 to about 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram.

Another preferred aspect of the present invention provides a denture stabilizing composition comprising a safe and adhesive effective amount of at least two denture adhesive ingredients, wherein one of said denture adhesive ingredients is an acid lower alkyl vinyl ether-maleic acid copolymer or salt thereof described above. It is preferably a co-adhesive, as previously described.

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The following examples illustrate, but are not limited to, the practice of the invention, and combine both essential and possibly present ingredients. These examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Examples of the invention.

Example 1

To a reaction vessel equipped with a high speed stirrer and containing 94 parts (4.7 kg) of purified water heated to 85 ° C, was slowly added 6 parts (300 grams) of methvinyl ether-maleic acid copolymer over 15 minutes. The temperature and agitation remain constant for 60 minutes after 15 minutes, the resulting adhesive polymer dispersion being characterized by an increase in viscosity and a decrease and stabilization of the reaction pH when the material is dispersed in water. Said material comprises the acid form of the methyl vinyl ether-maleic acid copolymer.

The resulting methyl vinyl ether-maleic acid (MVE / MA) copolymer solution is then dried using a hot steam drum dryer to evaporate the water content and obtain a high specific surface area polymeric salt, in flake form. The dried acid form of the MVE / MA copolymer is thus obtained, which is then milled using an air jet mill or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter, while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram. This copolymer is then passed through a 140 mesh screen and then through a 200 mesh screen (U.S.B.S. mesh set). The powder has a pH of 2.5 for a 1% solution in water. The particulate copolymer will hereinafter be abbreviated as the acid form of the MVE / MA copolymer.

When used in conjunction with conventional denture adhesives and applied to a wet denture in normal use, it will provide excellent stabilizing characteristics to the denture compared to those obtained with conventional denture adhesives alone applied alone.

Example 2

To a reaction vessel equipped with a high speed stirrer and containing 92.1 parts (1.842 kg) of purified water heated to 85 ° C was slowly added calcium hydroxide 1.9 parts (37.9 grams) and sodium hydroxide 0.3 parts (5.8 grams). ). Upon completion of the addition, the temperature of the slurry is kept constant during stirring at high speed. While keeping the heating and stirring constant, 5.71 parts (114 grams) of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkaline dispersion. The addition was carried out for 15 minutes. The temperature and stirring were kept constant for 60 minutes. After 15 minutes, the resulting adhesive polymer dispersion is characterized by increased viscosity and reduced and stabilized reaction pH and is a dispersion of said material in water. Said material comprises a mixed partial calcium-sodium salt of a methyl vinyl ether-maleic acid copolymer.

The resulting calcium-sodium salt of methyl vinyl ether-maleic acid copolymer (MVE / MA) is then dried in a tumble dryer while maintaining at 560-700 kPa with hot steam to evaporate the water and obtain a high specific surface area polymeric salt in the form of flakes. The dried calcium / sodium salt of the MVE / MA copolymer thus obtained is then milled using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter, while maintaining a specific surface area of about 0.7 to about 1, 5 square meters per gram. This copolymer is then screened through a 140 mesh screen and then through a 200 mesh screen (U.S.B.S. mesh set). The powder has a pH of about 6.5 for a 1% solution in water. Salt analysis indicated about 70.0 percent calcium neutralization, 10.0 percent sodium neutralization with 20% residual carboxyl groups. This individual salt will hereinafter be abbreviated herein as 70% Ca / 10% Na partial salt of MVE / MA copolymer

The product, when used in conjunction with conventional denture adhesives and applied to a wet denture with normal use, provides dental stabilization characteristics superior to those obtained with individual conventional adhesives alone. for dental prostheses.

Example 3

To a reaction vessel equipped with a high speed stirrer and containing 92.4 parts (4.6 kg) of purified water heated to 85 ° C was slowly added 0.53 parts (26.3 grams) of zinc oxide and calcium hydroxide (64.6 grams). After the addition is complete, the temperature of the slurry is kept constant at high stirring speed. While keeping the heating constant and stirring, 5.76 parts (288 grams) of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkaline dispersion over 15 minutes. The temperature and stirring were kept constant for 60 minutes. After 15 minutes, the resulting adhesive polymer dispersion is characterized by increased viscosity and reduced and stabilized pH reaction of the material dispersion in water. Said material comprises a mixed partial calcium zinc salt of methyl vinyl ether-maleic acid copolymer.

The resulting solution of calcium-zinc salt of methyl vinyl ether-maleic acid copolymer (MVE / MA) is then dried using a drum dryer maintained at 560-700 kPa with hot steam to evaporate the water present and obtain a high specific surface area polymer salt in flake form. The dried calcium-zinc MVE / MA copolymer salt thus obtained is then milled using an air jet mill or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter, while maintaining a specific surface area of about 0.7 to about

1.5 square meters per gram. This copolymer is then screened through a 140 mesh screen followed by a 200 mesh screen (U.S.B.S mesh set). The powder has a pH of about 5.4 for a one percent solution in water. Analysis of the salt shows about 47.5 percent calcium neutralization, 17.5 zinc neutralization with 35% of the remaining carboxyl groups. copolymer.

The product, when used in conjunction with conventional denture adhesives and applied to normal use wet prostheses, provides dental stabilization characteristics that are superior to those of conventional dental adhesives alone.

Example 4

0.2 parts (18 grams) of zinc oxide and 0.92 parts of calcium hydroxide (82.7 grams) are slowly added to a reaction vessel equipped with a high speed stirrer containing 84.7 parts (7.6 kg) of purified water heated to 85 ^° C. ). After the addition is complete, the temperature of the slurry is kept constant at high stirring speed. While keeping the heating and stirring constant, 3.9 parts (348 grams) of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkaline dispersion, added over 15 minutes. After about 15 minutes, the resulting adhesive polymer dispersion is characterized by increased viscosity and a decrease and stabilization of the reaction pH in the dispersion of said material in water. Said material comprises a mixed partial calcium-zinc salt of methyl vinyl ether-maleic acid copolymer. The temperature and stirring were kept constant for 60 minutes. Next, a 1% sodium hydroxide solution was added over 30 minutes and the reaction was allowed to complete as indicated by stabilizing the reaction pH.

The resulting solution of calcium-zinc salt of methyl vinyl ether-maleic acid copolymer (MVE / MA) is then dried using a tumble dryer at 560-700 kPa with hot steam to evaporate the water content, and obtain a high specific surface area polymer salt in the form of flakes. The thus obtained dried calcium-zinc MVE / MA copolymer salt is then milled using an air jet or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about 1.5 square meters per gram. This copolymer is then sieved through a 140 mesh sieve and then through a 200 mesh sieve (U.S.B.S mesh set). The powder has a pH of about 5.7 for a one percent solution in water. Salt analysis indicated about 50 percent calcium neutralized carboxyl groups, zinc neutralized 9.9, and 5% sodium neutralized and 35% remaining unreacted carboxyl groups. This individual salt will hereinafter be abbreviated as 50% Ca / 9.9% Zn / 5% Na partial salt of the MVE / MA copolymer.

The product, when used in conjunction with conventional denture adhesives and applied to damp prostheses in normal use, provides stabilizing characteristics on dental prostheses, superior to those obtained with conventional dental adhesives alone.

Example 5

To a reaction vessel equipped with a high speed stirrer and containing 85.1 parts (7.7 kg) of purified water heated to 85 ° C, slowly add 0.1 parts (9 grams) of zinc oxide and calcium hydroxide - 1.1 parts (98.8). g). After the addition is complete, the temperature of the slurry is kept constant with stirring at high speed. While keeping the heating and stirring constant, 3.9 parts (347.2 grams) of methyl vinyl ether-maleic anhydride copolymer are added to the reaction vessel containing the alkaline dispersion. Add over 15 minutes. After about 15 minutes, the resulting adhesive polymer dispersion is characterized by an increase in viscosity and a decrease and stabilization of the reaction pH of the dispersion of said material in water. The temperature and stirring remain constant for 60 minutes. Then 890 grams of 1% sodium hydroxide solution are added over 30 minutes and the reaction is allowed to proceed to completion indicating stabilization of the reaction pH.

The resulting solution of calcium-zinc salt of methyl vinyl ether-maleic acid copolymer (MVE / MA) is then dried using a tumble dryer maintained at 560-700 kPa with hot steam to evaporate the water content and obtain a high specific surface area polymer salt in the form of flakes. The thus obtained dried calcium-zinc salt of an MVE / MA copolymer is then milled using an air jet mill or hammer mill to a bulk density of about 0.7 to about 1.1 grams per cubic centimeter while maintaining a specific surface area of about 0.7 to about

1.5 square meters per gram. This copolymer is then sieved through a 140 mesh sieve followed by a 200 mesh sieve (U.S.B.S mesh set). The powder has a pH of about 6.0 for a one percent solution in water. Salt analysis indicated about 60% calcium neutralized carboxyl groups, 5% zinc neutralized, and 5% sodium neutralized with 30% remaining unreacted carboxyl groups. This salt will be referred to herein as 60% Ca / 5% Zn / 5% For the partial salt of the MVE / MA copolymer,

The product, when used in conjunction with conventional denture adhesives and applied to normal denture prostheses, provides dental stabilization characteristics that are superior to those obtained using conventional dental adhesive alone.

Example 6

The procedure of Example 1 was repeated except that the following amounts of reactants were used: 3.9 parts (77.3 grams) of anhydride copolymer, 94.9 parts (1.9 kg) of purified water and 0.2 parts (3, 99 grams) of zinc oxide, 0.2 parts (3.99 grams) of sodium hydroxide and 0.83 parts (16.5 grams) of calcium hydroxide.

The resulting powder should have a bulk density of from about 0.7 to about 1.1 grams per cubic centimeter and a specific surface area of about 0.7 to about 1.5 square meters per gram. Salt analysis shows about 45 calcium neutralized carboxyl groups and their initial number in the salt copolymer molecule, 9.9 percent zinc neutralization and 10% sodium neutralization, the salt will be hereinafter abbreviated as 45% calcium / 9.9% zinc / 10% sodium partial salt. MVE / MA copolymer.

Example 7

The general procedure of Example 5 is repeated except that appropriate amounts of zinc oxide, calcium hydroxide and sodium hydroxide are used to achieve tabulated substitutions and the following calcium (zinc) sodium salts of MVE / MA copolymer are obtained:

sodium calcium zinc 0 ⁶⁰ 5 5 55 5 10 60.5 2.5 10 65 2.5 15 40 9.9 20 40 9.9 5 55 9.9

Each of said MVE / MA copolymer salts should be a powder below 140 mesh U.S.B.S. sieve, having a bulk density of greater than 0.5 grams per cubic centimeter, while maintaining a specific surface area greater than 0.6 square meters per gram and providing significantly improved stabilization characteristics for dental prostheses. Each of said salts can be truncated as in Examples 1 to 5: calcium percentage / zinc percentage / sodium percentage for neutralization.

Example 8

Repeat the hydrolysis of the MVE / MA copolymer anhydride to the acid of Example 5. To a vessel containing 8.5 kg of purified water heated to 85 ° C was added 16.5 grams of strontium hydroxide octahydrate. During vigorous stirring, 99.4 grams of calcium hydroxide is slowly added. After the addition is complete, the temperature of the slurry is kept constant while stirring at high speed. While maintaining heating and constant stirring, 34.9 grams of methyl vinyl ether-maleic anhydride copolymer is added to the reaction vessel containing the alkaline dispersion over 20 minutes. A mixed partial calcium strontium salt of methyl vinyl ether-maleic acid copolymer is thus obtained.

Example 9

Stabilizing powder preparations for dental prostheses are prepared by mixing the following ingredients together:

% weight / weight

A B karey gum 53 53 sodium carboxymethylcellulose 16 16 sodium borate 7 7 47.5% Ca / 17.5 Zn mixed partial salt of MVE / MA copolymer 24 - 60% Ca / 5% Zn / 5% Na partial a salt of an MVE / MA copolymer - 24 100 100 sodium alginate 55 55 sodium carboxymethylcellulose 10 10 polyvinylpyrrolidone (average mol. weight. = 90,000) 15 15 65% Ca / 10% Zn mixed partial a salt of an MVE / MA copolymer 20 - 60.5% Ca / 2.5% Zn / 10% Na partial salt of MVE / MA copolymer - 20 100 100 sodium carboxymethylcellulose 50 50 70% Ca / 10% For mixed partial a salt of an MVE / MA copolymer 50 30 50% Zn unmixed partial salt MVE / MA copolymer - 20

100

100

Gantrez S-97 acid copolymer 60 30 sodium carboxymethylcellulose 40 40 70% Ca / 10% For mixed partial a salt of an MVE / MA copolymer - 30 100 100

Said MVE / MA free acid copolymer and said mixed or unmixed partial salts of MVE / MA copolymer should form a powder below 140 mesh - U.S.B.S. sieve, having a bulk density of greater than 0.5 grams per cubic centimeter, while maintaining a specific surface area greater than 0.6 square meters per gram.

In use, the above powders (typically 0.1-1 g) are placed on a pre-moistened denture, allowed to hydrate briefly, and the denture is inserted into the mouth and pressed into place, as with any dental adhesive known in the art. .

Example 10

Liquid-type denture stabilizing formulations are prepared by mixing the following ingredients:

% weight / weight A B mineral oil, heavy 44.9 43.9 petrolatum 3.0 3.0 colloidal silicon dioxide 1.5 1.5 sodium carboxymethylcellulose 30.5 30.5 menthol 0.1 0.1 47.5% Ca / 17.5% Zn mixed partial salt of MVE / MA copolymer. 20.0 -

% Ca / 5% Zn / 10% For mixed partial salt of MVE / MA copolymer - 20.0

100.0 100.0

In use, the above liquids (typically 0.1-1 g) are placed on a pre-moistened denture, allowed to hydrate briefly, and the denture is placed in the mouth and pressed into place in the same manner as well known denture adhesives. .

Example 11

Cream-type denture stabilizing preparations are prepared by mixing the following ingredients:

% weight / weight

A B C

mineral oil, heavy 24,824 24,824 24,824 sodium carboxymethylcellulose 22,000 22,000 22,000 petrolatum 19,016 19,016 19,016 silica, colloidal 1,100 1,100 1,100 Dye (oil - soluble in red) colored dispersion) 0,060 0,060 0,060 47.5% Ca / 17.5% Zn mixed partial salt of MVE / MA copolymer. 33,000 - - 55.0% Ca / 5% Zn / 10% Na mixed partial salt of MVE / MA copolymer - 33,000 - 70% Ca / 10% For partial blend a salt of an MVE / MA copolymer - - 16,500 50% Zn of unmixed partial salts of MVE / MA copolymer - - 16,500

Said MVE / MA free acid copolymer and said mixed or unmixed partial salts of MVE / MA copolymer should be powder below 140 mesh U.S.B.S. a sieve having a bulk density of greater than 0.5 grams per cubic centimeter, while maintaining a specific surface area greater than 0.6 square meters per gram.

In use, the above creams (typically 0.1-2 g) are placed on a pre-moistened dentures, allowed to hydrate briefly, and the dentures are placed in the mouth and pressed into place in the same manner as well known in the art. denture adhesives.

P1 / £ 33-91

Claims (10)

CLAIMS 1. A lower alkyl vinyl ether-maleic acid copolymer comprising a substantially repeating structural unit of formula I OR - CH - CH - CH - CH (1) ^of II 0-CC = 0 HOOH ^{the J} n wherein R is a C to C 4 alkyl radical, preferably methyl, n is an integer greater than one representing the number of times of said structural unit in a molecule of said copolymer and n is the size sufficient to characterize said copolymer as having a specific viscosity larger than 1.2 wherein the specific viscosity is determined in methyl ethyl ketone at 25 ° C and wherein said copolymer has a bulk density of 0.3 to 1.2 grams per cubic centimeter and a specific surface area of 0.5 to 2.5 square meters per gram. A lower alkyl vinyl ether-maleic acid copolymer partial salt comprising a substantially repeating structural unit of the formula I wherein R represents a C 1 -C 4 alkyl radical, preferably methyl, n is an integer greater than one representing the number of repeating structural units in the molecule 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 it contains., _R? by ^ 0? a ^ to.:. 4QÄM7-ú.v.ofnej. acids and how. a cationic salt function of from 0.1% to 85% of all initial carboxyl groups reacted with one or more cationic salt functions selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations mixtures thereof, and wherein said copolymer has a bulk density of from 0.3 to 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram. The partial salt of claim 3, wherein said cationic salt function is selected from the group of zinc, strontium, calcium and sodium cations and mixtures thereof and includes: a) from 0.1% to 65% of zinc or strontium cations, preferably 2.5% to 30% of zinc cations; and b) from 0.1% to 75% of calcium or sodium cations, preferably from 5% to 20% of sodium cations or mixtures thereof, and (c) from 40% to 70% of calcium cations of the total initial amount of carboxyl groups and from 10% to 40% of free acid, and wherein said salt has a bulk density of 0.6 to 1.2 grams per cubic centimeter and a specific surface area of 0; 6 to 2.5 square meters per gram. 4. A denture stabilizing composition, characterized by t. characterized in that the stabilizing component comprises an effective adhesive amount of a lower alkyl vinyl ether-maleic acid copolymer comprising a substantially repeating structural unit of formula (I) OR —-CH. — OH — CH — CH H r Z | I ' ¹ o = cc = o ho oh LJ _n - where R represents.; G. | a to X 1 alkyl radical, preferably methyl, n an integer greater than one, representing the number of repeating structural units in the molecule of said copolymer an is sufficiently large to characterize the copolymer as having a specific viscosity greater than 1.2, wherein the specific viscosity is determined in methyl ethyl ketone e at 25 ° C and wherein said copolymer has a bulk density of 0.3 to 1.2 grams per cubic centimeter and a specific surface area of 0.5 to 2.5 square meters per gram. 5. A denture stabilizing composition comprising, as a stabilizing component, an effective adhesive amount of a mixed partial salt of lower alkyl vinyl ether-maleic acid copolymers comprising a substantially repeating structural unit of formula (I). OR ---- CH: -CH — CH — CH ^from ii 0 = C = 0 HO OH wherein R represents a C 1 -C 4 alkyl radical, preferably methyl, n is an integer greater than one, representing the number of repeating structural units in the molecule of said copolymer and n is sufficiently large to characterize the copolymer as having a specific viscosity greater than 1.2; the specific viscosity is determined in methyl ethyl ketone at 25 ^° C, wherein said partial salt contains from 10% to 40% of free acid and as cationic salt function from 0.1% to 85% of all initial carboxyl groups reacted with one or more cationic salt functions, selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations and mixtures thereof, and wherein said copolymer has a bulk density of from 0.3 to 1.2 grams per cubic centimeter and specific surface area from about 0.5 to about -2.5 square meters. - · - ...... 6. The partial salt of claim 3, wherein said cationic function is selected from the group consisting of zinc, strontium, calcium and sodium cations and mixtures thereof and comprises: a) from 0.1% to 65% of zinc or strontium cations, preferably 2.5% to 30% of zinc cations; and b) from 0.1% to 75% of calcium or sodium cations, preferably from 5% to 20% of sodium cations or mixtures thereof, and c) from 40% to 70% of calcium cations of the total initial amount of carboxyl groups that have reacted and from 10% to 40% of free acid and wherein said salt has a bulk density of 0.6 to 1.2 grams per cubic centimeter and specific surface area from 0.6 to 2.5 square meters per gram. 7. A denture stabilizing composition comprising a safe and effective amount of at least two denture adhesive ingredients, wherein one of said denture adhesive ingredients is a lower alkyl vinyl ether-maleic acid copolymer comprising substantially repeating structural unit of formula I OR -CH-CH-CH-CH = CC ^of io-O ^^^ OH _and it _'tsp l ^ e ^ _fourth p.CB ^ <isiajaij.e .. € 4, .až.C4_alkyJov.ý radical ^ preferably methylene is an integer greater than one, representing the number of repeating structural units in the molecule of said copolymer and is large enough to characterize said copolymer as having a specific viscosity of greater than 1.2, wherein the specific viscosity is determined in methyl ethyl ketone at 25 ° C. And wherein said copolymer has a bulk density of from 0.3 to 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram. 8. A denture stabilizing composition, characterized by: w said composition comprising a safe and effective amount of at least two denture adhesive components, wherein one of said denture adhesive components is a mixed lower alkyl vinyl ether-maleic acid copolymer partial salt comprising a substantially repeating structural unit of formula I III η wherein R represents C 1-6 to C4 alkyl radical, preferably methyl, n is an integer greater than one, representing the number of repeating said structural units in the molecule of said copolymer and n is large enough to characterize the copolymer as having a specific viscosity greater than 1.2, wherein the specific viscosity is determined in methyl ethyl ketone at 25 ° C and conducted with from about 1% to about 40% of the free acid, and as a cationic salt function from 0.1% to 85% of the total initial carboxyl groups reacted with one or a plurality of cationic salt functions selected from the group consisting of zinc cations, strontium cations, sodium cations, calcium cations, magnesium cations, potassium cations and ammonium cations and mixtures thereof, and wherein said copolymer has a bulk density of from 0.3 to 1.2 grams per cubic centimeter and a specific surface area of from about 0.5 to about 2.5 square meters per gram. 9. The partial salt of claim 3, wherein said cationic salt function is selected from the group consisting of zinc, strontium, calcium and sodium cations and mixtures thereof and comprises: a) from 0.1% to 65% of zinc or strontium cations, preferably 2.5% to 30% of zinc cations; and b) from 0.1% to 75% of calcium or sodium cations, preferably from 5% to 20% of sodium cations or mixtures thereof, and c) from 40% to 70% of calcium cations of the total initial amount of carboxyl groups reacted and from 10% to 40% of free acid groups and wherein said salts have a bulk density of from 0.6 to 1.2 grams per cubic centimeter and specific surface area from 0.6 to 2.5 square meters per gram. A denture stabilizing composition according to any one of the preceding claims, wherein said polymeric material is selected from the group consisting of natural gums, synthetic polymers, carbohydrate derivatives, cellulose derivatives and mixtures thereof, and further comprising from 0.01% up to 5.0% menthol, menthyl lactate, peppermint oil, spearmint oil, leaf alcohol and paramentanecarboxamides and mixtures thereof.