JPH06503350A - Denture stabilizing composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] This invention relates to improvements in adhesives, particularly improved denture adhesives.

Background of the invention Ordinary removable dentures, dental plates, etc. are attached to a suitable plate or base. Consists of chipped teeth. Dentures serve as replacements for missing teeth and are commonly found in the oral cavity Serves as a full or partial tooth replacement. Although dentures are usually expertly manufactured, They don't fit perfectly. Furthermore, no matter how satisfied you are at first, The fit of the denture may vary due to natural shrinkage and changes in the gingiva, mucous tissue, etc. < (1oose) and becomes incomplete. Loosely and imperfectly fitted dentures are usually Corrected and stabilized with the use of denture adhesives. Denture adhesives are used for dentures and gums or tissues. It is used to fill the gap between Apply denture adhesive to the denture before placing the denture in the mouth. Applied to the tooth plate surface, it is closely connected to the gingival and mucous tissues for a perfect fit. Contact should be even. Denture adhesives are used not only for their adhesive properties but also for dentures. It is also prescribed to provide a cushion or gasket between the gums or tissues; This allows the denture to be reliably positioned within the oral cavity.

The requirements and characteristics for a satisfactory denture stabilizing composition are numerous and depend on numerous factors. Described by. Preferably, a single daily application of such a composition will separate the denture. It should become a cushion and function as an effective means for reliably positioning. It is possible. The composition typically undergoes storage under various climatic conditions such as high temperature and humidity. should retain its characteristics and properties in powder and cream form; be simple and easy to apply; not irritating or unpleasant to the user; safe and be non-toxic; have no unpleasant odor or color; have no unpleasant taste; Do not use; in some cases, preservatives that prevent or inhibit the growth of organisms normally found in the mouth. and exhibit bactericidal properties; in addition, food or secretions that remain under or near the dentures. It should function as an anti-septic or odor-decomposing agent. Stabilizing substances are dentures and gums Or it must be able to absorb water and saliva and swell to fill the gap between mucous tissue. do not have. Stabilizers do not attack or damage the denture by causing cracks in the denture plate material. Shouldn't. In addition, stabilizers are safe against bacteria, fungi, and enzyme systems found in the oral cavity. pH that does not irritate the oral mucosa, usually 5 to 8.5, preferably around neutral pH. Should have H. The mechanical strength of the stable mass formed by water absorption is Whether it is a gel or a colloid, it ensures that the denture remains in position under normal use. However, it is large enough to make it difficult to remove the denture when desired, or may damage the gums during removal. , should not be so large as to cause damage or obstruction to tissues or dentures.

There has been significant effort over the years to develop improved denture adhesives. Synthesis and Polymers and rubbers, both natural and natural, alone, in combination and in combination with various additives has been used.

Dhabhar and 5ch1dt Europe published on November 17, 1982 Patent No. 64,672 discloses carboquine methyl cellulose in a hydrophilic vehicle. (CMC) and an adhesive polymer fraction consisting of polyethylene oxide. This invention relates to a hydrophilic denture adhesive.

A1. Filed on July 31, 1984. Desialis European Patent Application Section No. 140,486 describes hydrophobically modified water-soluble polymers alone or in combination with CM The present invention relates to a denture adhesive composition containing C mixed with an alkali metal salt. Hydrophobic modification A combination of droxyalkyl cellulose, ethylene oxide and long chain epoxy alkanes Polymers are preferred for use in the composition.

Dhabhar, Heyd and Sch, published July 28, 1981 mjdt's U.S. Pat. No. 4,280,936 discloses a specific proportion of An improved denture adhesive containing CMC and polyethylene oxide.

Dhabhar and 5cha+1dt rice issued on October 2, 1984 National Patent No. 4,474,902 discloses a method containing Karaya gum in a hydrophilic vehicle. This invention relates to an improved denture adhesive. Furthermore, lower alkyl vinyl ether anhydrous male A mixture of partial salt of inic acid type copolymer and CMC or polyethylene oxide? Improved denture adhesives containing adhesive polymer fractions consisting of CMC and porous 1 to these same inventors, each relating to a denture adhesive containing lyethylene oxide. U.S. Pat. Nos. 4,514,528 and 198, issued April 30, 985; See U.S. Pat. No. 4,518,721, issued May 21, 2005. Change In a hydrophilic vehicle made of polyethylene glycol, the only adhesive component is 1985 for an improved denture adhesive containing polyethylene oxide Dhabhar and 5chiidt U.S. Pat. No. 4, issued June 11, See specification No. 522,956.

Another denture adhesive is US Pat. No. 4,530,940, issued July 23, 1989. No. 4,542,168, dated September 17, 1985, February 1, 1986 No. 4,569,955, issued on 1st.

H. G. P. Wlenecke U.S. Patent issued July 16, 1985 No. 4,529,748 describes various cellulose derivatives, acrylate polymers, - formed from film-forming materials such as methacrylate polymers and other film-forming materials. The present invention relates to a dental prosthetic adhesive made of

Gaf far U.S. Patent No. 4,138,4 issued February 6, 1979 Specification No. 77 describes anionic polymers containing carbon, sulfone and/or phosphonic acid groups. Breath odor control containing a zinc-polymer combination formed from zinc reacted with a limmer A rollable oral composition is disclosed.

U.S. patent issued October 10, 1961, by P. GerIlann et al. No. 3,003,988 discloses lower alkyl (1 to 4 carbon atoms) vinyl ether- Synthetic hydrophilic compound consisting of mixed partial salts and esters of maleic anhydride type copolymers A water-sensitive but water-insoluble substance for stabilizing dentures that is a colloidal substance. However, the above mixed partial salts and esters contain divalent calcium and -valent acetate. Both contain alkali (i.e. sodium, potassium and ammonium) cations. nothing.

U.S. Pat. No. 4,758,63 to 5hah et al., issued July 19, 1988. Specification No. 0 is a lower alkyl (C-04) vinyl nityl-maleic acid copolymer. with respect to zinc and strontium partial salts of The nitium cation is free from any other cation or ester functionality in the copolymer salt. Both are "unmixed" and the remaining initial carboxyl groups are unreacted.

These lower alkyl vinyl ether-maleic acid copolymers are “AVE” /MA copolymer°, methyl vinyl ether-maleic acid copolymer is “MVE /MA Coyt! Rimmer”.Furthermore, on November 7, 1990, European Patent Application Section 396 of Ho1eva and Gounaris, published on No. 411 discloses mixed-part MVE/MA copolymer salts.

Therefore, lower alkyl vinyl ether-maleic anhydride type copolymers Combinations of mixed and unmixed partial salts are known to be useful as denture adhesive compositions. ing.

exhibiting the above characteristics and importantly for a long period of time (10-14 hours) without the need for reapplication. The search continues for denture adhesives that maintain a secure fit for dentures. There is.

According to the present invention, improved adhesion and other characteristics are achieved by providing a specific bulk density and specific surface area. Specific acids and partial salts of lower alkyl vinyl ether-maleic acid copolymers with can be obtained in a denture stabilizing composition by using

The object of the present invention is to be easy to manufacture, stable in the oral cavity for a long period of time, and meet the requirements. An object of the present invention is to provide an improved denture adhesive that allows easy removal of dentures.

Another objective is to provide such stabilizers using toxicologically acceptable and palatable substances. It is to provide.

Another objective here is to use water in the presence of moisture, especially body fluids such as saliva, sweat and blood. The objective is to provide stabilizers that function well in the presence of chemicals.

These and other objects are achieved by the present invention in the manner disclosed below.

Summary of the invention The present invention essentially consists of a lower alkyl vinyl ether male consisting of the following repeating structural unit: Regarding adhesive and stabilizer compositions containing inic acid copolymers: In the above formula, R represents a C-C alkyl group; n is the upper limit in the molecule of the above copolymer. an integer of 2 or more representing the number of repeated occurrences of the above structural unit, where n is a specific viscosity of 1.2 or more is large enough to characterize the copolymer as having a specific viscosity of Measured in methyl ethyl ketone. The above copolymer is about 0.3 to about 1.2 g/ ctj bulk density and about 0.5 to about 2. 5rr? It has a specific surface area of /g.

Preferably these copolymers are partially salted (mixed or unmixed, preferably mixed). The partial salt contains about 10% to about 40% free acid and cationic salt functionality. from about 0.1% to about 85% of the total initial carboxyl groups corresponding to one or more cationic salts. the cationic salt functional group includes a zinc cation, a strontium cation, Sodium cation, calcium cation, magnesium cation, potassium cation selected from the group consisting of thione, ammonium cation and mixtures thereof; The copolymer has a bulk density of about 0.3 to about 1.2 g/ci and about 0.5 to about 2.5 g/ci. It has a specific surface area of rrr/g. One denture adhesive component is a copolymer of the present invention or A safe and adhesively effective amount of two or more types of denture adhesive ingredients, which are any of the mixed partial salts. Also disclosed are denture stabilizing compositions comprising: Bulk density is determined according to ASTM method B-52 (02,05 > Measured according to

Preferably, these copolymers or mixed partial salts are natural rubber, synthetic polymers, salts, etc. selected from the group consisting of tucharide derivatives, cellulose derivatives and mixtures thereof; used with water-sensitive polymeric materials.

All percentages and ratios used herein with respect to the neutralization of the salts of the present invention are Based on the stoichiometric percent of cations present in the salt. All pars used here Centages and proportions are by weight unless otherwise noted.

Detailed description of the invention The present invention essentially consists of a lower alkyl vinyl ether male consisting of the following repeating structural unit: Regarding stabilizer compositions containing inic acid copolymers: In the above formula, R represents a C-C4 alkyl group; n is in the molecule of the above copolymer. An integer of 2 or more representing the number of repeated occurrences of the above structural unit, where n is a specific viscosity of 1.2 or more. large enough to characterize the copolymer as having a specific viscosity of 25°C. of methyl ethyl ketone: the copolymer weighs about 0.3 to about 1.2 g. /c11 and a bulk density of about 0.5 to about 2. It has a specific surface area of 5d1g.

Preferably these copolymers are partial salts, said partial salts being about 10 to about 40% Of the total initial carboxyl groups reacted as free acid and cationic salt functional groups, approximately 0 ．． 1 to about 85% of one or more cationic salt functional groups, the cationic salt functional groups being Lead cation, strontium cation, sodium cation, calcium cation ion, magnesium cation, potassium cation, ammonium cation and from about 0.3 to about 1.2 g/ The bulk density of i and about 0°5 to about 2. It has a specific surface area of 5d1g.

Preferably the partial salt (preferably a mixture) contains one or more of said cations at a level of Contains about 0.1 to about 85%: about 0.1 to about 65%, more preferably about 2 to about 45% %, most preferably from about 2.5 to about 30% zinc or strontium cations (preferably preferably zinc), about 10 to about 75%, more preferably about 20 to about 65%, most preferably Preferably about 40 to about 65% calcium cations, about 0.1 to about 25%, more preferably about 0.1 to about 25% calcium cations. preferably about 0.1 to about 20% sodium cations and about 10 to about 40%, most preferably about 0.1% to about 20% sodium cations; Preferably about 20 to about 35% free acid.

The polymer salts can be used as hydroxides, acetates, carbonates, etc. in aqueous media. with functional groups typical of carboxylic acid reactants such as halides, lactates, etc. Any cationic calcium, sodium, ammonium and zinc or strobohydrate By interaction of either compound with AVE/MA copolymer (1) Advantageously, it is manufactured. In a preferred embodiment, zinc oxide and calcium The hydroxides of um and sodium are utilized.

Since zinc hydroxide is not commercially available, its use as a reactant is virtually non-existent in water supplies. Aqueous slurry of particulate zinc oxide that is soluble but hydrated to zinc hydroxide on the particle surface This can be done easily and more economically using . On the other hand, calcium hydroxide and Sodium and strontium hydroxide are available in either crystalline or powdered form and are It is soluble in 50 parts of fish. However, if treated with water (caution; heat generation) Aqueous solutions of strontium oxide forming oxides may also be used. Strontium carbonate Mu powder may also be used.

Anions that form toxic, irritating or polluting by-products are avoided or take special precautions. and treatment to ensure the removal and absence of such by-products from the polymer salt final product. This should be done in order to The specific compounds used are substantially pure, substantially The polymer salt should be substantially pure to ensure an off-white final product. be.

Lower alkyl vinyl ether maleic acid (AVE/MA) copolymer (1) is Corresponding lower alkyl vinyl ethers that can be easily hydrolyzed to acid copolymers (+) Methyl vinyl ether, ethyl vinyl ether to produce maleic anhydride copolymers ether, divinyl ether, propyl vinyl ether and imbutyl vinyl ether Copolymerizing lower alkyl vinyl ether monomers such as tel with maleic anhydride It can be easily obtained by Both anhydrous and acid forms are available from suppliers. Ru. For example, GAF of Tsane, New Chassis, has its “Guntlez” NT]? EZ) Trade name: “Gantrez S series” and “Gantrez AN series” respectively. Both the polymer free acid form (1) and the corresponding anhydrous form are supplied as the polymer. former acid In the series, Gantrez 5-97 (M, L-50,000) is particularly suitable. , in the latter anhydrous series, Gantrez AN-149 (M, V, -50,000) , Gantrez AN-169 (M, ν, -67,000) and Gantrez AN , -179 (M, V, -80, OOO) copolymers are particularly suitable. (2 -Butanone 1-10g/l as measured by membrane osmotic pressure method in 000ml solution b) AVE/MA copolymer having an average molecular weight of about 50,000 to about 80,000. The acidic and anhydrous forms of mer have the specific viscosity parameter of 1.2 or more. is also characterized. When the anhydrous copolymer is dissolved in water, the anhydrous bond chains are cleaved, As a result, a highly polar polymeric free acid (1) is formed. Therefore, compared to the acid form, The anhydrous form, which is relatively inexpensive, may be used as a convenient and inexpensive precursor to acids. high temperature is advantageously used to increase the rate of hydrolysis of anhydride to acid.

Generally, lower alkyl vinyl ether-maleic acid copolymer (1) or a pair thereof The anhydride is preheated to about 70-80°C under vigorous stirring to form a homogeneous mixture. added to the water. If an anhydrous precursor is utilized, the aqueous mixture is further heated to approximately 90°C under stirring to ensure complete hydrolysis to the acid form. is recommended.

Heating is then discontinued, but mixing continues until the batch becomes clear and the viscosity decreases at the same time. Continue until the temperature is low (approximately 65-75°C). In a preferred embodiment, cationic Aqueous solutions of zinc or strontium salt-forming compounds or e.g. particulate zinc oxide in water The dispersion has the desired zinc and calcium cation content desired in the final product. Mixed with calcium hydroxide in a slurry in sufficient quantities to prepared and subjected to continuous vigorous mixing to prevent local precipitation of the cationic polymer salt. Add slowly to the hot polymer acid solution under washing. Calcium and zinc are anti After the reaction, an aqueous solution of sodium hydroxide is added to the desired cation sodium in the final product. Add slowly in sufficient quantity to achieve content. Mixing after addition is followed to ensure that all salt-forming compounds react with the copolymer. Ru.

Alternatively, in this preferred embodiment, an aqueous solution containing a zinc and calcium source is provided. The liquid is preheated to 70-80°C under vigorous stirring to form a homogeneous slurry. . Next, lower alkyl vinyl ether-maleic acid copolymer (1) or a pair thereof Anhydride is added to the slurry, with additional additions to ensure complete hydrolysis. Heat to 90°C and stir. Or, AV E / MA copolymer, calci strontium oxide or zinc oxide powder is slurried in water at 25°C; It is then heated to 80-90°C so that the reaction takes place. Completion of this reaction step After completion, an aqueous solution of sodium hydroxide is slowly added. , the resulting AVE/ Zinc (or strontium), calcium in mixed partial salts of MA copolymers and sodium cations from about 10 to about 75%, preferably from about 20 to about 65%. , most preferably about 40 to about 65% calcium, about 0.1 to about 65%, preferably preferably from about 2 to about 45%, most preferably from about 2.5 to about 30% zinc or strontium. and about 0.1 to about 25%, preferably about 0.1 to about 20% sodium. neutralized state within the range of about 10 to about 40%, preferably about 20 to about 35%. It should be sufficient to yield the salt containing the free acid.

The reaction batch is then evaporated to form a high specific surface area polymer salt in flake form. 80-100 PSIG (approximately 5.6-7 kg/ Dry using a drum dryer maintained at

The resulting flakes exhibit desirable physical properties indicating satisfactory denture stabilizing properties. It is then subjected to crushing and sieving to maintain the desired high specific surface area.

These surface areas are incorporated herein for reference. armaeutical 5 sciences (teth edltion) Any suitable comminution technique, preferably as described in pp. 1535-1539 Preferably, it can be obtained by air jet grinding, bottle/disc or hammer grinding. Ru.

The salts are brittle and therefore provide suitable particle size and bulk density. for best results The drum-dried particles preferably have a particle size of about 0.3 to about 1.2, more preferably about 0.6 ground to a bulk density of ~1.2, most preferably about 0.7 to about 1.2 g/d. , simultaneously about 0.5 to about 2.5, more preferably about 0.6 to about 2.5, most preferably The range is about 0.7 to about 2. A specific surface value of 0rrr/g should be maintained.

The crushed particles can pass through a 140-200 mesh sieve (U, S, B, S, series). and should preferably be less than 0.3 mm in their largest dimension.

Wood acid copolymers and their winter use as denture adhesives in denture stabilizing compositions It has exceptional adhesive properties when in contact with water or saliva, making it extremely useful as a substance. have For such use, the salt in particulate form contains at least 1140 mesh U, S, B, S, sieve particle size; o, 3g/ca! or more, preferably 0.6 g/ctd or more Bulk density: pH between 3 and 8, preferably between 5 and 7.5 (pH measured on a 1% by weight dispersion in water) Preferably, it is characterized by:

Each of the present copolymer salts can be used as the sole adhesive component or as other active ingredients in denture stabilizing compositions. An effective amount of adhesive as a co-adhesive used in conjunction with the adhesive component, preferably at least 25% by weight You can use it as a percentage.

Preferably, the copolymer salt is used in combination with a co-adhesive in a denture stabilizing composition.

Preferably, the co-adhesive is natural rubber, synthetic polymer, saccharide derivative, cellulose. polymeric material selected from the group consisting of -acetic acid derivatives and mixtures thereof.

Generally, from about 15 to about 70% of the above mixed calcium/natium based on the total weight of the composition. Lithium/zinc or strontium salts are present.

Preferred co-adhesives include those with special swelling properties that form a slimy mass on contact with moisture. water-soluble hydrocolloids or polymers. Natural adhesives such as Both rubber and synthetic polymer rubbers are commonly used in denture stabilizing compositions and are water-mixable. Also suitable for co-adhesive action with the AVE/MA copolymer salt are, for example, color. Yam gum, gelatin, algin, sodium alginate, tragacanth, methylcephalate Lulose, acrylamide polymer, ethylene oxide polymer, polyvinyl resin lolidon, cationic polyacrylamide polymers, most preferably Carboxymethyl cellulose sodium and poly(vinyl methyl ether-male) mixed partial salts of inic acid) copolymers.

Therefore, in a preferred aspect of the present invention, a lower atom consisting essentially of the following repeating structural units: The effective adhesion amount of rukyl vinyl ether-maleic acid copolymer is used as a stabilizing component. Adhesive and denture stabilizing compositions are provided having: the above in the molecule of the polymer. An integer of 2 or more representing the number of repeated occurrences of the structural unit, where n is a specific viscosity of 1.2 or more The specific viscosity at 25°C is large enough to characterize the copolymer as having Measured in methyl ethyl ketone. The above copolymer is about 0.3 to about 1.2 g/ ci bulk density and from about 0.5 to about 2. It has a specific surface area of 5r+f/g.

Preferably these copolymers are partial salts, said partial salts being about 10 to about 40% Of the total initial carboxyl groups reacted as free acid and cationic salt functional groups, approximately 0 ．． 1 to about 85% of one or more cationic salt functional groups, the cationic salt functional groups being Zinc cation, strontium cation, sodium cation, calcium cation ion, magnesium cation, potassium cation, ammonium cation and from about 0.3 to about 1.2 g. /m and a specific surface area of about 0.5 to about 2.5 nf/g.

Another preferred aspect of the invention is a safe and adhesively effective amount of at least two dentures. Provided is a denture stabilizing composition comprising an adhesive component, in which case the denture adhesive component is One of them is the acid or part of the lower alkyl vinyl ether-maleic acid copolymer. It is salt content. Preferably, the co-adhesive is as described above.

Compositions of the invention include one or more ingredients that provide a sensory effect to the user, including flavor. It can optionally contain from 1.01 to about 5% fractional O. A suitable ingredient is menthol. Le, menthyl lactate, peppermint oil, spearmint oil, leaf alcohol and reference Watson et al., published January 23, 1979, incorporated herein by reference. Wilkinson Suwo as described in U.S. Pat. No. 4,136,163 available from Wtlkinson-3word (like WS-3). There are paramenthane carboxamide flavoring agents that can be used.

The compositions of the invention may be prepared in the form of powders, creams, ointments, liquids, pastes, water or films. They are manufactured using industry-recognized methods known to those skilled in the art. The composition of the present invention is drum-dried A Preferably made of VE/MA copolymers or their salts, which are AV Fluid energy, air jet or is ground using a suitable comminution technique such as hammer grinding.

Suitable examples of such prescriptions are both from Abhar et al., May 21, 1985. No. 4,518.721, issued on April 30, 1985; No. 4,514,528, both of which are incorporated by reference. Incorporated here for.

Preferably, these compositions contain from about 10% to about 70% of one or more ointment bases. Ru. Preferably this base is mineral oil or petrolatum, but it may also be mineral oil or petrolatum. Also useful are lyethylene glycol, paraffin, glycerin and mixtures thereof. Ru. Most preferred is a mixture of mineral oil and petrolatum.

Although the adhesive salt of the present invention is not particularly limited, it can be used for pharmaceutical purposes (for example, "oral drug delivery"). - and topical bandages) and water-based adhesives (e.g. where adhesion is required in the presence of water). It should be recognized that they can be used in a variety of general adhesive applications, including adhesives.

The following non-limiting examples describe embodiments of the invention in which both essential and optional components are combined. explain. These examples are for illustrative purposes only and do not limit the scope of the invention thereto. It should be understood that this is not the case.

Twist”- Contains 94 parts (4.7 kg) of purified water heated to 85°C equipped with a high-speed stirrer. methyl vinyl ether-maleic anhydride copolymer over 15 minutes into a reaction vessel containing Slowly add 6 parts of Rimmer (300 g). Temperature and mixing after 15 minutes and the resulting adhesive polymer dispersion remains constant for 60 min. characterized by an increase in viscosity and a decrease and stabilization of the reaction pH in the dispersion of the substance, The material consists of the acid form of a methylvinylnityl-maleic acid copolymer.

The resulting methylvinylnityl-maleic acid (MVE/MA) copolymer solution to evaporate the water and recover the polymer salt with high specific surface area in the form of flakes. using a drum dryer maintained at 80-100 PSIG with hot steam. and dry. The dry acid form of the MVE,/MA copolymer thus obtained is then about 0.7 to about 1.1 g while maintaining a specific surface area of about 0.7 to about 1.5 rrf/g Grind using an air jet or hammer mill to a bulk density of /ci. Next The copolymer of Sieve with sieve series). The powder has a pH of approximately 2.5 in a 1% solution in water. . This particular copolymer is referred to below by the abbreviation "MVE/MA copolymer acid form". Ru.

The product can be used in conjunction with conventional denture adhesives and applied to wet dentures in normal usage. better denture stability than can be obtained with concrete conventional denture adhesives themselves when It shows the characteristics of

Example 11 92.1 parts of purified water (1,842k g) in a reaction vessel containing 1.9 parts (37.9 g) of calcium hydroxide and hydroxide. Slowly add 0.3 part (5.8 g) of sodium chloride. After addition, slurry Keep the temperature constant under high speed mixing. While keeping heating and mixing constant Methyl vinyl ether was added to the reaction vessel containing the alkaline dispersion for 15 minutes. Add 5.71 parts (114 g) of maleic anhydride copolymer. Temperature and mixin The signal remains constant for 60 minutes. The adhesive polymer dispersion obtained after 15 minutes is Characterized by an increase in viscosity and a decrease and stabilization of the reaction pH in a dispersion of the above substances. The above substance is a mixed partial calcium ester of methyl and nyl ether-maleic acid copolymer. It consists of um sodium salt.

The resulting methyl vinyl ether-maleic acid (MVE/MA) copolymer A solution of calcium sodium salt is formed into flakes with a high specific surface area by evaporating water. was maintained at 80-100 PSIG with hot steam to recover the polymer salts of Dry using a drum dryer.

Then, the thus obtained dry calcium sodium MVE/MA copolymer The mer salt maintains a specific surface area of about 0.7 to about 1.5 rrr/g. Grind using an air jet or hammer mill to a bulk density of 1.1 g/i. Next This copolymer was passed through a 140-mesh sieve and then passed through a 200-mesh sieve (U, S, B , S, sieve series). The powder has a pH of approximately 6.5 in a 1% solution in water. have Analysis of the salt shows that approximately 70.0% is neutralized with calcium, and 10.0% is neutralized with calcium. Neutralized with sodium to show that 20% remain carboxyl groups. child The specific salt of This is referred to below as salt content.

The product can be used in conjunction with conventional denture adhesives and applied to wet dentures in normal usage. better denture stability than can be obtained with concrete conventional denture adhesives themselves when It shows the characteristics of

Example 1■1- 92.4 parts (4.6 kg) of purified water heated to 85°C with a high-speed stirrer 0.53 parts (26.3 g) of zinc oxide and calcium hydroxide Slowly add 1.30 parts (64.6 g) of Mums. After addition, temperature of slurry is kept constant under high-speed mixing. Aluminum while keeping heating and mixing constant. Methyl vinyl ether-anhydrous macerate was added to the reaction vessel containing the potash dispersion for 15 minutes. Add 5.76 parts (288 g) of leic acid copolymer. Temperature and mixing 6 Remains constant for 0 minutes. The adhesive polymer dispersion obtained after 15 minutes was Characterized by an increase in viscosity and a decrease and stabilization of the reaction pH in the dispersion of the substance, The substance is a mixed partial calcium of methyl vinyl nylon maleate copolymer. Consisting of zinc salt.

The resulting methylvinylnityl-maleic acid (MVE/MA) copolymer A solution of calcium zinc salt is evaporated to form a flake-like polyester with a high specific surface area. The drum was maintained at 80-100 PSIG with hot steam to recover the mer salt. Dry using a dryer. Then the dry calcium zinc thus obtained The MVE/MA copolymer salt maintains a specific surface area of about 0.67 to about 1.5 ri"7g. air jet or hammer to a bulk density of about 0.7 to about 1.1 g/cj. Grind using a grinder. This copolymer was then sieved through a 140-mesh sieve and then passed through a 200-mesh sieve. Sieve with mesh sieve (υ, S, B, S, sieve series). The powder is 1% in water It has a pH of about 5.4 in solution. According to an analysis of the salt, about 47.5% is calcium. 17.5% neutralized with zinc and 35% remaining carboxyl groups. to show that This particular salt has the abbreviation “47.5% Ca of MVE/MA copolymer. /17.5% Zn partial salt".

The product can be used in conjunction with conventional denture adhesives and applied to wet dentures in normal usage. better denture stability than can be obtained with concrete conventional denture adhesives themselves when It shows the characteristics of

1 wisdom 84.7 parts (7.6 kg) of purified water heated to 85°C with a high-speed stirrer In a reaction vessel containing 0.2 parts (18 g) of zinc oxide and 0.2 parts of calcium hydroxide. Slowly add 92 parts (82.7 g). After the addition is complete, the temperature of the slurry is increased rapidly. Keep constant under mixing. alkaline content while maintaining constant heating and mixing. Methyl vinyl ether-maleic anhydride was added to the reaction vessel containing the dispersion for 15 minutes. Add 3.9 parts (348 g) of acid copolymer.

The adhesive polymer dispersion obtained in about 15 minutes has a viscosity equal to that of the dispersion of the above substance in water. Characterized by an increase and a decrease and stabilization of the reaction pH, the above substances are methyl vinyl ether Consists of mixed partial calcium zinc salts of ther-maleic acid copolymers. temperature and Mixing remains constant for 60 minutes. Then, sodium hydroxide 890 g of 1% solution was slowly added over 30 minutes, and the reaction was stabilized by stabilizing the reaction pH. Proceed as indicated until complete.

The resulting methyl vinyl ether-maleic acid (MVE/MA) copolymer A solution of calcium zinc salt is evaporated to form a flake-like polyester with a high specific surface area. Dosage was maintained at 80 to 1' OOPSIG with hot steam to recover the mer salt. Dry using a ram dryer. Then the dry calcium chloride thus obtained The lead MVE/MA copolymer salt maintains a specific surface area of about 0.5 to about 1.5 n-r/g. While holding it, about 0.7 to about 1.1. Air jet or heat up to a bulk density of g/l-ll. Grind using a mill. This copolymer was then passed through a 140 mesh sieve. Then sieve with a 200 mesh sieve (U, S, B, S, sieve series). The powder is A 1% solution in water has a pH of about 5.7. In the analysis of its salt, the carboxyl group is approximately 50% neutralized with calcium, 9.9% with zinc, 5% with sodium shows that 35% of the carboxyl groups remain unreacted. this Specific salts are designated by the abbreviation “50% Ca/9.9% Zn/ of MVE/MA copolymer. It is hereinafter referred to as 5% Na partial salt 2.

The product can be used in conjunction with conventional denture adhesives and applied to wet dentures in normal usage. better denture stability than can be obtained with concrete conventional denture adhesives themselves when It shows the characteristics of

Example V 85.1 parts (7.7 kg) of purified water heated to 85°C with a high-speed stirrer 0.1 parts (9 g) of zinc oxide and 1.1 parts of calcium hydroxide in a reaction vessel containing (98.9 g) is added slowly. After the addition is complete, mix the temperature of the slurry at high speed. Keep constant under Thing. Alkaline dispersion while keeping heating and mixing constant of methyl vinyl ether-maleic anhydride over a period of 15 minutes into a reaction vessel containing Add 3.9 parts (347.2 g) of polymer. Adhesive polymer obtained in about 15 minutes -The dispersion increases the viscosity and decreases and stabilizes the reaction pH in a dispersion of the above substances in water. The material is a mixture of methyl vinyl ether-maleic acid copolymer. It consists of a combination of calcium and zinc salts. Temperature and mixing constant for 60 minutes It remains as it is. Then, 890 g of a 1% solution of sodium hydroxide was added over 30 minutes. Add slowly and allow the reaction to proceed to completion as indicated by stabilization of the reaction pH. .

The resulting methyl vinyl ether-maleic acid (MVE/MA) copolymer A solution of calcium zinc salt is evaporated to form a flake-like polyester with a high specific surface area. The drum was maintained at 80-100 PSIG with hot steam to recover the mer salt. Dry using a dryer. Then the dry calcium zinc thus obtained MVE/MA copolymer salt maintains a specific surface area of about 0.7 to about 1.5 rrl'/g air jet or hammer to a bulk density of about 0.7 to about 1.1 g/ci. Grind using a grinder. This copolymer was then sieved through a 140-mesh sieve and then passed through a 200-mesh sieve. Sieve through mesh sieves (U, S, B, S, sieve series). The powder is 1% in water It has a pH of about 6.0 in solution. Analysis of the salt shows that about 60% of the carboxyl groups are Neutralized with calcium, 5% with zinc, 5% with sodium , indicating that 30% of carboxyl groups remain unreacted. This particular salt stands for 60% Ca / 5% Z n / 5% Na portion of MVE/MA copolymer Hereinafter referred to as "salt".

The product can be used in conjunction with conventional denture adhesives and applied to wet dentures in normal usage. better denture stability than can be obtained with concrete conventional denture adhesives themselves when It shows the characteristics of

Example ■1 The procedure of Example I was repeated, but using the following amounts of reactants: Anhydrous copolymer 3. 9 parts (77.3 g), purified water 94.9 parts (1.9 kg), zinc oxide 0.2 parts (3 , 99g), 0.2 parts (3,99g) of sodium hydroxide and 0 calcium hydroxide. ．． 83 parts (16,5 g) of the resulting powder has a bulk density of about 0.7 to about 1.1 g/7 and It has a specific surface area of about 0.7 to about 1.5 rrl'/g. In the salt analysis, copoly Approximately 45% calcium neutralization of all initial carboxyl groups in the mer salt molecule, 9. 9% neutralization and 10% neutralization with sodium and the abbreviation “MVE/MA copolymer” 45% Calcium/9.9% Zinc/10% Sodium Partial Salt".

Example Vl+ By following the general procedure of Example V, except for appropriate amounts of zinc oxide, calcium hydroxide and MVE/MA copolymers were prepared using sodium hydroxide with the indicated substitutions. Obtain the following calcium/zinc/sodium salts: sodium calcium zinc 10 Bo, 5 2.5 10 85 2.5 15 40 9.9 20 40 9.9 5 55 9.9 Each of the MVE/MA copolymer salts shown has one 140 meshes U, S, B, S, In the case of sieved powder, it has a bulk density of O-5g1ci or more and 0.6rrr/g or more specific surface area and exhibits significantly beneficial denture stabilization characteristics. Each of the salts shown is Abbreviated as Calcium%/Zinc%/Sodium% Neutralization as done in Example 1-V. good.

Example ■111 Repeat the MVE/MA copolymer anhydride-to-acid hydrolysis procedure set forth in Example V. 85 Strontium hydroxide octahydrate in a container containing 8.5 kg of purified water heated to Add 16.5g of material. Boil 99.4 g of calcium hydroxide under vigorous mixing. Add slowly. After the addition is complete, the temperature of the slurry is kept constant under high speed mixing.

Methyl vinyl ether-anhydrous malei while maintaining constant heating and mixing. 34.9 g of acid copolymer was added to the reaction vessel containing the alkaline dispersion over a period of 20 minutes. Ru. This is a mixed partial calcium methyl vinyl ether-maleic acid copolymer. Produces strontium salts.

Example 1x The denture stabilizing powder composition is made by blending together the following: %v/v A. Karaya rubber 5353 Sodium carboxymethyl cellulose 161G Sodium borate 77 47.5% Ca/17, 5% Zn mixed partial salt of MVE/HA copolymer 2 4-MVE/HA copolymer 60%Ca15℃n15%Na partial salt -24B , sodium alginate 5555 Sodium carboxymethyl cellulose 1010 tons of polyhinyl vinyl Average M, V, -90,000) 15 85% ca of 15PVM/HA copolymer 7toHn mixed partial salt 20-MVP/HA copolymer 60.5% Ca/2 ．． 5% Zn/10% Na partial salt -20C, carboxymethyl cellulose sodium Umu 5050MVE/HA copolymer 70%Ca/10%Na mixed partial salt 5030MVE/) 50% Zn immiscible partial salt of 4A copolymer -20ioo io.

D, Gantrez 5-97 acid copolymer 6030 carboxymethyl cellulose Thorium 4040MVE/HA ml polymer 70%Ca/10%Na mixture Partial salt -30 of the above free acid MVE/MA copolymer and MVE/MA:polymer Mixed or unmixed partial salts shown are for 1140 mesh U, S, B, S, sieved powder. and a specific surface area of 0.6 rrf/g or more while having a bulk density of 0.5 g/d or more. maintain.

At the time of use, the above powder (typically 0 ．． 1 to Ig) on the pre-moistened denture, briefly hydrate it, insert the denture into the mouth, and apply it as appropriate. The liquid-pressure type denture stabilizing composition is manufactured by mixing together the following: : Heavy mineral oil 44.9 43.9 Petrolatum 3.0 3.0 Colloidal silica 1.5 1.5 Carboxymethyl cellulose sodium 30.5 30.5 Menthol 0. 1 0.1 47.5Ea/17.5% Zn mixed partial salt of MVE/HA copolymer 20.0 -MVE/MA copolymer 55%Ca15℃n/lo%Na mixed partial salt- 20,010 [1,0100,0 At the time of use, the liquid composition described above (typically Place 0.1 to Ig) on the pre-moistened denture, briefly hydrate it, and insert the denture into the mouth. and push it into the appropriate place.

Example x1 The cream type denture stabilizing composition is manufactured by mixing the following together: : Heavy mineral oil 24.824 24.824 24.824 carboxymethyl cellulose Sodium 22.000 22.000 22.000 Petrolatum 19 ．． 01B 19.01B 19.016 Colloidal silicon dioxide 1.100 1 ．． 100 1.100 Color agent (oil-soluble red dispersion) 0.060 0.060 0. O[i0MVE/HA near polymer 47.5%Ca/17.5%7. n Mixed partial salt 33.000--MVE/KA: 55.0% C of I polymer a15℃n/10% Na mixed partial salt -33,000-MVE/MA copolymer 70%Ca/10%Na partial mixed salt of --18,500MVE/HA copolymer -50℃n unmixed partial salt of -18,500 above free acid MVE/MA copolymer The indicated mixed or unmixed partial salts of the and MVE/MA copolymers are 1140 mesh U, S, B, S, 0.6 while having a high density of 0.5 g/i or more in case of sieve powder Maintain a specific surface area of rd/g or more.

When used, the above cream (typically Place 0.1-2 g) on the pre-moistened denture, briefly hydrate it, insert the denture into the mouth, Push it into place.

Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), 0A (BF , BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG. ), AT, AU, BB, BG, BR, CA, CH, C3, DE.

DK, ES, FI, GB, HU, JP, KP, KR, LK, LU, MG, MN, MW, NL, No, PL, RO, SD, SE, 5U (72) Inventor: Dabbar, Dadi, Jamshet, State of Connecticut, United States of America , Norwalk, Eliana, Rain, 17 (72) Inventor Gunaris, Michael, Konstantinos USA Penn. 3950 Circle, Jardel, Doylestown, Lubania

Claims (1)

[Claims] 1. Lower alkyl vinyl ether-malein consisting essentially of the following repeating structural units: It is an acid copolymer: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the above formula, R is represents a C1-C4 alkyl group, preferably methyl; n is in the molecule of the above copolymer is an integer of 2 or more representing the number of repeated occurrences of the above structural unit in , where n is 1.2 or more. sufficiently large to characterize the copolymer as having a specific viscosity of is measured in methyl ethyl ketone at 25°C; Copolymer with a bulk density of 2 g/cm2 and a specific surface area of 0.5-2.5 m2/g -. 2. Lower alkyl vinyl ether-malein consisting essentially of the following repeating structural units: A partial salt of an acid copolymer comprising: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R is a C1-C4 alkyl group, Preferably represents methyl; n represents the structural unit in the molecule of the copolymer. An integer of 2 or more representing the number of repeated occurrences, where n has a specific viscosity of 1.2 or more. is sufficiently large to characterize the above copolymer; the specific viscosity is methyl ethyl at 25°C. Measured in ketones; the partial salts contain 10-40% free acid and cationic salts. 0.1 to 85% of one or more types of carboxyl groups reacted as functional groups The cationic salt functional group includes a zinc cation, a strontium cation, and a cationic salt functional group. cation, sodium cation, calcium cation, magnesium cation, carbon Selected from the group consisting of lithium cations, ammonium cations and mixtures thereof The above copolymer has a bulk density of 0.3 to 1.2 g/cm2 and a bulk density of 0.5 to 2.5 Partial salt with a specific surface area of m2/g. 3. Cationic salt functional groups include zinc, strontium, calcium and sodium cationic salts. of all the initial carboxyl groups reacted, selected from the group of :(a) 0.1 to 65% of zinc or strontium cations, preferably zinc cations (b) Calcium cation or sodium cation 0.1 ~75%, preferably 5-20% of sodium cations or mixtures thereof; and (c) 40-70% calcium cation; and 10-40% free acid; It has a bulk density of 0.6 to 1.2 g/cm2 and a specific surface area of 0.6 to 2.5 m2/g. 4. The partial salt according to claim 3. 4. Lower alkyl vinyl ether-malein consisting essentially of the following repeating structural units: A denture stabilizing composition having an effective adhesion amount of an acid copolymer as a stabilizing component, :▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R is a C1-C4 alkyl group , preferably represents methyl; n is the above structural unit in the molecule of the above copolymer is an integer of 2 or more representing the number of repeated occurrences, and n has a specific viscosity of 1.2 or more. is sufficiently large to characterize the copolymer; the specific viscosity is The copolymer has a bulk density of 0.3 to 1.2 g/cm2. and a denture stabilizing composition having a specific surface area of 0.5 to 2.5 m2/g. 5. Lower alkyl vinyl ether-malein consisting essentially of the following repeating structural units: Denture stabilization assembly having an effective adhesion amount of a mixed partial salt of an acid copolymer as a stabilizing component A product that: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R is a C1-C4 alkyl group, Preferably represents methyl; n represents the structural unit in the molecule of the copolymer. An integer of 2 or more representing the number of repeated occurrences, where n has a specific viscosity of 1.2 or more. is sufficiently large to characterize the above copolymer; the specific viscosity is methyl ethyl at 25°C. Measured in ketones; the partial salts contain 10-40% free acid and cationic salts. 0.1 to 85% of one or more types of carboxyl groups reacted as functional groups The cationic salt functional group includes a zinc cation, a strontium cation, and a cationic salt functional group. cation, sodium cation, calcium cation, magnesium cation, carbon Selected from the group consisting of lithium cations, ammonium cations and mixtures thereof The above copolymer has a bulk density of 0.3 to 1.2 g/cm2 and a bulk density of 0.5 to 2.5 A denture stabilizing composition having a specific surface area of m2/g. 6. Cationic salt functional groups include zinc, strontium, calcium and sodium cationic salts. of all the initial carboxyl groups reacted, selected from the group of :(a) 0.1 to 65% of zinc or strontium cations, preferably zinc cations (b) Calcium cation or sodium cation 0.1 ~75%, preferably 5-20% of sodium cations or mixtures thereof; and (c) 40-70% calcium cation; and 10-40% free acid; It has a bulk density of 0.6 to 1.2 g/cm2 and a specific surface area of 0.6 to 2.5 m2/g. 6. The composition according to claim 5. 7. Denture stabilizing composition comprising safe and adhesively effective amounts of at least two denture adhesive ingredients one of the above denture adhesive components essentially consists of the following repeating structural units: It is a lower alkyl vinyl ether-maleic acid copolymer: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R is a C1-C4 alkyl group, Preferably represents methyl: n represents the structural unit in the molecule of the copolymer. An integer of 2 or more representing the number of repeated occurrences, where n has a specific viscosity of 1.2 or more. is sufficiently large to characterize the above copolymer; the specific viscosity is methyl ethyl at 25°C. measured in ketones; the copolymer has a bulk density of 0.3-1.2 g/cm2 and A denture stabilizing composition having a specific surface area of 0.5 to 2.5 m2/g. 8. Denture stabilizing composition comprising safe and adhesively effective amounts of at least two denture adhesive ingredients one of the above denture adhesive components essentially consists of the following repeating structural units: A mixed partial salt of lower alkyl vinyl ether-maleic acid copolymer: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R is a C1-C4 alkyl group, Preferably represents methyl; n represents the structural unit in the molecule of the copolymer. An integer of 2 or more representing the number of repeated occurrences, where n has a specific viscosity of 1.2 or more. is large enough to characterize the above copolymer: the specific viscosity is methyl ethyl at 25°C. Measured in ketones; the partial salts contain 10-40% free acid and cationic salt functionality. 0.1 to 85% of one or more carboxyl groups reacted as a group ion salt functional group, the cationic salt functional group being a zinc cation, a strontium cation, and a strontium cation. on, sodium cation, calcium cation, magnesium cation, potassium selected from the group consisting of um cations, ammonium cations and mixtures thereof. The above copolymer has a bulk density of 0.3 to 1.2 g/cm2 and a bulk density of 0.5 to 2.5 m A denture stabilizing composition having a specific surface area of 2/g. 9. Cationic salt functional groups include zinc, strontium, calcium and sodium cationic salts. of all the initial carboxyl groups reacted, selected from the group of :(a) 0.1 to 65% of zinc or strontium cations, preferably zinc cations (b) Calcium cation or sodium cation 0.1 ~75%, preferably 5-20% of sodium cations or mixtures thereof; and (c) 40-70% calcium cation; and 10-40% free acid; It has a bulk density of 0.6 to 1.2 g/cm2 and a specific surface area of 0.6 to 2.5 m2/g. 9. The composition according to claim 8. 10. Polymeric substances include natural rubber, synthetic polymers, saccharide derivatives, and cellulose. 0.01-5.0% selected from the group consisting of gas derivatives and mixtures thereof; menthol, menthyl lactate, peppermint oil, spearmint oil, leaf alcohol , paramenthane carboxamide, and mixtures thereof. The denture stabilizing composition according to any one of the above.