JPH029562B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel oral products containing reaction products of magnesium compounds with maleic acid copolymers, sulfoacrylic acid oligomers or tricarboxy-oxa-butanols or pentanols as active agents for inhibiting the formation of tartar. There are many oral compositions in the prior art that contain magnesium salts. For example, U.S. Pat.
No. 2216821 (Lang) states that magnesium oxides, hydroxides, carbonates, silicates or phosphates prevent decalcification of tooth enamel, and US Patent No. 3689636 (Suajda) states that it is painful Magnesium chloride is disclosed as a tooth pain reliever, and magnesium aminoalkylenephosphonate is disclosed in US Pat. No. 3,642,979 as a dental abrasive. The prior art also discloses a number of anticalculus agents, many of which are based on specific phosphonic acid type compounds and their pharmaceutically acceptable salts (including alkaline earth metal salts such as magnesium). be. The anti-tartar effect lies in the phosphonic acid compounds themselves, which are disclosed in US Pat.
3584116; 3683080 and 3737522 (also disclosing polyvalent phosphonates); U.S. Patent No. 3639569 (disclosing triphosphonated amines);
No. 3960888 (which discloses pyrrolidine-diphosphonates). Prevention of tartar formation,
Calcium chelating reagents (chelating agents), which have traditionally been used as a delaying and removal means, tend to damage tooth enamel, so the above-mentioned phosphonates (phosphonic acids and their salts) are used instead.
has been used. Examples of sequestrants that can remove soft calculus and other calcium deposits from teeth without harmful side effects are U.S. Patent Nos. 3452049 and 3558769 (Globus).
, which is a magnesium polyalkanolaminoethylenediaminetetraacetate: gluconocitrate complex. Although polyvalent phosphonates are superior to chelating agents as effective tartar preventive agents, they adversely affect the post-eruption maturation of tooth enamel, as shown in U.S. Pat. No. 3,678,154 (Widder). (i.e., the above-mentioned patents disclose the addition of water-soluble fluorine compounds to counteract this adverse effect). Cyclohexane-hexacarboxylic acid and its water-soluble salts (including magnesium salts) for the treatment of tartar
is disclosed in US Pat. No. 3,920,837. Ammonium polyacrylate salts or ammonium-polyacrylic acid polymer complexes are used in toothpaste compositions for their dental effects of inhibiting and promoting demineralization on tooth enamel (West German patent No. 2164383). The use of water-soluble sodium salts of linear anionic polymers as anti-tartar agents has also been described in U.S. Pat.
3429963. This patent discloses that the hydrolyzed copolymers and/or polymers described above prevent tartar deposition due to their calcium ion sequestrant properties. U.S. Pat. No. 3,956,480 discloses mixtures of cationic microbicides and anionic polymers as effective inhibitors of tartar formation, and U.S. Pat. A wide range of combinations of anti-calculus agents and bis-biguanides are disclosed in the literature. However, none of the above-mentioned patents and known prior art discloses that the combination of certain types of polycarboxylates and magnesium salts inhibits tartar over a long period of time without adversely affecting tooth enamel. It has not been suggested that it has any significant effect on the prevention or control of cancer. It is therefore an object of the present invention to process the reaction products of magnesium salts with polycarboxylates selected from the group consisting of maleic acid copolymers, sulfoacrylic acid oligomers and tricarboxy-oxa-butanols or pentanols and their alkali metal salts. An object of the present invention is to provide an oral product containing a product as a tartar preventive agent. Another object of the present invention is to provide an oral product that is effective in preventing tartar formation over an extended period of time. Yet another object of the present invention is to provide an oral product that is effective in preventing plaque, tartar, caries, and periodontal disease. The mineralization of tooth deposits and the subsequent formation of dental calculus (hydroxyapatite or hydroxyapatite deposits) are caused by homogeneous nucleation (enrichment of Ca ²⁺ ions or orthophosphate ions) and/or heterogeneous nucleation. It is well known in the art that this occurs via development (specific salivary and bacterial proteins). However, in both cases, salivary Ca ²⁺ joins salivary orthophosphate ions to form hydroxyapatite (HAP).
leading to the generation of The production of HAP in vitro occurs in two separate steps: (1) When Ca ²⁺ is added to orthophosphate ions at constant PH (7.4, according to PH stat), rapid consumption of base occurs as a function of time (i.e., 1-4 minutes). (2) Base consumption then continues to decrease for about 15-20 minutes, after which a second absorption of base occurs. If this second rapid consumption of base is delayed in time or does not occur immediately, this indicates interference with HAP crystal growth. Therefore, HAP
Compounds that interfere with the crystal growth of tartar are effective anti-tartar agents. Magnesium ions (Mg ²⁺ ) are also known to reduce the overall crystallization rate by stabilizing the precursors (amorphous deposits) initially formed by Ca ²⁺ and orthophosphate ions. (See the paper entitled “Growth of Calcium Phosphate on Hydroxylapatite Crystals: Influence of Magnesium”, Arch. Oral Biol., 20, 803, 1975). This amorphous deposit is easily removed while the crystalline phase is difficult to remove. However, the residence time of Mg ²⁺ ions introduced from the outside in the oral cavity is short, and the Mg ²⁺ content of saliva is extremely low (J. Periodontal Res. 9, 211-221, 1974). By combining magnesium to form a complex (or complex salt) with a polycarboxylate selected from the group consisting of maleic acid copolymers, sulfoacrylic acid oligomers, and tricarboxy-oxa-butanols or pentanols, It has now been found that the efficacy of magnesium ions can be improved. Since polycarboxylates (i.e., polyvalent carboxylic acid compounds) have at least two carboxyl groups per molecule (e.g., maleic acid has two carboxyl groups per molecule), one carboxyl group After it is available for reaction with Mg ²⁺ (2/3 ionization), enough free COO ^- remains to react with tooth enamel. It has also been found that polyvalent carboxy compounds of the type used in the present invention permanently bond to tooth enamel. Therefore, an effective method of preventing tartar formation is achieved by using an oral composition containing a magnesium-polycarboxylate complex formed by combining a magnesium compound with the polycarboxylic compound described above. be done. The positively charged magnesium ions can react with the free carboxyl groups of the polycarboxylate to form a magnesium polycarboxylate complex. In the mouth, these magnesium compounds or complexes are adsorbed onto oral surfaces such as the teeth and oral mucosa, forming a storage/accumulation site for magnesium ions that gradually releases magnesium ions into the oral cavity over time. Ru. Therefore, the magnesium polycarboxylate complex of the present invention has greater persistence in tooth enamel than the magnesium ions themselves, and the complex continues to supply Mg ²⁺ ions over a long period of time. Thus, it has now been found that by treating the oral cavity with a mixture or compound of a magnesium compound and a polycarboxylate, tartar formation can be prevented without adversely affecting tooth enamel.
Such magnesium polycarboxylate complexes provide a means of attachment to the oral cavity as well as a reservoir of magnesium ions that are gradually released over time as an effective means of preventing plaque and tartar. More specifically, the present invention uses (1) a copolymer of maleic acid or its anhydride and an olefin having 2 or more carbon atoms per molecule, (2) an average molecular weight of less than 1000 as an essential tartar preventive agent. and (3) a polycarboxylate compound containing two or more ionizable carboxyl groups selected from the group consisting of tricarboxy-oxa-butanol or pentanol, and a physiologically acceptable dissociable magnesium compound. The present invention relates to an oral composition containing a magnesium polycarboxylate complex derived from and in which the polycarboxylate is ionically bonded to magnesium. Polycarboxylic acid compounds that form complexes with magnesium are well known in the art.
These contain two or more ionizable carboxyl groups, and in the present invention, they consist of copolymers of maleic acid or maleic anhydride and olefins having two or more carbon atoms, sulfoacrylic acid oligomers, and tricarboxy-oxa-butanol or pentanol. chosen from the group. They are either themselves water soluble, or their alkali metal or ammonium salts are water soluble, at least up to an in-use concentration of about 0.1 to about 10%, preferably 0.5 to 1.5%, of the oral composition. It is preferable to have one. Suitable examples of polycarboxylates include copolymers of maleic acid or maleic anhydride with ethylene, styrene, isobutylene, methyl vinyl ether or ethyl vinyl ether;
It has the following repeat unit: In the formula, M and M ₁ are hydrogen, sodium,
Potassium or ammonium, which may be the same or unusual, and X is ethylene, styrene, isobutylene, methyl vinyl ether or ethyl vinyl ether. Oligomers and their preparation are generally covered by U.S. Patent Nos.
Listed in 3859260. The sulfoacrylic acid oligomer used in the present invention has an average molecular weight of less than 1000 and can be represented by the following structural formula. In the formula, M is an alkali metal or ammonium ion, and n is greater than 6 and less than 10.
The sulfonate group is not adjacent to the carboxylic acid group. This type of sulfoacrylic acid oligomer is itself effective in inhibiting the formation of hydroxyapatite at a concentration of 3 x 10 ^-4 M or 33 ppm, as evidenced by the data in Table 1 below. It was discovered that

[Table] Magnesium complexes of sulfoacrylic acid oligomers are more effective in inhibiting HAP crystal growth than oligomers alone, even at dilute concentrations, as evidenced by the increased delay time values. In contrast, other polycarboxylate polymers, such as acrylic acid dimers, polyacrylic acid polymers with a molecular weight of 2000 or more, and high molecular weight polycarboxylate polymers, including polymaleic acid, have higher concentrations (i.e., 8.0 ×10 ^-4 M) was found to be inactive. Also, polyacrylic acid polymers do not exhibit persistence in tooth enamel. Structural formula below The low molecular weight polymaleic acid represented by
It was found to be active (effective) as such, as demonstrated by the data in the table. Table 2 n Concentration t (delay time) 5.0 4 × 10 ^-4 M Inert 4.0 4 × 10 ^-4 M 40 minutes 3.0 1 × 10 ^-4 M 30 minutes However, higher molecular weight polymaleic acid polymers also Magnesium complexes are effective in inhibiting HAP crystal growth, as demonstrated by the results in Table 3 below.

[Table] As shown in the results of Table 4 below, tricarboxy-oxa-butanol and pentanol are
Although by itself inactive in inhibiting HAP crystal growth, the magnesium complex was found to be effective as an inhibitor of HAP crystal growth.

[Table] ｜
COONa
Although citric acid is also a tricarboxylic acid, it was found to be ineffective in inhibiting HAP crystal growth. Citric acid does not show persistence in tooth enamel and does not diffuse well in aqueous media. The remarkable and unexpected effectiveness of tricarboxylic compounds such as the above structural formula may be due to the presence of hydroxyl groups and/or the specific configuration of the compound. The magnesium compound that forms the magnesium polycarboxylate complex by reaction or interaction with the polycarboxylate may be any physiologically acceptable dissociable magnesium salt, including water-soluble or water-insoluble organic or inorganic magnesium salts. Examples of suitable magnesium compounds that can be used include: magnesium acetate, magnesium acetylacetonate, magnesium ammonium sulfate, magnesium benzoate, magnesium bromide, beryllium magnesium orthosilicate, magnesium borate, magnesium butylphthalate, butyl xanthogen. Magnesium acid, Magnesium caprylate, Magnesium carbonate, Magnesium isovalerate, Magnesium D-lactate, Magnesium DL-lactate, Magnesium laurate, Magnesium hexafluorosilicate, Magnesium methacrylate, Magnesium molybdate, Magnesium naphthenate, Magnesium octoate , Magnesium oleate, Magnesium orthophosphate, Magnesium chloroanilate, Magnesium chlorate, Magnesium chromate, Magnesium citrate, Magnesium cyclohexylbutyrate, Magnesium chloride, Magnesium gallate, Magnesium fluoride, Magnesium α-glucoheptanoate, Gluconic acid Magnesium, magnesium glycerophosphate, magnesium hydroxide, magnesium 8-hydroxyquinoline, magnesium 12-hydroxystearate, magnesium iodide, magnesium acrylate, magnesium oxide, magnesium propionate, magnesium phenolsulfonate, magnesium pyridine-2-thiol- 1-
oxide, magnesium pyrophosphate, magnesium resinate, magnesium salicylate, magnesium sulfate, magnesium nitrate, magnesium selenide, magnesium stearate, magnesium sulfanilate, magnesium tartrate, magnesium tellurate, magnesium tungstate, magnesium valerate, magnesium vanadate, Magnesium tribromosalicylanilide, magnesium ricinoleate. Most of the above magnesium salts are water soluble.
Many insoluble magnesium salts also become water soluble when mixed with polycarboxylates and can serve as a means of carrying out the reaction or interaction between magnesium and polycarboxylates. The magnesium compound accounts for about 0.01-5%, preferably 0.025-1%, of the oral composition by weight. The preparation of an aqueous dispersion or solution of a magnesium polycarboxylate complex involves adding a magnesium salt (in dilute solution, paste or dry form) to a dilute solution of the polycarboxylate, and adjusting the amount of magnesium salt such that it produces a precipitate or gel. This can be done by stopping the addition before the amount is reached. With good stirring and careful addition so as not to exceed the amount of maximum solubility of the magnesium polycarboxylate complex, a clear solution or dispersion is obtained. This phenomenon is clearly demonstrated in Example 2. The pH of the polycarboxylate solution is preferably adjusted to about 7.0 with ammonium hydroxide or other suitable base prior to addition of the magnesium salt.
The final magnesium polycarboxylate solution has a pH of about 4.5-7.8. For example, a suitable magnesium polycarboxylate complex is a copolymer of methyl vinyl ether and maleic anhydride.
It is formed by adding a 0.4% solution of a magnesium salt such as MgCl ₂ to 100 ml of a 0.1% solution (adjusted to PH 7.0 with ammonium hydroxide) and mixing well. The resulting magnesium-maleic acid copolymer complex solution or dispersion has a pH of approximately
It is preferably 4.5 to 7.8. It is believed that the ionized carboxyl groups react or interact with magnesium ions to form a magnesium-copolymer complex. Regarding this,
Crisp et al., J.Dent, Res., 55(2), 229―308,
Especially 305-307, March/April 1976 issue; and
Begala et al., J.Phys.Chem., 76(2) , 254―260,
See the 1972 paper on counterion binding of polycarboxylates. Experimental results also demonstrate that the magnesium bond to the polymer is mostly ionic. Ionic bonds are the following (a) to (d)
will result in either of the following. (a) Chain crosslinking salt (b) Chain inner salt (c) Suspended half-salt (d) Chelate (ring) structures (such as copolymers of vinyl methyl ether and maleic anhydride) In (d), a divalent cation such as Mg forms a chelate with one carboxyl group and an ether oxygen. Therefore, it is thought that the magnesium carboxylate complex has ionic bonds, but the exact type of bond (it is possible that the above structures are mixed) has not been determined. The present invention will be further explained below with reference to Examples. In this specification, quantities are by weight unless otherwise specified. Example 1 0.2 g of magnesium chloride is dissolved in 15 ml of water and added under stirring to a 4% aqueous solution of a copolymer of maleic anhydride and methyl vinyl ether, followed by 200 g.
diluted to ml. A clear solution of magnesium-copolymer complex was obtained. Example 2 (a) 100 g of aqueous magnesium oxide paste containing 0.5% magnesium was mixed with a 1% aqueous solution of methylvinyether-maleic anhydride copolymer.
25 ml gradually with continuous stirring, then
Diluted with 75ml water. The pH of the resulting solution is 5.5
And it was slightly cloudy. The magnesium:copolymer ratio is 1:2. (b) 100 g of aqueous magnesium oxide paste containing 0.25% magnesium was added to 100 g of an aqueous solution containing 0.25% methyl vinyl ether-maleic anhydride copolymer with continuous stirring.
The resulting solution had a pH of 6.5 and was cloudy. The ratio of magnesium:anionic polymer is 2:1. (c) with 0.25% magnesium as above.
1.0% maleic acid copolymer (1:4 ratio)
An aqueous solution of a magnesium-copolymer complex was prepared. This had a pH of 3.5 and was transparent. Approximately 10 ml of 3N ammonium hydroxide was added to this clear solution to adjust the pH to 6.8 (oral pH), and the solution still maintained its transparency. This example demonstrates that the ratio of magnesium salt:maleic acid copolymer affects the solubility of the resulting magnesium-copolymer complex. Maximum solubility is demonstrated in clear solutions. A clear solution must be preferred, but slight turbidity can be tolerated. Example 3 A magnesium-copolymer complex was prepared by mixing 50 ml of a 0.05M aqueous solution of the following magnesium salt and 50 ml of a 2% aqueous solution of methyl vinyl ether-maleic anhydride copolymer, and adjusting the pH to 5 to 6 with ammonium hydroxide. Formed. The ratio of magnesium:maleic acid copolymer is 1:4. (a) Magnesium oxide (water-insoluble) (b) Magnesium chloride (water-soluble) (c) Magnesium glycerophosphate (water-soluble) (d) Magnesium salicylate (water-soluble) (e) Magnesium α-glucoheptanoate (water-soluble) (f) Magnesium propionate (water soluble) (g) Magnesium salt of 8-hydroxyquinoline (water insoluble) (h) Magnesium gluconate (water soluble) (i) Magnesium pyrophosphate (water insoluble, but dilute mineral acids soluble). The resulting solution or dispersion containing the magnesium-maleic acid copolymer complex was transparent. The ratio of magnesium salt to polycarboxylate in this example is 1:4, but this ratio may vary within a wide range, for example from about 1:40 to 4:1. Particularly good results with respect to tartar prevention and other beneficial effects in the oral cavity and on the tooth surfaces have been obtained so far with the simple application of aqueous solutions or dispersions of magnesium-polycarboxylate complexes. It is also within the scope of this invention to incorporate the complexes into a wide variety of oral compositions such as clear or cloudy mouthwashes, clear or opaque toothpastes, troches, chewing gums, tablets or powders, including dental vehicles. be understood. The complex can also be formed in situ during the manufacture of the oral composition, or even by dilution in the mouth. Alternatively, the magnesium compound and the polycarboxylate may simply interact in the oral cavity and do not form a detectable complex. Vehicles such as toothpaste (excipients, often referred to as dental vehicles) contain a liquid component and a solid component. Generally, the liquid will consist of water and/or a humectant such as glycerin, sorbitate, propylene glycol or polyethylene glycol 400 (including suitable mixtures thereof), using mixtures of water and one or more humectants. is generally advantageous. The total liquid content is generally about 20-90% by weight of the vehicle. In transparent and translucent vehicles, the liquid content of the toothpaste may be approximately 20-90% by weight, whereas in opaque vehicles,
The total liquid content is usually about 20-50% by weight. Preferred humectants are glycerin and sorbitol. Typically, the transparent vehicle (including translucent) will be about 0-80% glycerin by weight, about 20-80% glycerin by weight.
% sorbitol and approximately 20-80% water. Opaque vehicles typically weigh about 15 to 35
% glycerin and about 10-30% water. The solid portion of the vehicle is the gelling agent. In the present invention, the gelling agent is at least about
There is a carboxymethylcellulose alkali metal salt in an amount of 0.25% by weight. Other gelling agents may also be present. Examples of gelling agents that can be used in combination include viscarin, gelatin, starch, glucose, sucrose, polyvinylpyrrolidone, polyvinyl alcohol, gum tragacanth, gum Karaya, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, sodium alginate, and the like. Laporte Industries., Ltd.
Synthetic inorganic composite silicic acid viscosities and magnesium aluminosilicate, commercially available under the trademarks Laponite CP or SP, respectively, can also be used.
The solid portion of the vehicle, i.e. the gelling agent, is generally about 0.25-10% by weight of the toothpaste, preferably about
Present in amounts of 0.5-8%. Alkali metal salts of carboxymethyl cellulose include lithium,
There are sodium and potassium salts. A suitable substantially water-insoluble abrasive may also be added to the gel vehicle. A relatively large number of materials of this type are known in the art. Representative examples include dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, calcined alumina, magnesium carbonate, calcium carbonate, calcium pyrophosphate, calcium sulfate, bentonite, and mixtures thereof. Preference is given to using water-insoluble phosphates, sodium metaphosphate and/or calcium phosphates (eg dicalcium phosphate dihydrate). The magnesium polycarboxylate complexes of the present invention have been found to stabilize monofluorophosphate in oral compositions containing diphosphate dihydrate abrasives. Generally, such abrasives will account for more than half the weight of the solid components. Abrasive content varies over a wide range, but generally comprises about 75% of the total composition.
up to % by weight, especially about 20-75% by weight, although smaller amounts of abrasive may be used as discussed below. Suitable surfactants or detergent materials may also be incorporated into the gel vehicle; such compatible materials may also provide detergent, foaming, and antimicrobial properties, depending on the type of surfactant. is preferred and similarly selected. This type of detergent is generally a water-soluble organic compound, and may be structurally anionic, nonionic, or cationic. It is generally preferred to use water-soluble, non-synthetic, synthetic organic detergents. Suitable detergent materials are known and include, for example, water-soluble higher fatty acid monoglyceride monosulfate type detergents (e.g., sodium coconut monoglyceride monosulfate), higher alkyl sulfates (e.g., sodium lauryl sulfate),
Examples include alkylarylsulfonates (eg, sodium dodecylbenzenesulfonate), higher fatty acid esters of 1,2-dihydroxypropanesulfonates, and the like. The amount of various surfactants used is about 0.05 to 10%, preferably about 0.5 to 5% by weight of the toothpaste composition.
It is generally appropriate to fall within the range of . Substantially saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acid compounds (e.g., those in which the acyl group has 12 to 16 carbon atoms, U.S. Patent No. 2689170)
It is also an aspect of the present invention to use The amino acid moiety is generally a lower aliphatic saturated monoaminocarboxylic acid having about 2 to 6 carbon atoms;
Usually derived from monocarboxylic acid type compounds.
Preferred compounds are fatty acid amides of glycine, sarcosine, alanine, 3-aminopropanoic acid, and valine, having about 12 to 16 carbon atoms in the acyl group. For good results, it is preferred to use N-lauroyl, myristoyl or palmitoyl sarcoside compounds. Although the amide compounds can be used in the free acid form, they are preferably used in the form of their water-soluble salts, such as alkali metal, ammonium, amine and alkylolamine salts. Specific examples include N-lauroyl, myristoyl and palmitoyl sarcoside sodium and potassium salts;
These include the ammonium and ethanolamine salts of N-lauroyl sarcoside, N-lauroyl sarcosine, and the sodium salts of N-lauroylglycine and alanine. For convenience, references herein to "aminocarboxylic acid compounds,""sarcosides," etc. refer to such compounds in the form of free carboxylic acids or water-soluble carboxylic acid salts. A variety of other materials may also be incorporated into the vehicles of the present invention. Examples include preservatives, silicones, chlorophyll compounds, ammonifying substances (such as urea, diammonium phosphate, mixtures thereof), substances that can increase contrast with particles such as zinc oxide or titanium dioxide, and others. There are ingredients. Such auxiliary ingredients are incorporated into the compositions of the present invention in amounts that do not materially adversely affect the properties of the suitably selected compositions, and the amounts used are appropriate depending on the formulation of the composition. determined by quantity. Antimicrobial agents can also be used in the gelling vehicles of this invention. Typical antibacterial agents include the following: N ¹ -(4-chlorobenzoyl)-N ⁵ -(2,4
-dichlorobenzoyl) biguanide; p-chlorophenyl biguanide; 4-chlorobenzhydryl biguanide; 4-chlorobenzhydryl anil urea; N ¹ -3-lauroxypropyl-N ⁵ -p-chlorobenzyl biguanide; 1,6 -di-p-chlorophenylbiguanidohexane; 1-(lauryldimethylammonium)-8-
(p-chlorobenzyldimethylammonium) octane dichloride; 5,5-dichloro-2-guanidinobenzimidazole; N ¹ -p-chlorophenyl-N ⁵ -lauryl biguanide; 5-amino-1,3-bis(2-ethylhexyl) -3-methylhexahydropyrimidine; and non-toxic acid addition salts thereof. If antibacterial agents are used, the amount used should be approx.
0.1-5%, preferably about 0.5-5%. Suitable flavoring agents and sweeteners may be used to impart flavor to the compositions of the invention. Examples of suitable flavoring agents include flavored oils such as spearmint oil, peppermint oil, wintergreen oil, sweetsafras oil, clove oil, sage oil, eucalyptus oil, marjolan oil, cinnamon oil, lemon oil, and orange oil, and salicylic acid. There is methyl. Suitable sweeteners include cane sugar, lactose,
It contains maltose, sorbitate, sodium cyclamate, and saccharin. Flavoring agents and sweeteners may together make up about 0.01-5% or more of the compositions of the present invention. Fluorine-containing compounds that have beneficial effects on the protection and hygiene of the oral cavity (eg, reducing the solubility of enamel in acids and preventing caries) may also be incorporated into the gelling vehicle. Examples include sodium fluoride, stannous fluoride, potassium fluoride, potassium stannous fluoride (SnF ₂ -KF), thorium hexafluorostannate, stannous fluoride chloride, and sodium fluorozirconate. , and sodium monofluorophosphate. Such substances that dissociate or liberate fluorine-containing ions in water should be present in effective but non-toxic amounts, usually within the range of about 0.01% to 1% by weight of water-soluble fluorine. Appropriate. The oral product may be in liquid form, such as a mouthwash. The mouthwash contains a 20-99% by weight aqueous solution of a lower aliphatic alcohol, and this aqueous solution contains about 1-30% by weight of an alcohol such as ethanol, n-propanol or isopropanol. Oral products such as these are generally applied by brushing the teeth at least 11 times a day or by brushing the oral cavity 30 times a day.
Applied by rinsing for ~90 seconds. Representative examples of oral products of the present invention that can be applied in this manner are shown in the following examples. Example 4 Preparation of magnesium-polycarboxylate oral rinse. Total amount: 1 Solution A (mouthwash concentrate)

[Table] Solution B (Magnesium Polycarboxylate Complex) A 2% aqueous copolymer solution was prepared by adding methyl vinyl ether-maleic anhydride copolymer (Gatrez) to 500 ml of water. After adjusting the pH to 5.5 by adding 3N ammonium hydroxide, magnesium oxide was added in an amount of 0.050M with stirring.
The resulting mixture was a clear solution. 500 ml of solution A was added to 500 ml of solution B with continuous stirring (eg with a magnetic stirrer). The pH of this mixture was between 4 and 6, and a clear mouthwash was obtained. The final concentrations of magnesium salt and copolymer in this wash solution are 0.025M and 1%, respectively. When tested by equilibrium dialysis, the magnesium-maleate copolymer complex in typical mouthwash formulations retains its integrity even in the presence of salivary salts.
It was found that the dissociation rate was slow. The release rate of magnesium ions is slow and the retention time of magnesium in the oral cavity is longer.
The preventive effect of the oral composition containing the magnesium-copolymer complex of the present invention against tartar formation and other cavity diseases is enhanced. Example 5 Oral cleansing liquid ingredients % Ethyl alcohol 5.0 Non-ionic cleansing agent (Pluronic F-108*) 3.0 Flavoring agent 0.073 Glycerin 10.0 Satucharin 0.03 Gantrez119** (0.5% aqueous solution 20ml) 0.1 Magnesium chloride 0.4 Total amount 100 with water * Polyalkylene Oxide block polymer ※※ Maleic anhydride-methyl vinyl ether copolymer with a molecular weight of 250,000 Add magnesium chloride powder to a 0.5% aqueous solution of the copolymer and stir until dissolved. After adjusting the pH to 7.00 with ammonium hydroxide, a concentrated mouthwash containing all remaining ingredients is added to the magnesium-copolymer solution. A clear oral rinse solution with a pH of 5.3 was obtained, which was very effective in inhibiting tartar formation over a long period of time. The ratio of magnesium salt:polycarboxylate is 4:1. Example 6 Instead of 0.1% maleic acid copolymer, sulfoacrylic acid oligomer (ND-
2) A mouthwash was prepared according to the method of Example 5, except that 1.0% was used. A clear oral rinse with a pH of 7.8 was obtained, which was an effective tartar prevention composition for a long period of time. The magnesium salt:oligomer ratio is 2:5. Example
7 Instead of 0.1% maleic acid copolymer, tricarboxylate (OTB) as listed in Table 4 above
A mouthwash was prepared according to the method of Example 5, except that 0.5% was used. The resulting mouthwash was clear and had a pH of 7.0. The ratio of magnesium salt:polycarboxylate is 4:5. Example 8 Toothpaste ingredient percentage Copolymer of Example 1 1.0 Magnesium chloride 0.025 Nonionic detergent* 1.00 Glycerin 22.00 Sodium pyrophosphate 0.25 Carboxymethyl cellulose 0.85 Satucalin (Na salt) 0.20 Sodium benzoate 0.50 Calcium carbonate (precipitated) 5.00 Phosphoric acid Dicalcium dihydrate 46.75 Flavoring agent 0.80 With water Total amount 100.00 * Tween80: Polyoxyethylene (20 moles of ethylene oxide) - sorbitan monooleate. A magnesium-copolymer complex is prepared according to the method of Example 4. The remaining ingredients are stirred to form a base paste, which is then mixed with the magnesium-copolymer complex. In this case, the same volumes or weights of base paste and pre-prepared magnesium copolymer complex are used. In the formulation of chewing gums and lozenges, effective amounts, such as about 0.01 to 5% of the magnesium compound and about 0.1 to 10% of the polycarboxylate, are incorporated into an inert carrier or dissolved in a suitable vehicle. Magnesium polycarboxylate complexes can also be incorporated into mouth sprays. A typical lozenge formulation contains the following ingredients in weight percent based on the weight of the total composition. Sugar 75-98% Corn syrup 1-20% Flavor oil 0.1-1% Coloring agent 0-0.03% Tablet lubricant 0.1-5% Water 0.2-2% Polycarboxylate 01-10% Magnesium compound 0.01-5 % Sugar-free embossed candy can also be prepared containing the complexes of the present invention. In the manufacture of this type of product, which generally contains powdered sorbit instead of sugar, the powdered sorbit is mixed with a synthetic sweetener and then flavoring, coloring, and tablet lubricant are added. This formulation is placed in a tablet press and embossed into the final product. Naturally, many variants of the above method can also be used for producing embossed candy. A typical chewing gum contains the following ingredients in weight percent based on the total composition of the gum. Gum base: Approximately 10-40% Cane sugar: Approximately 50-75% Corn syrup (or glucose)
About 10-20% Flavoring About 0.4-5% Polycarboxylate About 0.1-10% Magnesium Compound About 0.01-5% The composition of another chewing gum (sugar free) is as follows. Gum base approx. 10-50% Binders approx. 3-10% Fillers (sorbit, mannite or mixtures thereof) approx. 50-80% Artificial sweeteners and flavors approx. 0.1-5% Polycarboxylates approx. 0.1-10% Magnesium compounds About 0.01-5% Some sugar-free gums use an aqueous sorbit solution as the binder component, containing about 10-80%, preferably about 50-75%, by weight of sorbit in water. In another example, about 30-60% by weight as a binder,
Preferably, a gum arabic/water system containing about 45-50% by weight of gum arabic powder is used. The above chewing gum formulation is only an example;
Many alternative formulations are described in the prior art literature and may be utilized in the practice of the present invention. It is also possible to produce satisfactory chewing gum products containing a gum base, a flavoring agent, and a magnesium polycarboxylate complex in accordance with the teachings of the present invention. There are many types of ingredients simply referred to as "gum base" in the above compositions. Generally, gum base is
It is manufactured by heating and mixing various components such as natural rubber, synthetic resin, wax, and plasticizer by a method well known in the art. Typical examples of ingredients found in chewing gum bases include vegetable chews such as chicle, crown gum, nispero, rosidinha, jelutong, pendare, periro ( perillo), Nisier ivy, tunu, etc.; synthetic masticants such as butadiene-styrene polymer, isobutylene-isoprene copolymer,
paraffin, petroleum wax, polyethylene, polyisobutylene, polyvinyl acetate, etc.; plasticizers, such as lanolin, stearic acid, sodium stearate, potassium stearate, etc. A preferred component of the compositions of the present invention increases the prophylactic action, aids in the complete and sufficient dispersion of the compositions of the present invention throughout the oral cavity, and makes the compositions of the present invention more acceptable as cosmetic products. It is a nonionic organic surfactant. Nonionic surfactants provide cleaning and foaming properties to the composition, as well as keeping the flavoring agents in solution (ie, solubilizing flavor oils). Additionally, nonionic surfactants are fully compatible with the magnesium polycarboxylate complexes of the present invention, forming stable homogeneous compositions with excellent tartar control properties. The nonionic organic surfactants used in the present invention are known in the industry and are water-soluble products obtained from the condensation of alkylene oxides or equivalent reagents with reactive hydrogen-containing hydrophobes. The hydrophobic organic compound may be an aliphatic, aromatic or heterocyclic compound, but the first two types are preferred. Preferred types of hydrophobic substances are higher aliphatic alcohols and alkylphenols, but carboxylic acids,
acid amide (carboxamide), mercaptan,
Other types such as sulfonamides can also be used. Condensation products of higher alkylphenols and ethylene oxide are among the preferred nonionic compounds. Typically, the hydrophobic moiety will have at least about 6 carbon atoms, preferably about 8 or more carbon atoms, and may have a carbon number of about 50 or more carbon atoms. The amount of alkylene oxide varies considerably depending on the hydrophobe, but as a general rule at least about 5
moles of alkylene oxide should be used.
The upper limit of the amount of alkylene oxide also varies, but there is no specific limit. Large amounts of alkylene oxide, such as 200 moles or more per mole of hydrophobe, can also be used. Ethylene oxide is preferred;
Although it is the mainstream oxyalkylating agent, other lower alkylene oxides such as propylene oxide and butylene oxide may also be used alone or in place of a portion of ethylene oxide. Other suitable non-ionic compounds are polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids derived from petroleum oxidation products. Such esters typically have about 10 to 22 carbon atoms in the acid moiety and about 12 to 30 moles of ethylene oxide or its equivalent. Yet another example of a nonionic surfactant is an alkylene oxide condensation product with a higher fatty acid amide. The number of carbon atoms in the fatty acid group is generally about 8 to 22;
This is condensed with about 10 to 50 moles of ethylene oxide, the preferred alkylene oxide. Corresponding carboxamides and sulfonamides can also be used as substantial equivalents. Yet another class of nonionic products are oxyalkylated higher aliphatic alcohols. The aliphatic alcohol has at least about 6 carbon atoms, preferably about 8 or more carbon atoms. The most preferred alcohols are lauryl, myristyl, cetyl, stearyl and oleyl alcohols, which are condensed with at least about 6 moles of ethylene oxide, preferably about 10 to 30 moles of ethylene oxide. A typical nonionic product of this type is oleyl alcohol condensed with 15 moles of ethylene oxide. The corresponding alkyl mercaptans condensed with ethylene oxide are also suitable for the compositions of the invention. The amount of nonionic surfactant used varies from about 0.2 to 3.0% by weight of the total composition, depending on the type of surfactant as well as the type and amount of other ingredients in the oral composition. Although the invention has been described above in connection with specific examples,
As will be apparent to those skilled in the art, various modifications may be made within the scope of the invention.

Claims (1)

[Scope of Claims] 1. A magnesium polycarboxylate complex of a magnesium compound and a polycarboxylate compound is included as an essential tartar preventive agent, and the ratio of the magnesium compound to the polycarboxylate compound is 1:40 to 4:1. PH is in the range of 4.5~
7.8, the magnesium compound constitutes 0.01-5% by weight of the total oral product, and the polycarboxylate compound constitutes 0.1-10% by weight, dental cream, mouthrinse, An oral product for use in the form of a troche, lozenge, chewing gum, dental tablet, powder or mouth spray, wherein the polycarboxylate contains ionizable carboxyl groups, and wherein: (a) maleic acid or maleic anhydride; and an olefin having at least 2 carbon atoms per molecule; (b) a sulfoacrylic acid oligomer having an average molecular weight of less than 1000; and (c) tricarboxy-oxa-butanol or pentanol. , an oral product wherein said polycarboxylate compound is ionically bound to a dissociable physiologically acceptable magnesium compound. 2 Copolymers of maleic acid or maleic anhydride (wherein M and M ₁ are each hydrogen, sodium, potassium or ammonium, and may be the same or different, X is selected from the group consisting of ethylene, styrene, isobutylene, methyl vinyl ether and ethyl vinyl ether). A product according to claim 1, comprising units. 3 Sulfoacrylic acid oligomer has the following structural formula: (wherein M is an alkali metal or ammonium ion, and n is greater than 6 and less than 10). 4 The tricarboxy compound is 3-oxa-2,
The product of claim 1, which is the trisodium salt of 2,4-tricarboxybutanol-1. 5. The product of claim 2, wherein the polycarboxylate is a copolymer of maleic anhydride and methyl vinyl ether. 6. The product of claim 1, wherein the magnesium compound is magnesium oxide. 7. The product of claim 1, wherein the magnesium compound is magnesium chloride.