US3639569A - Oral compositions for calculus retardation - Google Patents

Oral compositions for calculus retardation Download PDF

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Publication number
US3639569A
US3639569A US706685A US3639569DA US3639569A US 3639569 A US3639569 A US 3639569A US 706685 A US706685 A US 706685A US 3639569D A US3639569D A US 3639569DA US 3639569 A US3639569 A US 3639569A
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tris
amine
calculus
phosphonoalkyl
compositions
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US706685A
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Ralph F Medcalf Jr
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Procter and Gamble Co
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Procter and Gamble Co
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55—Phosphorus compounds

Definitions

  • the field of this invention is oral compositions which term is used herein to designate products which in the ordinary course of usage are retained in the oral cavity for a time sufficient to contact substantially all of the dental surfaces, but are not intentionally ingested.
  • Such products include, for example, dentifrices, mouthwashes, prophylaxis pastes and topical solutions.
  • Dental calculus or tartar as it is sometimes called, is a deposit which forms on the surfaces of the teeth at the gingival margin. Supragingival calculus appears principally in the areas near the orifices of the salivary ducts; e.g., on the lingual surfaces of the lower anterior teeth and on the buccal surfaces of the upper first and second molars, and on the distal surfaces of the posterior molars.
  • Mature calculus consists of an inorganic portion which is largely calcium phosphate arranged in a hydroxylapatite crystal lattice structure similar to bone, enamel and dentine.
  • An organic portion is also present and consists of desquamated epithelial cells, leukocytes, salivary sediment, food debris and various types of microorganisms.
  • the mature calculus As the mature calculus develops, it becomes visibly white or yellowish in color unless stained or discolored by some extraneous agency. In addition to being unsightly and undesirable from an aesthetic standpoint, the mature calculus deposits are constant sources of irritation of the gingiva and thereby are a contributing factor to gingivitis and other diseases of the supporting structures of the teeth, the irritation decreasing the resistance of tissues to endogeneous and exogenous organisms.
  • the chemical approach to calculus inhibition generally involves chelation of calcium ion which prevents the calculus from forming and/or breaks down mature calculus by removing calcium.
  • a number of chelating agents have been employed for this purpose. See, for example, British Pat. 490,384, granted Feb. 15, 1937, which discloses oral compositions containing ethylenediaminetetraacetic acid, nitrilotriacetic acid and related compounds as anticalculus agents; German Auslegeschrift 1,149,138, published May 22, 1963, which discloses certain Water-soluble digylcolates as anticalculus agents; and US. Patent 1,516,206 which discloses oral compositions containing various sugar lactones for this purpose.
  • tris(phosphonalkyl) amines and salts thereof posses the surprising capacity to retard the development of dental calculus without removing calcium from dental enamel or otherwise damaging the tooth structure when employed in oral compositions maintained within defined pH limits.
  • tris(phosphonalkyl)amines as used hereinafter is intended to encompass both the free acid and salt forms.
  • compositions of this invention retard calculus formation by a mechanism that is believed to involve the inhibition of hydroxylapatite crystal growth as will be discussed more fully hereinafter.
  • the tris(phosphonalkyl)amines employed in the compositions of this invention resist hydrolysis in aqueous products and therefore remain in an active form throughout the normal shelf-life of such products.
  • This invention is an oral composition effective in inhibiting the formation of dental calculus without adversely affecting the tooth structure comprising 1) from about .0l% to about 10% by weight of at least one tris(phosphonoalkyl)amine selected from the group consisting of those having the formula:
  • R R R R R R and R are each hydrogen or lower alkyl (1-4 carbon atoms), and pharmaceutically acceptable salts thereof, such as alkali metal (e.g., sodium and potassium), alkaline earth metal (e.g., calcium and magnesium), non-toxic heavy metal (e.g., stannous and indium), and ammonium or low molecular weight substituted ammonium (e.g., mono-, di-, and triethanolammoniurn) salts; and (2) a carrier suitable for use in the oral cavity, the pH of the composition being within the range from about 4.0 to about 11.0.
  • alkali metal e.g., sodium and potassium
  • alkaline earth metal e.g., calcium and magnesium
  • non-toxic heavy metal e.g., stannous and indium
  • ammonium or low molecular weight substituted ammonium e.g., mono-, di-, and triethanolammoniurn
  • tris(phosphonoalkyl)amines for the purpose of this invention are tris(phosphonomethyl)amine; tris(l phosphonoethyl)amine; tris(2-phosphono-2-propyl)amine; and their pharmaceutically acceptable salts.
  • T ris(phosphonomethyl)amine is especially preferred.
  • additional compounds are exemplary of those which can be used herein:
  • the concentration of tris (phosphonoalkyl) amines in the oral compositions of this invention can range from about .0l% to about 10% by weight. Oral compositions which in the ordinary course of usage could be accidentally ingested should contain lower concentrations. Thus, a mouthwash in accordance with this invention preferably contains less than about 3% by weight of tris(phosphonoalkyl)amine. Dentifrice compositions, topical solutions and prophylaxis pastes, the latter to be administered professionally, can contain up to about 10% by weight, preferably from about 0.1% to about 5.0% by weight of tris (phosphono alkyl) amine.
  • the pH of the compositions of this invention can range from about 4.0 to about 11. Below about pH 4.0 damage to the dental enamel can occur in spite of the relative safety of the tris(phosphonoalkyl)amines. Above about pH 11.0 difficulty is encountered in formulating products having satisfactory flavor and mildness. A preferred pH range is from about 6.0 to about 8.0.
  • the pH of the composition is determinative of the predominant salt form of the tris(phosphonoalkyl)- amines present therein. For example, at pH 7.0 using sodium hydroxide tris(phosphonomethyl)amine is predominantly in the tetrasodium form.
  • the test group of animals revealed a 44% reduction in calculus. From a study of related structures it is believed that the tris(phosphonoalkyl)amines are not appreciably absorbed in the digestive tract, thus any anticalculus effect observed in this test is due to topical exposure of the dental surfaces to the tris(phosphonoalkyl)amine during ingestion rather than any systemic effect.
  • 1 ml. of a 0.1 M stock solution of NaH PO -H O is diluted with 22 ml. of distilled water.
  • 1 ml. of an aqueous solution of the disodium salt of tris(phosphonomethyl)- amine at a concentration sufficient to provide the desired ultimate concentration in the reaction mixture is added to the diluted NaH PO solution and the solution is adjusted to pH 7.4 with NaOH.
  • To this solution is added 1 ml. of a 0.1 M solution of CaCl -2H O preadjusted to pH 7.4 with NaOH. This mixture is held at a constant pH of 7.4 throughout the reaction period.
  • the solution is filtered through a 0.45 Millipore filter pad, dried, and analyzed by X-ray diffraction.
  • the solid calcium phosphate precipitated from the above-described solution without a tris(phosphonoalkyl)amine gives a typical hydroxylapatite pattern, while the calcium phosphate precipitated under the same conditions but in the presence of small amounts of the tris(phosphonoalkyl)amines of this invention is amorphous to X-rays.
  • the safety of tris(phosphonoalkyl)amines for use in contact with dental surfaces is determined by the Continuous Immersion Test conducted as follows: Mature human teeth are immersed in aqueous solutions or dispersions of oral compositions containing a tris (phosphonoalkyl)amine in accordance with this invention at pH 7.0 and pH 10. Every four hours the teeth are examined for decalcification. Under visible light, enamel decalcification can be detected by a loss of luster, white opaque spots or slight surface roughening. The teeth are examined macroscopically and microscopically at the end of seven days. If no decalcification is observed through this period, the compositions cause no damage to dental enamel, and are considered safe in this respect for use in the oral cavity.
  • abrasives for use herein are the particulate thermosetting polymerized resins as described by Cooley et al. in US. Pat. 3,070,510, granted Dec. 25, 1962.
  • Suitable resins include, for example, melamines, phenolics, ureas, melamine-ureas, melamine-formaldehydes, urea formaldehydes, melamine urea-formaldehydes, cross-linked epoxides, and cross-linked polyesters.
  • Suitable abrasives include alumina and the insoluble non-calcium metaphosphates such as sodium metaphosphate. Mixtures of abrasives can also be used.
  • the total amount of abrasive in the dentifrice embodiments of this invention can range from 0.5 to 95% by weight of the dentifrice.
  • toothpastes contain from 20% to 60% by weight of abrasive.
  • Abrasive particle size preferably ranges from 2, to 20 Suitable sudsing agents are those which are reasonably stable and form suds throughout a wide pH range, pref.- erably non-soap anionic organic synthetic detergents.
  • Such agents are water-soluble salts of alkyl sulfate having from 10 to 18 carbon atoms in the alkyl radical, such as sodium lauryl sulfate, water-soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon atoms, such as sodium monoglyceride sulfonates; salts of C -C fatty acid amides of taurine, such as sodium N-methyl-N-palmitoyl tauride; salts of C -C fatty acid esters of isethionic acid; and substantially saturated aliphatic acyl amides of saturated monoaminocarboxylic acids having 2 to 6 carbon atoms and in which the acyl radical contains 12 to 16 carbon atoms, such as sodium N-lauroyl sarcoside. Mixtures of two or more sudsing agents can be used.
  • the sudsing agent can be present in the dentifrice compositions of this invention in an amount from 0.5 to weight of the total compositions.
  • thickening agents are hydrovyethylcellulose and water-soluble salts of cellulose ethers such as sodium carboxymethylcellulose and sodium carboxymethylhydroxyethylcellulose.
  • Natural gums such as gum karaya, gum arabic, and gum tragacanth can also be used.
  • Colloidal magnesium aluminum silicate or finely divided silica can be used as part of the thickening agent to further improve texture.
  • Thickening agents in an amount from 0.5% to 5.0% by weight of the total composition can be used.
  • humectantmaterial in a toothpaste to keep it from hardening.
  • Suitable humectants include glycerine, sorbitol, and other edible polyhydric alcohols.
  • the humectant can comprise up to about 36% by weight of the toothpaste composition.
  • Suitable flavoring agents include oil of Wintergreen, oil of peppermint, oil of spearmint, oil of sassafras, and oil of clove.
  • Sweetening agents which can be used include saccharin, dextrose, levulose and sodium cyclamate.
  • Toothpaste compositions substantially identical to the composition of Example I are prepared with the dipotassium salt of tris(phosphonomethyl)amine; the diammonium salt of tris(phosphonomethyl)amine; the monocalcium salt of tris (phosphonomethyDamine; and the monomagnesium salt of tris(phosphonomethyl)amine, respectively, rather than the disodium salt of tris(phosphonomethyl)amine, adjusting the pH to 5.9. These compositions substantially retard calculus formation and do not decalcify dental enamel.
  • each of the above compositions materially reduces the accumulation of calculus on the surfaces of teeth. No decalcification is observed after seven days exposure of dental enamel to these compositions.
  • a prophylaxis paste for use by the dentist for removal of stains and polishing the teeth after mechanical removal of calculus deposits is formulated as follows:
  • Toothpowders and the like can be prepared by conventional methods and containing, in addition to the usual ingredients, an amolmt of tris(phosphonoa1kyl)amine Within the ranges specified herein, to provide an effective means of retarding calculus formation without damaging the tooth structure.
  • a dentifrice composition containing from about 5% to about 95% by weight of a dentifrice abrasive selected from the group consisting of fi-phase calcium pyrophosphate, particulate thermosetting polymerized resin, alumina, sodium metaphosphate and mixtures thereof, and having a pH within the range from about 4.0 to about 11.0, the improvement comprising the incorporation therein of from about 0.1% to about 5.0% by weight of a tris(phosphonoalkyl)amine selected from the group consisting of those of the formula:
  • R R R R R R and R are each hydrogen or lower alkyl, and the pharmaceutically acceptable salts thereof.
  • composition of claim 1 wherein the tris(phosphonoalkyl)amine is tris(phosphonomethyl)amine or a pharmaceutically acceptable salt thereof.
  • a mouthwash composition consisting of a flavoring agent, glycerine, ethanol, sweetener, emulsifier and water, the improvement comprising the incorporation therein of from 0.1% to about 5.0% by weight of a tris(phsphonoalkyl)amine selected from the group consisting of those of the formula:
  • R R R R R R and R are each hydrogen or lower alkyl and the pharmaceutically acceptable salts thereof.
  • composition of claim 3 wherein the tris(phosphonoalkyl)amine is tris(phosphonomethyl)amine or a pharmaceutically acceptable salt thereof.
  • a chewing gum composition containing a chewing gum base and having a pH within the range from about 4.0 to about 11.0, the improvement comprising the incorporation therein of from about 0.1% to about 5.0%
  • composition of claim 5 wherein the tris(phosphonoalkyl)amine is tris(phosphonomethyl)amine or a pharmaceutically acceptable salt thereof.
  • a dental prophylaxis paste composition containing a dental abrasive and having a pH within the range from about 4.0 to about 11.0, the improvement which comprises the incorporation therein of from about 0.1% to about 5.0% by weight of a tris (phosphonoalkyDamine selected from the group consisting of those of the formula:
  • R R R R R and R are each hydrogen or lower alkyl, and the pharmaceutically acceptable salts thereof.
  • composition of claim 7 wherein the tris(phosphonoalkyl)amine is tris(phosphonomethyl)amine or a pharmaceutically acceptable salt thereof.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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US706685A 1968-02-19 1968-02-19 Oral compositions for calculus retardation Expired - Lifetime US3639569A (en)

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BE (1) BE728532A (en))
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DK (1) DK119571B (en))
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864472A (en) * 1972-11-06 1975-02-04 Colgate Palmolive Co Clear lemon-flavored mouthwash
US3947570A (en) * 1972-11-06 1976-03-30 Colgate-Palmolive Company Oral product
US4143128A (en) * 1976-02-25 1979-03-06 Colgate Palmolive Company Oral compositions for calculus retardation
US4144324A (en) * 1976-10-08 1979-03-13 Colgate Palmolive Company Oral compositions for calculus retardation
US4233288A (en) * 1979-03-12 1980-11-11 Cornell John A Gum emulsified liquid package for delivering and preserving liquid content in the mouth
US5000943A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Canine biscuits containing an inorganic pyrophosphate
US5000973A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Nutritionally-balanced canine biscuits containing an inorganic pyrophosphate
US5000940A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Devices, compositions and the like having or containing an inorganic pyrophosphate
US5011679A (en) * 1989-05-30 1991-04-30 Nabisco Brands, Inc. Raw hide having a coating containing an inorganic pyrophosphate
US5015485A (en) * 1989-05-30 1991-05-14 Nabisco Brands, Inc. Dog biscuits having a coating containing an inorganic pyrophosphate
US5047231A (en) * 1989-05-30 1991-09-10 Nabisco Brands, Inc. Raw hide containing an inorganic pyrophosphate
US5094870A (en) * 1989-05-30 1992-03-10 Nabisco Brands, Inc. Canine biscuits containing an inorganic pyrophosphate
US5114704A (en) * 1989-05-30 1992-05-19 Nabisco Brands, Inc. Raw hide having a coating containing an inorganic pyrophosphate
US6455080B1 (en) 1997-12-29 2002-09-24 Wm. Wrigley Jr., Company Chewing gum containing controlled release acyclic carboxamide and method of making
US6627233B1 (en) 1997-09-18 2003-09-30 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents
US20070248717A1 (en) * 2004-02-26 2007-10-25 Johnson Sonya S Confections Containing a Blend of Physiological Cooling Agents
EP1935252A1 (en) 1997-09-18 2008-06-25 WM. Wrigley Jr., Company Chewing gum composition
EP2478777A1 (en) 2005-12-23 2012-07-25 Kraft Foods Global Brands LLC Composition providing a cooling sensation substantially similar to that provided by menthol
EP2559424A1 (en) 2005-10-05 2013-02-20 Kraft Foods Global Brands LLC Cooling composition comprising trimethyl isopropyl butanamide

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3766349A (en) * 1971-11-12 1973-10-16 G Codrino Pushbutton switch, provided with a lighted ideogram
IE37842B1 (en) * 1972-06-30 1977-10-26 Procter & Gamble Oral compositions for plaque caries and calculus retardation with reduced staining tendencies

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA753207A (en) * 1967-02-21 Monsanto Company Antiseptic compositions

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864472A (en) * 1972-11-06 1975-02-04 Colgate Palmolive Co Clear lemon-flavored mouthwash
US3947570A (en) * 1972-11-06 1976-03-30 Colgate-Palmolive Company Oral product
US4143128A (en) * 1976-02-25 1979-03-06 Colgate Palmolive Company Oral compositions for calculus retardation
US4144324A (en) * 1976-10-08 1979-03-13 Colgate Palmolive Company Oral compositions for calculus retardation
US4233288A (en) * 1979-03-12 1980-11-11 Cornell John A Gum emulsified liquid package for delivering and preserving liquid content in the mouth
US5114704A (en) * 1989-05-30 1992-05-19 Nabisco Brands, Inc. Raw hide having a coating containing an inorganic pyrophosphate
US5000973A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Nutritionally-balanced canine biscuits containing an inorganic pyrophosphate
US5000940A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Devices, compositions and the like having or containing an inorganic pyrophosphate
US5011679A (en) * 1989-05-30 1991-04-30 Nabisco Brands, Inc. Raw hide having a coating containing an inorganic pyrophosphate
US5015485A (en) * 1989-05-30 1991-05-14 Nabisco Brands, Inc. Dog biscuits having a coating containing an inorganic pyrophosphate
US5047231A (en) * 1989-05-30 1991-09-10 Nabisco Brands, Inc. Raw hide containing an inorganic pyrophosphate
US5094870A (en) * 1989-05-30 1992-03-10 Nabisco Brands, Inc. Canine biscuits containing an inorganic pyrophosphate
US5000943A (en) * 1989-05-30 1991-03-19 Nabisco Brands, Inc. Canine biscuits containing an inorganic pyrophosphate
US20040247743A1 (en) * 1997-09-18 2004-12-09 Wm. Wrigley, Jr. Company Chewing gum containing physiological cooling agents
US20070202212A1 (en) * 1997-09-18 2007-08-30 Wm. Wrigley Jr. Company Chewing gum containing controlled release acyclic carboxamides
US6627233B1 (en) 1997-09-18 2003-09-30 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents
US20080199565A1 (en) * 1997-09-18 2008-08-21 Wm. Wrigley Jr. Company Chewing Gum Containing Physiological Cooling Agents
US20050019445A1 (en) * 1997-09-18 2005-01-27 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents
US7078066B2 (en) 1997-09-18 2006-07-18 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents and method of making
US20070098842A1 (en) * 1997-09-18 2007-05-03 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents
US20030082271A1 (en) * 1997-09-18 2003-05-01 Wm. Wrigley, Jr. Company Chewing gum containing controlled release acyclic carboxamides
EP1935252A1 (en) 1997-09-18 2008-06-25 WM. Wrigley Jr., Company Chewing gum composition
US7364761B2 (en) 1997-09-18 2008-04-29 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents and method of preparing
US6455080B1 (en) 1997-12-29 2002-09-24 Wm. Wrigley Jr., Company Chewing gum containing controlled release acyclic carboxamide and method of making
US20070248717A1 (en) * 2004-02-26 2007-10-25 Johnson Sonya S Confections Containing a Blend of Physiological Cooling Agents
EP2559424A1 (en) 2005-10-05 2013-02-20 Kraft Foods Global Brands LLC Cooling composition comprising trimethyl isopropyl butanamide
EP2478777A1 (en) 2005-12-23 2012-07-25 Kraft Foods Global Brands LLC Composition providing a cooling sensation substantially similar to that provided by menthol

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DE1908067B2 (de) 1977-08-11
GB1232889A (en)) 1971-05-19
DE1908067A1 (de) 1969-09-04
BE728532A (en)) 1969-08-18
DK119571B (da) 1971-01-25
AT285051B (de) 1970-10-12
FR2002164B1 (en)) 1973-01-12
NO125796B (en)) 1972-11-06
FR2002164A1 (fr) 1969-10-17
NL6902561A (en)) 1969-08-21
FI50054C (fi) 1975-12-10
IT1056004B (it) 1982-01-30
FI50054B (en)) 1975-09-01
SE355493B (en)) 1973-04-30
CH527614A (de) 1972-09-15

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