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Publication numberUS2955985 A
Publication typeGrant
Publication dateOct 11, 1960
Filing dateJul 2, 1956
Priority dateJun 18, 1956
Publication numberUS 2955985 A, US 2955985A, US-A-2955985, US2955985 A, US2955985A
InventorsMartin Kuna
Original AssigneeBristol Myers Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Dentifrice compositions
US 2955985 A
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Description  (OCR text may contain errors)

Patented Oct. 11, 1960 iiee% DENTIFRICE coMrosrrroNs Martin Kuna, Westfield, NJ., assignor to Bristol-Myers Company, New York, N.Y., a corporation of Delaware No Drawing. Filed July 2, 1956, Ser. No. 595,133

Claims. (Cl. 167-93) This invention relates to a dentifrice, and more particularly to a dentifrice in paste, powder or liquid form, which tends to reduce the normal susceptibility of the teeth to attack from acid.

It is generally accepted that dental caries result at least partially from the acids formed by microorganisms in the mouth in the course of their metabolism. These acids, when in contact with the teeth, attack the enamel of the teeth, dissolving the enamel, and result in tooth decay. A considerable amount of research effort has been devoted to find a means of protecting the teeth against the attack of these acids. Numerous proposals have been advanced to solve the problem. Those skilled in the dentifrice art are familiar with these proposals. One proposal was the incorporation of a basic ammonium salt in a dentifrice. These were known as the ammoniated dentifrices. Another was the use of chlorophyll in a dentifrice. Another was the incorporation of a socalled anti-enzyme, such as sodium lauryl sulfate, into a dentifrice. While some of these proposals have given indications of being helpful, none of them has provided satisfactory protection of the teeth against the ravages of acids, such as are formed in the mouth. I

It is an object of the present invention to provide an improved dentifrice having the property of reducing the normal susceptibility of the teeth to acid attack.

It is another object of the present invention to incorporate in a dentifrice an agent affording protection to the teeth enamel against acid attack and resisting calculus formation on the teeth.

Other objects will be apparent to those skilled in the 7 art from reading the description which follows.

The present invention is based upon the discovery that a dentifrice containing as an essential ingredient or comwherein n is an integer from 1 to 5, inclusive, x is an integer from 1 to 3, inclusive, y equals 3x, and'M is hydrogen, an alkali-metal or an ammonium ion. The preferred esters are those in which n is an integer from 2 to 4, inclusive, x is 1, y is 2; and M is an alka i-metal or an ammonium ion, desirably the latter. The ammonium salt of 1,1,7-trihydroperfiuoroheptyl phosphate has provided excellent results. The contemplated alkalimetals are lithium, potassium and sodium, preferably the latter.

The esters of phosphoric acid and their water-soluble salts defined above will be referred to in this specification as the fluoroalkyl phosphates.

2 The fluoroalkylphosphates contemplated for incorpor ation into the dentifrices of the invention fall withinthe following three types.

H CF CH OPO(OM -(monoester) H (CF 2 CH Ol P0 OM )--(diester) [H (CF CH O] PO(triester) wherein n and M have the same definitions as above. As indicated above, the water-soluble salts of the monoesters, and particularly their ammonium salts, are pre ferred because of their greater water-solubility, whereas the triesters have substantially reduced solubility in water and are therefore not the preferred esters for use in the invention. The triesters, as a class, frequently are liquids and therefore are not as suitable in the preparation of dry powder dentifrices.

The selected fluoroalkyl phosphates and their watersoluble salts described above are known chemical compounds and per se do not constitute a part of this invention. These esters and their salts and their methods of preparation are described in U.S. Patent No. 2,597,702 of A. F. Benning. It is intended to incorporate by reference the entire disclosure of the patent into this specification. These esters may be produced by several methods, including the reaction between an appropriate fluorinated alk anol and phosphorus pentoxide or phosphorus oxy- I chloride.

Among the preferred fluoroa'lkyl, phosphates contemplated for employment in the'dentifrices of the invention are: l,1,7-trihydroperfluoroheptyl phosphate" and its ammonium salt; l,1,3-trihydroperfluoropropyl phosphate and phosphate, etc., and mixtures of them. The ammonium ion in the salts may be replaced with an alkali-metal ion to form the sodium, potassium or lithium salts.

While the concentration of the selected fiuoroalkyl phosphate or its salts in the dentifrice may Vary, best results are obtained where the selectedphosphatecon-f stitutes betweenabout' 0.05% and '2;0%, andipre ferab'ly" between 1.0% and 1.8%, by weight of the total dentifrice composition. Below 0.05% the phosphate may be ineffective, and above 2.0% it may not be utilized efiiciently.

Where the dentifrice is a paste or powder it is desirable to incorporate into the dentifrice a solid polishing agent, such as dicalcium phosphate, calcium pyrophosphate', tri calcium phosphate or powdered chalk (calcium carbonate), etc. Non-calcium-containing polishingagents, such as aluminum oxide, titanium dioxide, ground pumice, 1

powdered nylon, etc., may be employed.

In addition to the selected fiuoroalkyl phosphate and polishing agent- (when desired), the dentifrice can contain as optional ingredients a soap or synthetic detergent as a surface tension depressant. Soaps of high molecular weight fatty acids, including, for example, -sodium and potassium soaps of myristic, stearic and palmitic acids and the fatty acid mixtures of palm oil and coconut oil, as well as diglycol laurate, diglycol stearate and glyco-. stearine, can be employed. Typical synthetic detergents include the alkyl sulfates and sulfonates having alkyl' groups of from about 8 to'about 18 carbon atoms, such as sodium lauryl sulfate, the sulfated fatty alcohols derived from coconut oil and palm oil, sodium cetyl sulfate," sulfated sperm oil fatty alcohols and sodium oleyl sulfate, sulfated glycerides, such as oleyl, stearic, palrnitic and ricinoleic glycerides, usually in the form of mixed glycerides and sulfonated hydrocarbons having from 8 to 20 carbon atoms, such as sulfonated decanes, dodccan e s. andoctadecanes. Particularly good results are obtained:

diammonium 1,1,9 trihydroperfiuorononyl' with Tweens, such as Tween 20 which is the polyoxyethylene derivative of sorbitan, and Atlas G-2160 which is the polyoxyethylene derivative of mannitan. Another type is the Drucals, such as sodium lauryl isethionate, or sodium mixed alkyl isethionates.

Other optional conventional components of a dentifrice which may be present include flavoring materials, such as the flavoring oils (peppermint oil, etc.) sweeteners, such as sucrose, glueose, saccharin and sodium cyclamate, and harmless coloring materials, in proportions to give any desired taste or flavor or other effect.

In a preferred embodiment of the invention, the dentifrice is in the form of a paste, and in this event it will contain a carrier and softener and a binder in amounts to give the dentifrice a smooth texture and good flowability. Glycerin and sorbitol are preferred humectants, carriers and softeners, but syrup, glucose and invert sugars and honey can also be employed. As binders there can be used carboxymethylcellulose, gum tragacanth, sodium alginate, Irish moss, gum acacia, pectin, etc. Those skilled in the dentifrice art will know other carriers, softeners and binders. The pastes may be either of the aqueous type, containing substantial amounts of water (above 18%), or of the relatively anhydrous type, containing less than 5% water. Formulations are given below for both types.

In addition to pastes, the dentifrices of the invention may be in the form of powders or liquids. The main difference between a paste and powder is that the latter contains little or no water and usually no binder or softener. A liquid usually differs from a paste in that it is more fluid and it contains no solid polishing agent.

The following are general formulations of tooth pastes, powders and liquids of the type contemplated according to the present invention (parts are expressed in terms of parts by weight):

Aqueous tooth paste Parts by weight Relatively anhydrous tooth paste Parts by weight Fluoroalkyl phosphate 0.05 to 2.0 Water to 4.5 Binder 0.3 to 1.2 Polishing agent 45 to 70 Humectant 25 to 45 Detergent 0 to 2 Sweetener 0.03 to 0.10 Flavoring oils 0.9 to 1.2

Powder Parts by weight Fluoroalkyl phosphate 0.05 to 2.0 Polishing agent 93.6 to 98 Detergent 1 to 3 Flavoring oils 0.85 to 1.2 Sweetener 0.1 to 0.2

Liquid Parts by weight Fluoroalkyl phosphate 0.05 to 2.0 Water 60.1 to 92 Detergent 1.5 to 5 Softener 5 to 30 Binder or suspending agent 0.5 to 1.5 Flavoring agent 0.85 to 1.2 Sweetener 0.1 to 0.2

EXAMPLE I The following is an example of a tooth paste formulation:

Ingredient: Parts by weight Monoammonium 1,1,7-trihydroperfluoroheptyl phosphate 1.0 Deionized water 22.9 Soluble saccharin 0.15 Carboxymethylcellulose (HV-l20) 1.0 Dicalcium phosphate 49.0 Sorbitol 23.05 Sodium lauryl sulfate 1.8 Flavoring oils 1.10

EXAMPLE II The following is an example of a series of tooth paste formulations:

Ingredient A B Ammonium di- (1, 1, 5-trihydroperfluoramyl) phosphate 1. 80 Diammonium 1 ,1, Q-trihydroperfluorononyl phosphate 1. 80 Deionized water 22. 90 22. 90 Soluble saecharin 0.15 0.15 Carboxymethylcellulose (H 20 1.0 1.0 Dicalcium phosphate 50.0 50.0

Sorbitol 23.05 23.05 Flavoring oils 1. 10 1.10

EXAMPLE III The following is an example of a series of tooth paste formulations:

Ingredient A l B C l D Monoammonium 1,1,7-trihydroperfluoroheptyl phosphate 1. 8 0. 9 1.0 1.0 22. 90 22. 90 22.8 22. 5 Soluble saecharin 0.15 0.15 0.15 0.15 Garboxymethylcellulose (EV-120)-.. 1.0 1.0 1.0 1.0 Diealcium phosphate 50.0 50.0 49. 0 49. 65 Sorbitol 23.05 23.05 23.05 23.05

Drucal (CHD)-(a mixture of sodium lauryl isethionate and sodium myristyl isethionate) 0.9 Sodium lauryl sulfate 1.0 1. 50 Flavoring oils 1. 1 1.1 1.1 1.1

EXAMPLE IV The following is an example of a tooth paste formulation which is relatively anhydrous, i.e., having less than 5% water:

Ingredient: Parts by weight Monoammonium 1,1,7 trihydroperfluoroheptyl phosphate 1.55 Water, deionized 4.35 Glycerin U.S.P. 41.0

Saccharin, soluble U.S.P. 0.05 Carbomethylcellulose (HV-120) 0.50 Dicalcium phosphate 50.85 Sodium lauryl sulfate 1.80 Flavoring oils 1.0

5 EXAMPLE v The following is an example of a series of tooth powder formulations:

Ingredient A B Monoamlmonium-l,1,7-tr1hydroperfluoroheptyl ate EXAMPLE VI The following is an example of a series of liquid dentifrice formulations:

Ingredient A B Monoammonium-l,1,7-trihydroperfluorohepty1 phosphate 1. 5 1. 5 Sorbitol 20. O 15. Water 75.0 79. Carboxymethylce llulose 1. 0 1. O Soluble saccharin 0. 15 0.15 Polyoxyethylene sor 1. 5 1. 5 Flavoring oils 0. 85 1.0

[H(CF ,,CH O],;PO(OM) wherein n is an integer from 1 to 5, inclusive, 2: is an 6 integer from 1 to 3, inclusive, y equals 3x, and M is a member selected from the class consisting of hydrogen, an alkali-metal ion and an ammonium ion.

2. A dentifrice comprising a dentifrice vehicle and at least about 0.05% by weight of a fluoroalkyl phosphate of the formula:

H(CF CH OPO(OM) wherein n is an integer from 1 to 5, inclusive, and M is a member selected from the class consisting of hydrogen, an alkali-metal ion and an ammonium ion.

3. A dentifrice is accordance with claim 1, in which the vehicle is a paste.

4. A dentifrice in accordance with claim 1, in which the vehicle is a powder.

5. A dentifrice in accordance with claim 1, in which the vehicle is a liquid.

6. A dentifrice in accordance with claim 1, which also contains a polishing agent.

7. A dentifrice in accordance with claim 1, which also contains a surface tension depressant.

8. A dentifrice in accordance with claim 7, wherein the surface tension depressant is a synthetic detergent.

9. A dentifrice in accordance with claim 1, which also contains a binder.

10. A dentifrice in accordance with claim 1, wherein the fluoroalkyl phosphate is' monoammonium-1,1,7-trihydroperfluoroheptyl phosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,692,264 Wojcik Oct. 19, 1954 FOREIGN PATENTS 158,717 Australia Sept. 9, 1954 OTHER REFERENCES Shourie et al: J. Dent. Res., August 1950, pp. 529-533.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2692264 *May 2, 1950Oct 19, 1954Hooker Electrochemical CoQuaternary ammonium containing compounds containing fluoroalkyl monocyclic aromatic hydrocarbon groups
AU158717B * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3152181 *Jan 18, 1961Oct 6, 1964Us Vitamin Pharm CorpAlkoxypropylene biguanides
US3183230 *Jan 13, 1961May 11, 1965Us Vitamin Pharm CorpHaloaralkyl biguanides
US3308207 *May 4, 1964Mar 7, 1967Douglas Aircraft Co IncPolyfluorinated phosphate esters
US3308208 *May 4, 1964Mar 7, 1967Douglas Aircraft Co IncPolyfluorinated phosphate esters
US3939261 *Aug 30, 1974Feb 17, 1976Colgate-Palmolive CompanyFlavored dentifrice
US4071615 *Oct 16, 1975Jan 31, 1978Colgate Palmolive CompanyDipeptide sweetener
US4170636 *Dec 29, 1977Oct 9, 1979Minnesota Mining And Manufacturing CompanyFluorine compounds
US4243658 *Apr 2, 1979Jan 6, 1981Minnesota Mining And Manufacturing CompanyPerfluoroalkanesulfonamidoalkyl carboxylic acids, dentifrices
US4304766 *Aug 11, 1980Dec 8, 1981Minnesota Mining And Manufacturing CompanyA dentifrice of prophylactic fluoride and an anionic membrane-forming compound; hydrophobic barriers
US4353892 *Aug 13, 1981Oct 12, 1982Forsyth Dental Infirmary For ChildrenFluoride preparations containing surface-active agents
US4366146 *Sep 18, 1981Dec 28, 1982Minnesota Mining & Manufacturing Co.Compositions and method for reducing elution of therapeutic agents from teeth
US4470964 *Sep 27, 1982Sep 11, 1984Minnesota Minning And Manufacturing CompanyComposition and method for reducing elution of therapeutic agents from teeth
US4485090 *Sep 27, 1982Nov 27, 1984Minnesota Mining And Manufacturing CompanyAftercoating with anionic polymer which complexes with tooth calcium
US4510127 *Sep 27, 1982Apr 9, 1985Minnesota Mining And Manufacturing CompanyCompositions and method for reducing elution of therapeutic agents from teeth
USRE31787 *May 7, 1982Jan 1, 1985Minnesota Mining And Manufacturing CompanyDentifrices, fluoride
WO1979000455A1 *Dec 28, 1978Jul 26, 1979Minnesota Mining & MfgComposition and method for inhibiting plaque formation
WO1979000456A1 *Dec 28, 1978Jul 26, 1979Minnesota Mining & MfgCompositions and methods for inhibiting plaque formation
WO2014000982A1 *May 22, 2013Jan 3, 2014Unilever PlcOral care compositions
Classifications
U.S. Classification424/52
International ClassificationA61K8/41, A61K8/55, A61Q11/00, A61K8/70, A61K8/30
Cooperative ClassificationA61K8/556, A61Q11/00, A61K8/416, A61K8/70, A61K8/55
European ClassificationA61K8/70, A61K8/55, A61Q11/00, A61K8/55F, A61K8/41L