CA1127971A - Methyloxathiazinone dioxide in oral compositions - Google Patents

Abstract

METHYLOXATHIAZINONE DIOXIDE IN
ORAL COMPOSITIONS
Abstract Disclosed herein is a mouthwash composition consisting essentially of:
(A) from about 0.05% to about 0.80% by weight of 6-methyloxathiazinone dioxide or an alkali metal or alkaline earth metal salt thereof as a sweetening agent;
(B) from about 5% to about 60% of ethyl alcohol;
(C) from about 5% to about 20% of a humectant;
(D) from about 0.1% up to 1.0% of a water-soluble fluorine containing compound; and (E) balance, water and minors.
The 6-methyloxathiazinone dioxide or alkali metal or alkaline earth metal salt thereof imparts desirable sweetness characteristics to the mouthwash and is compatible with the other ingredients of the mouthwash; and the compositions have superior stability as compared with oral compositions containing other artificial sweetening agents.

Description

~ ) ` - ~

METHYLOXATHIAZINONE DIOXIDE IN
ORAL COMPOSITIONS

James J. Benedict Technical Field The present invention xelates to oral compositions which 5 contain 6-methyloxathiazinone dioxide or an alkali metal or alkaline earth metal salt thereof as a sweetening agent.
In recent years a considerable amount of work has been conducted in the oral composition area in an effo~t to develop compositions having a high degree of consumer acc~ptance~
10 One of the more important factors related to consumer accep-tance is product taste, which is determined to a large extent by flavor ~nd sweetness characteristicsO Sweetness is yener-ally imparted to oral compositions by the use of artificial sweeteners. The use of artificial sweeteners is advantageous 15 in oral compositions as they are non-cariogenic. This non-cariogenicity apparently arises from the fac~ that these ar-tificial sweeteners are not metabolized by oral bacteria to form acids in the mouth, said acids being the primary cause of dental cariesO
Heretofore, the synthetic sweeteners of choice for use in oral compositions have been the cyclamates, which are not now permissible ingredients in oral products, and the saccharin compounds, which are currently being investi-gated by the government for possible restriction~ Although 25 the saccharin compounds are still widely used, they possess sweetness characteristics which may leave a lingering bitter aftertaste perceived by some users.
While saccharin and the cyclamates are the most common of the artificial sweetening agent:s, numerous other artifi-30 cial sweetening agents are known in the artO Examples includevarious dihydrochalcones having sugar substituents (glyconic dihydrochalcones), 5-(3-hydroxyphenoxy)-1~!-'etrazole, (6-(trifluoromethyl)-tryptophane], dipeptide sweetenin~ agents, monoammonium glycyrrhizinate, p-ethoxyphenylurea, ?
,. .,-`.,- 1 . . . : . , .

d,l-tryptophan, p-anisylurea, d-trypto~han, amino acetic acid and 3,4-dihydro-1,2,3-ora~hizin-~-one as disclosed in U.S. Patent 3,932,606, January 13, 1976 to Barth et alO
While all of the above compounds possess sweetness characteristics, not every sweetening agent is suitabl~
for use in oral compositions such as toothpastes and mouth-washes. The primary concern in formulating a toothpas~e or a mouthwash is to achieve a product that is effecti~e - for its intended useO Toothpastes, mouthwashes and similar oral compositions are complex composition~: which must be ef-fective, safe and have consumer acceptabilityO In formula-ting such compositions, numerous unpredictable problems are frequently encountered. These problems are often associated with the swe~tening agent which must be compatible with the rest of the base composition, safe for use in the oral cavity, and impart desirable sweetness characteristics. Not only is it imperative that the sweetening agent meet the above critetia, but in addition, it must be readily available at a price which is not economi ~ ly prohibitive for the use intended. It is evident cnat the discovery of novel oral compositions having all these desirable and necessary charac-teristics represents a significant advance in the oral com~
position art.
The present applicant has discovered that 6-methyl- -oxathiazinone dioxide and its alkali metal and alkaline earth salts not only pro~ide a sweeter oral product than similar compounds such as that described in the aforementioned U.S. Patent No. 3,932,606 but also is more suitable for use in oral compositions for reasons of safety and compatibility.

Background Art 6-methyloxathiazinor.e dioxide is known in the art~
It has been described as an artificial sweetening agent possessing a sweetness of about 130 times that of sucrose when tested as the sodium or potassium salt. (Ciauss and J
- 11~7`971 Jensen, An~ewar.dte Chemie, "Oxathia~inone Dioxide - A New Group of Sweetening Agents," Vol. 12, NoO 11, pp. 869-942, ~ovO, 19730) The compound is also described in U~SO Patent 3,689,486, September 5, 1972 to Clauss et al.
It is a primary object of the present invPntion to pro-vide novel oral compositions having desirable sweetness chara~teristics imparted to them by 6-methyloxathiazinone dioxide and its salts~

Disclosure of the Invention The present invention resides in the discovery that oral compositions which contain from about 0.05% to about 0.8%, preferably from about 0.1% to about 0.6%,of 6-methyl-oxathiazinone dioxide or a salt thereof as a sweetening agent possess hishly desirable sweetness characteristics with no undesirable aftertaste. In addition to impar.ing highly desirable sweetness characteristics to said oral compositions, 6-methyloxathiazinone dioxide has been found to be surprisingly compatibie with other components of such compositions, resulting in a stable, desirable composition.
As used herein, the term "oral composition" means a product, which in the ordinary course of usage, is not in-tentionally ingested, but is retained in the oral cavity for a time sufficient to contact substantially all of the dental surfaces. P_eferred compositions for purposes of the pre-sent invention include toothpastes, toothpowders, mouth-washes, mouthsprays and the likeO

Detailed De~cription Of The Invention ~ 50re specifically, it has been discovered that highly desirable sweetness characteristics are imparted to certain oral compositions such as dentifrices, mouthwashes and the like which contain from about 0.05~ to about 0.8% by weight of 6-methyloxathia~inone dioxide or an alkali metal or al-kaline earth metal salt thereof.
Preferabl~, the ~ral compositions within the scope o~
3; the present invention which contain from about 0.3~ to about ( ` ` ~
.

_ 5 _ 0.6% are more preferred for use in dentifrice compositions, with an amount of from about Q.075~ to about 0.15% being most pre-fer-ed for mouthwash compositions. The most preferred salt is the potassium salt.
Not only does the present invention reside in the discovery that 6-methyloxathiazinone dioxide and its alkali metal and alkaline earth metal salts can be utilized in oral compositions to give a co~patible product having a highly de~irable sweetness characteristics, but evenmore surpris-ing is the discovery that the stability of such a product is superior to a product ~ade with analogous materials.
.

The structure of 6-methyloxathiazinone dioxide is C ~
O = C \ O
''/
N - S
H O

Preferred Compositions A typical dentifrice compositirn falling within the scope of the present invention contains one or more abra-sive polishing materials, sudsing agents, flavor and sweet-ening agents. In addition, toothpastes generally contain humectants and binders. Optiona7 ingredients such as water-soluble fluorides and antibacterials may be added. Other ingredients such as preservatives, buffers and coloring agents may also be added to add to the desirability of the composition.
More particularly, a toothpaste composition falling within the scope of the present invention consists of:
~A) from about 0.05% to about 0.~0~ of 6-methyloxathia---' zinone dioxide or an alkali metal or alkaline earth metal ~alt thereof as a sweetening age~t;
(B) from about 0.5~ to about 95% by weight of an abrasive material;

- llZ7971 (C) from about 0.5~ to about 5O0% of a sudsing agent;
(D) from about 0.1~ to about 5OO~ of a binder mater-ial;
(E) up to about 50% of a humectant material;
S (F) from about 0.01% to about 1.0% of a water-soluble fluorine-containing compound; and (G) balance, water and minorsO
The preferred toothpaste compositions of the present invention contain the potassium salt of 6-methyloxathia-lQ zinone dioxide as the sole sweetening agent in an amount of from about 0.3% to about 0.6%.
6-methyloxathiazinone dioxide is well known and can be made in accordance with the procedure disclosed in U.S.
Patent 3,689,486, Toothpaste compositions typically contain sudsing agents in an amount of from about 0.5% to about 5~0%O Suit-able sudsing agents for use ir. the dentifrices of this in-vention are those which yield substantial levels of foam and which are otherwise acceptable for use in the oral cav-20 ity. Examples of suitable sudsing agents include the water-soluble salts of alkyl sulfate having from 10 to 18 carbon atoms, such as sodi~m lauryl sulfate; water-soluble salts of sulfonated monoglycerides, such as sodium coconut mono-glyceride sulfonate; water-soluble salts of fatty acid 25 amides of taurine, such as sodium N-methyl-N-palmitoyl tauride; water-soluble salts of fatty acid esters of ise-thionate; and substantially saturated aliphatic acyl amides of saturated aliphatic monoaminocarboxylic acid having 2 to 6 carbon atoms and in which the acyl radical contains 3~ 12 to 16 carbon atoms, such as sodium N-lauryl sarcosinate.
Certain nonicnic sudsing agents such as sorbitan monooleate polyoxyethylene are also suitable~ Mixtures of two or more sudsing agents can also be used. A sudsing agent selected from the group consisting of sodium lauryl sulfate, sodium 3~ coconut monoglyceride sulfonate, and mixtures thereof is most preferred.
The abrasive polishing material contemplated for use in the present invention can be any material which does r ~.~2797~ :

not excessively abrade dentinO These include, for example, calcium carbonate, di.calcium orthophosphate dihydrate, cal-cium pyrophosphate, tricalcium phosphate, calcium polymeta-phosphate, insoluble sodium polymetaphosphate, hydrated S alumina, and resinous abrasive materials such ~s particulate condensation products of urea and formaldehyde, and others such as disclosed by Cooley et al in UOSO Patent 3,070,510 granted December 25, 19620 Silica xerogels as disclosed in U.S. Patent 3,538,230 t.o Pader et al on November 3, 1970 10 can also be used~ Synthetic amorphous silicas such as silica aerogels and pyrogenic silicas can also be used, preferably in combination with other abrasive materialsO Still other abrasive materials inc'ude zirconium silicate and mixtures thereof with other cle~ning and polishing agents as set forth in U.S. Patent 3,450,813 to Mu~.ler which issued on June 17, 1969~ -I
Preferred abrasives for use in the present inventionare those selected from the group consi~ting of calcium 20 pyrophosphate, silica Xerogels, silica ~oge~s and mixtures thereof.
The total amount of abrasive materials in the denti-frice embodiments of the present invention can range from about 0.5~ to about 95% by weight of the dentifriceO Pre-fer~bly, amounts of from about 10% to about 60% by weightare used.
In toothpastes, it is desirable to employ binders such as hydroxyethyl cellulose and water-soluble salts of cellulosic ethers including sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose; or natural gum~ including gum karaya, gum arabic, xantham gum and gum tragacanth~ Seaweed derivatives such as Irish moss and alginates can also be used. Colloidal magnesium aluminum silicate, hydrophobic clays such as bentonite, or finely divided silica can be used as part of the binding agent to improve the texture of the product~ Other suitable com-pounds includc high molecular weisht carboxyvinyl polymers such as ~Carbopol 940n* supplied by the B. F. Goodrich Chemical Company. Binding agents selected from the group consisting * Trademark of sodium carboxymethyl cellulose, magnesium aluminum sili-cate, hydroxyethyl cellulose, Irish moss, xantham gum and mixtures thereof are most preferred, in amounts of from about 0.1% to about 5.0%~
It is also desirable to include humectants in tooth-pastes. Preferred humectants include glycerine, sorbitol and other edible polyhydric ~lcohols and mixtures thereof.
These materials can comprise up to about 50~ of the toothpaste composition.
In eddition to the above ingredients, toothpastes of the present invention may contain oral heal~h agents, Examples of such compounds include fluorine-containing com-pounds such as stannous flu~ride, sodium ~luor~de, lithium f~uoride, indium fluoride, potassium fluoride, ammonium fluoride, sodium fluorostannite, stannous chlorofluoride, sodium monofluorophosphate, sodium hexafluoroantimonate, and anticalculus agents such as ethane-l-hydroxy-l, l-diphos-phonic acid (E~DP) and others as disclosed in UOS. Patent 3,959,45~, May 25, 1976 to Agricola et al. Preferred oral health agents for use in the present invention are those selected from the ~roup consisting of sodium fluoride and stannous fluoride. Such compounds are generally present in amounts of from about 0.01~ to about 1O0%.
The toothpaste compositions of the present invention may also contain various minor ingredients including water and/or ethyl alcohol, coloring agents, colored particles, preser~ati~es, buffering agents, flavoring agents and anti-bacterials. These minor ingredients in tota} can ~e present in amounts of up to about 50~.
Examples of suitable flavoring agents include heliotro-pyl nitrile, paramethoxy cinnamaldehyde, wintergreen oil (methyl salicylate), oil of peppermint, oil of spearmint, al~d the like, and mixtures thereof. Generally, flavoring a~ents are present in amounts of from about 0.001~ to about 1.0~.
Examples of suitable antibacteria; compositions for use in the dentifrices of the present invention include chlor-hexidine, cetyl pyridinium chloride, and domiphen bromide.
Said com~ositions can be utilized in amounts of from about 0.01~ to about 0~10~.

Other preferred compositicns within the scope of the present invention include mouthwashes and similar composi-tions such as concentrated mouthsprays~ Mouthwashes gener-ally comprise a water/ethyl alcohol solution and flavoring and sweetening materials. The alcohol provides an antibac-terial effect and also solubilizes the flavoring materials.
In addition, mouthw~shes may contain as optional ingredients a variety of oral health agents, additional anti-bacterial agents, emulsifiers and surfactants, humectants, flavoring and colorins agentsO >
More specifically, mouthwashes contemplated for use in the present invention consist of:
(A) from about 0.05% to about 0.8% by weight of 6-methyloxathiazmone dioxide or an a~ali m~tal or a~ine ear~ metal salt thereof as a sweetening agent;
(B) from about 5~ to about 60~ of ethyl alcohol;
(C) fi~,labout 5% tD about 20~ of a humK~nt; from about 0.1~ up to 1.0% of a water-soluble fluDr~oontaining o~ound; and (E) balanae, water and minors.
Most preferably, the mouthwash compositions of the present invention contain from about 0.075~ to about 0.15%
of the potassium salt of 6-methyloxathiazinone dioxide.
Examples of suitable humectants for use in the mouth-washes contemplated for use in the present invention include glycerine, sorbitol, and other edible polyhydric alcohols or mixtures thereof. Amounts of from about 5% to about 20 are preferred. ~or the purposes of the present inven~ion, glycerine is most preferred~
In addi~ion to the above ingredients, mouthwashes and sLmilar compositions falling within the scope of the present invention may also contain as minor ingredients oral health agents including fluoride compounds such as sodium and in-dium fluoride, and anticalculus agents such as ethane-l-hydroxy-l, l-diphosphonic acid (EHDP), and similar compounds as disclosed in U.S. Patent 3,~95,4~8, Agricola et al, 3~ Other ~inor ingre-~ients such as flavor and coloring agents, buffers, surface active agents such as sorbitan monooleate polyoxyethylene, additional antibacterial agents, astringents, and water may also be used.

Examples of suitable flavorina agents for use in the mouthwashes of the present invention include heliotropyl nitrile, oil of spearmint, wintergreen oil (methyl salicylate), oil of peppermint, and mixtures thereof. Said flavoring 5 agents are generally present in amounts of from about 0 001%
to about 1~0%o Examples of optional antibacterial agents are chlorhex-dine, cetyl pyridinium chloride and domiphen bromide which are generally used in amjunts of from about 0.01~ to about 10 0.10%.
The aforesaid moutnwash compositions can also be ad-ministered in vaporizer or aerosol forms. When administered in aerosol forms, commonly available propellants such as hydrocarbons and fluorohalogen derivatives, for example, 15 dichlorotetrafluoroethane, octafluorocyclobutane, dichloro-difluoromethane, and tetrafluorodichloroethane can be usedO
The above mouthwash compositions can also be prepared in a concentrated form for use as a mouthspray.
.

Method of Manufacture The compositiGns of the present invention can be pre-pared using conventional methods well known and accepted in the oral composition field.

ndustrial Applicability The compositions of the present invention are useful in 2S the oral hygiene areaO The dentifrices and mouthwashes are used in the usual manner.

' ) 112797~

The following examples further describe and demonstrate the preferred embodiments within the scope of the present invention. Said examples are given solely for the purpose of illustration and are not to be construed as limitations 5 of this invention, as many variations thereof are possible without departing from the spirit and scope thereof~ Unless otherwise indicated, all percentages herein are by weightO

EXAMPLE I

A toothpaste having the following composition is pre-10 pared utilizing conventional methodsO
Ingredient Percent ~y Weight Calcium pyrophosphate 40.00 Sorbitol (70% aqueous solution)20.40 Glycerine 10.20 15 Sodium coconut monoglyceride sulfonate 0.82 Sodium lauryl sulfate ~.80 Sodium carboxymethyl cellulose 1~00 Magnesium aluminum silicate 0~40 Stannous fluoride 0040 20 Flavor(spearmint) 0.90 Color 0.05 .Sweetener (potassium salt of 6-methyl- 0.55 oxathiazinone dioxide) Water and minors balance The composition of this invention, when used as in-tended, is an effective dentifrice formulation possessin~
highly desirable sweetness and stability characteristics.
Toothpaste compositions are prepared in accordance with Example I except that calcium carbonate, dicalcium 30 orthophosphate dihydrate, calcium polymetaphosphate, silica xerogels as disclosed in U.S~ Patent 3,538,230, insoluble sodi~m polymetaphospha.te, resinous abrasive materials such as particulate condensation pro~ucts of urea and formaldehyde as disclosed by Cooley et al in U.S. Patent 3,070,510, zir-35 conium si3.icate compositior.s as disclosed hy Muhler inU.S~ Patent 3,450,813, hydrated alumina, and synthetic l~Z7971 amorphous silicas are used, respectively, in place of calcium pyrophosphateO The result in each instance is a desirable toothpaste composition possessing pleasing sweetness charac-teristics.
S Compositions are prepared as in Example I, except that stannous fluoride is replaced by an equi~alent amount of sodium fluoride, lithium fluoride, potassium fluoride, am-monium fluoride, stannous chlorofluoride, sodium monofluo-rophosphate, indium fluoride, and sodium hexafluoroantimon-10 ate, respectively. The result in each instance is an effec-tive toothpaste composition having pleasing sweetness characteristics.
A toothpaste composition is prepared as in Example I
which contair.s in addition about loO~ of ethane-l-hydroxy-15 l,l-diphosphonic acid (E~DP). The result is a dentifrice formulation having desirable sweetness charac~eristics and calculus inhibiting properties.

EXAMPLE II

A toothpaste composition is prepared having the follow-20 ing formulation:
Ingredient Percent by Weight Calcium pyrophosphate 40.00 Sorbitol (70~ aqueous solution)20.40 Glycerine 10.20 25 Sodium coconut monoglyceride sulfonate 0.80 Sodium carboxymethyl cellulose 1.20 Sodium coconut alkyl sulfate ~20% active) 2.30 Sodium fluoride 0.22 Sweetener (sodium salt of 6-methyloxathia-~0 zinone dioxide) 0060 Flavor (peppermint) 0 90 Green urea formaldehyde agglomerates0.65 Water and minors balance The toothpaste of t~.is example exhibits good efficacy 35 while possessing highly desira~le sweetness, flavor and sta-bility characteristics.

~;Z797~

Toothpaste compositions are prepared in accordance with Example II except that calcium carbonate, dicalcium orthophosphate dihydrate, calcium ~olymetaphosphate, silica xerogels as disclosed in U.S. Patent 3,538,230, insoluble 5 sodi~m polymetaphosphate, resinous abrasive materials such as particulate condensation products of urea and formaldehyde as disclosed by Cooley et al in UOS~ Patent 3,070,510, zir-coni~n silicate composit.ions as disclosed in U.S. Patent 3,450,813 hydrated alumina, and synthetic amorphous silicas 10 are used, respectively, in place of calcium pyrophosphate.
The resul~ in each instance is a desirable toothpaste com-position possessing ple~sing sweetness characteristicsO
Compositions are ~repared as in Example II, except that sodium fluoride is replaced by an equivalent amount 15 of stannous fluoride, lithium fluoride, potassium fluoride, . ammonium fluoride, stannous chlorofluoride, sodium mono-fluorophosphate, indium fluoride, and sodium hexafluoroanti-monate, respectivelyO The result in each instance is an ef-fective toothpaste composition having pleasing sweetness 20 characteristicsO

. EXAMPLE III

A dentifrice is prepared by conventional means having the following formula:
Ingredient Percent by Weight 25 Silica xerogel 12.00 Silica aerogel 5~00 Hydroxyethyl cellulose 1.50 Glycerine 34O76 Stannous fluoride 0O41 30 Flavor (wintergreen) 0.95 Color (FD&C Blue #1) 0O03 21~.s~dium lauryl sulfate-79% glycerine 6.00 mlx ure Sweetener (potassium salt of 6-methyl- 0.40 35 o~athiazinone dioxide) Water and minors ~alance -The above composition is a stable, effective, trans-lucent dentifrice having desirable sweetness characteris-tics.
Compositions are prepared as in Example III except that stannous fluoride is replaced by an equivalent amount 5 of sodium fluoride, lithium fluoride, potassium fluoride, ammonium fluoride, stannous ch~orofluoride, sodium monofluo-rophosphate, indium fluoride, and sodium hexafluoroantimonate, respectively~ The result in each instance is an effective toothpaste composition having pleasing sweetness characteris-10 ticso EXAMPLE IV

A mouthwash is prepared having the following formulation:
Ingredient Percent by ~eight Glycerine 10.00 15 Ethyl alcohol 17.00 Cetyl pyridinium chloride 0.05 Sorbitan monooleate polyoxyethylene 0.13 Flavor (wintergreen) - 0-09 Sweetener (potassium salt of 6-methyl- 0.11 20 oxathiazinone dioxi~e) Water and minors balance The above composition possesses highly desirable mouth freshening characteristics and possesses desirable sweetness characteristics as well.
A composition is prepared substantially in accordance with Example IV, except that the cetyl pyridinium chloride i5 replaced by chlorhexidine, domiphen bromide and mixtures thereof. The result is a desirable mouthwash having favor-able sweetness characteristics.
Compositions in accorda~ce with Example IV are prepared e:ccept that the wintergreen oil therein i~ replaced by oil of peppermint, oil of spearmint and mixtures thereof. In each instance, a desirable mouthwash having most favorable swe~tness and flavor characteristics results.

Claims (3)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A mouthwash composition consisting essentially of:
(A) from about 0.05% to about 0.80% by weight of 6-methyloxathiazinone dioxide or an alkali metal or alkaline earth metal salt thereof as a sweetening agent;
(B) from about 5% to about 60% of ethyl alcohol;
(C) from about 5% to about 20% of a humectant;
(D) from about 0.1% up to 1.0% of a water-soluble fluorine containing compound; and (E) balance, water and minors.

2. The mouthwash composition of claim 1 wherein the 6-methyloxathiazinone dioxide salt is a potassium salt and is present in an amount of from about 0.075% to about 0.15%.

3. The mouthwash composition of claim 1 wherein the humectant is glycerine.