Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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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
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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
H CH3
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;
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(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
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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~.
7971
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.
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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.
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112797~
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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
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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.
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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.
