Foaming dentifrice containing nonionic surface active agent

A foaming dentifrice containing a nonionic surface active agent. Foam is achieved through inclusion of about 1-10% by weight of a polyoxyethylene-polyoxypropylene block copolymer in combination with about 0.5-7% by weight of xanthan or xanthan about 0.5-7% by weight of and up to about 5% by weight of resinous poly (ethylene oxide) in a dentifrice comprising about 20-80% by weight of a liquid humectant vehicle.

This invention relates to a foaming dentifrice and in particular to a 
dentifrice in which nonionic surface active agent is employed. 
Foam is a desirable characteristic of dentifrices since it spreads the 
dentifrice throughout the oral cavity during toothbrushing, thereby aiding 
in contacting the dentifrice with tooth surfaces and providing a 
characteristic mouth feel. 
Foam, particularly full-bodied foam, is generally achieved by the use of an 
anionic surface active agent. Other surface active agents, and 
particularly non-ionic surface active agents, typically do not foam as 
well as the anionic surface active agents. Of the many anionic surface 
active agents only a few have been used commercially in dentifrices; the 
most commonly used one being sodium lauryl sulfate. 
Anionic surface active agents may cause some mild side effects which some 
users may find somewhat undesirable. For example some users may experience 
temporary moderate irritation in the oral cavity, mild bitterness, 
sloughing of some oral mucosa or an unpleasant flavor reaction when 
drinking or eating citrus shortly after toothbrushing, when a dentifrice 
containing an anionic surface active agent is used. 
Although it has been known that surface active properties could be provided 
to a dentifrice by a nonionic surface active agent, such an agent has not 
been commonly used since foaming is lost, unless supplemented with an 
anionic surface agent. 
It is an advantage of this invention that a dentifrice containing a 
nonionic surface active agent and a particular binding agent is employed 
in which desirable stable full-bodied foaming is obtained. 
It is a further advantage of this invention that the dentifrice employed is 
sweet without requiring the presence of a sweetening additive, and 
non-irritating, while also not being prone to cause users to experience 
sloughing of oral mucosa or have an adverse citrus flavor reaction after 
use of the dentifrice. 
Further advantages of the invention will be apparent from consideration of 
the following specification. 
In accordance with certain of its aspects, this invention relates to a 
dentifrice comprising about 20-80% by weight of a liquid humectant 
vehicle, about 0.5-7% by weight of xanthan gum, and about 1-10% by weight 
of a surface active agent consisting essentially of a nonionic 
polyoxyethylenepolyoxypropylene block copolymer. Preferably up to about 5% 
by weight of resinous poly (ethylene oxide) is also present. 
The nonionic surface active agent employed in the instant invention is a 
block copolymer containing polyoxyethylene and polyoxypropylene. Such 
block copolymers are available from Wyandotte Chemicals Corporation under 
the trademark "Pluronic". They may be liquid, paste or solid and are 
generally chemically defined in terms of the molecular weight of the 
polyoxypropylene hydrophobic moiety and the percent of weight of the 
polyoxyethylene hydrophilic moiety. The following block copolymers are 
available from Wyandotte: 
______________________________________ 
% 
PLURONIC PHYSICAL HYDRO- MOL. WT. 
NUMBER CHARACTER PHIL HYDROPHOBE 
______________________________________ 
L 121 LIQUID 10 4000 
L 101 LIQUID 10 3250 
L 81 LIQUID 10 2250 
L 61 LIQUID 10 1750 
L 31 LIQUID 10 950 
L 122 LIQUID 20 4000 
L 92 LIQUID 20 2750 
L 72 LIQUID 20 2050 
L 52 LIQUID 20 1750 
L 42 LIQUID 20 1200 
P 123 PASTE 30 4000 
P 103 PASTE 30 3250 
L 63 LIQUID 30 1750 
L 43 LIQUID 30 1200 
P 104 PASTE 40 3250 
P 94 PASTE 40 2750 
P 84 PASTE 40 2250 
L 64 LIQUID 40 1750 
L 44 LIQUID 40 1200 
P 105 PASTE 50 3250 
P 85 PASTE 50 2250 
P 75 PASTE 50 2050 
P 65 PASTE 50 1750 
L 35 LIQUID 50 950 
F 127 SOLID 70 4000 
F 87 SOLID 70 2250 
F 77 SOLID 70 2050 
F 108 SOLID 80 3250 
F 98 SOLID 80 2750 
F 88 SOLID 80 2250 
F 68 SOLID 80 1750 
F 38 SOLID 80 950 
______________________________________ 
The preferred nonionic block copolymers are solid (or flake) materials and 
the most preferred are Pluronic 108 (80% polyoxyethylene: 3250 molecular 
weight polyoxypropylene) and F 87 (70% polyoxyethylene: 2250 molecular 
weight polyoxypropylene). The nonionic surface active agent is employed in 
the dentifrice in amount of about 1-10% by weight, preferably about 2-5% 
and most preferably about 3%. 
The binding or gelling agent system of xanthan or xanthan and resinous poly 
(ethylene oxide) co-operates with the nonionic surface active agent to 
provide stable full-bodied foaming and desirable mouth feel 
characteristics to the dentifrice. Xanthan gum, in the concentrations 
described, provides a stable full-bodied foam. The mouth feel 
characteristics can be modified as desired by the addition of resinous 
poly (ethylene oxide). 
Resinous poly (ethylene oxide) has been disclosed as a dentifrice gelling 
or binding agent in U.S. Pat. No. 2,991,229 to Ivison. Its presence 
smooths the texture of the dentifrice. 
The poly (ethylene oxides) employed in this invention are solid, colorless, 
water-soluble resins. They appear to form homogeneous systems in water in 
all proportions, although the relatively higher molecular weight ethylene 
oxide polymers merely swell on the addition of small amounts of water. On 
the addition of greater amounts of water, the polymers pass into solution. 
The water solutions are viscous, the viscosity increasing both with the 
concentration of the polymer in the solution and the reduced viscosity of 
the polymer. The ethylene oxide polymers employed in this invention show 
little change in melting point with increased reduced viscosity (an 
indication of increased molecular weight) and the melting point, as 
measured by change in stiffness with temperature, was found to be about 
65.degree..+-.2.degree. C. throughout the range of reduced viscosities of 
from about 1.0 to about 10, and greater. These polymers, upon X-ray 
examination, disclose a crystalline structure similar to that exhibited by 
polyethylene. The crystallization temperature, as determined from 
measuring the break in the cooling curve, is about 55.degree. C. 
To facilitate the understanding of the instant invention, various terms 
will be defined. At the outset it should be noted that the word "poly 
(ethylene oxide)" as used throughout the specification and claims refers 
to ethylene oxide polymers which have a reduced viscosity in acetonitrile 
of at least 0.5 and upwards to 75, and higher. 
Unless otherwise stated, by the term "reduced viscosity", as used herein, 
is meant a value obtained by dividing the specific viscosity by the 
concentration of the ethylene oxide polymer in the solution, the 
concentration being measured in grams of polymer per 100 milliliters of 
solvent at a given temperature, and is regarded as a measure of molecular 
weight. The specific viscosity is obtained by dividing the difference 
between the viscosity of the solution and the viscosity of the solvent by 
the viscosity of the solvent. The reduced viscosities herein referred to 
are measured at a concentration of 0.2 gram of poly (ethylene oxide) in 
100 milliliters of acetonitrile at 30.degree. C. (unless stated 
otherwise). 
Granular poly (ethylene oxide) results from the suspension polymerization 
of an agitated reaction mixture comprising ethylene oxide in contact with 
a polymerization catalyst therefor and in the presence of an inert organic 
diluent, e.g., heptane, in which ethylene oxide is soluble and the 
resulting poly (ethylene oxide) is insoluble). Granular poly (ethylene 
oxide) thus produced is obtained in a finely-divided solid particle state 
and resembles finely-divided sand in particle size. Unlike the granular 
poly (ethylene oxide) resulting from the suspension polymerization 
process, the bulk and solution polymerization processes yield a polymer 
which is substantially a homogeneous mass either conforming to the shape 
of the reaction vessel or, after driving off the organic medium, for 
example, by mechanical extrusion, e.g., Marshall Mill (under vacuum and at 
slightly elevated temperatures), resembles layers or sheets. This polymer 
subsequently can be reduced in particle size, for example, by dicing or 
the like. 
The term "granular" refers to the particle size of the ethylene oxide 
polymers prepared by suspension polymerization. A granular product is one 
which is a free-flowing state and comprises particles averaging less than 
5 mesh in size (U.S. Standard Size Sieve). When present, the poly 
(ethylene oxide) comprises up to about 5% by weight of the dentifrice, 
perferably about 0.1-1.5%. 
Xanthan has been disclosed as a dentifrice gelling or binding agent in U.S. 
Pat. application Ser. No. 293,424, filed Aug. 17, 1981, based on British 
Application No. 80 26943 filed Aug. 19, 1980 by Colgate Palmolive Company. 
Xanthan gum is a fermentation product prepared by action of the bacteria of 
the genus Xanthomonas upon carbohydrates. Four species of Xanthomonas, 
viz. X. campetris. X. phaseoli, X. malvocearum, and X. carotae are 
reported in the literature to be the most efficient gum producers. 
Although the exact chemical structure is not determined, it is generally 
accepted to be a heteropolysaccharide with a molecular weight of several 
million. It contains D-glucose, D-mannose, and D-glucoronic acid in molar 
ratio of 2.8:3:2.0. The molecule contains 4.7% acetyl and about 3% 
pyruvate. The proposed chemical structure configuration can be found in 
McNeely and Kang, Industrial Gums, ed. R. L. Whistler, CH XXI 2nd Edition, 
New York, 1973. The procedure for growing, isolating and purifying the 
xanthan gum is found in Manufacturing Chemist, May 1960, pages 206-208 
(including mention at page 208 of potential use of gums therein described 
for formulating toothpastes). 
Use of special grades of xanthan gum, such as described in U.S. Pat. No. 
4,263,399 are within the scope of this invention. A grade described in 
U.S. Pat. No. 4,263,399 is a xanthan gum in which up to about 1.6% of the 
carboxyl groups are bound to calcium and the remaining carboxyl groups are 
bound to sodium, potassium, a mixture of sodium and potassium or other 
non-calcium cations. 
The xanthan gelling agent is present in amount of about 0.5-7% by weight of 
the dentrifice, preferably about 1.5-3%. 
Since the nonionic surface active agent is used in the present invention, 
the moderate bitterness generally contributed by an anionic surface active 
agent is not experienced by users. Accordingly, sweetening agents which 
are often added to dentifrices at least in part to overcome the 
bitterness, are less needed in the dentifrice of this invention in 
comparison with prior art practice. Indeed, sufficient satisfactory 
sweetness can be readily provided by the low sweetening character of many 
humectants which are commonly employed in dentifrice compositions. Such 
humectants are comprised in the liquid phase of the dentifrice, typically 
together with water. Typical humectants include sorbitol (as 70% aqueous 
solution), glycerine, maltitol, xylitol and polyethylene glycol 400. The 
liquid phase comprises about 20-80% by weight of the dentifrice, 
preferably about 30-60%, with water (if present) typically being in amount 
up to about 60% and humectant typically being about 20-60%. It is noted 
that maltitol is disclosed as a dentifrice ingredient in Japanese Patent 
Publications 73/10241 and 65/15120. 
The liquid vehicle and gelling agent and other components of the dentifrice 
are proportioned to form a cream or gel mass of desired consistency which 
is extrudible from an aerosol or pump container or a collapsible tube (for 
example aluminum, lead or plastic). 
The dentifrice typically contains a dentally acceptable polishing agent 
which is generally substantially water-insoluble of the type commonly 
employed in dental creams. Representative polishing agents include, for 
example, dicalcium phosphate, tricalcium phosphate, insoluble sodium 
metaphosphate, aluminum hydroxide including hydrated alumina, calcined 
alumina, colloidal silica, magnesium carbonate, calcium carbonate, calcium 
pryophosphate, bentonite, etc. including suitable mixtures thereof. When 
employed, it is preferred to use the water insoluble phosphate salts as 
the polishing agent and more particularly insoluble sodium metaphosphate 
and/or a calcium phosphate such as dicalcium phosphate dihydrate in dental 
creams. When visually clear gels or opacified gels are employed, a 
polishing agent of colloidal silica, such as those sold under the 
trademark Syloid as Syloid 72 and Syloid 74 or under the trademark 
Santocel as Santocel 100 and synthetic alkali metal aluminosilicate 
complexes or silica containing combined alumina may be particularly 
useful. When employed, the polishing agent content is generally in amounts 
from about 15 to 75% by weight in a dental cream and about 5 to 50% by 
weight in a clear or opacified gel. 
The compositions of the present invention, may also contain a 
fluorine-containing compound having a beneficial effect on the care and 
hygiene of the oral cavity, e.g., diminution of enamel solubility in acid 
and protection of the teeth against decay. Examples thereof include sodium 
fluoride, stannous fluoride, potassium fluoride, potassium stannous 
fluoride (SnF.sub.2.sup.- KF), potassium fluorozirconate, sodium 
hexafluorostannate, stannous chlorofluoride, and sodium 
monofluorophosphate. These materials, which dissociate or release 
fluorine-containing ions, suitably may be present in an effective but 
non-toxic amount, usually within the range of about 0.1 to 1% by weight, 
based on the water soluble fluorine content thereof. Sodium fluoride, 
stannous fluoride and sodium monofluorophosphate are particularly 
preferred, as well as mixtures thereof. 
Antibacterial agents may also be employed in the oral preparations of the 
instant invention to provide a total content of such agents of up to about 
5% by weight. Typical antibacterial agents include 
N.sup.1 -(4-chlorobenzyl)-N.sup.5 -(2,4-dichlorobenzyl) biguanide; 
p-chlorophenyl biguanide; 
4-chlorobenzyhydryl biguanide; 
4-chlorobenzydrylguanylurea; 
N-3-lauroxypropyl-N.sup.5 -p-chlorobenzylbiguanide; 
1-(lauryldimethylammonium)-8-(p-chlorobenzyldimethylammonium) octane 
dichloride; 
5,6-dichloro-2-guanidinobenzimidazole; 
N.sup.1 -p-chlorophenyl-N.sup.5 -laurylbiguanide; 
1,6-di-p-chlorophenyl biguanidohexane; 
1,6-bis(2-ethylhexyl biguanido) hexane; 
5-amino-1,3-bis(2-ethylhexyl)-5-methylhexahydropyrimidine; 
and their non-toxic acid addition salts. 
Synthetic finely divided pyrogenic silica such as those sold under the 
trademarks Cab-O-Sil M-5, Syloid 244, Syloid 266 and Aerosil D-200 may 
also be employed in amounts of about 1-5% by weight to promote thickening 
or gelling and to improve clarity of the dentifrice. 
The taste of the new compositions may be modified by employing suitable 
flavoring or sweetening materials. Examples of suitable flavoring 
constituents include the flavoring oils, e.g. oils or spearmint, 
peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, 
cinnamon, lemon and orange as well as methylsalicylate. Suitable 
sweetening agents include sucrose, lactose, maltose, sorbitol, sodium 
cyclamate, perillartine and saccharine. Suitable, flavor agent may 
comprise from about 0.01 to 5% or more of the composition of the instant 
invention. As mentioned above, sweetening agents are less necessary in the 
dentifrice of the present invention than in dentifrices of the prior art 
which have contained anionic surface active agent since slight bitterness 
from the anionic surface active agent need not be masked. Nevertheless, if 
desired, for instance, if the flavor has a pronounced menthol note, about 
0.05-1% of sweetening agent can be used to provide taste modifications as 
desired. 
Various other materials may be incorporated in the dentifrice formulations 
of this invention. Examples thereof are coloring or whitening agents or 
dyestuffs, preservatives, silicones, chlorophyll compounds, ammoniated 
materials such as urea, diamoniumphosphate and mixtures thereof, and other 
constituents. The adjuvants are incorporated in the instant compositions 
in amounts which do not substantially adversely effect the properties and 
characteristics are desired and selected and used in proper amount 
depending upon the particular type of preparation involved. 
The following specific example is further illustrative of the nature of the 
present invention but it is understood that the invention is not limited 
thereto. Dentifrice formulations are prepared in the usual manner, except 
as indicated, and all amounts and proportions are by weight except as 
otherwise indicated.

EXAMPLES 
The following opacified gel dentifrices are prepared: 
______________________________________ 
EXAMPLE 
1 Control 
2 
______________________________________ 
Glycerine 10.0 10.0 
Maltitol 15.0 15.0 
Sodium aluminosilicate 
(silica with combined 
alumina) 18.0 18.0 
Pluronic 108 block 
copolymer -- 3.0 
Sodium lauryl sulfate 
1.0 -- 
Xanthan 2.0 2.0 
Polyox WSR 301 0.2 0.2 
Sodium monofluorophos- 
phate 0.76 0.76 
Titanium dioxide 0.4 0.4 
Low menthol flavor 
0.5 0.5 
Sodium saccharin 0.2 -- 
Color solution (1%) 
0.05 0.05 
Water Q.S. to 100 
Q.S. to 100 
______________________________________ 
The dentifrice of Example 1 with sodium lauryl sulfate has desirable foam 
character but a bitter taste. The dentifrice of Example 2 also has very 
good stable full-bodied foam character even though no anionic surface 
active agent is employed. The foam remains throughout the oral cavity, 
with desirable mouth feel, when the dentifrice is brushed onto the teeth. 
Moreover, it has no bitter note even though no sweetener is added. If the 
flavor were to have a high menthol note, it would be readily masked with 
0.1 part of sodium saccharin. The dentifrices have fine smooth texture. 
Similar desirable results are obtained when xanthan of Example 2 is 
replaced with the low-calcium xanthan of Example 1 of U.S. Pat. No. 
4,263,399. 
Similar foam and feel is attained when other block copolymers of 
polyoxyethylene and polyoxypropylene replace Pluronic F-108, particularly 
Pluronic F 87. 
Polyox WSR-301 is available from Union Carbide Corp. as granules of water 
soluble poly (ethylene oxide) resin having a molecular weight of about 
4,000,000 and a Brookfield viscosity of 1650-3850 cps. (25.degree. C., 
spindle 1, speed 2 rpm) when in water at 1% by weight. Likewise, similar 
foam and feel is attained when other water-soluble poly (ethylene oxide) 
resins available from Union Carbide Corp. as Polyox WSR-N-10WSR-N-80, 
WSR-N-750, WSR-N-3000, WSR-205 and WSR-1105 replace Polyox WSR-301, in 
different concentrations. 
The silica with combined alumina employed in the above dentifrices and in 
those of Examples 3 to 11 below is obtained from the J. M. Huber, Corp. of 
Havre de Grace, Maryland, as Zeo 49. 
The following clear gel (3 and 4) and opacified gel (5 and 6) dentifrices 
are prepared: 
______________________________________ 
EXAMPLES 
3 4 5 6 
______________________________________ 
Glycerine 10.0 -- 10.0 -- 
Sorbitol (70%) 16.0 -- 15.0 -- 
Maltitol 16.0 35.0 15.0 30.0 
Sodium aluminosilicate 
(silica with combined 
alumina) 22.0 18.0 18.0 18.0 
Pluronic F-108 3.0 3.0 5.0 -- 
Pluronic F-87 -- -- -- 3.0 
Xanthan 1.5 2.0 2.0 2.0 
Polyox WSR-301 0.2 0.2 0.2 0.2 
Sodium monofluorophos- 
phate 0.76 0.76 0.76 0.76 
Titanium dioxide 
-- -- 0.4 0.4 
Low menthol flavor 
0.5 0.5 0.5 0.5 
Color solution (1%) 
0.05 0.05 0.05 0.05 
Water Q.S. Q.S. Q.S. Q.S. 
to 100 to 100 to 100 
to 100 
______________________________________ 
The dentifrices of Examples 3 and 4 are clear and those of Examples 5 and 6 
are opacified,. They have smooth texture. All four have very good stable 
full-bodied foam, with that of the dentifrice of Example 5 being more full 
then with the dentifrices of Examples 3 and 4. A higher amount of foam 
occurs with the dentifrices of Examples 6. All foams provide desirable 
mouth feel throughout the entire oral cavity during tooth brushing. There 
are no bitter notes. 
The following dentifrices are prepared: 
______________________________________ 
EXAMPLES 
7 8 9 10 11 
______________________________________ 
Maltitol 30.0 30.0 30.0 30.0 30.0 
Sodium alumino- 
silicate (silica with 
combined alumina) 
12.0 12.0 12.0 18.0 15.0 
Calcined alumina 
5.0 5.0 5.0 5.0 
2.0 
Pluronic F-108 
3.0 3.0 3.0 3.0 3.0 
Xanthan 2.0 2.0 2.0 1.7 2.0 
Polyox WSR-301 
0.2 -- -- 0.2 0.2 
WSR-1105 -- 0.2 -- -- -- 
WSR-N-750 -- -- 1.0 -- -- 
Sodium mono- 
fluorophosphate 
0.76 0.76 0.76 0.76 0.76 
Titanium dioxide 
0.4 0.4 0.4 0.4 0.4 
Low menthol flavor 
0.5 0.5 0.5 0.5 0.5 
Water Q.S. Q.S. Q.S. Q.S. Q.S. 
to 100 to 100 to 100 
to 100 
to 100 
______________________________________ 
The dentifrices of Examples 7-11 provide high cleaning effectiveness and 
have good, stable, full-bodies foam. They have smooth texture, with the 
dentifrices of Examples 7,10 and 11 containing Polyvox WSR-301 having the 
best texture. All foam to provide desirable mouth feel throughout the 
entire oral cavity during toothbrushing. There are no bitter notes. 
The following dentifrices are prepared: 
______________________________________ 
EXAMPLES 
12 13 14 15 
______________________________________ 
Glycerine 10.0 10.0 10.0 10.0 
Sorbitol (70%) 
15.0 15.0 15.0 15.0 
Maltitol 15.0 15.0 15.0 15.0 
Dicalcium phosphate 
dihydrate 30.0 30.0 15.0 15.0 
Anhydrous dicalcium 
phosphate -- -- 10.0 -- 
Calcined alumina 
-- -- -- 10.0 
Pluronic F-108 
3.0 3.0 3.0 3.0 
Xanthan 2.0 2.0 2.0 2.0 
Polyox WSR-301 
-- 0.2 0.2 0.2 
Sodium monofluoro- 
phosphate 0.76 0.76 0.76 0.76 
Titanium dioxide 
0.4 0.4 0.4 0.4 
Low menthol flavor 
0.5 0.5 0.5 0.5 
Water Q.S. Q.S. Q.S. Q.S. 
to 100 to 100 to 100 
to 100 
______________________________________ 
The dentifrices of Examples 12-15 provide good, stable full-bodied foam. 
Those of Examples 13-15 (which contain the Polyox material) have 
particularly fine, smooth texture. The foam from all gives desirable mouth 
feel throughout the oral cavity during toothbrushing. Even though no 
sweetener is used, the dentifrices are quite sweet in taste. 
This invention has been described with respect to the above illustrative 
dentifrices and it will be understood that modifications and variations 
thereof obvious to those skilled in the art to be included within the 
spirit and purview of this application and the scope of the appended 
claims.