Crystalline alumino-silicates (zeolites) are multifunctional in dentifrice compositions thereby reducing the number of components required in such formulations. The pH-adjusted zeolites can keep the pH of the dentifrice in the range where caries formation is impossible. The pH-adjusted synthetic or natural zeolites can be prepared or obtained in a particle size range that provides both abrasive cleansing and polishing or lustering of the teeth. The fine particle size and water absorbing capabilities of the zeolite can also provide thickening. Such multifunctional performance allows considerable simplification in the formulation of dentrifice compositions.

BACKGROUND OF THE INVENTION 
This invention relates to improved dentifrice formulations. In particular, 
it involves the use of pH-modified synthetic and/or natural zeolites as 
multifunctional components for dentifrices. 
In the United States alone, estimates place the cost of repairing the 
effects of tooth decay at six billion dollars annually. The first line of 
defense is the individual's own dental hygiene program. For each person, 
this primarily involves daily use of a dentifrice to clean the teeth. 
Modern dental research has shown that decay results from localized 
demineralization of tooth enamel. This demineralization is caused by the 
action of acids which are formed by specific bacteria metabolizing 
fermentable carbohydrates. These bacteria are found adhering to the plaque 
which forms on the teeth, often comprising as much as 70% of the plaque 
itself. Further studies have shown that demineralization takes place at a 
pH of 5.5 or less. Above pH 6 demineralization ceases. (H. J. Sanders; 
Chemical and Engineering News, Feb. 25, 1980.) 
Therefore, a proper dentifrice formulation used to clean the teeth, sweeten 
breath, and reduce tooth decay must do the following: 
a. Keep the pH at 6 or above--the non-demineralization zone; and 
b. Remove the plaque which serves as a situs for the specific bacteria 
whose metabolic action is the prime cause of tooth decay. 
Additionally, since the dentifrice is for human use, it must be 
biologically compatible and safe for repeated use. 
Besides the above objective criteria, dentifrices must be esthetically 
acceptable to the persons who will use them. Taste and texture must be 
pleasing and the dentifrice must not produce any unpleasant sensory 
perceptions. Organoleptic testing has shown that despite objective 
usefulness of a dentifrice, it will be rejected if its psycho-sensory 
effects are objectionable. 
Modern dentifrice compositions contain numerous components that have 
various therapeutic and cosmetic functions. Most of these compositions 
contain some sort of abrasive cleansing agent which aids in the removal of 
adherent deposits on the teeth. Particulate matter of specific hardness 
and certain particle size, shape and structure is utilized as such 
abrasives. These particles must also be compatible with other toothpaste 
ingredients and safe for repeated human use. Abrasives that are described 
in the patent literature and have found commercial application include 
silica xerogels, hydrated silicas, hydrated aluminas, calcium carbonate, 
dicalcium phosphate (anhydrous and dihydrate), calcium pyrophosphate and 
insoluble sodium metaphosphate. These agents are usually 2 to 30 .mu.m in 
size. Products of about 10 .mu.m appear to find the most commercial 
acceptance. Insoluble crystalline materials such as quartz have been found 
too abrasive for safe use on human dentition. 
Many dentifrice formulations contain a polishing or lustering agent in 
addition to the abrasive. These materials are generally softer and of 
smaller particle size than the abrasives. These agents are not useful in 
removing adherent stains and other material from the teeth; instead, they 
provide so-called luster to the teeth by a fine polishing action. Some of 
the agents used in this capacity include diatomaceous earth, pyrogenic and 
aerogel silicas and amorphous alumino-silicates. U.S. Pat. Nos. 3,911,104 
and 4,036,949 disclose the use of amorphous alumino-silicates for such 
polishing agents. These materials have very high silica-to-alumina ratios 
and are not considered abrasives. 
A desirable ingredient for dentifrices is one that provides both abrasive 
and polishing actions. Such a dual-purpose material greatly simplifies the 
formulation and production of these multi-component products. Most 
abrasive particles must be .about.10 .mu.m or more in size to provide 
adequate action while particles of less than about 1 .mu.m are required 
for polishing action. Producing particulate products with such bi-modal or 
wide range particle size distribution is difficult, expensive and is not 
done. Some silicas suggested as abrasives are crushed during use to 
provide particles of the correct size for polishing. The materials that 
provide sufficient crushed particles for good polishing often exhibit poor 
abrasion. 
Additional siliceous or similar materials are required to thicken 
toothpastes as well as provide carriers for many additional ingredients. 
Zeolites have been suggested as components in toothpastes and powders. 
Frank (German Empire Patentschrift 378010) suggested the use of what he 
called the base exchanging property of zeolites to aid in the dissolution 
of scale. He pointed out that a toothpaste using fine zeolitic powder had 
a pronounced effect on scale. Menkart and Ricciuti suggested (U.S. Pat. 
No. 3,250,680) the use of anhydrous zeolites in cosmetic preparations to 
produce a pleasant warm sensation on hydration during use. Their purpose 
was an esthetic satisfaction, rather than an objective use. Harth and 
Becker (U.S. Pat. No. 4,209,504) suggest the use of zeolites as a 
polishing agent in toothpaste. The main thrust of their invention is the 
use of zeolite as an agent with no corrosive effect on unlacquered 
aluminum surfaces. None of these inventions suggested the use of zeolite 
as an aid in control of dental caries. 
Kato et al. (K. Kato, M. Shiba, Y. Okamoto, N. Nagata; Reports of the 
Institute for Medical and Dental Engineering I, 85: 1973) pointed out the 
compatibility of zeolites with fluoride ion, which is used as a caries 
preventive. 
None of the above suggestions or inventions point to the use of zeolite, 
natural or synthetic, as a caries preventive in itself, or allude to the 
possibility of modifying the zeolite so that it can serve in this 
function. In addition, there are no commercially available dentifrices 
which contain zeolite (45 FR 20666-20691). 
Most commercially available dentifrices have pH's below the 
demineralization thresold. For example, the following table gives pH 
values for the commonly used abrasives in stannous fluoride dentifrices 
(45 FR 20681). 
TABLE I 
______________________________________ 
Hydrogen Ion Concentration (pH) 
Maximum Test 
Abrasive Test Value 
Dilution (w/w) 
______________________________________ 
Insoluble sodium 
4.2-5.4 1:10 
metaphosphate 
Silica 4.6-5.1 1:10 
Calcium pyrophosphate 
4.4-5.1 1:10 
______________________________________ 
The above pH's are well within the range at which demineralization occurs. 
It would be advantageous to have a formulation outside of the 
demineralization range which is still acceptable psychosensorily to the 
persons who will use it. 
It is the prime objective of this invention to have the component zeolite 
impart a pH of 6 or above to the formulation, but below the pH level at 
which there is personal objection to the taste and sense of dehydration in 
the mouth. Also, there is no offensive texture. It is an additional object 
of this invention, simultaneously with provision for aiding in caries 
control, to provide zeolites, natural and/or synthetic, as a 
multifunctional component in dentifrices, providing as well polishing and 
lustering action and abrasion of plaque, thereby simplifying formulation 
and manufacture of such compositions. 
SUMMARY OF THE INVENTION 
We have found that crystallized metal alumino-silicates (zeolites) provide 
an array of functions when compounded into a dentifrice. Natural or 
synthetic zeolites of the correct particle size range function as 
abrasives and polishing agents. Surprisingly, this dual functionality does 
not require a very wide particle distribution since the zeolites provide 
excellent abrasive action at particle sizes that are about an order of 
magnitude smaller than comparable prior art materials. Zeolites of such 
small size contribute the thickening action required for toothpaste. 
Therapeutic cations such as calcium, indium and stannous ions can be 
exchanged into the zeolite and added as an integral part of the abrasive. 
Most surprisingly, we have found that zeolites can be acid-modified without 
appreciably destroying their crystalline structure. Authorities in the 
field state that strong acid will decompose zeolites (D. W. Breck; Zeolite 
Molecular Sieves; John Wiley and Sons; New York: 1974, p. 502 cf.) with 
either the formation of gel or with separation of insoluble silica without 
formation of gel. The specific result depends on the initial Al/Si in the 
starting zeolite. Only mordenite and clinoptilolite have been successfully 
treated with acid. Normally pH's of slurried zeolites are in the alkaline 
range; for example, a 10% slurry of Zeolite NaA has a pH of 10-10.5. Our 
organoleptic studies indicate that pH-unmodified zeolites are unacceptable 
as a dentifrice component. The high pH produces sensory perceptions which 
are distasteful to the user and lead to rejection of the dentifrice. Our 
pH-modified zeolites would obviate such results and would result in a 
personal acceptance. 
A pH-modified zeolite can contribute to the maintenance of the proper pH in 
the oral environment, which will inhibit the formation of caries. In 
addition, zeolites can function as abrasives, lustering agents, 
thickeners, and carriers of ionic and non-ionic components. 
This unusual and unexpected combination of capabilities has never been 
available to dentifrice formulators. Such use of zeolites allows new 
combinations to be formulated as well as simplifying their preparation to 
a degree not previously possible. 
THE INVENTION 
Our multifunctional components for dentifrice compositions comprise various 
crystalline metallo alumino-silicates or mixtures thereof. These materials 
are also known as zeolites, and both natural and synthetic zeolites can be 
employed as our unique dentifrice component. We usually use synthetic 
zeolites since they are readily available and of consistent properties. 
U.S. Pat. Nos. 2,882,243-4; 3,012,853; 3,130,007 and 3,329,628 among many 
others describe zeolites that are suitable as well as methods for 
preparing them. While most zeolites can be employed according to our 
invention we usually use zeolites that conform to the following formula: 
EQU M.sub.x/n [(AlO.sub.2).sub.x (SiO.sub.2).sub.y ]ZH.sub.2 O 
In this formula x and y are integers; the mole ratio of x to y is in the 
range of 0.001 to 2.0 and Z is an integer from about 1 to 250. M is a 
metal and n is the valance of said metal. 
We often use the various metal forms of Zeolite A which conform to the 
formula: 
EQU M.sub.12/n [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]ZH.sub.2 O 
We also use the various metal forms of the less siliceous faugasite type 
zeolite such as Zeolite X, for example, which has the formula: 
EQU M.sub.85/n [(AlO.sub.2).sub.85 (SiO.sub.2).sub.107 ]ZH.sub.2 O 
The various metal forms of Zeolite Y can be useful. Such synthetic zeolites 
are most conveniently prepared by the thermal treatment of an 
alumino-silicate gel which is prepared by mixing aqueous sources of 
silica, alumina and alkali. The hydrothermal treatment causes the desired 
species to crystallize. Conventional filtering, washing, drying and 
deagglomeration steps complete the preparation. 
Synthetic zeolites are usually prepared in the sodium form while natural 
zeolites are rarely found in the sodium form. However, any desired metal 
form can be produced by proper ion exchange procedure. The zeolite can be 
completely or partially exchanged to achieve greater compatibility with 
other toothpaste ingredients or greater safety for repeated human use. The 
zeolite can be used as an ion carrier so that said ion can be added with 
the zeolite. Stannous, indium, calcium and magnesium ions among others can 
be added in this manner. 
Zeolites appear to be unique dentifrice abrasives in that they are 
effective even though they have a small ultimate particle size. Our 
zeolites are approximately an order of magnitude smaller than presently 
commercially acceptable abrasives that exhibit about the same or less 
abrasion. Since the zeolites are effective at such small sizes they also 
function as polishing or lustering agents without crushing or 
fragmentation. The small particle size and liquid absorbing capacity of 
our zeolite also enable it to thicken or provide good pasting properties 
when used in toothpastes. A single component that provides these three 
functionalities greatly simplifies formulation and manufacture of 
dentifrices. 
A unique use of the internal structure of zeolite involves enzymes which 
have been found to have beneficial effects in toothpastes as described in 
U.S. Pat. Nos. 4,058,595 and 4,082,841. These patents are hereby 
incorporated by reference as fully describing the enzymes which are used 
in combination with our zeolites. The enzymes employed are protase, 
carbohydrase or lipase. Mixtures of these materials are effective. These 
compounds require the presence of group IIA or IIB metal ions to enhance 
performance and provide stability. The incorporation of these materials in 
our zeolite is carried out as follows. The zeolite is provided in or 
ion-exchanged into the desired metal form, usually calcium or zinc. Then 
the zeolite is heated to remove the water from the pores and cages of the 
zeolite. The enzymes or mixture of enzymes are absorbed into the zeolite 
and incorporated into the dentifrice. This procedure assures a high enzyme 
activity on use. 
Numerous other ingredients constitute the balance of the composition and 
provide various therapeutic, cosmetic and conditioning functions. 
Humectants prevent hardness in the toothpaste and include, among others, 
glycerol, sorbitol and propylene glycol. Binders are important for obvious 
reasons and include gum tragacanth, sodium carboxymethylcellulose, 
methylcellulose, hydroxyethylcellulose, propylene glycol alginate, Indian 
gum, Irish moss, carrageenan, starch agar agar and the like. Other 
ingredients include soaps and synthetic detergents, flavoring agents such 
as sweeteners and oxygen releasers, buffers, preservatives and coloring 
agents. 
The multifunctional nature of zeolites in dentifrice compositions requires 
the use of a variety of zeolite types and a wide range of use levels in 
such compositions. The types of zeolites that are useful have been 
previously discussed. 
Usually zeolites of the A and X structures are used. The calcium and sodium 
forms of these zeolites are most commonly used. Depending on the purpose 
for including zeolite very little of the zeolite (about 1% or so) may be 
formulated into the dentifrice. On the other hand a dentifrice powder 
might contain well over 90% zeolite. In general, we have found about 5 to 
80% of a dentifrice can advantageously comprise a zeolite, a mixture of 
zeolites, an ion-exchanged zeolite, an impregnated zeolite or a mixture of 
all these types. We prefer to use 10 to 65% of said materials in a 
formulation. While zeolites with many metal ions are useful we have found 
that zeolites that have 20 to 100% of the metal sites exchanged with 
calcium, magnesium, or zinc appear to be the most useful. Zeolites 
exchanged to between 10 and 50% of the available exchange sites with 
stannous or indium ions provide useful therapeutic levels in dentifrice 
compositions. 
The following procedure illustrates certain of the steps by which a zeolite 
can be prepared and utilized as a dentifrice composition. Zeolite NaA was 
prepared by hydrothermal treatment of an appropriate alumino-silicate gel. 
The particle size of this material averaged 2.8 .mu.m. This material was 
tested as an abrasive and was found to have an RDA (radioactive dentin 
abrasion) value of 127. This zeolite was converted to Zeolite CaA by ion 
exchange. The zeolite was slurried in water and formed into a filter cake 
of about 3/8" on a vacuum filter. Then a solution of 0.1 N CaCl.sub.2 in 
water was passed through the filter cake in 20 minutes. Sufficient 
solution was used to provide sufficient Ca.sup.++ ions to replace all of 
the Na.sup.+ ions. The result was that 87% of the exchangeable sodium 
ions were replaced with calcium. This product had an RDA value of 117 
while the particle size remained the same. To a vigorously stirred 10% 
slurry of the zeolite 3 N hydrochloric acid (HCl) is very slowly added 
until the pH of the solution is in the 5.5-6.0 range. The sodium form 
before calcium exchange can be pH adjusted by the slow addition of 8 N 
sulfuric acid (H.sub.2 SO.sub.4) to a 10% slurry of the zeolite. Other 
zeolites are treated in a similar manner. Our chemical analysis has shown 
that for calcium exchanged zeolites this pH modification is accomplished 
by replacing approximately 2% of the exchangeable cations with H.sub.3 
O.sup.+, whereas, for the sodium forms of the zeolites approximately 10% 
of the cations must exchange to H.sub.3 O.sup.30. Table II shows some of 
the properties of typically pH-modified zeolites, while Table III gives 
the chemical analysis of some typical pH-modified zeolites. 
TABLE II 
______________________________________ 
Properties of pH-Modified Zeolites 
Powders 
Final Crystal- 
Slurry 
LOI linity % By Wt. 
Acid pH (%) % XRD* Na.sub.2 O 
CaO 
______________________________________ 
NaA H.sub.3 PO.sub.4 
8.5 19.1 101 -- -- 
(Experimental) 
" 7.0 19.8 97 15.9 -- 
" 6.0 23.1 83 14.7 -- 
" 5.0 20.7 5 8.4 -- 
" 4.0 24.3 12 6.6 -- 
HCl 7.0 21.1 97 -- -- 
None 10.7 20.8 100 17.6 -- 
NaA None 11.0 20.4 94 18.2 -- 
(Commericial) 
H.sub.2 SO.sub.4 
6.0 16.1 90 15.6 -- 
NaX H.sub.3 PO.sub.4 
5.0 26.8 71 -- -- 
(Experimental) 
" 4.0 26.8 29 -- -- 
None 10.8 22.5 98 -- -- 
NaX None 10.2 22.8 103 15.3 -- 
(Commercial) 
H.sub.2 SO.sub.4 
5.5 25.1 108 12.6 -- 
CaA H.sub.3 PO.sub.4 
7.0 18.4 100 0.78 17.5 
(Experimental) 
" 6.0 19.8 100 0.64 15.1 
" 5.0 20.7 93 0.49 14.4 
" 4.0 21.8 96 0.25 13.9 
None 9.2 24.6 100* 0.78 14.4 
______________________________________ 
*Crystallinity measured against well characterized standards. 
TABLE III 
__________________________________________________________________________ 
Chemical Analyses of pH-Modified Zeolites.sup.a,b 
Key Property NaHA 
CaHA NaHX CaHx 
__________________________________________________________________________ 
SiO.sub.2 (wt %) 33.2 
32.0 
33.4 
37.1 
37.2 
35.7 
Al.sub.2 O.sub.3 (wt %).sup.c 
28.9 
29.6 
30.2 
26.2 
26.7.sup.d 
25.3 
Na.sub.2 O (wt %) 16.0 
2.2 4.5 13.1 
9.1 5.4 
CaO (wt %) -- 13.8 
11.5 
-- -- 8.2 
H.sub.2 O (wt % by LOI) 
21.9 
22.4 
20.4 
23.6 
27.0 
25.4 
Totals 100.0 
100.0 
100.0 
100.0 
100.0 
100.0 
Si/Al Atom Ratio 0.97 
0.92 
0.94 
1.20 
1.18 
1.20 
Slurry pH (5% sol. in 
6.8/-- 
9.2/7.3 
8.4/7.5 
-- 7.0/6.0 
6.3/6.0 
D.degree..I. H.sub.2 O/in .1N NaCl sol) 
Meq Na.sup.+ (anhydrous) 
6.61 
0.92 
1.82 
5.53 
4.02 
2.34 
Meq Ca.sup.++ (anhydrous).sup.e 
-- 6.34 
5.15 
-- -- 3.92 
Meq H.sub.2 O (anhydrous) 
0.77 
0.12 
0.41 
0.86 
2.37 
0.14 
##STR1## 10/10 
2/88 
6/75 
13/13 
37/37 
2/63 
__________________________________________________________________________ 
.sup.a Commerical NaA used as starting material. 
.sup.b Commerical NaX used as starting material. 
.sup.c Determined by difference. 
.sup.d Determined by analytical methods. 
.sup.e Determined by difference; total sodium as reported in Table II. 
In order to check the integrity of the crystalline structure, four zeolite 
powders that had been pH-modified in the manner described above were 
subjected to re-exchange. In each case 25 grams of the zeolite powder was 
dispersed in 200 ml of deionized water, and the slurry was adjusted to a 
pH of .about.11 using .about.5% NaOH. After filtering, the materials were 
washed with deionized water and air-dried. For the calcium-exchanged 
samples, an additional step involving washing the filter cakes with a 500 
ml solution of 10% CaCl.sub.2.2H.sub.2 O was included. The crystallinity 
was measured by X-ray diffraction (XRD) is reported in Table IV. These 
results indicate that no significant reduction in crystallinity occurred 
during the preparation of these samples. Further evidence to support the 
premise that no structural changes occurred in these products is provided 
by comparing the constant values of the Si/Al atom ratios in Tables 2 and 
3. More severe treatment, e.g., at pH 4, would cause extensive structural 
damage, especially to Zeolite A. 
TABLE IV 
______________________________________ 
Crystallinity of pH-Modified Zeolites.sup.a 
Crystallinity (% XRD).sup.b 
Na--A CaA Na--X CaX 
______________________________________ 
Initial Material 
94 --.sup.a 
103 --.sup.a 
After pH Modification 
90 81 108 109 
After pH Modification 
94 89 109 109 
and Back-Exchange.sup.c 
Lowest Slurry pH During 
5.9 5.9 5.4 5.4 
Modification 
______________________________________ 
.sup.a Commercial Na--A and commercial NaX zeolites were used as the 
starting materials, respectively, for these samples. 
.sup.b Moisture contents (LOI) of all samples are in the range that does 
not affect XRD measurements. 
.sup.c Back-exchange procedure described in text. 
The pH-modified zeolites are compatible with fluoride ion supplying 
chemicals used in dentifrice formulations. In the following discussions, 
MHZ represents a zeolite with cation M and pH modification, for example, 
NaHA, sodium A zeolite which has been pH-modified as described above. 
The abrasive properties of zeolites are realized at very small average 
particle sizes. While most prior art abrasives are required in particle 
sizes up to 30 .mu.m to realize their abrasive nature, the abrasive nature 
of zeolite is apparent in materials of particle sizes of 10 .mu.m or less. 
We prefer zeolites of 5 .mu.m or less with a lower limit of about 0.5 
.mu.m. A most preferred range is 0.5 to 3.5 for zeolites such as Zeolite 
NaHA, Zeolite CaHA, Zeolite NaHX and Zeolite CaHX. Some examples of 
zeolites and their abrasive action are summarized in the following table; 
calcium pyrophosphate is the standard, and the value therefor is 100. 
TABLE V 
______________________________________ 
Radioactive Dentin Abrasion Values for Zeolites 
and Prior Art Materials 
Average Particle 
RDA 
Abrasive Agent Size (.mu.m) Value 
______________________________________ 
Calcium Pyrophosphate 
-- 100 
Prior Art Silica Xerogel 
8.0 117 
Experimental Zeolite NaHA 
2.8 127 
Experimental Zeolite NaHA 
4.6 166 
Experimental Zeolite CaHA 
2.8 117 
Commercial Zeolite NaA 
6.6 166 
Commercial Zeolite NaA 
4.2 174 
Commercial Zeolite NaA 
3.0 110 
Experimental Zeolite NaHX 
3.4 154 
______________________________________ 
These results indicate that pH-modified zeolites of relatively small 
particle size are very effective abrasives. 
Toothpaste compositions that are formulated with zeolites and can 
accommodate water in the composition have the following compositions. 
______________________________________ 
General 
Preferred 
______________________________________ 
Zeolite (% by weight) 
5-80 10-65 
Humectant (% by weight) 
10-75 15-55 
Water (% by weight) 10-50 15-45 
Sodium Lauryl Sulfate/Glycerin* 
3-10 3-10 
Binder 2-5 2-5 
______________________________________ 
*Mixture consists of 79% Sodium Lauryl Sulfate and 21% glycerin. 
The balance of the composition to 100% consists of optional and cosmetic 
ingredients such as sweeteners, oxygen release agents, buffers, 
preservatives and coloring and flavoring agents. 
Toothpastes which contain a fluoride or enzyme source should be formulated 
with the following composition. 
______________________________________ 
General 
Preferred 
______________________________________ 
Zeolite (% by weight) 
5-80 10-65 
Humectant 10-90 15-75 
Sodium Lauryl Sulfate/Glycerin* 
3-15 3-15 
Binder 2-7 2-7 
Flavorant and Colorant 
0.5-4 0.5-2 
Fluoride or Enzyme Source 
0.05-0.75 
.2-.75 
______________________________________ 
*Mixture consists of 79% Sodium Lauryl Sulfate and 21% glycerin. 
The balance of the composition consists of optional and cosmetic 
ingredients such as sweeteners, oxygen release agents, buffers, 
preservatives and coloring agents. Water not associated with the other 
ingredients is not added to this composition.

EXAMPLES 
The following examples illustrate certain embodiments of our invention but 
do not indicate the scope of our invention which is fully described in the 
specification and claims. All proportions are in parts by weight (pbw) or 
weight percent (%) unless otherwise specified. 
Example 1 
A toothpaste composition using zeolite as an abrasive/polishing agent 
having the following composition was prepared. 
______________________________________ 
Zeolite NaHA (2.8 .mu.m average particle size) 
44.0 pbw 
Sorbitol Syrup (70% in water) 
35.0 pbw 
NaCMC 0.3 pbw 
Stannous Fluoride 0.4 pbw 
21% Sodium Lauryl Sulfate/79% Glycerin 
12.0 pbw 
Saccharin 0.2 pbw 
Coloring Agents 0.2 pbw 
Flavorants 0.2 pbw 
Water To 100 pbw 
______________________________________ 
This composition showed completely satisfactory abrasion and cleansing 
effects, and was personally acceptable. 
Example 2 
The Zeolite NaA described was ion-exchanged using a solution of CaCl.sub.2 
to provide Zeolite CaA wherein 93% of the available sodium was replaced by 
calcium. This material was pH-modified and substituted for the Zeolite 
NaHA in the composition described in Example 1. This composition exhibited 
satisfactory abrasion and cleansing effects and personal acceptability. 
Example 3 
The Zeolite CaHA as described in Example 2 was formulated into the 
following dentifrice. 
______________________________________ 
Zeolite CaHA 41.0 pbw 
Sorbitol Syrup 44.0 pbw 
21% Sodium Lauryl Sulfate/79% Glycerin 
15.8 pbw 
Saccharin 0.2 pbw 
Colorant 0.5 pbw 
Flavorant 0.2 pbw 
Stannous Fluoride 0.03 pbw 
Water To 100 pbw 
______________________________________ 
This composition shows zeolite as an abrasive, lustering agent, thickening 
agent and a carrier for stannous fluoride. The results are satisfactory. 
Example 4 
The zeolite of example 2 was formulated as follows: 
______________________________________ 
Zeolite CaHA 41.0 pbw 
Sorbitol Syrup 44.0 pbw 
21% Sodium Lauryl Sulfate/79% Glycerin 
15.8 pbw 
Saccharin 0.2 pbw 
Colorant 0.5 pbw 
Flavorant 0.2 pbw 
Sodium Fluoride 0.02 pbw 
Water To 100 pbw 
______________________________________ 
The results are satisfactory. 
Example 5 
The zeolite of Example 2 was formulated as follows: 
______________________________________ 
Zeolite CaHA 41.0 pbw 
Sorbitol Syrup 44.0 pbw 
21% Sodium Lauryl Sulfate/79% Glycerin 
15.8 pbw 
Saccharin 0.2 pbw 
Colorant 0.2 pbw 
Flavorant 0.2 pbw 
Sodium Monofluorophosphate 
0.04 pbw 
Water To 100 pbw 
______________________________________ 
The results are satisfactory. 
Example 6 
The NaHA of Example 1 was substituted for CaHA in Examples 3, 4 and 5. 
Example 7 
Two samples of Zeolite NaHX are prepared with average particle sizes of 2.2 
.mu.m and 3.4 .mu.m. Each of these materials is substituted for the 
Zeolite CaHA in the composition described in Example 3, 4 and 5, with 
satisfactory results. 
Example 8 
The sample of Zeolite NaX with a particle size of 2.2 .mu.m is 
ion-exchanged to the calcium form using CaCl.sub.2 solution. Over 90% of 
exchangeable sites are converted from sodium to calcium. This zeolite is 
pH-adjusted and substituted for Zeolite CaHA in Examples 3, 4 and 5 with 
satisfactory results. 
Example 9 
The Zeolite CaHX described in Example 8 is substituted for 1/3 (22 pbw) of 
the Zeolite CaHA in the composition described in Example 2. The zeolite 
composition is 22 pbw of Zeolite CaHX with completely satisfactory 
results.