Anti-plaque and anti-tartar dentifrices in plastic pump dispensers

A dental composition, such as a paste or gel dentifrice containing triclosan, as an antibacterial agent which acts to decrease plaque on the teeth, and polyphosphate for anti-tartar actions, is packaged in a finger actuatable pump-type plastic dispensing container which is made of or includes a solid polymeric material, such as a polyfluoroethylene, which is compatible with triclosan, so that excessive loss of its anti-plaque activity on storage is avoided, which losses have been noted when various other plastics have been employed as dispensing container component materials. Alternatively, others of such plastic may be employed for dispensing container parts when a stabilizer, such as a terpene, e.g., limonene, is present in the dentifrice. The dentifrice preferably also contains a tooth hardening propotion of a source of fluoride ions, a stabilizing proportion (in conjunction with the fluoride source) for the polyphosphate, of a polyvinyl methyl ether-maleic anhydride copolymer, and normal dentifrice adjuvants.

This invention relates to packaged anti-plaque dental compositions which 
comprise an antibacterial agent, triclosan (THDE, 
2',4,4'-trichloro-2-hydroxydiphenylether), as an effective anti-plaque 
component, and polyphosphate as an effective anti-tartar component which 
compositions are packaged in a pump-type dispensing container which 
includes a polymeric plastic material in contact with the oral 
composition, which plastic is compatible with the triclosan in the 
composition. 
Although various plastics may diminish the anti-plaque action of triclosan, 
certain plastics, such as polyfluoroethylene and polyvinyl chloride, have 
been found to be compatible with triclosan and it has been discovered that 
they do not cause excessive losses of antibacterial and anti-plaque 
activities of dentifrices contacting them during storage at room 
temperature and even at elevated temperatures. Also, applicant has 
discovered that when contacting parts of the container are of a plastic 
which is not in itself entirely compatible with triclosan compatibility 
can be improved by incorporating in the dentifrice formula a stabilizing 
proportion of a material discovered by applicant to have stabilizing 
properties, such as a terpene, e.g., limonene, or an essential oil 
(natural or synthetic), which may be a component of a flavoring material 
for the dentifrice, and thereby can perform a dual function in the 
packaged dentifrice. Such stabilizer is present in sufficient proportion 
so that the dentifrice, as packaged and dispensed, is effective in 
anti-plaque action, which is a major object of this invention. 
The packaged dentifrices of the invention preferably include in the 
dentifrice compositions fluoride or a source of fluoride ions for tooth 
hardening and anti-caries actions, and polyvinyl methyl ether/maleic 
anhydride copolymer, which, in conjunction with the fluoride, stabilizes 
the polyphosphate anti-tartar agent and improves the anti-plaque action of 
triclosan. 
Plaque on teeth is considered to be a causative factor of negative 
periodontal conditions, and dental plaque is a precursor of calculi. 
Plaque may form on any part of the tooth surface, including the gingival 
margin. It makes the teeth appear dull and in addition to promoting 
development of calculi, it has been implicated in occurrences of 
gingivitis. Therefore, dentifrices that contain anti-plaque components 
which prevent or inhibit the development of plaque on the teeth are 
valuable dental care aids. Tartar or dental calculus is also known to be 
causative of gingivitis and dental decay, and makes the teeth appear dull 
and unattractive. Although it has been known that antimicrobial agents in 
dentifrices may reduce plaque, various other antibacterial compounds than 
triclosan often are of disadvantageous characteristics which 
contraindicate their employment in such oral compositions. For example, 
cationic antibacterial compounds, such as quaternary ammonium halides, 
tend to discolor the teeth and may be inactivated by the presence of 
anionic materials in the dentifrices (and often it will be desirable to 
employ anionic surfactants or detergents in dentifrices. Triclosan can be 
inactivated by nonionic surfactants and by various plastics, as has been 
discovered by applicant, Thus, an object of this invention has been to 
incorporate triclosan and similar compounds, such as DDDE 
(2,2'-dihydroxy-5,5'-dibromo-diphenyl ether), in dentifrices for their 
anti-plaque activity and to store such dentifrices in and dispense them 
from packages or containers in which they will not lose an excessive 
proportion of such activity on storage, before intended use, or during 
dispensing. In prior art triclosan dentifrices, as delivered from the 
dispenser, the triclosan delivery has not been in an effective amount to 
significantly reduce plaque when employed once or twice daily at 1.5 grams 
of dentifrice in one minute brushings, which is considered to approximate 
normal brushing practice. To be effective, such uses should result in at 
least a 25% reduction in plaque after three weeks' use, compared to 
similar usage of a control toothpaste. 
Triclosan is described in U.S. Pat. No. 4,022,880 as an antibacterial agent 
in combination with an anti-calculus agent (which provides zinc ions), and 
it is disclosed in German patent specification (OLS) No. 35 32 860 in 
combination with a copper compound. It is also mentioned in European 
patent applications No's. 0 161 989 and 0 161 899, and in European patent 
application No. 0 220 890 it is disclosed in dentifrices with polyethylene 
glycol and oil based flavor. 
Various types of dentifrices are known, including paste, gel, powder, 
liquid, tablet, lozenge, sachet and packeted dentifrices. Such products 
have been packed in deformable tubes, pressurized dispensers, packets, 
bottles, jars and other containers, including pump dispensers. In recent 
years such containers have often been made of synthetic organic polymeric 
plastics or of laminates which include such plastics, and plastic pump 
dispensers are now utilized in toothpaste packages that are marketed. 
Interactions between dentifrices and the materials of containers in which 
they were packed have been known, such as reaction between toothpastes and 
aluminum containers, and to prevent such reactions containers have been 
especially treated or different container materials have been employed. 
However, applicant does not believe that before this invention it had been 
known to the prior art that plastic pump dispenser materials of 
construction could adversely affect the anti-plaque activities of 
triclosan (and DDDE and similar anti-plaque agents) that had been 
incorporated in such dispensers, in which they came into contact with such 
plastics, nor does he believe that it had been discovered that certain 
plastics could be employed for such container parts without causing losses 
of the anti-plaque activities of triclosan and related halogenated 
diphenyl ethers (triclosan only will be referred to later herein, for 
simplicity) or that losses of such anti-plaque activity of dentifrices 
packed in dispensers in contact with "reactive" plastics (which react 
with, absorb or otherwise reduce the anti-plaque activity of the 
dentifrice) could be inhibited or prevented by incorporation in the 
dentifrices of terpenes, such as limonene, and other stabilizing 
components of flavoring materials. 
Polyphosphates, which are anti-tartar components of the invented packaged 
dentifrices, tooth hardening and stabilizing fluoride or other source of 
fluorine ions, and polymeric polycarboxylate, such as the polyvinyl methyl 
ether/maleic anhydride copolymers, which can increase the effectivenesses 
of the polyphosphate and fluoride, and act to inhibit development of 
calculi, are dental preparation components that are known to the art. U.S. 
patent application Ser. No. 07/398,772, filed Aug. 25, 1989, U.S. Pat. 
Nos. 4,323,551, 4,515,772 and 4,627,977, and European patent application 
89 200 710.5 are considered to be of relevance to such aspects of the 
present invention. 
Hand holdable pump dispensers for viscous materials, which are the 
preferred dispensing containers for the dentifrices in accordance with the 
invention are described in U.S. Pat. Nos. 4,684,044 and 4,691,847 (Realex 
Corporation) and in U.S. Pat. No. 4,776,496 (Guala S.p.A.). The pump 
dispensers illustrated in those patents are of the finger actuated, 
floating piston type. 
In accordance with the present invention a dispensing container of a 
viscous anti-plaque and anti-tartar dentifrice comprises such a 
dentifrice, which comprises an effective anti-plaque proportion of 
triclosan and an effective anti-tartar proportion of polyphosphate, in a 
pump dispenser having a walled dispensing chamber in which the dispensing 
chamber walls and parts of the pump dispenser that contact the dentifrice 
during storage and during dispensing thereof are of material(s) that 
is/are compatible with the triclosan and polyphosphate in the dentifrice 
and do(es) not cause excessive loss(es) of anti-plaque and anti-tartar 
properties of the dentifrice during storage thereof in and dispensing 
thereof from the container. The losses of anti-plaque activity are 
desirably held by the present invention to less than 25% on aging at room 
temperature and at elevated temperature, e.g., three weeks at 40.degree. 
C., and such activity will preferably be maintained at such a level for at 
least a year at room temperature. Such stabilization of the triclosan 
(which is evidenced by such limited losses of anti-plaque activity) is 
effected by employing for dispenser parts plastics that are compatible 
with the triclosan, such as polyfluorocarbons, preferably of the 
polyfluoroethylene type, e.g., polytetrafluoroethylene, or polyvinyl 
compounds, preferably polyvinyl halides, e.g., polyvinyl chloride. 
However, an alternative technique is to include a stabilizing material in 
the dentifrice which material may be a terpene, e.g., limonene, or a 
flavor incorporating such a terpene or other stabilizer. Such stabilizing 
action may be inhibition of chemical reactions of the triclosan with the 
plastic or with other materials in the presence of the plastic, may be 
inhibition of sorption of the triclosan by the plastic, or may be another 
mechanism, unknown at the present. The described compositions preferably 
also include the previously mentioned fluoride and copolymer in such 
proportions as to be effective in their desired functions.

In FIG. 1 there is illustrated a pump dispenser of the type described in 
U.S. Pat. No. 4,776,496, which will be referred to as the Guala pump. For 
clarity, the contents of paste, gel or other viscous dentifrice are not 
illustrated in the drawing but it is to be understood that they occupy the 
volume between the floating piston and the outlet from the container. 
Dispenser 11 includes a base 13, cylindrical outer wall 15, floating 
compartment bottom 17, elastic or resilient membrane 19, actuator 21, 
which includes retractable nozzle cover portion 23, discharge conduit 25, 
and outlet nozzle 27. Numeral 29 represents the compartment in which the 
dentifrice is stored before discharge. In operation, depression of 
actuator 21 by thumb or finger pressure while the container is being hand 
held causes retraction of nozzle cover portion 23 and opens nozzle 27, 
while at the same time moving the nozzle, discharge conduit 25 and 
membrane 19 downwardly. Membrane 19, being elastic or resilient, is 
flattened somewhat by the downward motion and because floating bottom 17 
is designed so that it can move only upwardly, dentifrice is discharged 
from compartment 29 through conduit 25 and nozzle 27. Upon release of the 
pressure against actuator 21 it returns to its initial position, due to 
the spring action of leaf spring part 31 and the conduit and nozzle return 
to their initial positions, as resilient membrane 19, with the mechanical 
pressure on it having been removed, also returns to its initial position. 
Atmospheric pressure (also called air pressure herein) moves bottom 17 
upwardly a distance sufficient to compensate for the volume of dentifrice 
discharged. It will be noted that because bottom 17 and membrane 19 are 
similarly shaped the pump dispenser is capable of discharging 
substantially all the contents of the container (except for such portion 
which may fill conduit 25). 
In FIG. 2 another type of dispenser for paste, gel or other viscous 
dentifrices is illustrated, which is like that described in U.S. Pat. No. 
4,684,044, and which also resembles that of U.S. Pat. No. 4,691,847. Such 
dispenser will be referred to in this specification as the Realex pump. As 
in the description of the pump dispenser of FIG. 1, the contents of 
dentifrice are not illustrated in the drawing. Pump dispenser 33 comprises 
a base 35, cylindrical outer wall 37, floating piston compartment bottom 
39 and pumping piston 41, which is connected with discharge conduit 43 and 
nozzle 45. Actuator 47 includes a nozzle cover portion 49. In the drawing 
a cap 51 is illustrated in place, protecting the upper portion of the pump 
dispenser and preventing unintentional depression of the actuator and 
discharge of contents. Operation of the Realex pump dispenser is 
essentially the same as that of the Guala dispenser. Cap 51 is removed and 
finger pressure is applied to actuator 47, which first causes nozzle cover 
portion 49 to be retracted, after which such pressure moves pumping piston 
41 downwardly, together with discharge conduit 43 and nozzle 45, 
compressing helical spring 53. Such downward movement of the assembly 
forces dentifrice upwardly through conduit 43 and out nozzle 45 because 
floating piston 39 is incapable of downward motion. A measured amount of 
dentifrice is discharged if actuator 47 is pressed down to its limited 
bottommost position. Upon relaxation of pressure on the actuator, spring 
53 returns the pumping piston, conduit and nozzle assembly to initial 
position and floating piston 39 moves upwardly, due to air pressure, a 
distance sufficient to compensate for the volume of dentifrice dispensed. 
In the above descriptions of the packages of FIGS. 1 and 2 the terms 
"upwardly" and "downwardly" are used in a relative sense only and it will 
be apparent to the reader of this specification that dispensings of the 
packages' contents may be effected while the container is held in various 
orientations, including inverted positions. 
The various internal parts of the pump dispensers that contact the 
dentifrice are preferably of plastic(s) that do not inactivate triclosan 
or polyphosphate, but the polyphosphate is sufficiently stable so that 
inactivation thereof in the dispensing container is not usually a serious 
problem. If it is not feasible to utilize plastics that have the necessary 
physical properties for the various contacting parts and still are 
compatible with triclosan other plastics may be employed, preferably such 
as adversely affect triclosan least, and preferably in such cases the 
toothpaste composition (or gel dentifrice) will include a stabilizing 
substance such as limonene or other operative terpene or flavor component. 
However, it is considered better to avoid employing any co-polyester 
polyether elastomers, such as have in the past been used for pumping 
membranes, which plastics appears to be especially active against 
triclosan in dentifrices. Instead, it may be preferred to utilize 
laminates which contain polyethylene terephthalate, ethylene vinyl alcohol 
or ethylene vinyl acetate, sandwiched between outer layers of polyethylene 
or some other such suitable plastic, with the total thickness often being 
in the range of 0.0005 to 0.01 inch, and with the inner layer being 5 to 
50% of the thickness. Sometimes one or more of the layers may be 
metallized, as by aluminum or other suitable metal. 
Because triclosan is to some extent photosensitive, it will sometimes be 
desirable for the pump dispensers of this invention to include containers, 
closures and caps which are coated or laminated with a chemical or 
physical light screening material, many of which are known, to prevent 
transmission to the dentifrice and to the triclosan therein of any 
inactivating radiation, e.g., ultraviolet light. Also, such containers may 
desirably be opaque to prevent such actinic radiation from inactivating 
the triclosan in the dentifrice. 
The cause(s) of inactivation by plastics of triclosan in packaged 
dentifrices has/have not yet been established. Research to date has not 
pinpointed the mechanism responsible for losses of such desirable activity 
and so far test results do not conclusively point to either chemical 
reactions or physical absorptions. Tests of some oral preparations 
containing triclosan show that when they are aged in dispensing containers 
at room temperature, 38.degree. C. and 49.degree. C., for up to twelve 
weeks, there can be "excessive" losses (over 25% of the effect of the 
initial concentration of triclosan being lost) when such a preparation has 
been in contact with such container walls and parts of low density 
polyethylenes, high density polyethylenes, polyethylene terephthalates, 
polypropylenes, nylons, polyallomers and polymethylpentenes. Similarly, 
high losses result when such storage is in containers with inner walls or 
parts of co-polyester/polyether elastomers, such as those which had 
previously been employed in Guala pump membranes. In other experiments it 
was found that polyfluorocarbons and polyfluoroethylenes, such as 
polytetrafluoroethylenes, polyvinyl chlorides, polycarbonates and 
polysulfones did not absorb or react with excessive proportions of 
triclosan. However, polycarbonates and polysulfones are brittle and hence 
can be unsuitable for employment for some dispensing container parts. 
Polyvinyl chlorides can sometimes impart a foreign taste to dentifrices, 
and therefore might be avoided as a packaging material, except in cases 
where such taste is compatible with the taste of the flavoring employed. 
Thus, of all the polymeric plastic materials available, polyfluoroethylene 
is an especially satisfactory material for use in the present containers 
or packages, and does not seriously diminish the anti-plaque activity of 
triclosan. However, as was indicated previously, by incorporating in the 
oral compositions of suitable stabilizing compounds for triclosan, such as 
terpenes, of which limonene is representative, essential oils (which often 
contain terpenes) and other flavor components with similar "stabilizing" 
properties, one is able to reduce the activity losses of the triclosan 
when dentifrices containing it are in contact with containers or container 
parts made of the various mentioned polymeric plastics which are 
"stabilizable", so that excessive losses in anti-plaque activity do not 
occur. Therefore, one needs not be dependent on polyfluoroethylene as a 
dispenser material, providing that the dentifrice also contains a 
stabilizing proportion of terpene or other suitable "stabilizer". When 
such stabilizer is present in the oral compositions or when 
polyfluoroethylene (or polyvinyl chloride, polycarbonate or polysulfone) 
is the only polymeric plastic in contact with the oral composition, 
storage losses of anti-plaque activity are less than 25%, and preferably 
will be less than 10%, even after ambient to relatively high temperature 
storage, for example 20.degree. to 40.degree. C., for periods of time of 
several weeks to up to a year or more. It is considered that the most 
stable dentifrices are those which include a stabilizing proportion of 
terpene or other suitable stabilizer and also include contacting container 
parts of polyfluoroethylene (or any of the other unreactive plastics) 
only. Although the terpenes and essential oils are the primary stabilizers 
according to the present invention, other flavor components may also 
contribute to the stabilization of the anti-plaque material, either by 
interfering with any destabilizing chemical reaction or by inhibiting 
absorption of the triclosan by the plastic (or by other unknown 
mechanism). Thus, it has been theorized that some components of 
dentifrices that tend to solubilize triclosan can act to maintain it in 
the dentifrice and inhibit or prevent its migration into the plastic. On 
the other hand, it has also been theorized that such a solubilizing action 
could promote migration of the solubilized triclosan into the plastic. 
Because the issue has not been resolved applicants are not bound by either 
theory. Also, while it is desirable for the terpenes and other stabilizers 
to be flavor components, that is not necessary, and the stabilizer may be 
useful solely for stabilization. 
Although it is preferred that the packages of this invention include 
internal walls and parts which come into contact with the packaged 
dentifrices that are of or are lined with synthetic organic polymeric 
plastic material, it is within the invention to utilize other solid 
(and/or film-forming) polymeric materials, whether or not they are 
synthetic, organic or even plastic. Thus, polyethylene glycols and 
methoxypolyethylene glycols, such as those of the Carbowax.RTM. type, 
e.g., Carbowax 4,000 and Carbowax 6,000, may often be employed as lining 
materials in dispensers for dentifrices. Well known silicon polymers, such 
as siloxanes, and natural organic film-forming materials, such as gums, 
e.g., carrageenan, tragacanth, karaya, may also be useful as liners for 
the present pump dispensers. Additionally solid polymeric materials, such 
as cellulose, starches and derivatives thereof, may also be employable as 
liners and coatings for container materials where such contact the present 
triclosan-containing dentifrices. 
The dentifrices of this invention are comprised of three classes of 
components, vehicle, polishing material and surfactant (or detergent). 
Triclosan is normally present in the vehicle of the packaged dentifrices, 
which vehicle usually comprises about 10 to 80%, preferably 50 to 80% (the 
figures are on a final composition basis) of the dentifrice. Of the 
vehicle, about 20 to 90% preferably 30 to 80%, will be water, about 20 to 
80%, preferably 30 to 60%, will be humectant, such as glycerol, sorbitol, 
propylene glycol, polyethylene glycol or any suitable mixture thereof and 
0.5 to 10%, preferably 1 to 5%, will be gelling agent, such as sodium 
carboxymethyl cellulose, Irish moss, iota carrageenan, calcium 
carrageenan, or hydroxyethyl cellulose or the like, including any suitable 
mixtures thereof. Although triclosan is essentially insoluble in water it 
is soluble or at least readily dispersible in the described dentifrice 
vehicle. The polishing material of the dentifrice will normally be from 
about 10 to 50%, preferably 15 to 25% thereof and such polishing material 
may be colloidal silica, precipitated silica, hydrated silica, sodium 
aluminosilicate, insoluble sodium metaphosphate, hydrated alumina, 
calcined alumina, dicalcium phosphate dihydrate, anhydrous dicalcium 
phosphate or calcium carbonate, or other known polishing agent, or any 
mixture thereof. The surfactants include anionic, nonionic, cationic and 
zwitterionic surfactants but often the employment of nonionic surfactant 
is avoided in the packaged dentifrices of this invention because of its 
adverse affect on triclosan, and the employments of cationic and 
zwitterionic surfactants are also often avoided because they tend to stain 
or darken the teeth. Thus, synthetic organic anionic surfactants, which 
are also detergents, are the preferred cleaning agents in the present 
dentifrices, and of these, sodium lauryl sulfate and other sodium higher 
alkyl sulfates of 10 to 18 carbon atoms in the alkyl groups thereof are 
preferred, although various other well known sulfated and sulfonated 
detergents, preferably of similar carbon chain lengths, may be substituted 
for them, at least in part. The surfactant or detergent content, usually 
anionic detergent content, is normally in the range of 0.2 to 10%, 
preferably 0.5 to 5%, and more preferably 1 to 3%. 
In the packaged dentifrices there will very preferably also be present an 
effective anti-tartar (and anti-calculus) proportion of polyphosphate. 
Representative examples of the polyphosphate for the purpose of this 
description, include metaphosphates, such as sodium hexametaphosphate, 
polyphosphates, such as sodium tripolyphosphate, and pyrophosphates, such 
as tetrasodium pyrophosphate (which is most preferred), disodium diacid 
pyrophosphate and trisodiumonoacid pyrophosphate, the corresponding 
potassium salts, and the like. Such polyphosphates also include the linear 
molecularly dehydrated polyphosphate salts which are generally employed in 
the forms of their wholly or partially neutralized water soluble alkali 
metal (e.g., potassium and preferably sodium) or ammonium salts, and any 
mixtures thereof. In the present invention the polyphosphates are employed 
in the dentifrices in concentrations of 0.1 to 3% typically 0.5 to 3%. and 
more preferably 1.5 to 2.5%, e.g., about 2%. Particularly desirable are 
tetraalkali metal pyrophosphates, including mixtures thereof, such as 
tetrasodium pyrophosphate, tetrapotassium pyrophosphate and mixtures 
thereof. 
To improve the anti-calculus and anti-tartar effectiveness of the 
dentifrice an inhibitor against enzymatic hydrolysis of the polyphosphate 
is desirably present. Such an agent is a fluorine ion source sufficient to 
supply 25 p.p.m. to 5,000 p.p.m., preferably 500 to 3,000 p.p.m. of 
fluorine ions (or fluoride ions) in the dentifrice. 
Sources of fluorine ions or fluorine-providing components for inhibiting 
the actions of acid phosphatase and pyrophosphatase enzymes on 
polyphosphate (and thereby for increasing anti-tartar and anti-calculus 
effectiveness of the polyphosphate) in the present dentifrices are well 
known in the art, and usually also function as tooth hardeners and 
anti-caries agents. These compounds may be slightly soluble in water or 
may be fully water soluble. They are characterized by their ability to 
release fluorine ions in water and by their relative inertness toward 
other compounds of the dentifrices. Among these materials are inorganic 
fluoride salts, such as soluble alkali metal and alkaline earth metal 
salts, e.g., sodium fluoride, potassium fluoride, ammonium fluoride, 
calcium fluoride, copper fluorides, such as cuprous fluoride, zinc 
fluoride, barium fluoride, tin fluoride, sodium fluorosilicate, ammonium 
fluorosilicate, sodium fluorozirconate, ammonium fluorozirconate, sodium 
monofluorophosphate, aluminum mono- and difluorophosphates, and 
fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides, 
such as sodium and stannous fluorides, sodium monofluorophosphate 
(MFP.RTM.) and mixtures thereof are preferred. 
The amount of fluorine-providing compound in the present oral preparations 
is dependent to some extent upon the type of compound, its solubility, and 
the types of oral preparations, but it should be a non-toxic amount, 
generally in the range of about 0.005 to about 3.0% and preferably in the 
range of 0.05 to 1% in the dentifrice. 
Typically, in the cases of alkali metal fluorides, this component is 
present in an amount up to about 2% by weight, e.g., 0.05 to 2%, based on 
the weight of the preparation, and preferably in the range of about 0.1 to 
1%, e.g., about 0.33%. In the case of sodium monofluorophosphate, the 
compound may be present in an amount of about 0.1 to 6%, typically 0.5 to 
1%, e.g., about 0.76% or 0.8%. 
In another preferred aspect of this invention the dentifrice comprises an 
agent that is effective to enhance the antibacterial and anti-plaque 
effect of the triclosan. Such antibacterial enhancing agent (AEA) is 
preferably of an average molecular weight in the range of about 1,000 to 
about 1,000,000 and desirably contains a functional group which enhances 
the antibacterial effect and an organic group which enhances retention of 
such antibacterial effect. 
The AEA is preferably a synthetic anionic polymeric polycarboxylate which 
is also an inhibitor of alkaline phosphatase enzyme. In U.S. Pat. No. 
4,627,977 (Gaffar et al.) there is described the use of polycarboxylates 
for inhibiting salivary hydrolysis of pyrophosphate anticalculus agents in 
combination with a compound which acts as a source of fluoride ion. It is 
to be understood that the synthetic anionic polymeric polycarboxylates so 
disclosed, when containing or modified to contain the retention-enhancing 
group mentioned above, are operative as AEA's in the compositions and 
articles of the invention, and are in fact, components of preferred 
embodiments thereof. 
The mentioned synthetic anionic polymeric polycarboxylates are often 
employed in the form of their free acids or preferably partially or more 
preferably fully neutralized water soluble or water swellable (hydratable, 
gel/forming) alkali metal (e.g., potassium and preferably sodium) or 
ammonium salts. Preferred are 1:4 to 4:1 copolymers of maleic anhydride or 
equivalent acid with another polymerizable ethylenically unsaturated 
monomer, preferably methyl vinyl ether/maleic anhydride having a molecular 
weight (M.W.) of about 30,000 to about 1,000,000. These copolymers are 
available from GAF Corporation as, for example, Gantrez.RTM. AN 139 
(M.W.=500,000), AN 119 (M.W.=250,000); and preferably S-97 Pharmaceutical 
Grade (M.W.=70,000). 
Other polymeric polycarboxylates which are operative as AEA's and contain 
or are modified to contain retention-enhancing groups include those 
disclosed in U.S. Pat. No. 3,956,480, such as the 1:1 copolymers of maleic 
anhydride with ethyl acrylate, hydroxyethyl methacrylate, 
N-vinyl-2-pyrollidone, or ethylene, the latter being available for example 
as Monsanto EMA No. 1103, M.W. 10,000 and EMA Grade 61, and 1:1 copolymers 
of acrylic acid with methyl or hydroxyethyl methacrylate, methyl or ethyl 
acrylate, isobutyl vinyl ether or N-vinyl-2-pyrollidone. 
Additional operative polymeric polycarboxylates are disclosed in U.S. Pat. 
Nos. 4,138,477 and 4,183,914, which contain or may be modified to contain 
retention-enhancing groups. These include copolymers of maleic anhydride 
with styrene, isobutylene or ethyl vinyl ether, polyacrylic, polyitaconic 
and polymaleic acids, and sulfoacrylic oligomers of a M.W. as low as 
1,000, which is available as Uniroyal ND-2. 
Other suitable anionic polymers that may be employed as AEA's are described 
in greater detail in U.S. Pat. No. 3,956,480 and in Ser. No. 07/398,605, 
both of which are incorporated herein by reference. The percentage of such 
AEA(s) in the described compositions will normally be in the range of 0.2 
to 5%, preferably being 0.5 to 4% and more preferably 1 to 3%, e.g., 2% 
In dentifrice compositions the effective amount of triclosan will normally 
be in the range of 0.1 to 1.0%, more preferably 0.2 to 0.5 or 0.6%, e.g., 
about 0.3%, and often not exceeding 0.8% because of possible mouth numbing 
effects at higher concentrations, and not being less than indicated to 
avoid ineffectiveness against plaque. Preferably the dispensed dentifrices 
will contain proportions of triclosan within the given ranges but when the 
initial concentration thereof is within the given range a loss of up to 
25% will be acceptable and such dispensed compositions are within the 
scope of the invention and are effective. 
For stabilized dentifrices that are to be packaged in containers containing 
plastic walls or other parts, wherein the plastics are those which are 
"reactive" with triclosan, 0.01 to 2% of terpene(s) or stabilizer(s), 
preferably 0.05 to 1% and more preferably 0.1 to 0.5% will be present in 
the dentifrice. Such stabilizers may be present in a suitable flavoring 
agent for the dentifrice, if desired (and it often is), and will be at 
least 5% of the flavor, preferably at least 10%, more preferably at least 
25% and most preferably at least 50%. 
The various plastics that were previously described as the components of 
container and/or dispenser parts have been described only briefly because 
it is considered that their chemical natures and degrees of polymerization 
are well known, so detailing thereof is unnecessary in this specification. 
If further details are wanted reference may be made to Modern Plastics 
Encyclopedia, which is published on an annual basis by McGraw-Hill Inc., 
New York, N.Y. 
The stabilizer terpenes, which term, for the purpose of this specification, 
includes the terpene hydrocarbons and oxygenated derivatives thereof, 
include such compounds as dl-limonene, menthol, diterpenes, polyterpenes 
and derivatives thereof, many of which are found in various essential oils 
and other flavors. In addition to being useful as stabilizers for 
triclosan they often contribute desirable flavors to the present 
dentifrices. Of the terpenes and their derivatives it is considered that 
limonene best balances these properties, although other terpenes, 
including those which are not flavors, are also useful, as are other 
emulsifiable lipophilic essential oils and flavoring agents which contain 
stabilizing components. 
For other details of formulations, components, adjuvants, manufacturings 
and uses, see the patents and applications previously mentioned in this 
specification, which are hereby incorporated by reference, as are text and 
periodical references. 
Manufacture of the described dentifrices is by any of various standard 
techniques for producing such classes of compositions. Referring to 
specific examples for simplicity, the triclosan is dispersed and/or 
dissolved in the vehicle portion of the dentifrice and the terpene is 
present in the flavoring agent. To make the dentifrice, the vehicle is 
prepared containing glycerol, sorbitol, and propylene glycol, gelling 
agents, triclosan and suitable adjuvants (including Gantrez S-97), and the 
vehicle and aqueous anionic detergent (preferably sodium lauryl sulfate or 
a mixture of sodium lauryl sulfate and sodium methyl cocoyl taurate) 
solution are mixed, followed by blending in of the polishing agent 
component, which may include the polyphosphate and fluoride, with the 
pre-mix. Finally, flavoring agent, including terpene, desirably dissolved 
in ethanol, is admixed and the pH is adjusted. 
In packaging of the dentifrice in the dispensing container it will be 
desirable to avoid contacting of the dentifrice with plastic parts of 
co-polyester/polyether elastomer and it will also be desirable to avoid 
contacting of any compositions not containing stabilizing agent (such as 
terpene or flavor containing it) with plastic parts made of those plastics 
previously listed in this specification as reactive with triclosan and 
other such antibacterial and anti-plaque compounds. It will be especially 
important to avoid the mentioned plastic parts for holding tanks or any 
other containers, piping, pumps or equipment, in which the triclosan or 
the dentifrice containing it may be held for any appreciable length of 
time or held for shorter lengths of time at elevated temperatures. 
Even when the packaged compositions of this invention are prepared and 
contacts of the dentifrices containing triclosan with the reactant 
plastics are avoided it will still be desirable to minimize exposures of 
such packaged dentifrices to heat and to light, both of which have been 
found to accelerate losses of anti-plaque activity. Thus, the invented 
compositions are preferably stored and packaged in opaque dispensers or 
ones that filter out actinic light, at a temperature in the range of 
10.degree. to 38.degree. C. Otherwise, the packaged dentifrices may be 
stored and used in normal manner and the desirable anti-plaque and 
anti-tartar effects thereof will be obtained. Such effects have been 
verified by laboratory testing and by evaluations of the teeth of 
volunteers serving on human panels, who employed the various packaged 
dentifrices and controls as directed. Significant improvements in 
anti-plaque activities of the compositions of this invention packaged in 
the described pump dispensers are observable compared to control 
dentifrices similarly packaged but wherein the dispenser includes plastic 
parts that are "reactive" with the triclosan and which do not contain 
stabilizing agent in the dentifrice. Such improvements are also found when 
dispensers made of "reactive" plastics (but not co-polyester/polyether 
elastomers) are employed with dentifrices containing terpenes and are 
compared to controls in which the dentifrices contain no terpenes and no 
flavoring agents. 
The following examples illustrate but do not limit the invention. Unless 
otherwise indicated, all percentages and proportions in these examples, 
the specification and the appended claims are by weight, and all 
temperatures are in .degree. C. 
EXAMPLE 1 
______________________________________ 
Component Percent 
______________________________________ 
Propylene glycol 10.00 
Iota carrageenan 0.75 
Sodium fluoride 0.33 
Sorbitol (70% aqueous solution) 
30.00 
Sodium saccharin 0.30 
Titanium dioxide 0.50 
Sodium hydroxide (50% aqueous solution) 
0.80 
.sup.+ Luviform .TM. (35% aqueous solution) 
4.76 
.sup.++ Zeodent .TM. 113 
20.00 
.sup.+++ Sident .TM. 22S 
2.00 
Sodium lauryl sulfate (94% active) 
1.60 
*Flavor 0.95 
**Triclosan 0.30 
100.00 
______________________________________ 
.sup.+ 35% Aqueous solution of polyvinyl methyl ether/maleic anhydride 
copolymer (BASF Corp.) 
.sup.++ Silica polishing agent (J. M. Huber Corp.) 
.sup.+++ Silica thickening agent (Degussa Co.) 
*Contains at least 25% of terpenes, e.g., limonene 
**Irgasan .RTM. DP 300, mf'd. by CIBAGEIGY 
A dentifrice of the above formulation is made in normal manner and is 
employed as a medium for testing the stability of triclosan when the 
dentifrice containing it is exposed to different plastics which are 
employed as materials of dispensing containers or parts thereof in which 
or in contact with which such dentifrices are stored and dispensed. The 
plastics for the tests are Pibiflex.TM. 46, made by Inmont, and 
Arnitel.TM. 460 EM, mf'd. by AKZO, which are plastics that are employed as 
the membranes or bellows of a pump dispenser, as illustrated in FIG. 1. 
Six samples of plastics are tested, three of each of the mentioned 
plastics, with each of the three being treated with a different mold 
release agent (to determine whether the nature of the release agent is 
relevant to the problem of triclosan stability in contact with plastics 
during storage). The release agents are Silicone Master.TM. (5% silicone 
oil and 95% polypropylene), Silicone Master plus Silicone Oil (with extra 
silicone oil) and Armid O Master.TM. (5% oleyl amide and 95% 
polypropylene), respectively. After two weeks storage of the test samples 
in contact with the dentifrice at different temperatures (room 
temperature, 38.degree. C. and 49.degree. C.), the dentifrice samples are 
removed from the plastic container materials and the plastics are washed 
with water and immersed in methanol to dissolve any triclosan which might 
have been taken up by them during storage. The methanol washings are 
collected and are analyzed, using high performance liquid chromatrography. 
It is found that essentially the same types of absorptions of triclosan 
take place with the different membrane materials and although there are 
variations between them and such are somewhat dependent on the release 
agents employed, the results are essentially the same in all cases. The 
co-polyester/polyether elastomers are found to absorb significant 
percentages of triclosan from the dentifrice, which results are 
confirmable when the co-polyester/polyether elastomers are used as bellows 
materials in pump dispensers containing the described dentifrice and other 
dentifrices within the invention. Accordingly, it is considered 
undesirable to employ co-polyester/polyether elastomers in contact with 
the present dentifrices and that is even so when the dentifrices contain 
terpenes or contain flavoring materials which include terpenes (which are 
present in the flavoring of the dentifrice formulation), to the extent of 
at least 0.1% of the dentifrice. 
When the tests are repeated, using Guala pump dispensers as containers for 
the dentifrices, with co-polyester/polyether elastomer membranes of 
Arnitel.TM., the losses of triclosan are also unacceptable but when the 
co-polyester/polyether elastomer is replaced by others of the acceptable 
plastics, e.g., Teflon.RTM. polyfluoroethylene, the triclosan activity is 
improved to within acceptable limits. Also, other plastic parts of such 
pump dispensers, such as polypropylene inner walls thereof, are not found 
to absorb excessive amounts of triclosan and do not seriously decrease the 
anti-plaque activity of the dentifrice, apparently due to the presence of 
terpenes in the flavoring agent of the contained dentifrice. 
A panel test is run, involving at least ten human subjects, who employ the 
dentifrice of this example, dispensed from polyethylene terephthalate- and 
polyethylene-lined dispensing containers, in twice-a-day brushings for one 
month, during which time plaque evaluations of the subjects' teeth are 
made by trained observers. The test results establish that the dentifrice 
composition has a definite anti-plaque activity and also prove that the 
triclosan has not been unacceptably inactivated, and still is present in 
an effective antibacterial and anti-plaque proportion in the dentifrice. 
Similar good results are obtainable when pump dispensers like that 
illustrated in FIG. 2 are employed and comprise dispensing containers 
including walls and other parts of high and low density polyethylenes, 
polypropylenes, polyallomers, nylons, acrylics, polyfluorocarbons, 
polyvinyl halides, polycarbonates, and/or polysulfones. Such stability of 
the triclosan is also obtainable when the terpene content is decreased or 
when terpenes are omitted, providing that the plastic parts are of 
polytetrafluoroethylene, polyvinyl chloride, polycarbonate and/or 
polysulfone. 
The dentifrice formula will desirably also include 1.5 to 2.5%, e.g., 2%, 
of a polyphosphate (sodium hexametaphosphate, tetrasodium pyrophosphate, 
or sodium tripolyphosphate, or a mixture thereof), preferably the 
pyrophosphate, to give the dentifrice desired anti-tartar action. It is 
also highly preferable for such compositions to contain a fluorine ion 
releasing compound, such as 0.3% of sodium fluoride or 0.8% of sodium 
monofluorophosphate, and 2% of polyvinyl methyl ether/maleic anhydride 
copolymer, for their functions that were previously mentioned herein. 
Additions of such materials to the formula is compensated for by 
decreasing the water content accordingly. 
EXAMPLE 2 
______________________________________ 
Component Percent 
______________________________________ 
Glycerol 7.00 
Propylene glycol 3.00 
Iota carrageenan 0.75 
Sorbitol (70%) 30.00 
Sodium saccharin 0.30 
Sodium fluoride 0.33 
Titanium dioxide 0.50 
Gantrez S-97 (13% solution) 15.00 
Deionized water 16.07 
Sodium hydroxide (50% aqueous solution) 
0.80 
***Zeodent 113 20.00 
.degree.Sylodent .RTM. 15 3.00 
Flavoring agent (containing at least 25% of terpenes) 
0.95 
Sodium lauryl sulfate 2.00 
Triclosan 0.30 
100.00 
______________________________________ 
***Polishing agent (J. M. Huber Corp.) 
.degree.Silica thickening agent (W. R. Grace Corp.) 
A toothpaste of the above formula is made and is stored in Guala.TM. pump 
dispensers having bellows membranes of the Arnitel type. The dentifrice is 
also filled into dispensing containers having laminated walls of 
polyethylene terephthalate in the interior of the laminate, which contain 
the dentifrice. The dentifrices are aged at 5.degree. C., 25.degree. C., 
and 39.degree. C., for two, four and six weeks. After such aging periods, 
the dentifrices are dispensed at the rate of about 1.5 grams per day and 
at weekly intervals the triclosan contents of the dispensed dentifrice are 
determined by analyses. In the case of the Guala pump dispenser with 
Arnitel membrane the dispensed dentifrice loses about 27% of the 
triclosan, which is excessive and objectionable. The loss is about 
constant, regardless of storage temperature or time of storage, which can 
be explained by theorizing that the triclosan is absorbed by the pump 
membrane, with which it is in contact prior to dispensing. Such membrane 
is of a co-polyester/polyether elastomer, which class of plastics is to be 
avoided as a container material or as a part in a pump dispenser for 
dentifrices containing triclosan. However, when the elastomeric 
co-polyester/polyether membrane is replaced by one made of any of the 
previously mentioned acceptable plastics, such as polyethylene 
terephthalate, which can serve as membrane materials in modified pump 
dispensers (modified to compensate for different properties of such 
plastics) or as pumping pistons in Realex type pumps triclosan stability 
is increased and the dispensed composition is satisfactory and effective 
as an anti-plaque toothpaste. It is notable that the Realex pump design 
does not require an elastic or flexible plastic component, and on that 
basis such pump may be considered superior in design to the Guala pump 
because it allows a greater selection of plastics for the pumping piston 
and so better allows one to avoid uses of any objectionable plastics. 
Incorporation of tetrasodium pyrophosphate, sodium tripolyphosphate or 
sodium hexametaphosphate, as in Example 1, (preferably 2% of the 
pyrophosphate) makes the dentifrice anti-tartar, as well as anti-plaque. 
Gel dentifrice formulations in such pump dispensers behave similarly to 
toothpastes with respect to triclosan stability after storage and on 
dispensing. 
In similar tests, using polyethylene terephthalate-lined dispensing 
containers little loss (less than 5%) of triclosan is noted, indicating 
that the presence of the terpenes (0.1% or more of the composition), 
including limonene, in the flavoring agent or as the flavoring agent, 
prevents loss of the triclosan or inactivation thereof. When 
polyfluoroethylene-lined tubes are employed there is little loss of 
triclosan, even when the flavoring agent is omitted from the dentifrice 
composition and such is also the case when polyvinyl chloride is employed 
as a primary material in contact with the dentifrice and or when 
polysulfone or polycarbonate package parts are in contact with such 
dentifrice. 
In the above formulas the polishing systems are siliceous rather than being 
based on alumina. When the polishing agents are changed to aluminas, the 
triclosan stability problems previously mentioned as having been noted 
with some plastics are decreased, but they still exist. Also, the 
presences of terpenes in the dentifrices promote triclosan stability, as 
such presences do in similar dentifrice compositions based on siliceous 
polishing agents. 
EXAMPLE 3 
The dentifrices of the foregoing examples may be varied in composition 
.+-.10% and .+-.25% for the various components thereof, providing that 
such percentages are not outside ranges given elsewhere in this 
specification, and operative and effective anti-plaque and anti-tartar 
products are obtainable, which are dispensable in effective anti-plaque 
and anti-tartar state from the mentioned dispensing containers that are 
made of compatible plastics. Such products also will behave in similar 
manners, with the triclosan anti-plaque agent being sufficiently stable in 
the presence of polyfluoroethylene, polyvinyl chloride, polycarbonate and 
polysulfone packaging or package component materials, even when no 
flavoring agent and no terpenes are present in the dentifrices, and being 
stable in the presence of polyethylenes, polypropylenes, polyethylene 
terephthalates, polymethylmethacrylates, polyallomers, nylons and 
polymethylpentenes, as package or component materials, when a stabilizing 
terpene, such as limonene, or a stabilizing flavor component is present in 
the dentifrice. The packaged dentifrices of this example that contain 
polyphosphate, source of fluorine ions and AEA are also of effective 
anti-tartar, anti-calculus, anti-caries, tooth hardening and stabilizing 
(of the polyphosphate against enzymatic action) properties. When the AEA 
materials and fluoride are omitted the polyphosphate's anti-tartar and 
anti-calculi properties can be adversely affected by enzymatic action of 
the saliva but will still be present. As with the other packaged 
dentifrices and mouthwashes previously discussed, because of excessive 
absorption or other adverse action with respect to triclosan by 
co-polyester/polyether and other such elastomers, uses of such materials 
will preferably be avoided. 
EXAMPLE 4 
Dentifrices of the formulas of Examples 1 and 2 are made and are dispensed 
after one month's storage at 30.degree. C., from containers lined with 
polyethylene, in one case, and polyethylene terephthalate, in another, 
onto bristled toothbrushes. The amounts of toothpaste on the toothbrushes 
are in the range of 0.8 to 2.0 grams with 1 to 1.5 g. being preferred. 
When 1.5 g. is dispensed the active triclosan in the dentifrice on the 
brush is about four milligrams (with only 10% of the triclosan being 
inactivated). When storage is for a longer time or at a higher temperature 
or with a more destabilizing plastic in contact with the dentifrice during 
storage the packaged dentifrices can contain about 3.5 mg. of triclosan in 
the 1.5 g. on the brush. 
The described dispensed dentifrices are employed to brush the teeth, with 
typically about 0.8 to 2 g. being dispensed onto toothbrushes for each 
brushing. Brushings are twice a day, morning and night, one minute at a 
time, for four weeks, after which definite improvement in anti-plaque 
action is apparent, compared to a control dentifrice that contains no 
triclosan, and when polyphosphate is also present anti-tartar effects are 
also noticeable. Improvement in anti-plaque action is also visible, 
compared to an unflavored control (containing no terpene) that contains 
triclosan which is dispensed from polyethylene and polyethylene 
terephthalate lined containers. 
For more details about the pump dispensers, materials of construction 
thereof and dentifrice composition components of the invention, if 
desired, please see the previously mentioned or referred to patents, 
applications, texts, bulletins and/or articles, which are hereby 
incorporated herein by reference. 
The invention has been described with respect to various examples, 
illustrations and embodiments thereof but is not to be limited to these 
because it is evident that one of skill in the art, with the present 
specification before him/her, will be able to utilize substitutes and 
equivalents without departing from the invention.