Title of Invention


Abstract An oral composition comprising : (i) from about 0.001% to about 20% of beads which comprise a zinc salt that has an average particle size ranging from about 0.01 to about 5mm; and (ii) a dental base
Full Text FORM -2
THE PATENTS ACT, 1970 (39 of 1970)
(See Section 10)
HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the nature of the invention and the manner in which it is to be performed.


The invention concerns anti-tartar dental compositions based on zinc citrate which have improved taste.
U.S. Patent 4,022,880 (Vinson et al.), U.S. Patent 4,647,452 (Ritchey et al.) and U.S. Patent 5,372,803 (Williams et al.) all disclose toothpastes comprising zinc citrate.
A major drawback of zinc citrate formulations is that the zinc ion imparts a relatively bitter taste. Smokers are particularly sensitive to the adverse taste.
Accordingly, it is an object of the present invention to provide an oral composition formulated with a zinc anti-tartar salt characterized by an improved taste.
The present invention thus provides an oral product comprising:
(i) from 0.001% to 20% of beads which include a zinc salt having a weight average particle size ranging from about 0.01 to about 5 mm; and
(ii) a dental base.
The bitter taste of zinc salts can be improved by incorporating the zinc salt in the form of relatively large active beads. On an equal zinc salt weight basis, the beads are at least as effective in anti-tartar activity as solubilized or dispersed non-complexed zinc salts of the known art.

Zinc salts usable for the present invention may include inorganic or organic counterions. Inorganic zinc salts include counterions such as halides (e.g. chloride, bromide and iodide), sulfates, nitrates, phosphates and combinations thereof. Preferably, the counterion is organic and suitable
organic counterions include C2-C20 compounds, especially
carboxylates. Preferred organic counterions include citrates, malates, malonates, maleates, adipates, succinates, acetates, propionates, lactates, tartrates, glycolates and combinations thereof. Most especially preferred is zinc citrate trihydrate.
Amount of the beads may range from 0.01 to 20%, preferably from 0.5 to 10%, optimally from 1 to 5% by weight of the total oral product.
Optionally, a gum may be incorporated into the beads of the present invention. Illustrative gums are polysaccharides including sodium carboxymethyl cellulose (CMC), hydroxyethylcellulose, methylcellulose, ethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, gum tragacanth, gum arabic, gum karaya, pectin, carageenan, guar, xanthan gum, starch and combinations thereof. Most preferred are the cellulose type gums, especially sodium carboxymethyl cellulose (CMC). All molecular weight types of sodium CMC may be useful, although the medium viscosity grade such as the 9M grade is most suitable.
Beads of the present invention normally will contain essentially only zinc citrate. In a less preferred but useful embodiment, the beads may be formed by the complexion

of the zinc salt with a gum in the presence of water to form gel particles. Relative weight ratios of the zinc salt to gum in this preferred embodiment ranges from 10,000:1 to 10:1, preferably from 1,000:1 to 100:1 by weight.
In some embodiments of the present invention, water may be present within the beads. In those situations, the relative weight ratios of the zinc salt to water in the beads may range from 50:1 to 1:50, preferably from 20:1 to 1:1, optimally from 10:1 to 6:1 by weight.
Typically the amount of zinc salt in the beads is 100%. However, in some embodiments the amount of zinc salt in the beads may range from 15 to 99%, sometimes from 50 to 95%, but optimally from 90 to 100% by weight of the beads. When a gum is present, amounts of the gum within the bead may range from 0.001 to 2%, preferably from 0.1 to 1%, optimally from 0.25 to 0.5% by weight of the beads. The remainder of the bead '■ composition generally is water present in amounts from 1 to 60%, preferably from 2 to 40%, optimally from 5 to 20% by weight of the beads.
Weight average particle size of the beads and also of the zinc salt may range from 0.01 to 5 mm, preferably from 0.05 to 3 mm, optimally from 0.1 to 2 mm. Bulk density of the beads may range from 0.75 to 0.95, preferably from 0.80 to 0.90, optimally from 0.81 to 0.84 gm/cc.
Beads according to the present invention are prepared prior to introduction into a dental base with other ingredients of the oral product. Zinc salt and any optional ingredients

such as gum and water can be formed by mixing in a Hobart-type blending apparatus.
In one embodiment, the beads are visually distinct in the dental base. This may be accomplished by the beads being opaque and the base being substantially transparent. Alternatively, the beads may appear as clear bodies colored differently from a transparent or opaque base.
Besides the beads, the oral product will contain a dental base in an amount of 80 to 99% by weight. Ingredients of the dental base may include humectants, thickeners, abrasives, anti-caries agents, surfactants, colorants, flavorants, opacifiers, water and a variety of special actives (e.g. desensitization agents such as potassium nitrate, peroxides and anti-bacterials such as triclosan).
Surfactants useful herein may be of the anionic, nonionic, cationic, zwitterionic or amphoteric type. Most preferred are sodium lauryl sulphate, sodium dodecylbenzene sulfonate and sodium lauryl sarcosinate. Amounts of the surfactant may range from 0.5 to 10%, preferably from 1 to 5% by weight of the dental base.
Humectants useful herein are usually polyols. Illustrative of this category are sorbitol, maltitol, mannitol, glycerin, propylene glycol, xylitol, hydrogenated corn syrup, polyethylene glycols and mixtures thereof. Amounts of the humectant may range from 1 to 60%, preferably from 5 to 50%, optimally from 10 to 40% by weight of the dental base.

Thickeners useful herein may be the same gums as utilized to complex with the zinc salts. However, these gums will be formulated into the dental base rather than into the pre¬formed beads. Illustrative thickeners include sodium carboxymethyl cellulose, ethylcellulose, carageenan, xanthan gum, pectin, chemically modified starches and acrylates. The
latter may be crosslinked polyacrylates such as Carbopol^
934. Inorganic thickeners are exemplified by silica aerogels and magnesium aluminum silicate, commercially available as
Veegum . Amounts of the thickener may range from 0.01 to
30%, preferably from 0.1 to 20%, optimally from 0.5 to 5% by weight of the dental base.
A fluoride anti-caries compound normally is usually present as part of the dental base. Illustrative of such fluoride compounds are sodium fluoride, potassium fluoride, calcium fluoride, stannous fluoride, stannous monofluorophosphate, sodium monofluorophosphate and copper fluoride. Most preferred is sodium fluoride. These sources should release anywhere from 25 to 5,000 ppm of fluoride ion. The anti-caries compound will normally be present in an amount from 0.01 to 5%, preferably from 0.1 to 2.5%, optimally from 0.2 to 1.5% by weight of the dental base.
Abrasives may also be present in the dental base. Illustrative materials include sodium metaphosphate, dicalcium phosphate, calcium pyrophosphate, silica, alumina, chalk, insoluble bicarbonate salts and mixtures thereof. Amounts of the abrasive may range from 1 to 80%, preferably from 5 to 50% by weight of the dental base.

When the oral compositions are gels, structurants may be necessary". Particularly useful as a structurant are polyoxyethylene-polyoxypropylene copolymers such as those
sold under the trademark Pluronic®. These materials are also
known as Poloxamere and employed in amounts from 5 to 30%, preferably from 18 to 25% by weight of the dental base.
Flavors may also be part of the dental base. These flavors may be based on oils of spearmint and peppermint. Examples of other flavoring materials include menthol, clove, wintergreen, eucalyptus and aniseed. Flavors may range in amount from 0.1 to 5% by weight of the dental base.
Sweetening agents may also be included in the dental base. Illustrative agents include saccharin, sodium cyclamate, aspartame, acesulfame, xylitol and combinations thereof at levels from 0.1 to 10% by weight of the dental base.
Other additives may also be incorporated into the dental base. These may be anti-tartar agents, colorants, preservatives, silicones, other synthetic or natural polymers
such as Gantrez S97 , and mixtures thereof.' Amounts of these
other ingredients may range from 0.01 to 20% by weight of the dental base.
Water may be present in the dental base in amounts from 1 to 95%, preferably from 10 to 60%, optimally from 20 to 50% by weight of the dental base.

The term "comprising" is meant not to be limiting to any subsequently stated elements but rather to encompass nori-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.
The following examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated.
Zinc salt beads of the present invention were prepared in several different ways. One procedure utilized a Hobart bowl. Zinc citrate was added to the bowl and a 2% CMC solution was slowly added with mixing until the beads formed. They were then air dried and sieved. A second method for preparation was via a ribbon blender, again adding a 2% solution of CMC to the dry zinc citrate.
Fluidized bed technology can also be utilized for manufacture of the beads. By this procedure zinc citrate was suspended in the fluid bed reactor while a nozzle sprayed a 2% solution of CMC. The spray drier utilized for this purpose was a GPCG-5, ex Glatt Technologies with a Schlick 924 nozzle. This model was able to produce 5-7 kilogram batches. The 2% CMC solution was sprayed using a peristaltic pump along with pressurized air at the nozzle to

atomize the spray. Achievement of optimum results required swift introduction of the CMC, use of cool air to fluidize, and maintenance of the product temperature during drying so that it stayed below 40°C. The relatively cool air prevented solids from sticking together before the beads were formed. During drying, the temperature quickly rose after water was removed. Care was taken not to over-dry which could lead to a frail bead. When the temperature reached 35°C, the batch was considered dried.
A typical gel dentifrice composition incorporating the beads of" this invention is described below.

An opaque toothpaste with the beads of this invention has a formula as described below.

A comparative taste test is reported under this Example. Two formulas were evaluated. The first was according to Example 2 wherein zinc citrate was present in the form of complexed insoluble beads. A comparative experiment" utilized the same formula as in Example 2 except that an equivalent amount of zinc citrate was solubilized within the formula rather than present as insoluble beads.

A flavor tasting panel was assembled consisting of thirteen persons. ' They rated the zinc citrate bead and the non-bead solubilized toothpaste after brushing, according to a series of organoleptic attributes. Ratings were on a scale of 1 to 5, where 1 = poor and 5 = excellent. After brushing -with both products, the panelists chose their preference. Table III below lists results of the flavor test. Values provided in the second and third column are average ratings except for the "preference" entry where 9 people chose the bead product, 3 people chose the control (zinc citrate solubilized) and 1 person had no preference.
Flavor Test

The tests indicate that the zinc citrate in bead form was favored in six of the seven taste categories. Only foam was found to be better in the comparative formula. The overall

preference, by a wide margin, was for zinc citrate in the bead form rather'than solubilized.
Zinc citrate beads were prepared in a Chilsonator . This
equipment compacts the zinc citrate powder by forcing the powder between two counter rotating rolls. As the volume decreases through a region of maximum pressure, the material is formed into a solid compact or sheet. As the rolls turn toward each other, the material in a slip region moves downward at a rate less than the surface speed of the rolls. In a nip region, the materials are caught or trapped by the rolls and move at a same speed as the roll surface, this forces the material through the region of maximum pressure, which is on a line between the centers of the two rolls. After compaction, the resultant material is fed into a
FitzMill® granulator to gently cut the compacted material
into beads which are separated by screens into appropriate sizes.
For the present Example, the Chilsonator was operated at a
roll speed of 5.0 rpm, a Vertical Screw Feed of 80 rpm, a Horizontal Screw Feed of 15 rpm, and a pressure of 700 psi. The angle of repose of zinc citrate was 45°. The loose density of the zinc citrate bead was 0.61 g/cc. The compact
thickness of the resultant ribbon from the Chilsonator
before milling was 0.15 inches. After granulation, the resultant particles were sieved to obtain samples of

different average particle size. These sizes were evaluated in a dental base outlined under Table I above.
Twelve people participated in a bead evaluation panel. All brushed their teeth with four products containing different particle size beads, all of which dentifrices were fielded blind. The study was cross-over in nature, the products being randomized and panelists brushing with two products during the course of one day and then two more products the following day. After each brushing, a brief questionnaire was filled out. The tables below display the results. The term "sensory" refers to a combination score of flavor while brushing, aftertaste and mouthfeel while brushing.
Particle Size of Zinc Citrate Beads vs. Sensory

TABLE V Panelist Rating of Excellent For Overall Liking

Overall sensory properties peaked in the average particle size area between 0.65 and 0.225 mm. This was also the area within which maximum ratings for overall liking and texture were given.

1. An oral composition comprising :
(i) from about 0.001% to about 20% of beads which comprise a zinc salt
that has an average particle size ranging from about 0.01 to about 5mm; and
(ii) a dental base
2. The composition as claimed in claim 1 wherein the zinc salt is zinc citrate trihydrate
3. The composition as claimed in claim 1 wherein the zinc salt has an average particle size ranging from about 0.1 to about 2mm.
4. The composition as claimed in claim 1 wherein the beads further comprise a gum.
5. The composition as claimed in claim 1 wherein the gum is a cellulose.
6. The composition as claimed in claim 1 wherein the gum is sodium carboxymethyl cellulose.
7. The composition as claimed in claim 1 wherein the ratio of zinc salt to gum ranges from about 1,000:1 to about 100:1.
8. The composition as claimed in claim 1 wherein the dental base comprises a material selected from the group consisting of humectants, thickeners, surfactants, colorants, flavorants, anti-caries agent abrasives, opacifiers, water and combinations thereof.
9. The composition as claimed in claim 1 wherein the beads are pre-formed and then combined into the dental base.
10. The composition as claimed in claim 1 wherein the beads are opaque and the dental base is transparent.
Dated this 21at day of October 2004
Dr. Sanchita Ganguli Of S.MAJUMDAR & CO. Applicant's Agents


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Patent Number 205782
Indian Patent Application Number 588/MUMNP/2004
PG Journal Number 42/2008
Publication Date 17-Oct-2008
Grant Date 10-Apr-2007
Date of Filing 21-Oct-2004
# Inventor's Name Inventor's Address
PCT International Classification Number A 61 K 7/16
PCT International Application Number PCT/EP03/04240
PCT International Filing date 2003-04-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/132046 2002-04-25 U.S.A.