Indian Patents. 235942:ORAL COMPOSITION

Title of Invention	ORAL COMPOSITION
Abstract	An opaque toothpaste composition and method for making such, the toothpaste comprising water, a zinc salt, a chelating agent for the zinc salt, the chelating agent having a log Ks1 as herein defined of from 3.0 to 7.0, and an abrasive present at from 10% to 70% by weight of the composition, said abrasive comprising calcium carbonate.

Full Text	J7197 FORM -2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) ORAL COMPOSITION 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 invention and the manner in which it is to be performed WO 2006/012987 PCT/EP2005/007718 - 1 - ORAL COMPOSITION The present invention relates to an opaque toothpaste composition comprising bioactive zinc salts in a chalk 5 formulation. The invention also relates to a method for making said composition. EP-A1-0 740 932 (Unilever) discloses a visually-clear gel type dentifrice comprising a zinc salt which is more water 10 soluble than zinc citrate, an amino acid which can bind zinc and a low refractive index type abrasive silica. US 5 470 561 (Klugkist) discloses an anti-plaque mouthwash comprising a zinc salt and triclosan. The composition may 15 also comprise glycine and has a pH of between 4 and 8, preferably between 5 and 7, the preferred pH being 6. GBA-2 052 978 (Unilever) discloses a toothpaste comprising zinc salts with glycine and a pH of from 4.5 to 8.0. 20 US 5 632 972 (Williams) discloses a method for minimising damage to gingival and periodontal tissue by delivering a first component comprising zinc and a second component comprising a bicarbonate. 25 US 4 425 325 (Sapone et al) discloses an oral composition containing biologically active zinc ions with glycine and having an adjusted pH of about 4.5 to 9.4. 30 GB 1 319 247 (Beecham INC) discloses a non-liquid anticalculus dental composition comprising a idental vehicle, WO 2006/012987 PCT/EP2005/007718 - 2 - and a zinc, cupric or zirconium complex of a fluorinated \|5- diketone. US 4 325 93 9 (Shah) discloses an alkali metal or ammonium 5 zinc citrate prepared for use in dental compositions and especially in mouthwash compositions. US 5 188 820 (Cummins et al) discloses oral compositions such as dentifrices comprising a mixture of a stannous salt 10 such as stannous fluoride or stannous pyrophosphate and a zinc salt such as zinc citrate. Nevertheless, there has been no attempt in the prior art to produce a toothpaste composition comprising a zinc salt and 15 calcium carbonate as an abrasive. This is due to the undesirable reaction which occurs between the calcium carbonate and the zinc ions to form carbon dioxide. The gas produced in this reaction inflates the closed container in which the composition is stored and will eventually lead to 20 bursting when stored for extended periods of time, for example, between manufacture and use. Furthermore, the production of carbon dioxide reduces the bioavailability of the zinc ions to act as anti-microbial agents, thereby reducing the efficiency of the zinc salts. 25 In a first aspect of the present invention there is provided an opaque toothpaste composition comprising a zinc salt, water, a chelating agent for the zinc salt, the chelating agent having a log KSl as herein defined of from 3.0 to 7.0, 30 and an abrasive present at from 10% to 70% by weight of the WO 2006/012987 PCT/EP2005/007718 - 3 - toothpaste composition, said abrasive comprising calcium carbonate. The present invention provide an optimum balance between 5 making enough zinc ions bioavailable and capable of interacting with bacteria without forming deleterious amounts of carbon dioxide. This reduces the risk of any gassing of the container in which the composition is stored and, therefore, allows the zinc salt to be stable within the 10 calcium carbonate composition for extended periods of time, for example during storage. The zinc salt is present at from 0.01 to 5% by weight of the toothpaste composition, preferably from 0.5 to 3.0% by 15 weight of the composition. Where the zinc salt is sparingly soluble, for example zinc citrate, the log Ksl of the chelating ligand with the zinc ion is equal to or greater than the log Kgl of the acid anion and the zinc ion of the sparingly soluble zinc salt. However, water soluble zinc 20 salts are preferred. Suitable zinc salts include zinc chloride, zinc sulphate and zinc fluoride. The preferred zinc salt is zinc sulphate which, in this, type of formulation, provides the optimum balance as described above. 25 It is preferred that the chelating agent for the zinc salt has a log Ksl of from 4.0 to 6.0. The log Ksl is the logarithm of the primary Stability Constant which is the binding affinity for a particular ligand with a particular 30 metal ion, in the present invention zinc. For example, when the chelating agent is glycine, the primary Stability WO 2006/012987 PCT/EP2005/007718 - 4 - Constant is the binding affinity for one glycine ligand with the free zinc ion and is defined by the following: Ksl= [ML]/[M].[L], where [ML] is the concentration of the metal-ligand complex, [M] is the concentration of the free metal 5 ion and [L] is the concentration of the free ligand. Since [L] is a function of the solution pH, due to the required initial deprotonation of the ligand, as a reference point, the log Ksl values described were recorded at pH 7.4. 10 The chelating agent is present at from 0.001 to 6% by weight of the composition, preferably at from 0.5 to 4.0% by weight of the composition. Preferred chelating agents include alkali metal salts of citric acid, alanine, glycine and serine. The most preferred is glycine, which provides an 15 optimal balance between being able to protect the zinc salt from hydrolysis (leading to the formation of carbon dioxide) in the chalk system and keeping it soluble and bioavailable. The abrasive system is present at from 10 to 70% by weight of the toothpaste composition, preferably at from 20 to 60% 20 and most preferably at from 35 to 45% by weight of the toothpaste composition. The abrasive system employed in the present invention is calcium carbonate based. This does not prevent the use of 25 non-calcium carbonate abrasives in addition, such as silicas, tungsten carbide and silicon carbide. In a preferred embodiment the abrasive system comprises at least 50% by weight calcium carbonate, more preferably at 30 least 75% by weight calcium carbonate and most preferably at least 95% by weight calcium carbonate. In the most preferred WO 2006/012987 PCT/EP2005/007718 - 5 - embodiment Of the present invention the abrasive system comprises 100% by weight calcium carbonate although mixtures of calcium carbonate and additional abrasives are possible. 5 Preferred calcium carbonates include fine ground natural chalk since it has a surprising stability with regard to its interactivity with zinc salts. The term fine ground natural chalk (FGNC) is a known term in the art and suitable examples of such are disclosed in US 2003/0072721 Al (Riley) 10 the contents of which with regards to the definition, types and grades of FGNC are incorporated herein by reference. Nevertheless, by FGNC is meant chalk which is obtained by milling limestone or marble deposits. Preferably, the FGNC comprises particulate matter of weight-based median particle 15 size ranging from 1 to 15 am and BET surface area ranging from 0.5 to 3 m2/g. The composition according to the invention also preferably comprises a fluoride ion source such as an alkali metal salt 20 of monofluorophosphate, preferably sodium monofluorophosphate. Such fluoride ion source will be present at such an amount to provide free fluoride ion at from 100 to 2000 ppm, preferably from 900 to 1500 ppm. 25 The toothpaste composition according to the invention comprise further ingredients which are common in the art, such as: antimicrobial agents, e.g. chlorhexidine, sanguinarine 30 extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; bis-guanides, such as WO 2006/012987 PCT/EP2005/007718 - 6 - Chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2' methylenebis-(4-chloro-6-bromophenol); 5 anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.; anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta 10 phosphate and casein; plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates; 15 vitamins such as Vitamins A, C and E; plant extracts; desensitising agents, e.g. potassium citrate, potassium 20 chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts; anti-calculus agents, e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and 25 phosphocitrates etc.,- biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.; flavours, e.g. peppermint and spearmint oils; 30 proteinaceous materials such as collagen; WO 2006/012987 PCT/EP2005/007718 - 7 - preservatives; opacifying agents; 5 colouring agents; pH-adjusting agents; sweetening agents; 10 pharmaceutically acceptable carriers, e.g. starch, sucrose, water or water/alcohol systems etc.; surfactants, such as anionic, nonionic, cationic and 15 particulate abrasive materials such as silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates zwitterionic or amphoteric surfactants; hydroxyapatites, trimetaphosphates, 20 insoluble hexametaphosphates and so on, including agglomerated particulate abrasive materials, usually in amounts between 3 and 60% by weight of the toothpaste •composition. Preferred abrasives are chalk and silica, more preferably fine ground natural chalk. 25 Humectants such as glycerol, sorbitol, propyleneglycol, xylitol, lactitol etc.; binders and thickeners such as sodium carboxymethyl- 30 cellulose, hydroxyethyl cellulose (Natrosol®), xanthan gum, WO 2006/012987 PCT/EP2005/007718 - 8 - gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol®; polymeric compounds which can enhance the delivery of active 5 ingredients such as antimicrobial agents can also be included; buffers and salts to buffer the pH and ionic strength of the toothpaste composition; and 10 other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, colour change systems, and 15 so on. Liposomes may also be used to improve delivery or stability of active ingredients. 20 In a second aspect of the invention there is provided a method of making an opaque toothpaste composition according to the first aspect the method comprising the steps of forming a zinc-chelate solution and buffering to a pH which is equal to or higher than that of the calcium carbonate in 25 an aqueous suspension before mixing with the suspended calcium carbonate. Further materials such as flavours may be added to the final mix. Except in the operating and comparative examples, or where 30 otherwise explicitly indicated, all numbers in this WO 2006/012987 PCT/EP2005/007718 - 9 - description indicating amounts of material ought to be understood as modified by the word 'about'. The term ‘comprising’ is meant not to be limiting to any 5 subsequently stated elements but rather to encompass non-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 10 'comprising' as defined above. Embodiments according to the invention shall now be discussed with reference to the following non-limiting examples. 15 EXAMPLE 1 The following example formulation is an embodiment according to the invention. It is made by mixing first the zinc 20 sulphate heptahydrate with glycine (and other minors) and buffering to a pH of from 8.5 to 9.5 with sodium hydroxide. The calcium carbonate, surfactant and structurants are then added to the zinc-chelate mix. The flavours are added last. WO 2006/012987 PCT/EP2005/007718 - 10 - EXAMPLE 2 5 The Table shows the upper aqueous solution pH that can be attained without precipitating zinc hydroxide when the zinc is protected by a 1:3 ratio of zinc to acetic acid or glycine acting as ligands. 10 WO 2006/012987 PCT/EP2005/007718 - 11 - In other words at a 1:3 ratio of zinc to ligand and where acetate is the ligand zinc hydroxide will form when the pH of the composition reaches just below 6. The pH of toothpaste compositions comprising calcium carbonate as 5 abrasive typically reaches as low as 8 with most being much above 8 and even as high as 10. Accordingly, of the two, only glycine can act as ligand for zinc in a chalk toothpaste since only such a ligand can 10 prevent formation of zinc hydroxide and the resulting carbon dioxide on reaction with calcium in the chalk. WO 2006/012987 PCT/EP2005/007718 12 - CLAIMS 1. An opaque toothpaste composition comprising water, a zinc salt, a chelating agent for the zinc salt, the 5 chelating agent having a log Ksl as herein defined of from 3.0 to 7.0, and an abrasive present at from 10% to 70% by weight of the toothpaste composition, said abrasive comprising calcium carbonate. 10 2. An opaque toothpaste composition according to claim 1, wherein the composition has a pH of from 8.0 to 10.0 3 . An opaque toothpaste composition according to any-preceding claim, wherein the calcium carbonate is fine 15 ground natural chalk. 4. An opaque toothpaste composition according to any preceding claim, wherein the composition comprises a fluoride ion source. 20 5. An opaque toothpaste composition according to any preceding claim, wherein the zinc salt is a water soluble zinc salt. 25 6. An opaque toothpaste composition according to any preceding claim, wherein the zinc salt is zinc sulphate. 7. An opaque toothpaste composition according to any 30 preceding claim, wherein the chelating agent is WO 2006/012987 PCT/EP2005/007718 - 13 5 glycine. 8. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is serine. 9. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is alanine. 10 10. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is an alkali metal salt of citric acid. 11. An opaque toothpaste according to any preceding claim 15 comprising an agent selected from the group consisting of anti-caries agents, anti-tartar agents, anti-malodour agents, whitening teeth agents, anti-gingivitis agents and mixtures thereof. 20 12. Method of making an opaque toothpaste composition, the toothpaste comprising water, a zinc salt, a chelating agent for the zinc salt, the chelating agent having a log Ksl as herein defined of from 3.0 to 7.0, and an abrasive present at from 10% to 70% by weight of the 25 toothpaste composition, said abrasive comprising calcium carbonate, the method comprising: -forming a zinc-chelate solution and buffering to a pH which is equal to or higher than that of the calcium 30 carbonate in an aqueous suspension before mixing with WO 2006/012987 PCT/EP2005/007718 - 14 - Calcium carbonate and optionally adding any further materials at any stage. Dated this 1st day of February 2007

Full Text

J7197
FORM -2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
ORAL COMPOSITION
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 invention and the manner in which it is to be performed

WO 2006/012987

PCT/EP2005/007718

- 1 -
ORAL COMPOSITION
The present invention relates to an opaque toothpaste composition comprising bioactive zinc salts in a chalk
5 formulation. The invention also relates to a method for making said composition.
EP-A1-0 740 932 (Unilever) discloses a visually-clear gel type dentifrice comprising a zinc salt which is more water
10 soluble than zinc citrate, an amino acid which can bind zinc and a low refractive index type abrasive silica.
US 5 470 561 (Klugkist) discloses an anti-plaque mouthwash comprising a zinc salt and triclosan. The composition may
15 also comprise glycine and has a pH of between 4 and 8, preferably between 5 and 7, the preferred pH being 6.
GBA-2 052 978 (Unilever) discloses a toothpaste comprising zinc salts with glycine and a pH of from 4.5 to 8.0.
20
US 5 632 972 (Williams) discloses a method for minimising damage to gingival and periodontal tissue by delivering a first component comprising zinc and a second component comprising a bicarbonate.
25
US 4 425 325 (Sapone et al) discloses an oral composition containing biologically active zinc ions with glycine and having an adjusted pH of about 4.5 to 9.4.
30 GB 1 319 247 (Beecham INC) discloses a non-liquid
anticalculus dental composition comprising a idental vehicle,

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- 2 -
and a zinc, cupric or zirconium complex of a fluorinated |5-
diketone.
US 4 325 93 9 (Shah) discloses an alkali metal or ammonium
5 zinc citrate prepared for use in dental compositions and especially in mouthwash compositions.
US 5 188 820 (Cummins et al) discloses oral compositions such as dentifrices comprising a mixture of a stannous salt
10 such as stannous fluoride or stannous pyrophosphate and a zinc salt such as zinc citrate.
Nevertheless, there has been no attempt in the prior art to produce a toothpaste composition comprising a zinc salt and
15 calcium carbonate as an abrasive. This is due to the undesirable reaction which occurs between the calcium carbonate and the zinc ions to form carbon dioxide. The gas produced in this reaction inflates the closed container in which the composition is stored and will eventually lead to
20 bursting when stored for extended periods of time, for example, between manufacture and use. Furthermore, the production of carbon dioxide reduces the bioavailability of the zinc ions to act as anti-microbial agents, thereby reducing the efficiency of the zinc salts.
25
In a first aspect of the present invention there is provided an opaque toothpaste composition comprising a zinc salt, water, a chelating agent for the zinc salt, the chelating
agent having a log KSl as herein defined of from 3.0 to 7.0,
30 and an abrasive present at from 10% to 70% by weight of the

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toothpaste composition, said abrasive comprising calcium carbonate.
The present invention provide an optimum balance between
5 making enough zinc ions bioavailable and capable of interacting with bacteria without forming deleterious amounts of carbon dioxide. This reduces the risk of any gassing of the container in which the composition is stored and, therefore, allows the zinc salt to be stable within the
10 calcium carbonate composition for extended periods of time, for example during storage.
The zinc salt is present at from 0.01 to 5% by weight of the toothpaste composition, preferably from 0.5 to 3.0% by
15 weight of the composition. Where the zinc salt is sparingly soluble, for example zinc citrate, the log Ksl of the chelating ligand with the zinc ion is equal to or greater than the log Kgl of the acid anion and the zinc ion of the sparingly soluble zinc salt. However, water soluble zinc
20 salts are preferred. Suitable zinc salts include zinc
chloride, zinc sulphate and zinc fluoride. The preferred zinc salt is zinc sulphate which, in this, type of formulation, provides the optimum balance as described above.
25
It is preferred that the chelating agent for the zinc salt has a log Ksl of from 4.0 to 6.0. The log Ksl is the logarithm of the primary Stability Constant which is the binding affinity for a particular ligand with a particular
30 metal ion, in the present invention zinc. For example, when the chelating agent is glycine, the primary Stability

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Constant is the binding affinity for one glycine ligand with the free zinc ion and is defined by the following: Ksl= [ML]/[M].[L], where [ML] is the concentration of the metal-ligand complex, [M] is the concentration of the free metal
5 ion and [L] is the concentration of the free ligand. Since [L] is a function of the solution pH, due to the required initial deprotonation of the ligand, as a reference point, the log Ksl values described were recorded at pH 7.4.
10 The chelating agent is present at from 0.001 to 6% by weight of the composition, preferably at from 0.5 to 4.0% by weight of the composition. Preferred chelating agents include alkali metal salts of citric acid, alanine, glycine and serine. The most preferred is glycine, which provides an
15 optimal balance between being able to protect the zinc salt from hydrolysis (leading to the formation of carbon dioxide) in the chalk system and keeping it soluble and bioavailable. The abrasive system is present at from 10 to 70% by weight of the toothpaste composition, preferably at from 20 to 60%
20 and most preferably at from 35 to 45% by weight of the toothpaste composition.
The abrasive system employed in the present invention is calcium carbonate based. This does not prevent the use of
25 non-calcium carbonate abrasives in addition, such as silicas, tungsten carbide and silicon carbide.

In a preferred embodiment the abrasive system comprises at least 50% by weight calcium carbonate, more preferably at
30 least 75% by weight calcium carbonate and most preferably at least 95% by weight calcium carbonate. In the most preferred

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embodiment Of the present invention the abrasive system comprises 100% by weight calcium carbonate although mixtures of calcium carbonate and additional abrasives are possible.
5 Preferred calcium carbonates include fine ground natural
chalk since it has a surprising stability with regard to its interactivity with zinc salts. The term fine ground natural chalk (FGNC) is a known term in the art and suitable examples of such are disclosed in US 2003/0072721 Al (Riley)
10 the contents of which with regards to the definition, types and grades of FGNC are incorporated herein by reference. Nevertheless, by FGNC is meant chalk which is obtained by milling limestone or marble deposits. Preferably, the FGNC comprises particulate matter of weight-based median particle
15 size ranging from 1 to 15 am and BET surface area ranging from 0.5 to 3 m2/g.
The composition according to the invention also preferably comprises a fluoride ion source such as an alkali metal salt
20 of monofluorophosphate, preferably sodium
monofluorophosphate. Such fluoride ion source will be present at such an amount to provide free fluoride ion at from 100 to 2000 ppm, preferably from 900 to 1500 ppm.
25 The toothpaste composition according to the invention
comprise further ingredients which are common in the art, such as:
antimicrobial agents, e.g. chlorhexidine, sanguinarine
30 extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; bis-guanides, such as

WO 2006/012987

PCT/EP2005/007718

- 6 -
Chlorhexidine digluconate, hexetidine, octenidine,
alexidine; and halogenated bisphenolic compounds, such as 2,2' methylenebis-(4-chloro-6-bromophenol);
5 anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.;
anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta
10 phosphate and casein;
plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates;
15 vitamins such as Vitamins A, C and E;
plant extracts;
desensitising agents, e.g. potassium citrate, potassium 20 chloride, potassium tartrate, potassium bicarbonate,
potassium oxalate, potassium nitrate and strontium salts;

anti-calculus agents, e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and
25 phosphocitrates etc.,-
biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.; flavours, e.g. peppermint and spearmint oils;
30
proteinaceous materials such as collagen;

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preservatives;
opacifying agents;
5 colouring agents;
pH-adjusting agents;
sweetening agents; 10
pharmaceutically acceptable carriers, e.g. starch, sucrose, water or water/alcohol systems etc.;
surfactants, such as anionic, nonionic, cationic and
15 particulate abrasive materials such as silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates zwitterionic or amphoteric surfactants;
hydroxyapatites, trimetaphosphates,
20 insoluble hexametaphosphates and so on, including
agglomerated particulate abrasive materials, usually in amounts between 3 and 60% by weight of the toothpaste •composition. Preferred abrasives are chalk and silica, more preferably fine ground natural chalk.
25
Humectants such as glycerol, sorbitol, propyleneglycol, xylitol, lactitol etc.;
binders and thickeners such as sodium carboxymethyl-
30 cellulose, hydroxyethyl cellulose (Natrosol®), xanthan gum,

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gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol®;
polymeric compounds which can enhance the delivery of active
5 ingredients such as antimicrobial agents can also be included;
buffers and salts to buffer the pH and ionic strength of the toothpaste composition; and
10
other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, colour change systems, and
15 so on.
Liposomes may also be used to improve delivery or stability of active ingredients.
20 In a second aspect of the invention there is provided a
method of making an opaque toothpaste composition according to the first aspect the method comprising the steps of forming a zinc-chelate solution and buffering to a pH which is equal to or higher than that of the calcium carbonate in
25 an aqueous suspension before mixing with the suspended
calcium carbonate. Further materials such as flavours may be added to the final mix.
Except in the operating and comparative examples, or where
30 otherwise explicitly indicated, all numbers in this

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description indicating amounts of material ought to be
understood as modified by the word 'about'.
The term ‘comprising’ is meant not to be limiting to any
5 subsequently stated elements but rather to encompass non-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
10 'comprising' as defined above.
Embodiments according to the invention shall now be discussed with reference to the following non-limiting examples.
15
EXAMPLE 1
The following example formulation is an embodiment according to the invention. It is made by mixing first the zinc
20 sulphate heptahydrate with glycine (and other minors) and buffering to a pH of from 8.5 to 9.5 with sodium hydroxide. The calcium carbonate, surfactant and structurants are then added to the zinc-chelate mix. The flavours are added last.

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EXAMPLE 2
5 The Table shows the upper aqueous solution pH that can be attained without precipitating zinc hydroxide when the zinc is protected by a 1:3 ratio of zinc to acetic acid or glycine acting as ligands.

10

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In other words at a 1:3 ratio of zinc to ligand and where acetate is the ligand zinc hydroxide will form when the pH of the composition reaches just below 6. The pH of toothpaste compositions comprising calcium carbonate as
5 abrasive typically reaches as low as 8 with most being much above 8 and even as high as 10.
Accordingly, of the two, only glycine can act as ligand for zinc in a chalk toothpaste since only such a ligand can
10 prevent formation of zinc hydroxide and the resulting carbon dioxide on reaction with calcium in the chalk.

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12 -
CLAIMS
1. An opaque toothpaste composition comprising water, a zinc salt, a chelating agent for the zinc salt, the
5 chelating agent having a log Ksl as herein defined of from 3.0 to 7.0, and an abrasive present at from 10% to 70% by weight of the toothpaste composition, said abrasive comprising calcium carbonate.
10 2. An opaque toothpaste composition according to claim 1, wherein the composition has a pH of from 8.0 to 10.0
3 . An opaque toothpaste composition according to any-preceding claim, wherein the calcium carbonate is fine
15 ground natural chalk.
4. An opaque toothpaste composition according to any
preceding claim, wherein the composition comprises a
fluoride ion source.
20
5. An opaque toothpaste composition according to any
preceding claim, wherein the zinc salt is a water soluble zinc salt.
25 6. An opaque toothpaste composition according to any preceding claim, wherein the zinc salt is zinc sulphate.
7. An opaque toothpaste composition according to any
30 preceding claim, wherein the chelating agent is

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5

glycine.
8. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is serine.
9. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is alanine.

10 10. An opaque toothpaste composition according to any preceding claim, wherein the chelating agent is an alkali metal salt of citric acid.
11. An opaque toothpaste according to any preceding claim
15 comprising an agent selected from the group consisting of anti-caries agents, anti-tartar agents, anti-malodour agents, whitening teeth agents, anti-gingivitis agents and mixtures thereof.
20 12. Method of making an opaque toothpaste composition, the toothpaste comprising water, a zinc salt, a chelating agent for the zinc salt, the chelating agent having a log Ksl as herein defined of from 3.0 to 7.0, and an abrasive present at from 10% to 70% by weight of the
25 toothpaste composition, said abrasive comprising calcium carbonate, the method comprising:
-forming a zinc-chelate solution and buffering to a pH which is equal to or higher than that of the calcium
30 carbonate in an aqueous suspension before mixing with

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Calcium carbonate and optionally adding any further materials at any stage.
Dated this 1st day of February 2007

Documents:

156-MUMNP-2007-ABSTRACT(11-6-2009).pdf

156-MUMNP-2007-ABSTRACT(GRANTED)-(9-9-2009).pdf

156-MUMNP-2007-CANCELLED PAGES(11-6-2009).pdf

156-MUMNP-2007-CANCELLED PAGES(3-8-2009).pdf

156-MUMNP-2007-CLAIMS(1-2-2007).pdf

156-MUMNP-2007-CLAIMS(11-6-2009).pdf

156-MUMNP-2007-CLAIMS(3-8-2009).pdf

156-MUMNP-2007-CLAIMS(AMENDED)-(11-6-2009).pdf

156-MUMNP-2007-CLAIMS(GRANTED)-(9-9-2009).pdf

156-mumnp-2007-claims.doc

156-mumnp-2007-claims.pdf

156-MUMNP-2007-CORRESPONDENCE(11-6-2009).pdf

156-MUMNP-2007-CORRESPONDENCE(16-07-2008).pdf

156-MUMNP-2007-CORRESPONDENCE(22-6-2007).pdf

156-MUMNP-2007-CORRESPONDENCE(3-8-2009).pdf

156-MUMNP-2007-CORRESPONDENCE(8-2-2012).pdf

156-MUMNP-2007-CORRESPONDENCE(IPO)-(16-9-2009).pdf

156-mumnp-2007-correspondence-others.pdf

156-mumnp-2007-correspondence-received.pdf

156-mumnp-2007-description (complete).pdf

156-MUMNP-2007-DESCRIPTION(COMPLETE)-(1-2-2007).pdf

156-MUMNP-2007-DESCRIPTION(COMPLETE)-(11-6-2009).pdf

156-MUMNP-2007-DESCRIPTION(GRANTED)-(9-9-2009).pdf

156-MUMNP-2007-FORM 1(1-2-2007).pdf

156-MUMNP-2007-FORM 1(11-6-2009).pdf

156-MUMNP-2007-FORM 13(3-10-2007).pdf

156-MUMNP-2007-FORM 18(11-6-2009).pdf

156-mumnp-2007-form 2(11-6-2009).pdf

156-MUMNP-2007-FORM 2(COMPLETE)-(1-2-2007).pdf

156-MUMNP-2007-FORM 2(GRANTED)-(9-9-2009).pdf

156-MUMNP-2007-FORM 2(TITLE PAGE)-(11-6-2009).pdf

156-MUMNP-2007-FORM 2(TITLE PAGE)-(COMPLETE)-(1-2-2007).pdf

156-MUMNP-2007-FORM 2(TITLE PAGE)-(GRANTED)-(9-9-2009).pdf

156-MUMNP-2007-FORM 3(1-2-2007).pdf

156-MUMNP-2007-FORM 3(11-6-2009).pdf

156-MUMNP-2007-FORM 5(1-2-2007).pdf

156-MUMNP-2007-FORM 5(11-6-2009).pdf

156-mumnp-2007-form-1.pdf

156-mumnp-2007-form-2.doc

156-mumnp-2007-form-2.pdf

156-mumnp-2007-form-3.pdf

156-mumnp-2007-form-5.pdf

156-mumnp-2007-form-pct-isa-237.pdf

156-MUMNP-2007-GENERAL POWER OF ATTORNEY(11-6-2009).pdf

156-mumnp-2007-pct-search report.pdf

156-MUMNP-2007-POWER OF ATTORNEY(5-8-2009).pdf

156-MUMNP-2007-SPECIFICATION(AMENDED)-(3-8-2009).pdf

156-MUMNP-2007-WO INTERNATIONAL PUBLICATION REPORT(1-2-2007).pdf

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Patent Number

235942

Indian Patent Application Number

156/MUMNP/2007

PG Journal Number

38/2009

Publication Date

18-Sep-2009

Grant Date

09-Sep-2009

Date of Filing

01-Feb-2007

Name of Patentee

HINDUSTAN UNILEVER LIMITED

Applicant Address

Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai-400 020,

Inventors:

#	Inventor's Name	Inventor's Address
1	WATERFIELD PHILIP CHRISTOPHER	Unilever R&D Port Sunlight, Quarry Road East, Bebington, Wirral,Merseyside CH63 3JW

PCT International Classification Number

A61K8/27

PCT International Application Number

PCT/EP2005/007718

PCT International Filing date

2005-07-13

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	04257064.8	2004-11-15	EUROPEAN UNION
2	EP05250131	2005-01-13	EUROPEAN UNION
3	04254661.4	2004-08-03	EUROPEAN UNION
4	04254662.2	2004-08-03	EUROPEAN UNION
5	04257063.0	2004-11-15	EUROPEAN UNION