Title of Invention

A DETERGENT BAR COMPOSITION WITH IMPROVED WATER RETENTION CAPACITY

Abstract

"A detergent bar composition with improved water retention capacity, comprising of: (i) 10 - 80% detergent active (ii) 1-30% layered inorganic material having the general formula (M2+)1(N3+)a(OH-1)b(Ac)d eH20 wherein M2+ = one or more bipositive metal ion N3+ = tripositive metal ion and 'a' ranges from 0 to 1 OH"1 = hydroxyl, and 'b' ranges from 0.1 to 4 A"c = 'c' refers to the valency of the inter layer anion 'A' and 'd' ranges from 0 to 1 H20 = water of crysaliisation where *e' ranges from 0 to 10 where the charge neutrality is maintained i.e. 2 + 3a - (b + cd) = 0 (iii) 12-52% water or other liquid benefit agents and (iv) other conventional ingredients.

Full Text

FORM -2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10) IMPROVED DETERGENT BAR COMPOSITION WITH IMPROVED WATER RETENTION CAPACITY 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. 23-1-2004 Technical field: >X The invention relates to a synergistic composition of soap/detergent bars for personal or fabric washing or for hard surface cleaning. This invention particularly relates to detergent bar composition with improved water retention capacity without affecting sensory and physical properties. Background and prior art: Conventional detergent bars, based on soap for personal washing contain over about 70% by weight TFM, the remainder being water (about 10-20%) and other ingredients such as colour, perfume, preservatives, etc. Structurants and fillers are also present in such compositions in small amounts that replace some of the soap in the bar while retaining the desired hardness of the bar. A few known fillers include starch, kaolin and talc. Hard non-milled soaps containing moisture of less than 35% are also available. These bars have a TFM of about 30-65%. The reduction in TFM has been achieved by the use of insoluble particulate materials and/or soluble silicates. Milled bars generally have a water content of about 8-15% and the hard non-milled bars have a water content of about 20-35%. Fabric washing compositions contain, as an essential ingredient, a surfactant system whose role is to assist in removal of soil from the fabric and its 2 suspension in the wash liquor. Detergent bars require an acceptable physical strength so that they retain their structural integrity during handling, transport and use. The hardness of the bars, at the time of manufacture and subsequently, is an especially important property. The water content in the detergent bars is generally maintained around 6%. The binders and fillers used in NSD bars are typically minerals which generally exhibit wide variability in quality, by virtue of the fact that they are mined/Increasing the water content and retaining it in the bar is particularly useful for producing larger sized bars, which have an enhanced consumer impact. Commercially available detergent bars contain detergent active components and detergent builders, fillers, structurants, hardeners together with optional components for example abrasives, perfumes, colour and bleaching agents. Commercial hard surface cleaning compositions typically comprise one or more surfactants and a plurality of abrasives dispersed therein. Combinations of these together with electrolytes are generally used to form a suspending system as is well known in the art. Inorganic particulates form an essential ingredient of detergent formulations used for personal wash, fabric and especially of many hard surface cleaning compositions. Inorganic particulates generally employed are calcites, dolomites, feldspars, silica, silicates, other carbonates, bicarbonates, borates, sulphates. 3 Hydroxy carbonates of alkaline earth metals and layered double hydroxides of one or more alkaline earth and aluminium are also known to exist in their mineral form but have not been generally used in soaps and detergents. Hydroxy carbonates of alkaline earth metals are used as flow aids, as precursors for ceramics, refractories and layered double hydroxides of one or more alkaline earth and aluminium are used as catalyst precursors, adsorbents, antacids. EP557089 (Unilever, 1993), W09616634 (Unilever, 1996), disclose the use of i layered double hydroxides in cosmetic compositions for enhanced delivery of benefit agents. WO 96/25913 discloses the use of monophasic zinc hydroxycarbonate as f antimicrobial agents in personal care products, particularly products containing soap or synthetic detergents. This is restricted to making the zinc ions, which are known to provide antimicrobial activity available without affecting the product itself. It has now been found that use of these layered inorganic materials in detergent formulations can improve the water retention in the bars without affecting the j other physical and sensory properties. It also enables the incorporation of other ' liquid benefit agents in the bar. 4 Statement of the Invention According to the present invention there is provided a detergent bar composition comprising-(i) 10 - 80% detergent active (ii) 1-30% layered inorganic material having the general formula (M2+)1(N3+)a(OH-1)b(A-c)d eH20 wherein M2+ = one or more bipositive metal ion N3+ = tripositive metal ion and 'a' ranges from 0 to 1 OH_1 = hydroxyl, and xb' ranges from 0.1 to 4 A"c = V refers to the valency of the inter layer anion W and \j' ranges from 0 to 1 H20 = water of crysallisation where 'e' ranges from 0 to 10 where the charge neutrality is maintained i.e. 2 + 3a - (b + cd) = 0 (iii) 12-52% water or other liquid benefit agents and (iv) other conventional ingredients. Description of Invention It is particularly preferred that, the bipositive metal ion may be magnesium, calcium and/or zinc and the tripositive metal ion is aluminum. The anion may be mono-negative such as chloride or nitrate or di-negative such as carbonate or sulphate or tetraborate or tri-negative such as phosphate or borate. 5 According to the preferred aspect of the invention there is provided an improved detergent bar composition comprising 10-80% detergent active 1-30% a inorganic material having the general formula (M2+)T (OK1)b (A"c)d. eH20 Wherein M2+ = bi-positive metal ion is magnesium OH"1 = hydroxyl, and 'b' is 0.2 to 0.8 A'c = anion is carbonate and 'd' is 0.6 to 0.9 H20 = water of crystallisation where 'e' is 1 to 5 Where the charge neutrality is maintained, i.e. 2 - (b +cd) = 0 12-52% water or other liquid benefit agents. and, other conventional ingredients. According to another aspect of the invention there is provided a process for the preparation of an improved detergent bar composition comprising 10-80% detergent active wherein the 1-30% layered inorganic material having the general formula Wherein M2+ = one or more bipositive metal ion N3+ = tripositive metal ion and 'a' ranges from 0 to 1 OH'1 = hydroxyl, and 'b' ranges from 0.1 to 4 6 A'c = 'c' refers to the valency of the inter layer anion 'A' and 'd' ranges from 0 to 1 H20 = water of crystallisation where 'e' ranges from 0 to 10 Where the charge neutrality is maintained, i.e. 2 + 3a - (b + cd) = 0 12-52% water or other liquid' benefit agents, and other conventional ingredients, wherein the said layered inorganic material is generated in situ by mixing the mixed metal oxide precursor with the soap mass at a temperature range of 20-80°C in presence of water. The mixed metal oxide precursor is obtained by calcining the corresponding layered double hydroxide at a temperature range of 450-550°C. Detailed description of the invention: The essential feature of the invention is that the incorporation of certain layered inorganic basic salts such as hydroxy carbonates and layered double hydroxide in soaps and detergents helps in improving the water structuring and thus retention of the structured water in the bar during storage and use. Layered inorganic material: A number of natural and synthetic layered double hydroxides are known with various metallic cations wherein the divalent cations are magnesium, manganese, iron, cobalt, nickel, copper, zinc or calcium and the trivalent ones 7 are aluminium, chromium, manganese, iron, cobalt, nickel and lanthanum. It is particularly preferred that, the bipositive metal ion may be magnesium, calcium and/or zinc, the tripositive metal ion is; aluminum, and the anion may be mono negative such as chloride nitrate or di-negative such as carbonate sulphate or tetraborate or tri-negative such as phosphate or borate. / The layered inorganic materials used in the composition may be obtained commercially or may be prepared separately. The layered double hydroxides may be added to the neat soap before spray drying of the soap or to the dried soap noodles. Alternatively, the layered double hydroxides may also be generated in situ from its corresponding mixed metal oxide precursor. The mixed metal oxide precursor is obtained by calcining the corresponding layered double hydroxide at a temperature range of 450-550°C. The mixed metal oxide precursor is added to the soap before spray drying of the soap or to the dried soap noodles where it gets reformed to give the layered double hydroxide. Some of these layered inorganic materials are also available naturally as minerals. The layered inorganic material namely the hydroxy carbonate or layered double hydroxides are prepared by combining appropriate stoichiometric amounts of aqueous solutions of metal salts/co-mixtures of metal salts with aqueous sodium carbonate solutions at typically high temperatures of 80-90°C. The precipitate containing the layered inorganic material is filtered and washed thoroughly with copious amounts of water to remove all soluble electrolytes. This wet cake obtained is subjected to drying over night in an oven at 130°C. These materials 8 suitable for the detergent composition are typically white powders and have an average particle size in the range 5-12 microns. In case the particle size is larger the material is subjected to milling to get the desired particle size range. The layered inorganic material used as a structurant in soap/detergent systems in this composition, typically contained approximately 40% moisture and was free / flowing in nature. Examples of layered materials are hydromagnesite, hydrotalcites with carbonate, nitrate, sulphate, tetraborate as inter layer anions. Detergent active: VA^ Z~ The detergent active may be soap; or non-soap surfactants. The term soap \ c. denotes salts of carboxylic fatty acids. The soap may be derived from any of the triglycerides conventionally used in soap manufacture - consequently the carboxylate anions in the soap may contain from 8 to 22 carbon atoms. The soap may be obtained by saponifying a fat and/or a fatty acid using a suitable alkaline material containing sodium, potassium, aluminium or a mixture thereof. The saponification may also be carried out by reacting one or more precursors of detergent active with an aluminium containing alkaline material such as sodium aluminate with a solid content of 20 to 55% wherein the Al203 to Na20 is in a ratio of 0.5 to 1.55 by weight either in presence of or absence of one or more carboxylic acid which have an equivalent weight less than 150. The 9 carboxylic acid may be selected from aliphatic monocarboxylic acids that are not fatty acids and their polymers and more preferably they are Ci to C5 carboxylic acids and their polymers. Other suitable carboxylic acids are aliphatic or aromatic di, -tri-, or polycarboxylic acids and hydroxy- and amino carboxylic acids. The fats or oils generally used in soap manufacture may be such as tallow, tallow stearines, palm oil, palm stearines, soya bean oil, fish oil, castor oil, rice bran oil, sunflower oil, coconut oil, babassu oil, palm kernel oil, and others. In the above process the fatty acids are derived from oils/fats selected from coconut, rice bran, groundnut, tallow, palm, palm kernel, cotton seed, soya bean, castor etc. The fatty acid soaps can also be synthetically prepared (e.g. by the oxidation of petroleum or by the hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids, such as those present in tall oil, may be used. Naphthenic acids are also suitable. Tallow fatty acids can be derived from various animal sources and generally comprise about 1-8% myristic acid, about 21-32% palmitic acid, about 14-31% stearic acid, about 0-4% palmitoleic acid, about 36-50% oleic acid and about 0-5% linoleic acid. A typical distribution is 2.5% myristic acid, 29% palmitic acid, 23% stearic acid, 2% palmitoleic acid, 41.5% oleic acid, and 3% linoleic acid. Other mixtures with similar distribution, such as those from palm oil and those derived from various animal tallow and lard are also included. 10 Coconut oil refers to fatty acid mixtures having an approximate carbon chain length distribution of 8% C8, 7% do, 48% C12, 17% C14, 8% C16, 2% Ci8, 7% oleic and 2% linoleic acids (the first six fatty acids listed being saturated). Other sources having similar carbon chain length distributions, such as palm kernel oil and babassu kernel oil, are included within the term coconut oil. V The non-soap surfactants may be anionic, nonionic, cationic, amphoteric or zwitterionic or a mixture thereof. Suitable anionic detergent active compounds are water soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphuric acid ester radicals and mixtures thereof. Examples of suitable anionic detergents are sodium and potassium alcohol sulphates, especially those obtained by sulphating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulphonates such as those in which the alkyl group contains from 9 to 15 carbon atoms ; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow and coconut oil ; sodium coconut oil fatty acid monogiyceride sulphates ; sodium and potassium salts of sulphuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide ; sodium and potassium salts of alkyl phenol 11 ethylene oxide ether sulphate with from 1 to 8 units of ethylene oxide molecule and in which the alkyl radicals contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with sodium hydroxide where, for example, the fatty acids are derived from coconut oil and mixtures thereof. The preferred water-soluble synthetic anionic detergent active compounds are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulphonates and mixtures with olefin sulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates. The most preferred anionic detergent active compounds are higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of higher alkyl benzene sulphonates or of higher-alkyl toluene, xylene or phenol sulphonates, alkyl naphthalene sulphonates, ammonium diamyl naphthalene sulphonate, and sodium dinonyl naphthalene sulphonate. Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic 12 group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Particular examples inclucle the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R3NO, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of structure R3PO, where one group R is an alkyl group of from 10 to 18 carbon atoms, and the others are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylphosphine oxide; and dialkyl sulphoxides of structure R2SO where the group R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide; fatty acid alkylolamides; alkylene oxide condensates of fatty acid alkylolamides and alkyl mercaptans. 13 It is also possible to include amphoteric, cationic or zwitterionic detergent actives in the compositions according to the invention. The bar is made by conventional methods, e.g. by the frame cooling method or by extrusion (plodding) method! Typically, in the extrusion method, fatty acids are neutralised with an alkali either as such or in presence of non-soap detergent active/a few selected additives and dried to required moisture. The dried soap is then miagtTwith remaining minor additives/non-soap detergents if not added earlier in the mixer, mechanically worked in triple roll mill and plodded under vacuum in the form of billets. The billets are later stamped in the form of bars. Conventional ingredients: Other optional ingredients such as fillers, colour, perfume, opacifier, preservatives, one or more water soluble/insoluble particulate materials such as talc, alumina, borax, kaolin, polysaccharides, liquid benefit agents such as sunscreens, moisturisers, emollients, anti-ageing compounds, hair conditioning . - ■ • - ■ r—- - agents, and other conventional ingredients may be incorporated in the composition. The soap/detergent bars of the present invention have been found to demonstrate excellent visual appearance, feel, hardness, cleaning and lathering properties. 14 Illustrations of a few non-limiting examples are provided herein showing comparative results of the compositions according to the present invention and beyond the scope of the invention. Examples: i. Process for the preparation of magnesium hydroxy carbonate: 100 ml of one molar solution of magnesium sulphate was added drop wise into one molar solution of sodium carbonate in equal volumes over a period of 30 minutes under constant stirring. After the reaction the slurry was filtered through Whatman 1 filter paper. The precipitate was washed with hot water to remove the sodium sulphate and the precipitate was dried at 110°C until the moisture content dropped to approximately 40%. The precipitate of magnesium hydroxy carbonate obtained was characterised using powder pattern X ray diffraction and the same was used for the preparation of soap bars as described below. ii. Process for preparing the soap bar: The soap bars having the formulations as described in Table 1 were prepared by the following method. Soap noodles were taken in a sigma mixer to which, in the control formulations the inorganic material such as talc (Example 1 and 2), layered inorganic material such as magnesium hydroxy carbonate (Example 3 and Example 4) were added. In Example 5, magnesium hydroxide and in Example 6 magnesium carbonate was incorporated. The mass was mixed thoroughly for about 10 minutes and 15 then processed conventionally by milling and plodding in a two stage plodder, subsequently followed by stamping and wrapping. The samples prepared as described above were tested for hardness, water retention after storage under hot and dry condition (45°C and 40-70 relative humidity) by the following procedure. iii. Determination of hardness of the bar: Penetration Value (PV) Penetration value indicating the hardness of the bar was measured at 37°C using a cone penetrometer the details of a typical instrument and the method of measurement is given below. Cone type Penetrometer MANUFACTURER: Adair Dutt & Company, Bombay. RANGE OF MEASUREMENT: 0 - 40 mm RANGE OF VERIFICATION: 20 in steps of 5 Procedure of Measurement: Let the entire mass (comprises of penetrometer needle and standard weight) which just rests on the test sample, drop freely and thus penetrate the test mass to a specific distance for a specified period of time and read of this distance as 1/10th of mm. Take the average after repeating the exercise for at least 3 times. iv. Water retention: 16 The initial moisture in the soap bar was measured using an Infra red balance. Wrapped samples of the bar were weighed initially and stored under hot and dry (HD) conditions where the temperature was maintained at 45°C and relative humidity in the range 40-70% for 3 months. The weight of the samples was determined periodically and the data at the end of 3 months is presented. The % moisture and %weight loss of the soap bars was calculated. Table 1 Composition %wt. Ex1 Ex 2 Ex 3 Ex 4 Ex 5* Ex 6 Soap 72 68.7 77.4 68.7 77.4 77.4 Soda ash 0.9 0.9 0.9 0.9 0.9 0.9 Moisture 15.1 19.0 14.8 19.0 14.8 14.8 Talc 10 10 - - - - Mg hydroxy carbonate - - 5 10 - - Mg hydroxide - - - - 5 - Mg Carbonate - - - - - 5 Minor ingredients 2 1.4 1.9 1.4 1.9 1.9 Product Characteristics Penetration (PV.) 39 41 35 32 - 37 % Moisture after storage @ 45°C for 3 months 6.1 6.9 9.1 10.0 6.0 % weight loss after storage 9.7 13.0 6.3 10.0 - 9.5 The bar is highly alkaline and is unsuitable for use. The data presented in table 1 show that the physical properties of the bar having high moisture such as hardness, and processability is significantly improved by using Magnesium hydroxy carbonate as compared to talc. The moisture 17 retention in the soap bars where layered inorganic materials have been incorporated is higher as compared to control formulations having talc. It is not possible to process bars having magnesium hydroxide and it is generally unsuitable for use in soaps because of the very high alkalinity associated with these bars. However, use of magnesium hydroxide or magnesium carbonate does not help in providing moisture retention in soap bars that is provided by the use of magnesium hydroxy carbonate. The use of magnesium hydroxy carbonate does not interfere with the sensory properties of the bar such as feel, lather etc as is recorded by an internal panel. 18 WE CLAIM 1. "A detergent bar composition with improved water retention capacity, comprising of: (i) 10 - 80% detergent active (ii) 1-30% layered inorganic material having the general formula (M2+)1(N3+)a(OH-1)b(Ac)d eH20 wherein M2+ = one or more bipositive metal ion N3+ = tripositive metal ion and 'a' ranges from 0 to 1 OH"1 = hydroxyl, and 'b' ranges from 0.1 to 4 A"c = 'c' refers to the valency of the inter layer anion 'A' and 'd' ranges from 0 to 1 H20 = water of crysaliisation where *e' ranges from 0 to 10 where the charge neutrality is maintained i.e. 2 + 3a - (b + cd) = 0 (iii) 12-52% water or other liquid benefit agents and (iv) other conventional ingredients. 2. The composition as claimed in claim 1 wherein said layered inorganic material comprise of general formula (M2^ (OK1),, (A"c)d eH20 wherein M2 + the bipositive metal ion is magnesium i OH"1 is the hydroxyl group and 'b' is 0.2 - 0.8 . Ac the anion is carbonate and 'd' is 0.2- 0.8 H20 is water of crystallization where 'e' is 1-5 where the charge neutrality is maintained as 2 - (b +cd) = 0 3. The composition as claimed in anyone claims 1 to 2 wherein said bipositive metal ion is selected from magnesium, manganese, iron, cobalt, nickel, copper, calcium and zinc and preferably selected from magnesium, calcium and/or zinc. 4. The composition as claimed in any of preceding claims wherein the tripositive metal ion is selected from aluminium, chromium, manganese, iron, cobalt, nickel and lanthanum, preferably alumium. 5. The composition as claimed in any of precedingclaims wherein the anion of the layered inorganic material is mono-negative or di/negative or tri-negative. 19 6. The composition as claimed in anyone of claims 1 to 5 wherein the said layered material f comprise hydromagnesite, hydrotalcites with carbonate, nitrate, sulphate, tetraborate as inter / layer anions. f , 7. The composition as claimed in any of preceding claims wherein the detergent active is selected from soap grid) non soap surfactants. 8. The composition as claimed in claim 7 wherein the non soap surfactants is selected from anionic, nonionic, cationic, amphoteric or zwitterionic or a mixture thereof. 9. The composition as claimed in any of preceding claims wherein the liquid benefit agents are selected from sunscreens, moisturisers, emollients, anti-ageing compounds, hair condition agents and the like. 10. The composition as claimed in any of preceding claims wherein the other conventional ingredients comprise fillers, colour, perfume, opacifier, preservatives, one or more water soluble/insoluble particulate materials preferably talc, alumina, borax, kaolin, polysaccharides. 11. A process for preparation of aftJrppfoved detergent bar composition as claimed in claims 1 to 10 comprising of selectively blending : (i) 10 - 80% detergent active (ii) 1-30% layered inorganic material having the general formula wherein M2+ = one or more bipositive metal ion N3+ = tripositive metal ion and 'a' ranges from 0 to 1 OH"1 = hydroxyl, and 'b' ranges from 0.1 to 4 A"c - 'c' refers to the valency of the inter layer anion 'A' and \j' ranges from 0 to 1 H20 = water of crysallisation where 'e' ranges from 0 to 10 where the charge neutrality is maintained i.e. 2 + 3a - (b + cd) = 0 (iii) 12-52% water or other liquid benefit agents and (iv) other conventional ingredients, followed by processing to obtain the detergent in bar form. 20 12. The process as claimed in Claim 11 wherein said processing of the selective blend to obtain bar comprise mixing the mass thoroughly, processing by milling and plodding in the form of billets. 13. The process as claimed in any of claims 11 or 12 wherein the layered inorganic material used is generated in situ. 14. The process as claimed in Claim 13 wherein the layered inorganic material used is generated in sity by mixing the mixed metal oxide precursor with the soap mass at a temperature range of 20 to 80°C in the presence of water. 15. The process as claimed in claim 14 wherein the said mixed metal oxide precursor is obtained by calcining the corresponding layered double hydroxide at a temperature range of 450 -550°C. 16. The process as claimed in anyone claims 14 or 15 wherein said layered inorganic material is. generated in-situ by adding the mixed metal oxide precursor to the soap mass at a temperature range of 20 - 80°C before or after spray drying of the soap to form the layered inorganic material. 17. The process as claimed in anyone of claims 11 to 12 wherein said layered inorganic material is obtained by combining selective amount of aqueous solutions of metal salts/co-mixtures of metal salts with aqueous sodium carbonate solutions in the temperature range of 80 - 90°C followed by filtering of the precipitant, washing, drying and processing to obtain the layered material of desired particle size preferably 5-12 microns. 18. An improved detergent bar composition and its process of manufacture substantially as herein described and illustrated with reference to the accompanying examples. Dated 18th day of April 2002 S. MAJUMDAR Of S.MAJUMDAR & CO. Applicant's Agent 21

Documents:

354-mum-2001-cancelled pages(23-01-2004).pdf

354-mum-2001-claims(granted)-(23-01-2004).doc

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354-mum-2001-correspondence 1(06-04-2005).pdf

354-mum-2001-correspondence 2(20-04-2002).pdf

354-mum-2001-correspondence(ipo)-(30-06-2004).pdf

354-mum-2001-form 1(20-04-2001).pdf

354-mum-2001-form 19(23-06-2003).pdf

354-mum-2001-form 2(granted)-(23-01-2004).doc

354-mum-2001-form 2(granted)-(23-01-2004).pdf

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354-mum-2001-pct-ipea-409(18-04-2002).pdf

354-mum-2001-pct-isa-210(29-11-2002).pdf

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354-mum-2001-power of attorney(08-07-2002).pdf