|Title of Invention||
IMPROVEMENTS RELATING TO FABRIC TREATMENT COMPOSITIONS.
|Abstract||A fabric treatment composition for use in a laundering process which comprises at least one or mixture of surfactants selected from anionic surfactant, nonionic surfactant, cationic surfactant, and a probiotic microorganism, and a deposition aid, which results in the deposition of the probiotic onto fabric during a laundry treatment process.|
|Full Text||FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
The Patents Rules, 2003
(See Section 10 and Rule 13)
IMPROVEMENTS RELATING TO FABRIC TREATMENT COMPOSITIONS
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 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
IMPROVEMENTS RELATING TO FABRIC TREATMENT COMPOSITIONS Technical Field
The present invention relates to fabric treatment compositions and in particular to fabric treatment compositions comprising a so-called 'probiotic' particle.
The concept of probiotics is believed to have evolved from a hypothesis proposed by the Nobel Prize winning Russian scientist Metchnikoff, who postulated that the long healthy life of Bulgarian peasants resulted from their consumption of fermented milk products. It was believed that, when consumed, the fermenting bacillus (Lactobacillus) positively influenced the microflora of the colon, decreasing toxic microbial activities.
This intestinal microflora constitutes a metabolically active microbial environment, dominated by a relatively low diversity of genera, which in the gut of healthy individuals, exist as part of a relatively stable community.
Based on the guidelines of the WHO and FAO (FAO/WHO 2002) and the ILSI Europe workgroup on probiotics, probiotics can be defined as defined as:
"living micro-organisms, which, when ingested or locally applied in sufficient numbers confer one or more
specifically demonstrated functional or health benefits on the consumer beyond basic nutrition".
Among the microbes in the human intestinal tract are the Gram-positive lactic acid-producing genera Lactobacillus and Bifidobacterium. Most probiotics are from the Lactobacillus and the Bifidobacterium genera and have been selected for their ability to survive gastric transit and to adhere to intestinal epithelial cells.
Such strains can transiently colonise the gut by integrating into existing microflora and are believed to confer certain health benefits to consumers. In recent years the consumption of 'probiotics' has markedly increased.
The gut is not the only part of the human body to harbor microorganisms. Human skin has a resident, transient and temporary resident microflora. The resident micro-organisms are in a dynamic equilibrium with the host tissue and the microflora may be considered an integral component of the normal human skin. The great majority of these microorganisms are gram-positive and reside on the skin surface and in the follicles.
The host has a variety of structures, molecules and mechanisms which restrict the transient and temporary residents as well as controlling the population and dominance of the resident group. These include local skin anatomy, hydration, nutrients and inhibitors of various types. The resident microflora is beneficial in occupying a niche and denying its access to transients, which may be
harmful and infectious. Also, the residents are important in modifying the immune system.
EP 110550 proposes using probiotics for regulating the skin microflora. These may be applied directly to the skin in the form of lotions or shampoos.
WO 02/028402A1 discloses the use of probiotic lactic acid bacteria for balancing the skin's immune function under stress conditions (e.g. UV radiation) and reducing the tendency of skin to develop allergic reactions under such conditions. The carrier system for the probiotics is a food, a pharmaceutical product or a cosmetic product for oral or topical application.
WO 06/000992A1 discloses a cosmetic composition useful for preventing and/or treating sensitive and/or dry skin by treatment with probiotic micro-organisms combined with at least one divalent inorganic cation.
WO 05/089560A1 discloses water and milk based products containing probiotic microorganisms which are stable upon storage at 10°c and which are free from carbohydrate metabolites. The products are intended for ingestion where they benefit the gut microflora.
WO2005080539 discloses a process for the preparation of a detergent for cleaning fabrics whereby probiotics are introduced into the production process. These microbes then
generate enzymes and other actives that remove stains, such that the environmental impact of the detergent is reduced following the cleaning process.
None of the prior art suggests the use of probiotic particles in fabric treatment compositions, such as fabric cleaning products, where particles of probiotic microorganisms may be deposited onto a fabric carrier during a laundry process, such as a wash process, by means of a deposition aid.
Brief Description of the Invention
We have now determined that probiotic particles may be incorporated into fabric treatment compositions and delivered onto fabrics from laundry applications. Upon close contact with the skin, it is believed that these probiotic particles can be transferred from the fabric onto the skin, potentially conferring benefits as outlined above.
Definition of the Invention
In a first aspect the present invention there is provided a fabric treatment composition for use in a laundering process which comprises:
a) a surfactant selected from the group consisting of anionic surfactant, nonionic surfactant, cationic surfactant and mixtures thereof,
b) a probiotic particle, and
c) a deposition aid.
In a second aspect the present invention there is provided a laundering process of depositing probiotic particles on a fabric article comprising the step of treating a fabric article with a laundering composition according to the first aspect of the present invention.
Detailed Description of the Invention
The Probiotic Particle
For the purposes of this patent, the probiotics used herein are generally defined according to genus and species, and may also include the strain. Common abbreviations may be used, for example, Bifidobacterium lactis Bb-12, which may be abbreviated to B. lactis Bb-12 and Bifidobacterium bifidus Bb-12, which may be abbreviated to B. bifidum Bb-12.
The probiotic micro-organism particles can be used in the viable (live) form, in an inactivated form or in a dead form. The microorganisms can be at any stage of their life cycle (e.g. spore or vegetative cell state), in the presence or absence of materials that either encourage metabolism or keep metabolism static until required.
The colony forming unit (cfu) known in the art refers to the number of bacterial cells as measured by a microbiological count on an agar plate.
The probiotics are typically included in compositions of the
invention at levels of from 0.003 to 0.5 wt %, preferably
from 0.005 to 0.05 wt %, most preferably from 0.005 to 0.025
wt % by weight of the total composition.
Generally suitable probiotics for use in the present invention are chosen, in particular, from ascomycetes such as Saccharomyces, Yarrowia, Kluyveromyces, Torulaspora, Schizosaccharomyces pombe, Debaromyces, Candida, Pichia, Aspergillus and Penicillium, bacteria of the genus Bifidobacterium, Bacteroides, Fusobacterium, Melissococcus, Propioibacterium, Entexococcus, Lactococcus, Staphylococcus, Peptostrepococcus, Bacillus, Pediococcus, Micrococcus, Leuconostoc, Weissella, Aerococcus, Oenococcus and Lactobacillus and mixtures thereof.
More specific examples of probiotic microorganisms suitable for use in the present invention are Bifidobacterium adolescentis, Bifidobacterium bifidum, Bifidobacterium infantis, Bifidobacterium lactis, Bifidobacterium longum, Lactobacillus acidophilus, Lactobacillus alimentarius, Lactobacillus casei subsp. Casei, Lactobacillus casei Shirota, Lactobacillus paracasein Lactobacillus curvatus, Lactobacillus delbruckii subsp. Lactis, Lactobacillus gasseri, Lactobacillus johnsonii, Lactobacillus reuteri, Lactobacillus rhamnosus (Lactobacillus GG) , Lactobacillus sake, Lactococcus lactis, Streptococcus thermophilus, Straphylococcus carnosus and Staphylococcus xylosus, and mixtures thereof.
The preferred species are Lactobacillus johnsonii, Lactobacillus paracaseir Bifidobacterium adolescentis, Bifidobacterium longum and Bifidobacterium lactis NCC 2818 (also entitled (fib 12) (ATCC27536)) respectively deposited according to the Treaty of Budapest with the Pasteur Institute (28 rue du Docteur Roux, F-75024 Paris Cedex 15) on 30/06/92, 12/01/99, 15/04/99 and 10/06/2005 under the following designations: CNCM 1-1225, CNCM 1-2116, CNCM I-2168, CNCM 1-2170 and CNCM 1-3446, and the genus Bifidobacterium longum (BB536) . The Bifidobacterium lactis (CNCM 1-3446) strain can be obtained from Hansen (Chr. Hansen A/S, 10-12 Boege Alle, P.O. Box 407, DK-297D Hoersholm, Denmark).
The micro-organisms must be capable of surviving the pH conditions (typically pH 5-12) in the laundry compositions of the invention and have good resistance to ambient temperature fluctuations (including freeze-thawing temperatures) experienced by the compositions on storage. For the purposes of this application, "freeze-thawing" temperatures mean those temperatures typically experienced during storage, in both domestic and commercial environments, where the temperature may drop (typically during the night) to less than 5°C and then rise during the day to, for example, above 20°C. Such fluctuations are commonplace in colder climates and during the winter season. In warm climates, the probiotics should be resistant to higher ambient temperatures and typical fluctuations therein, for example from 20 to 40°C.
According to the invention the probiotic biomass can be frozen, dry powder, or wet (for example when separated from a fermented medium). The biomass incorporation into formulations can be achieved by post dosing after the formulation has been structured, by co-blending with one of the components, such as the oil phase, or by dispersing in the water phase before the active materials are added. The biomass can be in a granulated form with protective waxes before addition to the compositions in particular for detergent powder compositions.
Prebiotics are substances that selectively stimulate the growth and/or activity of one or more bacteria. Most potential prebiotics are sugars (mono- and di- saccharides) and carbohydrates (such as oligosaccharides), but other types of prebiotics are also known.
Excessive growth of the probiotics in the composition of the invention itself is not desirable because this can cause degradation of product properties. It is well known in the art to use biocides at low concentrations to keep microbial activity static. This inhibitory effect on microbial growth can be removed upon product dilution. Examples of suitable biocides for use in the present invention include Proxel (l,2-benzisothiazolin-3-one), available from, for example, Univar, Avecia and Uniqema; and Kathon CG (Methylchloroisothiazolinone and Methylisothiazolinone), available from Rhom and Haas.
It is further known that in laundry detergent compositions, the high concentration of surfactants as well as the high pH conditions act to inhibit microbial growth.
The Deposition Aid
Deposition of micro-organisms from laundry formulations of the invention onto a substrate may be achieved by any suitable route.
For example, by filtration, in which the particle size of the probiotic particles is such that the particles are trapped between the fibres of the fabric. The filtration mechanism requires particles or clusters of particles of a size comparable with the inter-yarn pore size.
The particle size is typically in the 1 to 30 micron range. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around 5 to 15 microns are preferred as they tend to be invisible to the eye and exhibit good deposition by filtration onto fabrics.
Deposition of micro-organisms from laundry formulations of the invention may also be achieved or enhanced over and above the delivery by filtration method, by polymer aided deposition.
Polymers suitable for the deposition of particles are disclosed in WO9709406 in which high MW polyethylene oxides (PEO) are used to deposit clay particles in the main wash;
EP0299575B1 and WO9527037, where high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol and poly ethylene imin.es are used to deposit clay particles in the main wash; and EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
WO 01/07546 Al discloses suitable rinse stage polymeric deposition aids for emulsion droplets including cationic guar polymers, cationic polyacrylamides, cationic potato starch, and cationic cellulose derivates.
Suitable examples of cationic polymers include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose) and cationic polyacrylamides such as PCG (ex Allied Colloids). Low charge density cationic polymeric aids are preferred where the composition of the invention is a detergent containing anionic surfactants. Suitable low charge density cationics include the modified potato starch Softgel BDA and. Softgel BDA CS range (ex Avebe) .
Suitable non-ionic deposition aids include high molecular weight PEO WSRN 750 (ex Union Carbide).
The particle size range of the probiotic for polymer aided deposition is preferably from 0.5 to 30 microns and more preferably from 1 to 20 microns.
A preferred approach for the deposition of probiotic particles, particularly for probiotic deposition from a main wash laundry application, is targeted polymeric deposition using the polysaccharide conjugate technology as disclosed in W099/36469, WO2004/056890A1, WO2005/21186A1, where a water-soluble or water-dispersible polysaccharide conjugate comprising a polymeric backbone and a benefit agent group attached to the polymeric backbone by a hydrolytically stable bond is used to deposit the benefit agent onto a fabric during a main wash process. Similarly, US6773811B2, which describes a particle with a cellulosic polysaccharide attached thereto (cellulose mono acetate (CMA)), and EP1117756B1, which claims beta 1-4 linked polysaccharides (LEG, xyloglucan etc) with a number of attached benefit agents. In the context of the present invention, the probiotic particle may be chemically bound to such a polysaccharide backbone via a hydrolytically stable bond.
The polysaccharide conjugate approach for use in the main wash has the advantage of targeting the substrate such that only the polymer-attached probiotic microorganisms become deposited onto the fabric and not the unwanted oily soil particles.
The preferred biomass particle size range for the polysaccharide conjugate approach is from 1 to 15 microns, preferably from 1 to 5 microns. This approach necessitates the deposition of a nanometer size of PVAC polymer shell on the probiotic to form a chemical bond between the particle and the polymer.
Another class of deposition aid polymers are phthalate-containing polymers. These polymers have the advantage that they are substantive to polyester type materials. They are based on polymers derivable from dicarboxylic acids and polyols, particularly a phthalate containing polymer, more preferably a polymer comprising units derived from (poly)ethylene glycol (PEG) and (poly)ethylene terephthalate (PET) or polyoxyethylene terephthalate (POET). Most preferably the polymer is a selected from the group comprising PET/POET, PEG/POET, PET/PEG and phthalate/glycerol/ethylene glycol polymers.
Materials of this type are widely available to the laundry formulator as they are commonly used as soil-release polymers.
Any polymeric soil release agent known to those skilled in the art can be employed in compositions according to the invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This is commonly done to enable stains occurring subsequent to treatment with the soil release agent to be more easily removed in later washing procedures.
The polymeric deposition aids useful herein especially include those soil release agents having one or more
nonionic hydrophilic components comprising oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene segments, and one or more hydrophobic components comprising terephthalate segments. Typically, oxyalkylene segments of these deposition aids will have a degree of polymerization of from 1 to about 400, although higher levels can be used, preferably from 100 to about 350, more preferably from 200 to about 300.
One type of preferred deposition aid is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate. The preferred molecular weight of this class of polymeric deposition aid agent is in the range of from about 5kD to about 55kD.
Another preferred polymeric deposition aid is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyethylene glycol of average molecular weight 0.2kD-40kD. Examples of this class of polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). Examples of related polymers can be found in US 4702857.
Another preferred polymeric deposition aid is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in US 4968451. Other suitable polymeric
soil release agents include the terephthalate polyesters of US 4711730, the anionic end-capped oligomeric esters of US 4721580, and the block polyester oligomeric compounds of US 4702857.
Preferred polymeric deposition aids also include the soil release agents of US 4877896 which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
Still another preferred deposition aid is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units,, oxyethyleneoxy and oxy-1,2-propylene units, The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred deposition aid of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
The polysaccharide and PET/POET conjugate approaches may be combined. If PET/POET polymers are used in the conjugate approach the probiotic particles become more substantive to polyester and polycotton.
Encapsulated Probiotic Particles
The probiotic particles can be protected in the compositions by any suitable encapsulation technique. One preferred approach involves coating the probiotic particles with a polymer in which the water solubility of the polymeric film can be adjusted depending on the level of surfactant as described in US 20040065578 (A1) and WO2006007911 (Al) both to Unilever. This allows dissolution of the film under dilution in the wash or rinse such that bare probiotics are deposited on the substrate.
Examples of such polymers comprise hydrophobically-modified polyols where solubility can be modified by adjusting the level of surfactant absorbed upon its surface. This enables a delivery system to be designed in which release of an active agent encapsulated by such a film may be triggered by adjusting, in particular lowering, the level of surfactant absorbed upon the surface of the film.
It has been further found that the level of surfactant absorbed upon the surface of a polymeric film comprising a hydrophobically-modified polyol can be lowered by dilution of the surfactant concentration in the surrounding environment and/or by increasing the temperature. This enables control over the release of bare probiotic particles, from an encapsulated form in the composition, in the wash or in the rinse depending on the type of polymer film.
It has been found that by hydrophobically modifying the structure of a water soluble polymeric film, such as a PVOH film, with a modifying group, e.g. with one or more acetal groups, the film remains substantially intact in the presence of an external surfactant, e.g. during the wash cycle of a laundry operation, and disintegrates when the concentration of the surfactant reduces sufficiently, e.g. during the rinse cycle of the laundry operation.
The polymeric film generally comprises a polymeric backbone derived from a polymer which is water soluble.
The polymeric film comprises a polymeric backbone derived from a polymer which is preferably water dissolvable or dispersible at a level of 0.3 g.dm-3 or greater, more preferably at a level of 0.5 g.dm"3 or greater, at 20°C.
The polymeric film generally comprises a hydrophobically-modified polyol, in particular a hydrophobically-modified PVOH.
The polymeric film for use in the present invention is a material whose solubility in water is dependent upon the concentration of the surfactant present. In general, the lower the concentration of surfactant, the greater the solubility of the polymer film and the faster it breaks down.
Without wishing to be bound by theory, it is believed that hydrophobic elements within the polymeric film interact with the surfactant to form a gelled network which renders the
surfactant-bound film insoluble; however, the interactions between the polymeric film and the surfactant break down on dilution and/or heating of the delivery system, thereby enabling the polymeric film to dissolve and the probiotic agent to be released.
A preferred method according to the invention of releasing the probiotic agent from the encapsulate, involves heating of the delivery system. Such a method is of particular benefit in the delivery of active agents, in particular cosmetic actives and pharmaceutical actives, to the human body. In such applications, the temperature increase on contact of the delivery system with the body may trigger the release of the probiotic particle.
In general, the probiotic agent is released from the polymer film encapsulate quicker when suspended in demineralised water than when suspended in an aqueous solution of the surfactant present in the delivery system. In preferred embodiments, the time taken for the release of the probiotic agent from the polymer film is considerably less in water than in an aqueous solution of the surfactant present in the delivery system. At 20°C, the time taken in water may be less than a third, in particular, less than one seventh, of the time taken in an aqueous solution of surfactant concentration 5 g.dm-3.
When a polyol is derivatised using the derivatising group, a hydrophobically-modified polyol is obtained. The polyol is hydrophobically-modified by the derivatising group.
Preferred derivatising groups include those based on parent groups selected from acetals, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes, aromatics. Especially preferred parent groups are aldehydes such as butyraldehyde, octyl aldehyde, dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral, and 4-aminobutyraldehyde dimethyl acetal, although it will be readily apparent to the person skilled in the art that other suitable parent groups having the requisite ClogP are also suitable for use in the polymeric film of the invention.
Particularly preferred derivatising groups are acetals, which may derived from aldehydes or their functional equivalents (e.g. dimethyl- or diethylacetals).
Preferred hydrophobically-modified polyols are hydrophobically-modified by acetal groups, in particular those having from 4 to 22 carbon atoms, and especially aromatic groups such as benzaldehyde derivatives. Hydrophobic modification using aromatic aldehydes has been found to deliver polymer films having superior interactions with surfactants, leading to better performing delivery systems. Substituted benzaldehydes, such as 2-benzaldehyde sulphonic acid and its salts may also be used.
Additional modifying groups may be present on the polymer backbone. For instance, amines may preferably be included as a modifying group since this makes the polymer more soluble in response to, for instance, the change in pH and/or ionic strength.
The derivatising group may comprise a hydrocarbyl chain. Such a hydrocarbyl chain may be optionally substituted with one or more hetero-atoms, such as oxygen or nitrogen.
The hydrocarbyl chain length of the derivatising group attached to the polymeric backbone is preferably from 3 to 22, more preferably from 4 to 18, even more preferably from 4 to 15, most preferably from 4 to 10, e.g. from 4 to 8. Hydrocarbyl chain lengths shorter than 3 are undesirable as, in use, the gel-like structure formed at the interface of the polymeric film and the surfactant will typically be too weak and will allow the polymer film to rupture too easily.
Hydrocarbyl chain lengths greater than 22 are undesirable as the parent material from which the derivatising group is obtained reacts poorly or not at all with the polymeric backbone.
The hydrocarbyl chain length of the parent material from which the derivatising group is obtained is preferably from 3 to 22, more preferably from 4 to 18.
In this context, the number of carbons in the hydrocarbyl group includes any carbon within the chain attached to any other functional group within the derivatising material. For instance, butyraldehyde has a hydrocarbyl chain length of 4.
The derivatising material is preferably present in the polymer at a level of from 0.1 to 40% by weight, based on
the total weight of the polymer, more preferably 2 to 30%, most preferably 5 to 15%, e.g. 8 to 12%.
Where the polymeric backbone is based on PVOH, the derivatising material is preferably present at a level such that the number ratio of the derivative groups to the free hydroxyl pairs on the backbone is from 1:3 to 1:30, more preferably 1:4 to 1:20, most preferably 1:7 to 1:15, e.g. 1:8 to 1:13.
Below a ratio of 1:30, the solubility of the polymer film tends to be too great, even in the presence of surfactant. Above a ratio of 1:3, the solubility of the polymer film tends to be too low, even in the absence of surfactant.
Preferred polymers from which the backbone of the derivatised polymeric film of the invention is formed include water-soluble resins such as PVOH, cellulose ethers, polyethylene oxide (hereinafter referred to as "PEO"), starch, polyvinylpyrrolidone (hereinafter referred to as "PVP"), polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethylcellulose, methylcellulose, polyethylene glycols, carboxymethylcellulose, polyacrylic acid salts, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethyl hydroxyethylcellulose, ethyl methylcellulose, hydroxyethyl methylcellulose. Water-soluble, PVOH film-forming resins are particularly preferred.
Generally, preferred water-soluble, PVOH-based film-forming polymers should have relatively low average molecular weight and high levels of hydrolysis. PVOH-based polymers preferred for use herein have an average molecular weight of from 1,000 to 300,000, preferably from 2,000 to 100,000, most preferably from 2,000 to 75,000. The level of hydrolysis is defined as the percent completion of the reaction where acetate groups on the resin are substituted with hydroxyl, -OH, groups (PVOH being derived from poly(vinyl acetate) by hydrolysis). A hydrolysis range of from 60-99% is preferred, while a more preferred range of hydrolysis is from about 88-99%. As used in this application, the term "PVOH" includes poly(vinyl acetate) compounds with levels of hydrolysis disclosed herein.
A particularly preferred polymer/polyol for use in the present invention is represented by the formula:
wherein the average number ratio of z to x is within the range of from 1:200 to 1:6, more preferably from 1:100 to 1:8, most preferably from 1:50 to 1:12, e.g. 1:30 to 1:14, y is the residual acetate remaining from the hydrolysis of the parent compound, which is preferably in the range of from 1-20 %, more preferably 1-10 %, most preferably 1-5 % and R is
an alkyl, alkenyl, or aryl group having from 3 to 22 carbon atoms. More preferably R is an alkyl group having from 3 to 6 carbon atoms or an aryl group.
Structural strength can be imparted to the polymeric film as described in the aforementioned patents US 20040065578 (Al) and WO2006007911 (Al) both to Unilever.
PVP films exhibit excellent adhesion to a wide variety of surfaces, including glass, metals, and plastics. Unmodified films of polyvinylpyrrolidone are hygroscopic in character. Dry polyvinylpyrrolidone film has a density of 1.25g.cm-3 and a refractive index of 1.53. Tackiness at higher humidities may be minimized by incorporating compatible, water-insensitive modifiers into the polyvinylpyrrolidone film, such as 10% of an aryl-sulfonamide-formaldehyde resin.
Suitable plasticisers for PVP-based films may be chosen from one or more of: phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate; polyols, e.g. glycerol, sorbitol, diethylene glycol diperlargonate, polyethylene glycol di-2-ethylhexanoate, dibutyl tartrate; polyol esters, e.g. hydroxy containing polycaprolactones, hydroxy containing poly-L-lactide; lower phthalates, e.g. dimethyl phthalate, diethyl phthalate, dibutyl pthalate; and sulfonamides, e.g. toluene sulfonamide, N-ethyltoluene sulfonamide.
Preferred water-soluble films may also be prepared from PEO resins by standard moulding techniques such as calendering, casting, extrusion, and other conventional techniques. The
polyethylene oxide films may be clear or opaque, and are inherently flexible, tough, and resistant to most oils and greases. These polyethylene oxide resin films provide better solubility than other water-soluble plastics without sacrificing strength or toughness. The excellent ability to lay flat, stiffness, and sealability of water-soluble polyethylene oxide films make for good machine handling characteristics.
Suitable plasticisers for PEO-based films may be selected from one or more of: phosphates, e.g. tris (2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate; polyols, e.g. glycerol, sorbitol, diethylene glycol diperlargonate, polyethylene glycol di-2-ethylhexanoate, dibutyl tartrate; lower phthalates, e.g. dimethyl phthalate, diethyl phthalate, dibutyl pthalate; and sulphonamides, e.g. toluene sulphonamide, N-ethyltoluene sulphonamide.
A trigger source in addition to absorbed surfactant depletion may also be employed. Suitable examples include those described in WO02/102956 (Al) such as sources/materials for causing changes in pH, temperature, electrolytic conditions, light, time or molecular structure. Such triggers may be used in combination with each others such as shear triggered release where the film breaks under body movement to expose bare probiotic agent to the skin.
Preparation of Encapsulated Probiotics
A 10wt% solution of PVOH in water was prepared by placing lOOg PVOH (Mowiol 20-98, trade name, ex Kuraray Specialities) and 900g demineralised water into a flask and heating to 70°C. To this, 10ml of hydrochloric acid (36% aqueous solution) was added to catalyse the reaction and then butyraldehyde was added. The mixture was then stirred at 70°C for 5 hours under an inert atmosphere, after which time the heating was stopped and agitation continued for a further 20 hours at room temperature. The reaction mixture was then brought to a pH of 7 using a sodium hydroxide solution.
The resulting solution was precipitated into acetone to yield the acetalised PVOH polymer and washed repeatedly with acetone (500ml) and then water (50ml). It was then dried under vacuum at 70°C overnight to yield a white polymer.
The extent of acetalisation was analysed to be 10.4%. The poly(vinyl alcohol)-butyral (PVA-BA) resin prepared above was diluted to a 7% m/m. solution with demineralized water into which 5mg of probiotic powder was suspended by agitation (the polymer-probiotic stock solution).
The stock solution was added drop wise from a nozzle container to the detergent composition specified in Table 1 while agitating the liquid using a three-blade stirrer. The presence of surfactant led to the precipitation of a polymeric film surrounding the probiotic particles. The
probiotic aggregate size of the encaps could be controlled by the intensity of agitation and nozzle size and flow.
For detergent powder applications the stock solution can be sprayed onto a bed of the base powder and allowed to dry.
The Fabric Treatment Compositions
The fabric treatment composition of the invention is suitable for use in a laundry process. Examples include a soaking product and a main-wash product. The compositions of the present invention are preferably laundry compositions, especially main wash (fabric washing) compositions.
The compositions of the invention may be in any physical form e.g. a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid, spray, stick, impregnated substrates, foam or mousse. In particular the compositions may be liquid, powder or tablet laundry compositions.
The liquid products of the invention may have pH ranging from 5 to 12. This pH range preferably remains stable over the shelf life of the product.
The active ingredient in the compositions is preferably a surface active agent. More than one active ingredient may be included. For some applications a mixture of active ingredients may be used, for example, the main wash compositions may also include a fabric softening agent.
The detergent composition of the invention may contain surface-active compounds (surfactants) chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
The composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight.
It is also possible to include certain mono-alkyl cationic surfactants which can be used in main-wash compositions for fabrics. Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+ X" wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Rl is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the
detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The compositions of the invention may contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of from C8 to C15. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%, by weight of the total composition.
The compositions of the invention may contain other anionic surfactants in amounts additional to the percentages quoted above. Suitable anionic surfactants are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly C8 to Cl5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
The detergent compositions of the invention may also contain non-ionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8 to C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the ClO to C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%, by weight of the total composition.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2-60%, preferably 15-40% most preferably 25-35%, by weight of the composition.
Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
The compositions of the invention, when used as main wash fabric washing compositions, will generally also contain one or more detergency builders. The total amount of detergency builder in the compositions will typically range from 5 to 80 wt%, preferably from 10 to 60 wt%, by weight of the compositions.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst) . Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na20. A1203. 0.8-6 Si02
These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency
builders are described, for example, in GB 1 429 143 (Procter &. Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof,
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite p (zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium weight ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium weight ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and
trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and
succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Compositions according to the invention may also suitably contain a bleach system. Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt%, preferably from 0.5 to 25 wt%. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 0.1 to 8 wt%, preferably from 0.5 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors. Especially preferred bleach precursors suitable for use in the present invention are N,N,N',N',-tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever), and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
The bleach system can be either supplemented with or replaced by a peroxyacid, examples of such peracids can be found in US 4 686 063 and US 5 397 501 (Unilever). A preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289. A particularly preferred example is phthalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1 - 12%, preferably 0.5 - 10%.
A bleach stabiliser (transition metal sequestrant) may also be present. Suitable bleach stabilisers include
ethylenediamine tetra-acetate (EDTA), the polyphosphonates such as Dequest (Trade Mark) and non-pliosphate stabilisers such as EDDS (ethylene diamine di-succinic acid). These bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A ,EP 458 398A and EP 509 787A (Unilever).
The compositions according to the invention may also contain one or more enzyme(s).
Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention. Examples of suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. Subtilis B. licheniformis, such as the commercially available
subtilisins Maxatase (Trade Mark), as supplied by Genencor International N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novozymes Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novozymes Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark). The preparation of these and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizer of U.S.A.).
Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used.
The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scope of the invention.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate. One
preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
The detergent composition when diluted in the wash liquor (during a typical wash cycle) will typically give a pH of the wash liquor from 7 to 10.5 for a main wash detergent.
Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or post-dosing those ingredients unsuitable for processing via the slurry. The skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/litre, more preferably at least 500 g/litre. Especially preferred compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components
in the requisite concentrations. Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent.
Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; soil release polymers; inorganic salts such as sodium sulphate; or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; fluorescers, photobleaches such as singlet oxygen and radical photobleach and decoupling polymers. This list is not intended to be exhaustive.
The fabric treatment compositions of the invention can also contain adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, and dyestuffs. The amounts of these various adjuvants are those conventionally used in the field under consideration and are, for example, from 0.01 to 20 % of the total weight of the composition. Depending on their nature, these adjuvants can be introduced into the fatty phase and/or into the aqueous phase.
When used in laundering, the substrate may be any substrate onto which it is desirable to deposit probiotic particles and which is subjected to treatment such as a washing or rinsing process.
In particular, the substrate may be a textile fabric.
The treatment of the substrate with the composition of the invention can be made by any suitable method such as washing, soaking or rinsing of the substrate but also by direct application such as spraying, rubbing, spotting, smearing, etc.
The treatment may involve contacting the substrate with an aqueous medium comprising the material of the invention.
The treatment may be provided as a spray composition e.g., for domestic (or industrial) application to fabric in a treatment separate from a conventional domestic laundering process. Suitable spray dispensing devices are disclosed in WO 96/15310 (Procter & Gamble) and are incorporated herein by reference. Alternatively, the composition may be applied through the iron's water tank, a separate reservoir or a spray cartridge in an iron, as described in EP1201816 and WO 99/27176.
Embodiments of the invention are now illustrated with reference to the following non-limiting examples. Unless stated otherwise, all proportions are given in weight percent by weight of the total composition except for probiotic ingredients which are in mg.
Table 1 - Composition of fabric washing liquids containing probiotic.
Example 1 2 3 4
Lactobacillus sp. (powder) (mg) 5.1 5.1
Lactobocillus Acidophilus and Bifidobacterium Bifidum* 5.1 5.1
Polymeric deposition aid
Jaguar C13-S 0.30
Softgel BDA 1.0
ZELCON! 5126 0.3
Polyox WSR N-750 0.3
Nonionic 7E0, branched (100%) 11.70 7.00 11.70 7.00
Fatty acid 5908 (100%) 2.65 1.5 2.65 1.5
SLES 3EO (70%) 16.71 10 16.71 10
Cationic Praepagen HY 2.30 1 2.30 1
NaCl (26% solution) 0.96 4.61 0.96 4.61
NaOH solution (50%) 1.40 0.74 1.40 0.74
1,2-benzisothiazolin-3-one (20%) (Proxel) 0.05 0.08 0.05 0.08
Propylene Glycol (100 %) 3.00 1.00 3.00 1.00
Boric acid (100%) 0.50 0.5 0.50 0.5
Perfume 0.5 0.35 0.5 0.35
Water to 100 to 100 to 100 To 100
Jaguar and Softgel are cationic guar and potato starch polymers
ZELCON is a nonionic hydrophilic polyester copolymer with repeating
segments of ethylene terephthalate units.
POLYOX WSR N-750 (ex Amerchol) is a nonionic deposition aid based on PEG
with a MW of about 7M.
Probiotic capsules (ex Boots Pharmacy) contain macrocrystalline cellulose, hydroxypropylmethylcellulose, Magnesium stearate,
Lactobacillus Acidophilus 4.5mg, cfu = 2.2xl08anci
Bifidobacterium Bifidum 0.6mg, cfu = 7.5xl07
1. A fabric treatment composition for use in a laundering
process which comprises:
a) a surfactant selected from the group consisting of anionic surfactant, nonionic surfactant, cationic surfactant and mixtures thereof/
b) a probiotic particle, and
c) a deposition aid.
2. A fabric treatment composition according to claim 1, wherein the probiotic particle is selected from the genera Lactobacillus, Bifidobacterium, Streptococcus, Lactococcus, Entercoccus and mixtvxes thereof.
3. A fabric treatment composition according to claim 2, wherein the probiotic particle is selected from Lactobacillus johnsonii, Lactobacillus paracasei, Bifidobacterium adolescentis, Bifidobacterium longum and Bifidobacterium lactis NCC 2818 (also entitled (Bb 12) (ATCC27536)).
4. A fabric treatment composition according to any-preceding claim, wherein the probiotic particle is present in an amount of from 0.003 to 0.5 wt %, preferably from 0.005 to 0.1 wt %, most preferably from 0.005 to 0.05 wt % by weight of the total composition.
5. A fabric treatment composition according to any preceding claim, wherein the probiotic is in a form selected from viable (live) form, inactivated form and dead form.
6. A fabric treatment composition according to any preceding claim, wherein the probiotic particle is in a spore or vegetative cell state.
7. A fabric treatment composition according to any preceding claim, wherein the deposition aid is selected from polyethylene oxide (PEG), polyethylene imine
(PEI), poly (acrylate), poly (acrylamide), cationic starches, polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymers and mixtures thereof.
8. A fabric treatment composition according to any one of claims 1 to 6, wherein the deposition aid is a polysaccharide or polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) conjugate chemically bond to the surface of the particles.
9. A fabric treatment composition according to any one of claims 1 to 6, wherein the deposition aid is a low charge density cationic polymer.
10. A fabric treatment composition according to claim 9, wherein the low charge density cationic polymer is a modified potato starch.
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11. A fabric treatment composition according to any preceding claim, wherein the probiotic particle is encapsulated.
12. A fabric treatment composition according to claim 11, wherein the probiotic particle is coated with a hydrophobically-modified polyol.
13. A fabric treatment composition according to any preceding claim, which is a fabric washing composition
14. A laundering process of depositing probiotic particles on a fabric article comprising the step of treating a fabric article with a fabric treatment composition as defined in any preceding claim.
|Indian Patent Application Number||597/MUMNP/2010|
|PG Journal Number||06/2017|
|Date of Filing||25-Mar-2010|
|Name of Patentee||HINDUSTAN UNILEVER LIMITED|
|Applicant Address||UNILEVER HOUSE, B.D. SAWANT MARG, CHAKALA, ANDHERI EAST, MUMBAI-400 099 MAHARASHTRA, INDIA|
|PCT International Classification Number||C11D 3/38,A61Q 19/00 ,C11D 3/386|
|PCT International Application Number||PCT/EP2008/062242|
|PCT International Filing date||2008-09-15|