Indian Patents. 211632:PACKAGED LIQUID DETERGENT COMPOSITION

Title of Invention	PACKAGED LIQUID DETERGENT COMPOSITION
Abstract	This invantion relates to the field of liquid detergents, in particular to a packaged transparent liquid detergent composition. A transparent liquid detergent comprising an encapsulated enzyme, enclosed within a translucent/transparent container.

Full Text	FORM -2 THE PATENTS ACT, 1970 (39 OF 1970) COMPLETE SPECIFICATION (See Section 10; rule 13) 1. TITLE OF INVENTION PACKAGED LIQUID DETERGENT COMPOSITION 2. HINDUSTAN LEVER LIMITED, Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai - 400 020, Maharashtra, India, a company incorporated under the Companies Act, 1913 The following specification particularly describes the nature of the invention and the manner in which it is to be performed. DETERGENT COMPOSITION TECHNICAL FIELD This invention relates to the field of liquid detergents, in particular to a packaged, transparent liquid detergent composition. BACKGROUND Transparent liquid detergent compositions are known in the art. GB-A-1,303,810 discloses clear liquid detergent compositions with a transparent aqueous or non-aqueous base comprising particles that are visually distinct and , have a diameter size of at least 0.5 mm. US-A-3,812,042 describes a clear . liquid detergent composition in a transparent, plastic container. US-A-5,427,708 , discloses a transparent liquid soap in a transparent container. WO 97/26315 I (Colgate) discloses transparent containers with specific chromaticity defined by x and y values. Specific dyes are used in the liquids to match the container. The reference does not disclose encapsulated enzymes or their effectiveness in transparent containers and liquids relative to non-encapsulated enzymes. When transparent liquid detergents are packaged in transparent containers, sensitive ingredients in the detergent composition may become affected by UV radiation. For example, UV radiation may cause the discoloration of liquid detergent composition in transparent containers. DE-A-2034562 and DE-A-2034563 describe the use of nitroalkanols to overcome the bleaching of colored liquid detergent compositions. Liquid detergent compositions comprising enzymes are preferred for their improved the cleaning performance. We have found that the activity of enzymes may also become adversely affected by UV radiation when the transparent liquid is packaged in a transparent container. Therefore, it is an object of the present invention to provide a packaged detergent composition comprising a transparent container and a transparent enzymatic aqueous liquid detergent composition wherein the enzymes are protected from the adverse effects of UV radiation. Surprisingly, it is found that when enzymes are present in a transparent liquid detergent in a transparent . container the harmful effects from UV radiation on the enzymes can be reduced by encapsulating said enzymes. SUMMARY OF THE INVENTION The present invention provides a packaged liquid detergent composition comprising a transparent or translucent container having a transmittance of , 25% or greater at wavelength of 410-800 nm and a transparent or translucent enzymatic detergent composition having a transmittance of greater than 50% of light using 1 cm cuvette at wavelength of 410-800 nm which container and detergent composition are transmissive of UV-B radiation. A preferred embodiment of the invention provides a packaged liquid detergent composition comprising a transparent container and a transparent enzymatic detergent composition wherein the enzymes are encapsulated, wherein after 7 days of accelerated storage of 20 g of the liquid detergent comprising 1.5 wt. % of enzyme capsules in a transparent container (e.g., polyethylene), wherein the sample is stored at 37°C while being exposed to UV light (e.g., UV-B light), whereby the liquid sample is positioned at a distance of about 20 cm from the bottom of the bottle to the UV light source, the enzyme activity is enhanced (e.g., more than 40% remaining activity, preferably more than 50%, more preferably more than 60% remaining activity). Another embodiment of the invention provides a packaged liquid detergent composition comprising a transparent/translucent container and a transparent/translucent enzymatic detergent composition wherein the enzymes are encapsulated, wherein the liquid detergent is structured, preferably externally structured. I DETAILED DESCRIPTION OF THE INVENTION The presently claimed invention provides a packaged detergent composition comprising a transparent or translucent container and a transparent or translucent aqueous enzymatic detergent composition characterized in that said enzymes are encapsulated to protect said enzymes from the adverse effects of UV light. Preferably, the enzymes in said packaged detergent composition have i a remaining enzyme activity of more than 40%, more preferably more than 50% and most preferably more than 60% after storage of 4 weeks at 376C. f The Container The transparent container according to the present invention preferably has a transmittance of more than 25%, more preferably of more than 30%, even more preferably of more than 40%, even more preferably of more than 50% in the visible part of the spectrum (approx. 410-800 nanometers). Enzyme deactivation as a result of UV-damage may occur at very low transmissions of UV-B radiation through the container wall. Alternatively, transparency may be defined as absorbency being less than 0.6 or the transmittance greater than 25%, wherein % transmittance equals:: For purposes of the invention, as long as one wavelength in the visible light range has greater than 25% transmittance, it is considered to be transparent/translucent. The transparent container according to the present invention comprises (high density) polyethylene (PE), polypropylene (PP), polycarbonate (PC) and/or polyethylene terephthalate (PETE), but this should not be considered limiting in any way. 1 Polyethylene containers were used for UV stability tests in the present invention and had transparency of 8% at 310 nm, 17.5% at 400 nrn, 25% at 500 nm and 31% at 600 nm. The container of the present invention may be of any form or size suitable for storing and packaging liquids for house hold use. For example, the container may be any size but usually the container will have a maximal capacity of 0.05 to 15 I, preferably, 0.1 to 5 I, more preferably from 0.2 to 2.5 I. Preferably, the container is suitable for easy handling. For example the container may have a handle or a part with such dimensions to allow easy lifting or carrying the container with one hand. The container preferably has a means suitable for pouring the liquid detergent composition and a means for re-closing the container. The pouring means may be of any size or form but, preferably will be wide enough for convenient dosing the liquid detergent composition. The closing means may of any form or size but usually will be screwed or clicked on the container to close thecontainer. The closing means may be cap which can be detached from the container. Alternatively, the cap can still be attached to the container, whether the container is open or closed. The closing means may also be incorporated in the container. The container may have a suitable form for refilling. For example, the container may comprise a re-closable aperture of such a size and position which renders it suitable for convenient refilling. Accordingly, the container of the present invention also encompasses refill packages: those container forms suitable for packaging refills of liquid detergent compositions. These refill packages may be of any form and size but usually will be of flexible material without means for re-closing such as sachets or Tetrapak™ like containers. Liquid Detergent The liquid detergent according to the present invention, may be aqueous or non-aqueous. Aqueous liquids may be internally or externally structured. Preferably, the liquid detergent according to the present invention is externally structured. Externally structured liquids may comprise polymers such as gellan, xanthan, polyacrylate, algin, guar, rhamsan, carrageenan, carbopol™ and carbopol-like polymers and mixtures thereof. Preferably, Externally structured liquids may comprise polymers selected from the group consisting of gellan, kappa-carrageenan, xanthan or mixtures thereof. Externally structured liquids may also comprise clays, silicates or mixtures thereof as structuring agents. The compositions of the invention have at least 50% transmittance of light using a 1 centimeter cuvette at wavelength of 410-800 nm, preferably 570-690 nm, wherein the composition is essentially free of dyes. Alternatively, transparency of the composition may be measured as having an absorbency in the visible light wavelength (about 410 to 800 nm) of less than 0.3 which is in turn equivalent to at least 50% transmittance using cuvette and wavelength noted above. For purposes of the invention, as long as one wavelength in the visible light range has greater than 50% transmittance, it is considered to be transparent/translucent. With transparent liquid detergent according to the present invention is meant that, the liquid detergent has absorbency of less than 0.3 or transmittance of greater than 50% at 410-800 nm, where transmittance equals: Enzyme deactivation as a result of UV-damage may occur at very low transmissions of UV-B radiation. Detergent Active The compositions of the invention contain one or more surface active agents selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof. The preferred surfactant detergents for use in the present invention are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants. Anionic Surfactant Detergents Anionic surface active agents which may be used in the present invention are those surface, active-compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophilic group, i.e. water solubilizing group such as carboxylate, sulfonate or sulphate group or their corresponding acid form. The anionic surface active agents include the alkali metal (e.g. sodium and potassium) water soluble higher alkyl aryl * sulphonates, alkyl sulphonates, alkyl sulphates and the alkyl poly ether sulphates. They may also include fatty acids or fatty acid soaps. One of the preferred groups of anionic surface active agents are the alkali metal, ammonium or alkanolamine salts of higher alkyl aryl sulphonates and alkali metal, ammonium or alkanolamine salts of higher alkyl sulphates. Preferred higher alkyl sulphates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 10 to 22 carbon atoms and more preferably 12 to 18 carbon atoms. The alkyl group in the alkyl aryl sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms. A particularly preferred alkyl aryl sulfonate is the sodium, potassium or ethanolamine C10 to C16 benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate. The primary and secondary alkyl sulphates can be made by reacting long chain lalpha-olefins with sulphites or bisulphites, e.g. sodium bisulfite. The alkyl sulphates can also be made by reacting long chain normal paraffin hydrocarbons with sulphur dioxide and oxygen as describe in U.S. Patent Nos. 2,503,280, 2,507,088, 3,372,188 and 3,260,741 to obtain normal or secondary higher alkyl sulphates suitable for use as surfactant detergents. The alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfonates can be employed, although they are not as good with respect to biodegradability. The alkane, i.e. alkyl, substituent may be terminally sulfonated or may be joined, for example, to the 2-carbon atom of the chain, i.e. may be a secondary sulfonate. It is understood in the art that the substituent may be joined to any carbon on the alkyl chain. The higher alkyl sulfonates can be used as the alkali metal salts, such as sodium and potassium. The preferred salts are the sodium salts. The preferred alkyl sulfonates are the C10 to C18 primary normal alkyl sodium and potassium sulfonates, with the C10 to C15 primary normal alkyl sulfonate salt being more preferred. Mixtures of higher alkyl benzene sulfonates and higher alkyl sulphates can be used as well as mixtures of higher alkyl benzene sulfonates and higher alkyl polyether sulfates. The alkali metal or ethanolamine alkyl aryl sulfonate can be used in an amount of 0 to 70%, preferably 2 to 50% and more preferably 5 to 20% by weight. The alkali metal or ethanolamine alkylsulfate can be used in admixture with the alkylbenzene sulfonate in an amount of 0 to 70%, preferably 5 to 50%, more preferably 5 to 20% by weight. Also normal alkyl and branched chain alkyl sulfates (e.g., primary alky! sulfates) may be used as the anionic component. The higher alkyl polyethoxy sulfates used in accordance with the present invention can be normal or branched chain alkyl and contain lower alkoxy groups which can contain two or three carbon atoms. The norma! higher alkyl polyether sulfates are preferred in that they have a higher degree of biodegradability than the branched chain alkyl and the lower poly alkoxy groups are preferably ethoxy groups. The preferred higher alkyl polyethoxy sulfates used in accordance with the present invention are represented by the formula: R1-0(CH2CH20)p-S03M, where R1 is C8 to C2o alkyl, preferably C10 to Ci8 and more preferably C12 to C15; p is 2 to 8, preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal, such as sodium and potassium, or an ammonium cation. The sodium and potassium salts are preferred. A preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a triethoxy C12 to C15 alcohol sulfate having the formula: C12-15-0-(CH2CH2O)3-SO3Na Examples of suitable alkyl ethoxy sulfates that can be used in accordance with the present invention are C12-15 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C12 primary alkyl diethoxy sulfate, ammonium salt; C12 primary alkyl triethoxy sulfate, sodium salt; Ol5 primary alkyl tetraethoxy sulfate, sodium salt; mixed C14.15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyi pentaethoxy sulfate, sodium salt; and mixed C10-18 normal primary alkyl triethoxy sulfate, potassium salt. The normal alkyl ethoxy sulfates are readily biodegradable and are preferred. The alkyl poly-lower alkoxy sulfates can be used in mixtures with each other and/or in mixtures with the above discussed higher alkyl benzenesulfonates, or alkyl sulfates. The alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfate, in an amount of 0 to 70%, preferably 5 to 50% and more preferably 5 to 20% by weight of entire composition. Nonionic Surfactant Part of the surfactant composition, according to the subject invention, may be nonionic surfactant. Generally the nonionic surfactant, whether sugar surfactant or not, should comprise about 10% to 100%, preferably 20 to 50% of the total surfactant composition. Sugar or glycoside surfactants suitable for use in accordance with the present invention include discussed in the following patents: U.S. 5,573,707 to Cole et al., U.S. 5,562,848 to Wofford et al., U.S. 5,542,950 to Cole et al., WO 96/15305 to Cole et al., U.S. 5,529,122 to Thach, WO 95/33036 to Urfer et al., and DE 4,234,241 to Schmidt. Nonionic surfactants which may be used include polyhydroxy amides as discussed in U.S. Patent No. 5,312,954 to Letton et al. and aldobionamides such as disclosed in U.S. Patent No. 5,389,279 to Au et al. Another class of sugar based surfactants which can be used include N-alkoxy or N-aryloxy polyhydroxy fatty acid amides discussed in WO 95/07256 to Schiebel et al., WO 92/06071 to Connor et al., and WO 92/06160 to Collins et al. These references are incorporated by reference into the subject application. Yet another class of sugar based surfactants are sugar esters discussed in GB 2,061,313, GB 2,048,670, EP 20122 and U.S. Patent No. 4,259,202 to Tanaka et al. Besides the sugar surfactants, other nonionic surfactants are described below: As is well known, the nonionic surfactants are characterized by the presence of a hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide {hydrophilic in nature). Typical suitable nonionic surfactants are those disclosed in U.S. Patent Nos. 4,316,812 and 3,630,929. Usually, the nonionic surfactants are polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of nonionic surfactant is the alkoxylated alkanols wherein the alkanol is of 9 to 18 carbon . atoms and wherein the number of moles of alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the alkanol is a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 alkoxy groups per mole. Exemplary of such compounds are those wherein the alkanol is of 10 to 15 carbon atoms and which contain 5 to 9 ethylene oxide groups per mole, e.g. Neodol 25-9 and Neodol 23-6.5, which products are made by Shell Chemical \| Company, Inc. The former is a condensation product of a mixture of higher fatty \ alcohols averaging 12 to 15 carbon atoms, with about 9 moles of ethylene oxide \| and the latter is a corresponding mixture wherein the carbon atoms content of I the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols. Another subclass of alkoxylated surfactants which can be used contain a precise alkyl chain length rather than an alkyl chain distribution of the alkoxylated surfactants described above. Typically, these are referred to as narrow range alkoxylates. Examples of these include the Neodol-1(R) series of surfactants manufactured by Shell Chemical Company. Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac by BASF. The Plurafacs are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxy! group. Examples include C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide or mixtures of any of the above. Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol or Neodol trademark: Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol. In the compositions of this invention, preferred nonionic surfactants include the C12-C15 primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 6 to 9 moles, and the C9 to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide. Cationic Surfactants Many cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, incorporated by reference. Specific cationic surfactants which can be used as surfactants in the subject invention are described in detail in U.S. Patent No. 4,497,718. As with the nonionic and anionic surfactants, the compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants knowrrtnlhe art; Of course, the compositions may contain no cationic surfactants at all. If included, cationics may comprise 0-20%, preferably 1-10% by weight of the total composition. Amphoteric Surfactants Ampholytic synthetic surfactants can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-soluble group, e.g. carboxylate, sulfonate, sulfate. Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1 -sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium . 2-(dimethylamino)octadecanoate, disodium \| 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium i octadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimida2ole, and \| sodium N,N-bis(2-hydroxyethyI)-2-sulfato-3-dodecoxypropylamine. Sodium 3-(dodecyIamino)propane-1 -sulfonate is preferred. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Specific examples of zwitterionic surfactants which may be used are set forth in U.S. Patent No. 4,062,647. The amount of active used may vary from 10 to 85% by weight, preferably 15 to 75% by weight, more preferably 20-70% by weight. As noted the preferred surfactant systems of the invention comprise linear alkyl sulphate, LES, nonionic and optionally soap (Monoethanoiamine-soap, Na-soap). Builders/Electrolytes Builders which can be used according to this invention include conventional t alkaline detergency builders, inorganic or organic, which should be used at levels from about 0% to about 20.0% by weight of the composition, preferably ! from 1.0% to about 10.0% by weight, more preferably 2% to 5% by weight. As electrolyte may be used any water-soluble salt. Electrolyte may also be a detergency builder, such as the inorganic builder sodium tripolyphosphate, or it may be a non-functional electrolyte such as sodium sulphate or chloride. Preferably the inorganic builder comprises all or part of the electrolyte. That is the term electrolyte encompasses both builders and salts. Examples of suitable inorganic alkaline detergency builders which may be used are water-soluble alkalimetal phosphates, polyphosphates, borates, silicates and also carbonates. Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates. Examples of suitable organic alkaline detergency builder salts are: (1) water-soluble amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyO-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates (see U.S. Patent No. 2,379,942); (3) water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and lithium salts of methylene diphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy-1,1 -diphosphonic acid hydroxyrnethanediphosphonic acid, carboxyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonicacid, and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No 3,308,067. In addition, polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate, tartrate disuccinate and mixtures thereof (TMS/TDS). Certain zeolites or aluminosilicates can be used. One such aluminosiiicate which is more fully described in British Pat. No. 1,470,250. A second water-insoluble synthetic aluminosiiicate ion exchange material useful herein is crystalline in nature and is more fully described in British Patent No. 1,429,143. Especially preferred builders include sodium citrate and sodium tetraborate pentahydrate. Enzymes One or more enzymes as described in detail below, may be used in the composition of the invention. If a lipase is used, the lipolytic enzyme may be either a fungal lipase producible by Humicola lanuginosa and Thermomyces lanuginosus, or a bacterial lipase which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Chromobacter viscosum var. lipolyticum NRRL B-3673. This microorganism has been described in Dutch patent specification 154,269 of Toyo Jozo Kabushiki Kaisha and has been deposited j with the Fermentation Research Institute, Agency of Industrial Science and " Technology, Ministry of International Trade and Industry/Tokyo, Japan, and added to the permanent collection under nr. KO Hatsu Ken Kin Ki 137 and is available to the public at the United States Department of Agriculture, Agricultural Research Service, Northern Utilization and Development Division at Peoria, Illinois, USA, under the nr. NRRL B-3673. The lipase produced by this microorganism is commercially available from Toyo Jozo Co., Tagata, Japan, hereafter referred to as "TJ lipase". These bacterial lipases should show a positive immunological cross-reaction with the TJ lipase antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950). All bacterial lipases showing a positive immunological cross-reaction with the TJ-lipase antibody as hereabove described are lipases suitable in this embodiment of the invention. Typical examples thereof are the lipase ex Pseudomonas fluorescens 1AM 1057 available from Amano Pharmaceutical Go., Nagoya, Japan, under the trade-name Amano-P lipase, the lipase ex Pseudomonas tragi FERM P 1339 (available under the trade-name Amano-B), the lipase ex Pseudomonas nitroreducens var. Iipolyticum FERM P1338, the lipase ex Pseudomonas sp. available under the trade-name Amano CES, the : lipase ex Pseudomonas cepacia, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. Iipolyticum NRRL B-3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum , lipases from U.S. Biochemical Corp. USA and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. An example of a fungal lipase as defined above is the lipase ex Humicola lanuginosa, available from Amano under the tradename Amano CE; the lipase ex Humicola lanuginosa as described in the aforesaid European Patent Application 0,258,068 (NOVO), as well as the lipase obtained by cloning the gene from Humicola lanuginosa and expressing this gene in Aspergillus oryzae, commercially available from NOVO industri A/S under the tradename "Lipolase". This lipolase is a preferred lipase for use in the present invention. While various specific lipase enzymes have been described above, it is to be understood that any lipase which can confer the desired lipolytic activity to the composition may be used and the invention is not intended to be limited in any way by specific choice of lipase enzyme. The lipases of this embodiment of the invention are included in the liquid detergent composition in such an amount that the final composition has a lipolytic enzyme activity of from 100 to 0.005 LU/ml in the wash cycle, preferably 25 to 0.05 LU/ml when the formulation is dosed at a level of about .1-10, more preferably .5-7, most preferably 1-2 g/liter. A Lipase Unit (LU) is that amount of lipase which produces 1/Fmol of titratable fatty acid per minute in a pH state under the following conditions: temperature 30/C; pH = 9.0; substrate is an emulsion of 3.3 wt.% of olive oil and 3.3% gum arabic, in the presence of 13 mmol/1 Ca2+ and 20 mmoI/1 NaCI in 5 mmol/1 Tris-buffer. Naturally, mixtures of the above lipases can be used. The lipases can be used in their non-purified form or in a purified form, e.g. purified with the aid of well-known absorption methods, such as phenyl sepharose absorption techniques. The proteolytic enzyme can be of vegetable, animal or microorganism origin. I Preferably, it is of the latter origin, which includes yeasts, fungi, molds and \| bacteria. Particularly preferred are bacterial subtilisin type proteases, obtained \ from e.g. particular strains of B. subtilis and B licheniformis. Examples of i suitable commercially available proteases are Alcalase, Savinase, Esperase, all of NOVO Industri A/S; Purafect and Properase from Genencor; Maxatase and Maxacal of Gist-Brocades; Kazusase of Showa Denko; BPN and BPN" proteases; Optimase from Solvay and so on. The amount of proteolytic enzyme, included in the composition, ranges from 0.05-50,000 GU/mg. preferably 0.1 to 50 GU/mg, based on the final composition. Naturally, mixtures of different proteolytic enzymes may be used. While various specific enzymes have been described above, it is to be understood that any protease whicli can confer the desired proteolytic activity to the composition may be used and this embodiment of the invention is not limited in any way by specific choice of proteolytic enzyme. In addition to lipases or proteases, it is to be understood that other enzyme such as cellulase (Carezyme™, Clazinase™, Celluzyme™), oxidase, amylase, peroxidase and the like which are well known in the art may also be used with the composition of the invention. The enzymes may be used together with co-factors required to promote enzyme activity, i.e., they may be used in enzyme x systems, if required. It should also be understood that enzymes having \| mutations at various positions (e.g., enzymes engineered for performance S and/or stability enhancement) are also contemplated by the invention. One I example of an engineered commercially available enzyme is Durazym™ from I Novo. Optional Ingredients ".. In addition to the enzymes mentioned above, a number of other optional ingredients may be used. Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine, borax and the like. Other materials such as clays, particularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. The bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Patent No. 401, 413 to Marriott and British Patent No. 461,221 to Marriott and Guam. In addition, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature. Improvements in the physical stability and anti-settling properties of the .composition may be achieved by the addition of a small effective amount of fsorbitol or an aluminum salt of a higher fatty acid, e.g., aluminum stearate, to Ithe composition. The aluminum stearate stabilizing agent can be added in an (amount of 0 to 3%, preferably 0.1 to 2.0% and more preferably 0.5 to 1.5%. .There also may be included in the formulation, minor amounts of soil \| suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, ! sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. Preferred : anti-redeposition agents include Alcosperse 725™ and sodium carboxylmethyl \| cellulose having a 2:1 ratio of CM/MC which is sold under the tradename I Relatin DM 4050 i Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include Tinopal LMS-X, Tinopal UNPA-GX, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dimorpholine dianilino stilbene sulfonate. Anti-foam agents, e.g. silicon compounds, such as Silicane L 7604, can also be added in small effective amounts. Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, e.g. formalin, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume and dyes and bluing agents such as Iragon Blue L2D, Detergent Blue 472/572 and ultramarine blue can be used. - Also, soil release polymers and cationic softening agents may be used. Anionic Polymer Anionic polymers of the invention are those polymers that have negatively charged groups attached covalently to the chain. Examples of synthetic anionic polymers are polyacrylic acid units in its partially and fully ionized forms, polyethylene sulfonic acid in its partially and fully ionized forms, poly(methacryiic acid) in its partially and fully ionized forms, poly(phosphoric acid) and its salts, poly(vinylsulfuric acid) and polyvinyl a!cohol-co-vinyl sulfuric acid) and their salts. A list of other synthetic anionic polymers can be found in, "Water-soluble Synthetic Polymers: Properties and Behavior" by P. Molyneux, Vol. II, CRC Press, 1985. This reference is hereby incorporated by reference into the subject application. Examples of commercially available synthetic anionic polymers are Sokalan series and Acusoi series of polyacryiic acids and copolymers of acrylic and maleic acids from BASF and Rohm & Haas respectively. Examples of unmodified and modified natural anionic polymers are alginic acid and its salts and modified starches such as carboxymethyl cellulose. A list of unmodified and modified natural anionic polymers can be found in, "Encyclopedia of Polymers and Thickeners" by R. Y. Lochhead and W. R. Fron in Cosmetics and Toiletries, Vol, 108, May 1993. The anionic polymer should be used in an amount comprising 0.1 to 10% by wt., preferably 0.25% to 5% by wt. of the composition. Other optimal ingredients which may be used are hydrotropes. In general, addition of hydrotropes helps to incorporate higher levels of surfactants into isotropic liquid detergents than would otherwise be possible due to phase separation of surfactants from the aqueous phase. Hydrotropes also allow a change in the proportions of different types of surfactants, namely anionic, nonionic, cationic and zwitterionic, without encountering the problem of phase separation. Thus, they increase the formulation flexibility. Hydrotropes function through either of the following mechanisms: i) they increase the solubility of the surfactant in the aqueous phase by changing the solvent power of the aqueous phase; short chain alcohols such as ethanol, isopropanol and also glycerol and propylene glycol are examples in this class and ii) they ;prevent formation of liquid crystalline phases of surfactants by disrupting the packing of the hydrocarbon chains of the surfactants in the micelles; alkali metal salts of alkyl aryl sulfonates such as xylene sulfonate, cumene sulfonate and ■alkyl aryl disulfonates such as DOWFAX(R) family of hydrotropes marketed by \ Dow Chemicals are examples in this class. j Preferred hydrotropes in the compositions of the present invention are polyols, I which may also act as enzyme stabilizers, such as propylene glycol, ethylene i glycol, glycerol, sorbitol, mannitol and glucose. Enzyme Encapsulate The enzyme encapsulate according to the present invention should \| effectively protect the enzyme from the adverse effect of UV radiation. Therefore it is essential that the enzyme is adequately contained in the encapsulate to prevent any significant leaking of the enzyme into the liquid detergent composition during storage. The enzyme encapsulate may contain polymeric material, but this is not a limiting condition. If polymers are present in the capsules, at least part of the polymeric material should not dissolve in the liquid detergent, whereas they disperse or dissolve upon dilution. Examples of synthetic polymeric materials are: - polyvinyl alcohol (PVA) of different molecular weight and degrees of hydrolysis, which is defined as a homopolymer or copolymer in which vinyl acetate is a starting monomer unit and in which most or all of the acetate moieties are subsequently hydrolyzed to alcohol moieties.(e.g. Airvol range from Air Products, Mowiol range from Hoechst) - polyamide (obtained via reaction between a diamine with a dicarboxylic acid) - polyester (obtained via reaction between a diol and a dicarboxylic acid) - polyurea - polyurethane - epoxy resin Other examples of natural polymers include: - methyl cellulose (e.g. Methocal A15LV ex Dow Chemical) - hydroxypropyicsliuiose (e.g. Klucel L or Klucel G ex Aqualon) - hydroxypropylmethylceliuiose - carrageenan (kappa or iota forms) (various types ex FMC) - alginate (e.g. Manucol DM or DH ex Kelco). - gellan gum (e.g. Kelcogel ex Kelco) - gelatine Further reference: Encyclopaedia of polymers and thickeners for cosmetics, vol. 108, May 1993, 95-135. If polymers are present in the capsules, they can be present as a small solid grains, either dispersed throughout the particle or preferentially located in part of the capsules, for example in the outside layer of the capsule. The polymers can also be present as hydrated particles, which can either be dispersed throughout the particle or located in a part of the capsule. Polymers can also be present in the core of the capsules, in the form of an onion ring inside the capsule or as a shell around the core. The enzyme capsules can also contain hydrophobic or fatty materials. Examples of this are: - Paraffins (preferably petroleum jelly) - Triglycerides - Fatty acids - Fatty alcohols - Mixtures of fatty acid and fatty acid soaps - Esters (e.g. ceto stearyl stearate) ■ If the capsules contain hydrophobic materials they should protect the enzyme , against moisture. The hydrophobic material should envelope the enzyme solid particles or droplets which are present in the capsule. j The capsules can contain also other ingredients: - density modifiers, e.g. sucrose - structurants, e.g. silica, or zeolite - fillers, e.g. talc, bentonite - scavengers, e.g., ammonium sulphate - plasticizers * - anti-agglomeration or layering agents - releasing agents Thus, in one preferred embodiment the enzyme encapsulate according to the present invention may comprise polymeric material. Preferably, the enzyme encapsulate comprise polymeric materials selected from the group consisting of polyvinylalcohol, polyamide, polyester, polyurea, polyurethane, epoxyresin, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, alginate, gellan gum, gelatine and mixtures thereof. Examples of enzyme encapsulates can be found in WO-93/07263, EP-A-585295, EP-A-356239, US-A-5,281,356, US-A-5,281,355 and GB 2,186,884. The enzyme encapsulate according to the present invention are between 30 and 5000 microns, preferably between 300 and 3000 microns, most preferably between 500 and 2500 microns. The particle shape can vary from irregular to spherical; in the preferred form they should be close to spherical, but this should not be limiting. The enzyme encapsulate according to the present invention have an enzyme encapsulated density.- as measured in the detergent solution - of between 700 and 2500 kg/m3, more preferably between 800 and 2000 kg/m3 and most preferably between 900 and 1500 kg/m3. The enzyme can be distributed homogeneously throughout the particle (matrix capsule), be located in the core of the capsule (core-sttell capsule) or be present in any other confined zone in the capsule, e.g. in an onion-ring shaped zone. The enzyme can be present in the capsules in solid form, as small particles, which can comprise pure protein or optionally a mixture of protein and other materials (optionally in a matrix with other components). The enzyme can also be present in the capsule in the form of small droplets an enzyme solution, or as mixture of solid and liquid (slurry). The enzyme encapsulate according to the present invention may comprise any detergent enzymes ihcfudihg protease lipase, amylase, peroxidase, cellulase or a mixture thereof. Examples of protease are commercially available types such as Alcalase™, Durazym™, Relase™, Savinase™ ex Novo Nordisk and Optimase™, Purafect ™ , Properase™ ex Genencor International. Examples of lipase are Lipolase™ ex Novo Nordisk and Lipomax™ ex Genencor International. Examples of cellulase are Celluzyme™ and Carezyme™ ex Novo Nordisk, and Clazinase™ ex Genencor International. Examples of amylase are Termamyl™ ex Novo Nordisk and Maxamyi™ ex \ Genencor International. is \| Preferably the enzyme according to the present invention is a protease. J When the enzyme according to the present invention is a protease, the protein I content is preferably in the range between 0.1 and 20%, more preferably \| between 0.5% and 10%, most preferably between 1% and 5%. i ! j When the enzyme according to the present invention is a protease, the enzyme activity is from 100 GU/mg and 20000 GU/mg, more preferably between 500 and 10000 GU/mg, most preferably between 1000 and 5000 GU/mg. EXAMPLES The following examples are intended to clarify the invention further and are not intended to limit the invention in any way. All percentages are intended to be percentages by weight, unless stated otherwise. Also when used in claims or specification, comprising is intended to include all elements, features etc. Example 1 Enzyme capsules were prepared as follows:: A polymer solution was prepared by dissolving 3.3 parts of Polyvinyl Alcohol (Alrvol 540 ex Air Products Inc) in 60.7 parts of water. Theni5.0 parts of Poly Acryl Acrylate (Acrysol ASE-60 ex Rohm & Haas) were added, followed by 30 parts of a 2% aqueous solution of NaOH. An enzyme dispersion in hydrophobe was prepared by dispersion of 15 parts of Optimase powder (Solvay, now part of Genencor International Inc.) into 59.5 parts of Snow white petrolatum (ex Penreco) at 60°C. Subsequently 25.5 parts of Trogrees Spray S (ex Penreco) was added to this dispersion followed by mixing for 30 minutes. An emulsion of 1 part of the enzyme dispersion in 6 parts of the polymer solution was prepared by using a 9.5mm (3/8") I.D. 12 element static mixer at a throughput rate of 12 ml/min. This emulsion was atomized by a Spraying Systems 35100 two-fluid nozzle at an air rate of 7100 cc/min. The droplets formed were collected in a hardening solution comprising 83.5 parts water, 15 parts sodium sulfate (ex Elf Atochem N.A.), 1.5 parts sodium tetraborate decahydrate (ex Textile Chemicals), 0.001 part of sodium dodecyl sulfate (ex Aldrich) and 0.001 part of antifoam Silicon AF-544 (ex Dow Corning). The enzyme capsules were subsequently separated from the hardening solution by screening. The enzyme activity of these capsules was 5-104 GU/g. Example 2 An enzymatic liquid detergent composition was prepared using the enzyme capsules from example 1 (size fraction from 500 -1000 um (microns)). The enzyme capsules were dispersed at a level of 1.5 wt.% into 20g of a transparent liquid detergent with a composition as outlined in Table 1, which resulted in an enzyme activity of 7.6-102 GU/g in the liquid detergent composition. Another enzymatic liquid detergent composition was prepared by adding an aqueous solution of Optimase powder (ex Solvay, now part of Genencor International, Inc.) to a transparent liquid detergent with a composition as outlined in Table 1. The enzyme concentration in the aqueous solution was chosen at such level that an enzyme activity of 7.6-102 GU/g in the liquid detergent composition was obtained. Care was taken that the enzyme activity of the liquid detergent composition with enzym© capsules was equal to the enzyme activity of the detergent composition whereto the enzyme was added as an aqueous solution. Samples containing 20g of the detergent with dissolved Optimase and samples containing 20g of the detergent with Optimase capsules were stored in transparent polyethylene containers of 47 mm diameter and 95 mm height. These samples weia.stored in an accelerated test at 37°C under exposure to two UV-B light sources of 20W (Philips TL20W12), whereby the samples were positioned at a distance of 20 cm from the bottom of the bottles to the UV-B light source. Comparative samples were stored in an accelerated test at 37°C in the absence of light. Samples were taken after two days and seven days storage and analyzed on residual enzyme activity with respect to the initial amount of enzyme activity prior to storage. The residual activities as a function of time on storage are shown in Table 2. The following important observations have been made: 1) For enzymes added from an aqueous solution, deactivation proceeds faster under exposure to UV-light than in the absence of light. 2) If the transparent bottles are exposed to UV-light, the storage stability of the enzyme which was added in the form of capsules is improved with respect to the storage stability of enzyme which was added to the liquid detergent in the form of a solution. 3) There is no difference between deactivation of the enzyme capsules under exposure to UV-light and in the absence of UV-light. This indicates that enzymes in the-capsules are protected against the adverse effects of UV-light. Table 1: Detergent formulation Table 2: Storage stability of enzyme and enzyme capsules in a liquid detergent in a transparent or translucent bottle, under exposure to UV-light, and in the absence of light Residual enzyme activity (in % with respect to the activity prior to storage) as a function of storage time. As clearly seen, deactivation is faster when there are no capsules thereby indicating that capsules protect from UV light. Example 3 Experimental Conditions J The samples (5g) of liquid detergents (Table 1) containing protease and lipase ! were added to (38cm) 1.5" diameter glass dishes with the top off and exposed to UV-C light at near 254 nm (measured at 110 mwatt/cm2 (71cm) (28" from the light source)) for 4 days). After each 24 hour period, the samples were weighed and topped off to replace evaporated water. To release enzyme from capsules, the capsules were homogenized at 10,000 rpm in. 2% Neodol 25-9 solution. Enzyme activity in the homogenized solution was measured using Casein as i the substrate. Percent remaining activity was calculated based on the initial I activity in the sample prior to UV exposure. mW/cm2, UVB= 6.17 mW/cm2 at the lamp). The HDL"s containing enzyme Similar experiments were carried out in a UV-A/B chamber (UVA= 1.01 mW/cm2, UVB= 6.17 mW/cm2 at the lamp). Th capsules were exposed to UV lights for 4 days. Table 3. A Detergent Formulation (Wisk Free & Clear, shown in ranges) *C12-C15 ethoxylated alkyl chain ethoxylated with 9 ethylene oxide units. Again, this shows improvement of stability when capsules were used. 5 ^r We Claim- 1. A packaged liquid detergent composition comprising a transparent or translucent container having a transmlttance of 25% or greater at wavelength of 410-800 nrr, and a transparent or translucent enzymatic detergent composition having a transmlttance of greater than 50% of fight using 1 cm cuvette at wavelength of 410-800 nm which container and detergent composition are transmissive of UV-B radiation characterised in that said enzymes are encapsulated, 2. A packaged detergent composition according to claim 1, wherein the enzyme encapsulate comprises polymeric material. 3. A packaged detergent composition according to claim 2, wherein the enzyme encapsulate polymeric material is selected from the group consisting of polyvinylaicohot, pofyamide, polyester, polyurea, polyurethane, epoxynssrn, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, alginate, gellan gum, gelatine and mixtures thereof. 4. A packaged detergent composition according to any preceding claim wherein the enzyme encapsulate is between 30 and 5000 urn (microns) in size, 5. A packaged detergent composition according to any preceding claim wherein the density of enzyme encapsulate as measured in me detergent solution is between 700 and 2500 kg/m3. 6. A packaged detergent composition according to any preceding claim wherein said enzyme encapsulate" comprises a detergent enzyme selected from the group consisting of protease, lipase, amylase, peroxidase, cellulase and a mixture thereof. 7. A packaged detergent composition according to claim 6, wherein the enzyme is a protease. 8. A packaged detergent composition according to claim 7, wherein protease content is in the range between 0.1 and 20%. 9. A packaged detergent composition according to claim 7 or claim 8, wherein the protease has an enzyme activity from 100 GU/mg to 20000 GU/mg. 10. A packaged detergent composition according to any preceding claim wherein the liquid detergent is aqueous. 11. A packaged detergent composition according to any preceding claim wherein the liquid detergent is externally structured. 12. A packaged detergent composition according to claim 11, wherein the liquid detergent is externally structured with polymers selected from the group consisting of gellan, xanthan, polyacrylate, algin, guar, rhamsan, carrageenan, carbopol-like polymers and mixtures thereof. 13. A packaged detergent composition according to any of the preceding claims, wherein the transparent container comprises a material selected from

Full Text

FORM -2
THE PATENTS ACT, 1970
(39 OF 1970)
COMPLETE SPECIFICATION
(See Section 10; rule 13)
1. TITLE OF INVENTION
PACKAGED LIQUID DETERGENT COMPOSITION
2. HINDUSTAN LEVER LIMITED, Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai - 400 020, Maharashtra, India, a company incorporated under the Companies Act, 1913

The following specification particularly describes the nature of the invention and the manner in which it is to be performed.

DETERGENT COMPOSITION
TECHNICAL FIELD
This invention relates to the field of liquid detergents, in particular to a packaged, transparent liquid detergent composition.
BACKGROUND
Transparent liquid detergent compositions are known in the art. GB-A-1,303,810 discloses clear liquid detergent compositions with a transparent aqueous or non-aqueous base comprising particles that are visually distinct and , have a diameter size of at least 0.5 mm. US-A-3,812,042 describes a clear . liquid detergent composition in a transparent, plastic container. US-A-5,427,708 , discloses a transparent liquid soap in a transparent container. WO 97/26315 I (Colgate) discloses transparent containers with specific chromaticity defined by x and y values. Specific dyes are used in the liquids to match the container. The reference does not disclose encapsulated enzymes or their effectiveness in transparent containers and liquids relative to non-encapsulated enzymes.
When transparent liquid detergents are packaged in transparent containers, sensitive ingredients in the detergent composition may become affected by UV radiation. For example, UV radiation may cause the discoloration of liquid detergent composition in transparent containers. DE-A-2034562 and DE-A-2034563 describe the use of nitroalkanols to overcome the bleaching of colored liquid detergent compositions.
Liquid detergent compositions comprising enzymes are preferred for their improved the cleaning performance. We have found that the activity of enzymes may also become adversely affected by UV radiation when the transparent liquid is packaged in a transparent container.

Therefore, it is an object of the present invention to provide a packaged detergent composition comprising a transparent container and a transparent enzymatic aqueous liquid detergent composition wherein the enzymes are protected from the adverse effects of UV radiation. Surprisingly, it is found that when enzymes are present in a transparent liquid detergent in a transparent . container the harmful effects from UV radiation on the enzymes can be reduced by encapsulating said enzymes.
SUMMARY OF THE INVENTION
The present invention provides a packaged liquid detergent composition comprising a transparent or translucent container having a transmittance of
, 25% or greater at wavelength of 410-800 nm and a transparent or translucent enzymatic detergent composition having a transmittance of greater than 50% of
light using 1 cm cuvette at wavelength of 410-800 nm which container and
detergent composition are transmissive of UV-B radiation.
A preferred embodiment of the invention provides a packaged liquid detergent composition comprising a transparent container and a transparent enzymatic detergent composition wherein the enzymes are encapsulated, wherein after 7 days of accelerated storage of 20 g of the liquid detergent comprising 1.5 wt. % of enzyme capsules in a transparent container (e.g., polyethylene), wherein the sample is stored at 37°C while being exposed to UV light (e.g., UV-B light), whereby the liquid sample is positioned at a distance of about 20 cm from the bottom of the bottle to the UV light source, the enzyme activity is enhanced (e.g., more than 40% remaining activity, preferably more than 50%, more preferably more than 60% remaining activity).

Another embodiment of the invention provides a packaged liquid detergent composition comprising a transparent/translucent container and a transparent/translucent enzymatic detergent composition wherein the enzymes are encapsulated, wherein the liquid detergent is structured, preferably externally structured.
I DETAILED DESCRIPTION OF THE INVENTION The presently claimed invention provides a packaged detergent composition comprising a transparent or translucent container and a transparent or translucent aqueous enzymatic detergent composition characterized in that said enzymes are encapsulated to protect said enzymes from the adverse effects of UV light. Preferably, the enzymes in said packaged detergent composition have
i a remaining enzyme activity of more than 40%, more preferably more than 50% and most preferably more than 60% after storage of 4 weeks at 376C.
f
The Container
The transparent container according to the present invention preferably has a
transmittance of more than 25%, more preferably of more than 30%, even more preferably of more than 40%, even more preferably of more than 50% in the visible part of the spectrum (approx. 410-800 nanometers).
Enzyme deactivation as a result of UV-damage may occur at very low transmissions of UV-B radiation through the container wall.

Alternatively, transparency may be defined as absorbency being less than 0.6 or the transmittance greater than 25%, wherein % transmittance equals::

For purposes of the invention, as long as one wavelength in the visible light range has greater than 25% transmittance, it is considered to be transparent/translucent.
The transparent container according to the present invention comprises (high density) polyethylene (PE), polypropylene (PP), polycarbonate (PC) and/or polyethylene terephthalate (PETE), but this should not be considered limiting in any way.
1 Polyethylene containers were used for UV stability tests in the present invention and had transparency of 8% at 310 nm, 17.5% at 400 nrn, 25% at 500 nm and 31% at 600 nm.
The container of the present invention may be of any form or size suitable for storing and packaging liquids for house hold use. For example, the container may be any size but usually the container will have a maximal capacity of 0.05 to 15 I, preferably, 0.1 to 5 I, more preferably from 0.2 to 2.5 I. Preferably, the container is suitable for easy handling. For example the container may have a handle or a part with such dimensions to allow easy lifting or carrying the container with one hand.
The container preferably has a means suitable for pouring the liquid detergent composition and a means for re-closing the container. The pouring means may be of any size or form but, preferably will be wide enough for convenient dosing the liquid detergent composition. The closing means may of any form or size but usually will be screwed or clicked on the container to close thecontainer. The closing means may be cap which can be detached from the container. Alternatively, the cap can still be attached to the container, whether the container is open or closed. The closing means may also be incorporated in the container.

The container may have a suitable form for refilling. For example, the container may comprise a re-closable aperture of such a size and position which renders it suitable for convenient refilling. Accordingly, the container of the present invention also encompasses refill packages: those container forms suitable for packaging refills of liquid detergent compositions. These refill packages may be of any form and size but usually will be of flexible material without means for re-closing such as sachets or Tetrapak™ like containers.
Liquid Detergent
The liquid detergent according to the present invention, may be aqueous or
non-aqueous. Aqueous liquids may be internally or externally structured. Preferably, the liquid detergent according to the present invention is externally structured.
Externally structured liquids may comprise polymers such as gellan, xanthan, polyacrylate, algin, guar, rhamsan, carrageenan, carbopol™ and carbopol-like polymers and mixtures thereof. Preferably, Externally structured liquids may comprise polymers selected from the group consisting of gellan, kappa-carrageenan, xanthan or mixtures thereof. Externally structured liquids may also comprise clays, silicates or mixtures thereof as structuring agents.
The compositions of the invention have at least 50% transmittance of light using a 1 centimeter cuvette at wavelength of 410-800 nm, preferably 570-690 nm, wherein the composition is essentially free of dyes.
Alternatively, transparency of the composition may be measured as having an absorbency in the visible light wavelength (about 410 to 800 nm) of less than 0.3 which is in turn equivalent to at least 50% transmittance using cuvette and wavelength noted above. For purposes of the invention, as long as one

wavelength in the visible light range has greater than 50% transmittance, it is considered to be transparent/translucent.
With transparent liquid detergent according to the present invention is meant that, the liquid detergent has absorbency of less than 0.3 or transmittance of greater than 50% at 410-800 nm, where transmittance equals:

Enzyme deactivation as a result of UV-damage may occur at very low transmissions of UV-B radiation.
Detergent Active
The compositions of the invention contain one or more surface active agents selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof. The preferred surfactant detergents for use in the present invention are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants.
Anionic Surfactant Detergents
Anionic surface active agents which may be used in the present invention are
those surface, active-compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophilic group, i.e. water solubilizing group such as carboxylate, sulfonate or sulphate group or their corresponding acid form. The anionic surface active agents include the

alkali metal (e.g. sodium and potassium) water soluble higher alkyl aryl * sulphonates, alkyl sulphonates, alkyl sulphates and the alkyl poly ether sulphates. They may also include fatty acids or fatty acid soaps. One of the preferred groups of anionic surface active agents are the alkali metal, ammonium or alkanolamine salts of higher alkyl aryl sulphonates and alkali metal, ammonium or alkanolamine salts of higher alkyl sulphates. Preferred higher alkyl sulphates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 10 to 22 carbon atoms and more preferably 12 to 18 carbon atoms. The alkyl group in the alkyl aryl sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms. A particularly preferred alkyl aryl sulfonate is the sodium, potassium or ethanolamine C10 to C16 benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate. The primary and secondary alkyl sulphates can be made by reacting long chain lalpha-olefins with sulphites or bisulphites, e.g. sodium bisulfite. The alkyl sulphates can also be made by reacting long chain normal paraffin hydrocarbons with sulphur dioxide and oxygen as describe in U.S. Patent Nos. 2,503,280, 2,507,088, 3,372,188 and 3,260,741 to obtain normal or secondary higher alkyl sulphates suitable for use as surfactant detergents.
The alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfonates can be employed, although they are not as good with respect to biodegradability. The alkane, i.e. alkyl, substituent may be terminally sulfonated or may be joined, for example, to the 2-carbon atom of the chain, i.e. may be a secondary sulfonate. It is understood in the art that the substituent may be joined to any carbon on the alkyl chain. The higher alkyl sulfonates can be used as the alkali metal salts, such as sodium and potassium. The preferred salts are the sodium salts. The preferred alkyl sulfonates are the C10 to C18 primary normal alkyl sodium and potassium sulfonates, with the C10 to C15 primary normal alkyl sulfonate salt being more preferred.

Mixtures of higher alkyl benzene sulfonates and higher alkyl sulphates can be used as well as mixtures of higher alkyl benzene sulfonates and higher alkyl polyether sulfates.
The alkali metal or ethanolamine alkyl aryl sulfonate can be used in an amount of 0 to 70%, preferably 2 to 50% and more preferably 5 to 20% by weight. The alkali metal or ethanolamine alkylsulfate can be used in admixture with the alkylbenzene sulfonate in an amount of 0 to 70%, preferably 5 to 50%, more preferably 5 to 20% by weight.
Also normal alkyl and branched chain alkyl sulfates (e.g., primary alky! sulfates) may be used as the anionic component.
The higher alkyl polyethoxy sulfates used in accordance with the present invention can be normal or branched chain alkyl and contain lower alkoxy groups which can contain two or three carbon atoms. The norma! higher alkyl polyether sulfates are preferred in that they have a higher degree of biodegradability than the branched chain alkyl and the lower poly alkoxy groups are preferably ethoxy groups.
The preferred higher alkyl polyethoxy sulfates used in accordance with the present invention are represented by the formula:
R1-0(CH2CH20)p-S03M,
where R1 is C8 to C2o alkyl, preferably C10 to Ci8 and more preferably C12 to C15; p is 2 to 8, preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal, such as sodium and potassium, or an ammonium cation. The sodium and potassium salts are preferred.

A preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a triethoxy C12 to C15 alcohol sulfate having the formula:
C12-15-0-(CH2CH2O)3-SO3Na
Examples of suitable alkyl ethoxy sulfates that can be used in accordance with the present invention are C12-15 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C12 primary alkyl diethoxy sulfate, ammonium salt; C12 primary alkyl triethoxy sulfate, sodium salt; Ol5 primary alkyl tetraethoxy sulfate, sodium salt; mixed C14.15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyi pentaethoxy sulfate, sodium salt; and mixed C10-18 normal primary alkyl triethoxy sulfate, potassium salt.
The normal alkyl ethoxy sulfates are readily biodegradable and are preferred. The alkyl poly-lower alkoxy sulfates can be used in mixtures with each other and/or in mixtures with the above discussed higher alkyl benzenesulfonates, or alkyl sulfates.
The alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfate, in an amount of 0 to 70%, preferably 5 to 50% and more preferably 5 to 20% by weight of entire composition.
Nonionic Surfactant
Part of the surfactant composition, according to the subject invention, may be
nonionic surfactant. Generally the nonionic surfactant, whether sugar surfactant or not, should comprise about 10% to 100%, preferably 20 to 50% of the total surfactant composition.

Sugar or glycoside surfactants suitable for use in accordance with the present invention include discussed in the following patents: U.S. 5,573,707 to Cole et al., U.S. 5,562,848 to Wofford et al., U.S. 5,542,950 to Cole et al., WO 96/15305 to Cole et al., U.S. 5,529,122 to Thach, WO 95/33036 to Urfer et al., and DE 4,234,241 to Schmidt.
Nonionic surfactants which may be used include polyhydroxy amides as discussed in U.S. Patent No. 5,312,954 to Letton et al. and aldobionamides such as disclosed in U.S. Patent No. 5,389,279 to Au et al.
Another class of sugar based surfactants which can be used include N-alkoxy or N-aryloxy polyhydroxy fatty acid amides discussed in WO 95/07256 to Schiebel et al., WO 92/06071 to Connor et al., and WO 92/06160 to Collins et al. These references are incorporated by reference into the subject application. Yet another class of sugar based surfactants are sugar esters discussed in GB 2,061,313, GB 2,048,670, EP 20122 and U.S. Patent No. 4,259,202 to Tanaka et al.
Besides the sugar surfactants, other nonionic surfactants are described below:
As is well known, the nonionic surfactants are characterized by the presence of a hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide {hydrophilic in nature). Typical suitable nonionic surfactants are those disclosed in U.S. Patent Nos. 4,316,812 and 3,630,929.

Usually, the nonionic surfactants are polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of nonionic surfactant is the alkoxylated alkanols wherein the alkanol is of 9 to 18 carbon . atoms and wherein the number of moles of alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the alkanol is a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 alkoxy groups per mole.
Exemplary of such compounds are those wherein the alkanol is of 10 to 15
carbon atoms and which contain 5 to 9 ethylene oxide groups per mole, e.g.
Neodol 25-9 and Neodol 23-6.5, which products are made by Shell Chemical | Company, Inc. The former is a condensation product of a mixture of higher fatty \ alcohols averaging 12 to 15 carbon atoms, with about 9 moles of ethylene oxide | and the latter is a corresponding mixture wherein the carbon atoms content of I the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups
present averages about 6.5. The higher alcohols are primary alkanols.
Another subclass of alkoxylated surfactants which can be used contain a precise alkyl chain length rather than an alkyl chain distribution of the alkoxylated surfactants described above. Typically, these are referred to as narrow range alkoxylates. Examples of these include the Neodol-1(R) series of surfactants manufactured by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac by BASF. The Plurafacs are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxy! group. Examples include C13-C15 fatty alcohol

condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide or mixtures of any of the above.
Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol or Neodol trademark: Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
In the compositions of this invention, preferred nonionic surfactants include the C12-C15 primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 6 to 9 moles, and the C9 to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
Cationic Surfactants
Many cationic surfactants are known in the art, and almost any cationic
surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, incorporated by reference. Specific cationic surfactants which can be used as surfactants in the subject invention are described in detail in U.S. Patent No. 4,497,718.
As with the nonionic and anionic surfactants, the compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants knowrrtnlhe art; Of course, the compositions may contain no cationic surfactants at all.

If included, cationics may comprise 0-20%, preferably 1-10% by weight of the total composition.
Amphoteric Surfactants
Ampholytic synthetic surfactants can be broadly described as derivatives of
aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-soluble group, e.g. carboxylate, sulfonate, sulfate. Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1 -sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium . 2-(dimethylamino)octadecanoate, disodium | 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium i octadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimida2ole, and | sodium N,N-bis(2-hydroxyethyI)-2-sulfato-3-dodecoxypropylamine. Sodium 3-(dodecyIamino)propane-1 -sulfonate is preferred.
Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Specific examples of zwitterionic surfactants which may be used are set forth in U.S. Patent No. 4,062,647.
The amount of active used may vary from 10 to 85% by weight, preferably 15 to 75% by weight, more preferably 20-70% by weight.
As noted the preferred surfactant systems of the invention comprise linear alkyl sulphate, LES, nonionic and optionally soap (Monoethanoiamine-soap, Na-soap).
Builders/Electrolytes
Builders which can be used according to this invention include conventional
t alkaline detergency builders, inorganic or organic, which should be used at levels from about 0% to about 20.0% by weight of the composition, preferably ! from 1.0% to about 10.0% by weight, more preferably 2% to 5% by weight.
As electrolyte may be used any water-soluble salt. Electrolyte may also be a detergency builder, such as the inorganic builder sodium tripolyphosphate, or it may be a non-functional electrolyte such as sodium sulphate or chloride. Preferably the inorganic builder comprises all or part of the electrolyte. That is the term electrolyte encompasses both builders and salts.
Examples of suitable inorganic alkaline detergency builders which may be used are water-soluble alkalimetal phosphates, polyphosphates, borates, silicates and also carbonates. Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates.

Examples of suitable organic alkaline detergency builder salts are: (1)
water-soluble amino polycarboxylates, e.g., sodium and potassium
ethylenediaminetetraacetates, nitrilotriacetates and N-(2
hydroxyethyO-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g.,
sodium and potassium phytates (see U.S. Patent No. 2,379,942); (3)
water-soluble polyphosphonates, including specifically, sodium, potassium and
lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and
lithium salts of methylene diphosphonic acid; sodium, potassium and lithium
salts of ethylene diphosphonic acid; and sodium, potassium and lithium salts of
ethane-1,1,2-triphosphonic acid. Other examples include the alkali metal salts
of ethane-2-carboxy-1,1 -diphosphonic acid hydroxyrnethanediphosphonic acid,
carboxyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid,
ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonic
acid, propane-1,1,2,3-tetraphosphonicacid, and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of polycarboxylate
polymers and copolymers as described in U.S. Patent No 3,308,067.
In addition, polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate, tartrate disuccinate and mixtures thereof (TMS/TDS).

Certain zeolites or aluminosilicates can be used. One such aluminosiiicate which is more fully described in British Pat. No. 1,470,250.
A second water-insoluble synthetic aluminosiiicate ion exchange material useful herein is crystalline in nature and is more fully described in British Patent No. 1,429,143. Especially preferred builders include sodium citrate and sodium tetraborate pentahydrate.
Enzymes
One or more enzymes as described in detail below, may be used in the
composition of the invention.
If a lipase is used, the lipolytic enzyme may be either a fungal lipase producible by Humicola lanuginosa and Thermomyces lanuginosus, or a bacterial lipase which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Chromobacter viscosum var. lipolyticum NRRL B-3673. This microorganism has been described in Dutch patent specification 154,269 of Toyo Jozo Kabushiki Kaisha and has been deposited j with the Fermentation Research Institute, Agency of Industrial Science and " Technology, Ministry of International Trade and Industry/Tokyo, Japan, and added to the permanent collection under nr. KO Hatsu Ken Kin Ki 137 and is available to the public at the United States Department of Agriculture, Agricultural Research Service, Northern Utilization and Development Division at Peoria, Illinois, USA, under the nr. NRRL B-3673. The lipase produced by this microorganism is commercially available from Toyo Jozo Co., Tagata, Japan, hereafter referred to as "TJ lipase". These bacterial lipases should show a positive immunological cross-reaction with the TJ lipase antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950).

All bacterial lipases showing a positive immunological cross-reaction with the TJ-lipase antibody as hereabove described are lipases suitable in this embodiment of the invention. Typical examples thereof are the lipase ex Pseudomonas fluorescens 1AM 1057 available from Amano Pharmaceutical Go., Nagoya, Japan, under the trade-name Amano-P lipase, the lipase ex Pseudomonas tragi FERM P 1339 (available under the trade-name Amano-B), the lipase ex Pseudomonas nitroreducens var. Iipolyticum FERM P1338, the lipase ex Pseudomonas sp. available under the trade-name Amano CES, the
: lipase ex Pseudomonas cepacia, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. Iipolyticum NRRL B-3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum
, lipases from U.S. Biochemical Corp. USA and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
An example of a fungal lipase as defined above is the lipase ex Humicola lanuginosa, available from Amano under the tradename Amano CE; the lipase ex Humicola lanuginosa as described in the aforesaid European Patent Application 0,258,068 (NOVO), as well as the lipase obtained by cloning the gene from Humicola lanuginosa and expressing this gene in Aspergillus oryzae, commercially available from NOVO industri A/S under the tradename "Lipolase". This lipolase is a preferred lipase for use in the present invention.
While various specific lipase enzymes have been described above, it is to be understood that any lipase which can confer the desired lipolytic activity to the composition may be used and the invention is not intended to be limited in any way by specific choice of lipase enzyme.
The lipases of this embodiment of the invention are included in the liquid detergent composition in such an amount that the final composition has a

lipolytic enzyme activity of from 100 to 0.005 LU/ml in the wash cycle, preferably 25 to 0.05 LU/ml when the formulation is dosed at a level of about .1-10, more preferably .5-7, most preferably 1-2 g/liter.
A Lipase Unit (LU) is that amount of lipase which produces 1/Fmol of titratable fatty acid per minute in a pH state under the following conditions: temperature 30/C; pH = 9.0; substrate is an emulsion of 3.3 wt.% of olive oil and 3.3% gum arabic, in the presence of 13 mmol/1 Ca2+ and 20 mmoI/1 NaCI in 5 mmol/1 Tris-buffer.
Naturally, mixtures of the above lipases can be used. The lipases can be used in their non-purified form or in a purified form, e.g. purified with the aid of well-known absorption methods, such as phenyl sepharose absorption techniques.
The proteolytic enzyme can be of vegetable, animal or microorganism origin. I Preferably, it is of the latter origin, which includes yeasts, fungi, molds and | bacteria. Particularly preferred are bacterial subtilisin type proteases, obtained \ from e.g. particular strains of B. subtilis and B licheniformis. Examples of i suitable commercially available proteases are Alcalase, Savinase, Esperase, all of NOVO Industri A/S; Purafect and Properase from Genencor; Maxatase and Maxacal of Gist-Brocades; Kazusase of Showa Denko; BPN and BPN" proteases; Optimase from Solvay and so on. The amount of proteolytic enzyme, included in the composition, ranges from 0.05-50,000 GU/mg. preferably 0.1 to 50 GU/mg, based on the final composition. Naturally, mixtures of different proteolytic enzymes may be used.
While various specific enzymes have been described above, it is to be understood that any protease whicli can confer the desired proteolytic activity to

the composition may be used and this embodiment of the invention is not limited in any way by specific choice of proteolytic enzyme.
In addition to lipases or proteases, it is to be understood that other enzyme such as cellulase (Carezyme™, Clazinase™, Celluzyme™), oxidase, amylase, peroxidase and the like which are well known in the art may also be used with the composition of the invention. The enzymes may be used together with co-factors required to promote enzyme activity, i.e., they may be used in enzyme x systems, if required. It should also be understood that enzymes having | mutations at various positions (e.g., enzymes engineered for performance S and/or stability enhancement) are also contemplated by the invention. One I example of an engineered commercially available enzyme is Durazym™ from I Novo.
Optional Ingredients
".. In addition to the enzymes mentioned above, a number of other optional ingredients may be used.
Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine, borax and the like.
Other materials such as clays, particularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. The bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These

bentonites are known to soften textiles as described in British Patent No. 401, 413 to Marriott and British Patent No. 461,221 to Marriott and Guam.
In addition, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature.
Improvements in the physical stability and anti-settling properties of the .composition may be achieved by the addition of a small effective amount of fsorbitol or an aluminum salt of a higher fatty acid, e.g., aluminum stearate, to Ithe composition. The aluminum stearate stabilizing agent can be added in an (amount of 0 to 3%, preferably 0.1 to 2.0% and more preferably 0.5 to 1.5%.
.There also may be included in the formulation, minor amounts of soil | suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, ! sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. Preferred : anti-redeposition agents include Alcosperse 725™ and sodium carboxylmethyl | cellulose having a 2:1 ratio of CM/MC which is sold under the tradename
I Relatin DM 4050
i
Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include Tinopal LMS-X, Tinopal UNPA-GX, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dimorpholine dianilino stilbene sulfonate.
Anti-foam agents, e.g. silicon compounds, such as Silicane L 7604, can also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, e.g. formalin, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume and dyes and bluing agents such as Iragon Blue L2D, Detergent Blue 472/572 and ultramarine blue can be used.
-
Also, soil release polymers and cationic softening agents may be used.

Anionic Polymer
Anionic polymers of the invention are those polymers that have negatively charged groups attached covalently to the chain. Examples of synthetic anionic polymers are polyacrylic acid units in its partially and fully ionized forms, polyethylene sulfonic acid in its partially and fully ionized forms, poly(methacryiic acid) in its partially and fully ionized forms, poly(phosphoric acid) and its salts, poly(vinylsulfuric acid) and polyvinyl a!cohol-co-vinyl sulfuric acid) and their salts. A list of other synthetic anionic polymers can be found in, "Water-soluble Synthetic Polymers: Properties and Behavior" by P. Molyneux, Vol. II, CRC Press, 1985. This reference is hereby incorporated by reference into the subject application. Examples of commercially available synthetic anionic polymers are Sokalan series and Acusoi series of polyacryiic acids and copolymers of acrylic and maleic acids from BASF and Rohm & Haas respectively.
Examples of unmodified and modified natural anionic polymers are alginic acid and its salts and modified starches such as carboxymethyl cellulose. A list of unmodified and modified natural anionic polymers can be found in, "Encyclopedia of Polymers and Thickeners" by R. Y. Lochhead and W. R. Fron in Cosmetics and Toiletries, Vol, 108, May 1993.
The anionic polymer should be used in an amount comprising 0.1 to 10% by wt., preferably 0.25% to 5% by wt. of the composition.
Other optimal ingredients which may be used are hydrotropes. In general, addition of hydrotropes helps to incorporate higher levels of surfactants into isotropic liquid detergents than would otherwise be possible due to phase separation of surfactants from the aqueous phase. Hydrotropes also allow a change in the proportions of different types of surfactants, namely

anionic, nonionic, cationic and zwitterionic, without encountering the problem of phase separation. Thus, they increase the formulation flexibility. Hydrotropes function through either of the following mechanisms: i) they increase the solubility of the surfactant in the aqueous phase by changing the solvent power of the aqueous phase; short chain alcohols such as ethanol, isopropanol and also glycerol and propylene glycol are examples in this class and ii) they
;prevent formation of liquid crystalline phases of surfactants by disrupting the packing of the hydrocarbon chains of the surfactants in the micelles; alkali metal salts of alkyl aryl sulfonates such as xylene sulfonate, cumene sulfonate and
■alkyl aryl disulfonates such as DOWFAX(R) family of hydrotropes marketed by
\ Dow Chemicals are examples in this class.
j Preferred hydrotropes in the compositions of the present invention are polyols, I which may also act as enzyme stabilizers, such as propylene glycol, ethylene i glycol, glycerol, sorbitol, mannitol and glucose.
Enzyme Encapsulate
The enzyme encapsulate according to the present invention should
| effectively protect the enzyme from the adverse effect of UV radiation. Therefore it is essential that the enzyme is adequately contained in the encapsulate to prevent any significant leaking of the enzyme into the liquid detergent composition during storage.
The enzyme encapsulate may contain polymeric material, but this is not a limiting condition. If polymers are present in the capsules, at least part of the polymeric material should not dissolve in the liquid detergent, whereas they disperse or dissolve upon dilution. Examples of synthetic polymeric materials are:
- polyvinyl alcohol (PVA) of different molecular weight and degrees of

hydrolysis, which is defined as a homopolymer or copolymer in which vinyl acetate is a starting monomer unit and in which most or all of the acetate moieties are subsequently hydrolyzed to alcohol moieties.(e.g. Airvol range from Air Products, Mowiol range from Hoechst)
- polyamide (obtained via reaction between a diamine with a dicarboxylic acid)
- polyester (obtained via reaction between a diol and a dicarboxylic acid)
- polyurea
- polyurethane
- epoxy resin
Other examples of natural polymers include:
- methyl cellulose (e.g. Methocal A15LV ex Dow Chemical)
- hydroxypropyicsliuiose (e.g. Klucel L or Klucel G ex Aqualon)
- hydroxypropylmethylceliuiose
- carrageenan (kappa or iota forms) (various types ex FMC)
- alginate (e.g. Manucol DM or DH ex Kelco).
- gellan gum (e.g. Kelcogel ex Kelco)
- gelatine
Further reference: Encyclopaedia of polymers and thickeners for cosmetics, vol. 108, May 1993, 95-135.
If polymers are present in the capsules, they can be present as a small solid grains, either dispersed throughout the particle or preferentially located in part of the capsules, for example in the outside layer of the capsule. The polymers can also be present as hydrated particles, which can either be dispersed throughout the particle or located in a part of the capsule. Polymers can also be present in the core of the capsules, in the form of an onion ring inside the capsule or as a shell around the core.

The enzyme capsules can also contain hydrophobic or fatty materials. Examples of this are:
- Paraffins (preferably petroleum jelly)
- Triglycerides
- Fatty acids
- Fatty alcohols
- Mixtures of fatty acid and fatty acid soaps
- Esters (e.g. ceto stearyl stearate)
■ If the capsules contain hydrophobic materials they should protect the enzyme , against moisture. The hydrophobic material should envelope the enzyme solid particles or droplets which are present in the capsule.
j The capsules can contain also other ingredients:
- density modifiers, e.g. sucrose
- structurants, e.g. silica, or zeolite
- fillers, e.g. talc, bentonite
- scavengers, e.g., ammonium sulphate
- plasticizers *
- anti-agglomeration or layering agents
- releasing agents
Thus, in one preferred embodiment the enzyme encapsulate according to the present invention may comprise polymeric material. Preferably, the enzyme encapsulate comprise polymeric materials selected from the group consisting of polyvinylalcohol, polyamide, polyester, polyurea, polyurethane, epoxyresin, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, alginate, gellan gum, gelatine and mixtures thereof.

Examples of enzyme encapsulates can be found in WO-93/07263, EP-A-585295, EP-A-356239, US-A-5,281,356, US-A-5,281,355 and GB 2,186,884.
The enzyme encapsulate according to the present invention are between 30 and 5000 microns, preferably between 300 and 3000 microns, most preferably between 500 and 2500 microns. The particle shape can vary from irregular to spherical; in the preferred form they should be close to spherical, but this should not be limiting.
The enzyme encapsulate according to the present invention have an enzyme encapsulated density.- as measured in the detergent solution - of between 700 and 2500 kg/m3, more preferably between 800 and 2000 kg/m3 and most preferably between 900 and 1500 kg/m3.
The enzyme can be distributed homogeneously throughout the particle (matrix capsule), be located in the core of the capsule (core-sttell capsule) or be present in any other confined zone in the capsule, e.g. in an onion-ring shaped zone.
The enzyme can be present in the capsules in solid form, as small particles, which can comprise pure protein or optionally a mixture of protein and other materials (optionally in a matrix with other components). The enzyme can also be present in the capsule in the form of small droplets an enzyme solution, or as mixture of solid and liquid (slurry).
The enzyme encapsulate according to the present invention may comprise any detergent enzymes ihcfudihg protease lipase, amylase, peroxidase, cellulase or a mixture thereof.

Examples of protease are commercially available types such as Alcalase™, Durazym™, Relase™, Savinase™ ex Novo Nordisk and Optimase™, Purafect ™ , Properase™ ex Genencor International.
Examples of lipase are Lipolase™ ex Novo Nordisk and Lipomax™ ex Genencor International.
Examples of cellulase are Celluzyme™ and Carezyme™ ex Novo Nordisk, and Clazinase™ ex Genencor International.
Examples of amylase are Termamyl™ ex Novo Nordisk and Maxamyi™ ex \ Genencor International.
is
| Preferably the enzyme according to the present invention is a protease.
J When the enzyme according to the present invention is a protease, the protein I content is preferably in the range between 0.1 and 20%, more preferably
| between 0.5% and 10%, most preferably between 1% and 5%.
i
!
j When the enzyme according to the present invention is a protease, the enzyme activity is from 100 GU/mg and 20000 GU/mg, more preferably between 500 and 10000 GU/mg, most preferably between 1000 and 5000 GU/mg.
EXAMPLES
The following examples are intended to clarify the invention further and are not intended to limit the invention in any way.
All percentages are intended to be percentages by weight, unless stated otherwise.

Also when used in claims or specification, comprising is intended to include all elements, features etc.
Example 1
Enzyme capsules were prepared as follows::
A polymer solution was prepared by dissolving 3.3 parts of Polyvinyl Alcohol (Alrvol 540 ex Air Products Inc) in 60.7 parts of water. Theni5.0 parts of Poly Acryl Acrylate (Acrysol ASE-60 ex Rohm & Haas) were added, followed by 30 parts of a 2% aqueous solution of NaOH.
An enzyme dispersion in hydrophobe was prepared by dispersion of 15 parts of Optimase powder (Solvay, now part of Genencor International Inc.) into 59.5 parts of Snow white petrolatum (ex Penreco) at 60°C. Subsequently 25.5 parts of Trogrees Spray S (ex Penreco) was added to this dispersion followed by mixing for 30 minutes.
An emulsion of 1 part of the enzyme dispersion in 6 parts of the polymer solution was prepared by using a 9.5mm (3/8") I.D. 12 element static mixer at a throughput rate of 12 ml/min. This emulsion was atomized by a Spraying Systems 35100 two-fluid nozzle at an air rate of 7100 cc/min.
The droplets formed were collected in a hardening solution comprising 83.5 parts water, 15 parts sodium sulfate (ex Elf Atochem N.A.), 1.5 parts sodium tetraborate decahydrate (ex Textile Chemicals), 0.001 part of sodium dodecyl

sulfate (ex Aldrich) and 0.001 part of antifoam Silicon AF-544 (ex Dow Corning). The enzyme capsules were subsequently separated from the hardening solution by screening. The enzyme activity of these capsules was 5-104 GU/g.
Example 2
An enzymatic liquid detergent composition was prepared using the enzyme capsules from example 1 (size fraction from 500 -1000 um (microns)). The enzyme capsules were dispersed at a level of 1.5 wt.% into 20g of a transparent liquid detergent with a composition as outlined in Table 1, which resulted in an enzyme activity of 7.6-102 GU/g in the liquid detergent composition.
Another enzymatic liquid detergent composition was prepared by adding an aqueous solution of Optimase powder (ex Solvay, now part of Genencor International, Inc.) to a transparent liquid detergent with a composition as outlined in Table 1. The enzyme concentration in the aqueous solution was chosen at such level that an enzyme activity of 7.6-102 GU/g in the liquid detergent composition was obtained.
Care was taken that the enzyme activity of the liquid detergent composition with enzym© capsules was equal to the enzyme activity of the detergent composition whereto the enzyme was added as an aqueous solution.
Samples containing 20g of the detergent with dissolved Optimase and samples containing 20g of the detergent with Optimase capsules were stored in transparent polyethylene containers of 47 mm diameter and 95 mm height.
These samples weia.stored in an accelerated test at 37°C under exposure to two UV-B light sources of 20W (Philips TL20W12), whereby the samples were positioned at a distance of 20 cm from the bottom of the bottles to the UV-B

light source. Comparative samples were stored in an accelerated test at 37°C in the absence of light.
Samples were taken after two days and seven days storage and analyzed on residual enzyme activity with respect to the initial amount of enzyme activity prior to storage.
The residual activities as a function of time on storage are shown in Table 2.
The following important observations have been made:
1) For enzymes added from an aqueous solution, deactivation proceeds faster under exposure to UV-light than in the absence of light.
2) If the transparent bottles are exposed to UV-light, the storage stability of the enzyme which was added in the form of capsules is improved with respect to the storage stability of enzyme which was added to the liquid detergent in the form of a solution.
3) There is no difference between deactivation of the enzyme capsules under exposure to UV-light and in the absence of UV-light. This indicates that enzymes in the-capsules are protected against the adverse effects of UV-light.

Table 1: Detergent formulation

Table 2: Storage stability of enzyme and enzyme capsules in a liquid detergent in a transparent or translucent bottle, under exposure to UV-light, and in the absence of light Residual enzyme activity (in % with respect to the activity prior to storage) as a function of storage time.

As clearly seen, deactivation is faster when there are no capsules thereby indicating that capsules protect from UV light.
Example 3
Experimental Conditions
J The samples (5g) of liquid detergents (Table 1) containing protease and lipase
! were added to (38cm) 1.5" diameter glass dishes with the top off and exposed to UV-C light at near 254 nm (measured at 110 mwatt/cm2 (71cm) (28" from the light source)) for 4 days). After each 24 hour period, the samples were weighed and topped off to replace evaporated water. To release enzyme from capsules, the capsules were homogenized at 10,000 rpm in. 2% Neodol 25-9 solution. Enzyme activity in the homogenized solution was measured using Casein as
i the substrate. Percent remaining activity was calculated based on the initial
I activity in the sample prior to UV exposure.

mW/cm2, UVB= 6.17 mW/cm2 at the lamp). The HDL"s containing enzyme
Similar experiments were carried out in a UV-A/B chamber (UVA= 1.01 mW/cm2, UVB= 6.17 mW/cm2 at the lamp). Th capsules were exposed to UV lights for 4 days.

Table 3. A Detergent Formulation (Wisk Free & Clear, shown in ranges)

*C12-C15 ethoxylated alkyl chain ethoxylated with 9 ethylene oxide units.

Again, this shows improvement of stability when capsules were used. 5
^r

We Claim-
1. A packaged liquid detergent composition comprising a transparent or translucent container having a transmlttance of 25% or greater at wavelength of 410-800 nrr, and a transparent or translucent enzymatic detergent composition having a transmlttance of greater than 50% of fight using 1 cm cuvette at wavelength of 410-800 nm which container and detergent composition are transmissive of UV-B radiation characterised in that said enzymes are encapsulated,
2. A packaged detergent composition according to claim 1, wherein the enzyme encapsulate comprises polymeric material.
3. A packaged detergent composition according to claim 2, wherein the enzyme encapsulate polymeric material is selected from the group consisting of polyvinylaicohot, pofyamide, polyester, polyurea, polyurethane, epoxynssrn, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, alginate, gellan gum, gelatine and mixtures thereof.
4. A packaged detergent composition according to any preceding claim wherein the enzyme encapsulate is between 30 and 5000 urn (microns) in size,
5. A packaged detergent composition according to any preceding claim wherein the density of enzyme encapsulate as measured in me detergent solution is between 700 and 2500 kg/m3.

6. A packaged detergent composition according to any preceding claim wherein said enzyme encapsulate" comprises a detergent enzyme selected from the group consisting of protease, lipase, amylase, peroxidase, cellulase and a mixture thereof.
7. A packaged detergent composition according to claim 6, wherein the enzyme is a protease.
8. A packaged detergent composition according to claim 7, wherein protease content is in the range between 0.1 and 20%.
9. A packaged detergent composition according to claim 7 or claim 8, wherein the protease has an enzyme activity from 100 GU/mg to 20000 GU/mg.

10. A packaged detergent composition according to any preceding claim wherein the liquid detergent is aqueous.
11. A packaged detergent composition according to any preceding claim wherein the liquid detergent is externally structured.
12. A packaged detergent composition according to claim 11, wherein the liquid detergent is externally structured with polymers selected from the group consisting of gellan, xanthan, polyacrylate, algin, guar, rhamsan, carrageenan, carbopol-like polymers and mixtures thereof.
13. A packaged detergent composition according to any of the preceding claims, wherein the transparent container comprises a material selected from

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in-pct-2001-00639-mum-form 1a(25-6-2004).pdf

in-pct-2001-00639-mum-form 2(granted)-(12-1-2004).pdf

in-pct-2001-00639-mum-form 2(granted)-(12-8-2004).doc

in-pct-2001-00639-mum-form 3(4-6-2001).pdf

in-pct-2001-00639-mum-form 5(4-6-2001).pdf

in-pct-2001-00639-mum-form-pct-ipea-409(4-6-2001).pdf

in-pct-2001-00639-mum-form-pct-isa-210(4-6-2001).pdf

in-pct-2001-00639-mum-petition under rule 137(12-8-2004).pdf

in-pct-2001-00639-mum-petition under rule 138(12-8-2004).pdf

in-pct-2001-00639-mum-power of attorney(12-1-2004).pdf

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Patent Number

211632

Indian Patent Application Number

IN/PCT/2001/00639/MUM

PG Journal Number

04/2008

Publication Date

25-Jan-2008

Grant Date

05-Nov-2007

Date of Filing

04-Jun-2001

Name of Patentee

HINDUSTAN LEVER LIMITED

Applicant Address

HINDUSTAN LEVER HOUSE ,165/166 BACKBAY RECLAMATION,MUMBAI-400 020

Inventors:

#	Inventor's Name	Inventor's Address
1	VAN DE SCHEUR FRANK THEODOR	HPCE HOUSEHOLD CLEANING INNOVATION, VIA LEVER GIBBS 3, 1-26841 CASALPUSTERLENGO,ITALY
2	BAE-LEE MYONGSUK	UNILEVER RESEARCH U.S. INC., 45 RIVER ROAD, EDGEWATER, NJ 07020,
3	EHRNSPERGER ERIC CHARLES	UNILEVER RESEARCH U.S. INC., 45 RIVER ROAD, EDGEWATER, NJ 07020,
4	GEERLINGS ESTHER	UNILEVER R&D VLAAEDINGEN OLIVIER VAN NOORTLAAN 120 3133 AT VLAARDINGEN,
5	GOEDENDORP PIETER LEENDERT	UNILEVER R&D VLAAEDINGEN OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN
6	VAN DIJK WILLEM ROBERT	UNILEVER R&D VLAAEDINGEN OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN
7	BUSCAN MARINELA	UNILEVER R&D VLAAEDINGEN OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN

PCT International Classification Number

C11D 3/386 ; C11D 17/04

PCT International Application Number

PCT/EP99/08893

PCT International Filing date

1999-11-09

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/213046	1998-12-16	U.S.A.