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EP1141206B1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
EP1141206B1
EP1141206B1 EP99963312A EP99963312A EP1141206B1 EP 1141206 B1 EP1141206 B1 EP 1141206B1 EP 99963312 A EP99963312 A EP 99963312A EP 99963312 A EP99963312 A EP 99963312A EP 1141206 B1 EP1141206 B1 EP 1141206B1
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EP
European Patent Office
Prior art keywords
detergent composition
enzyme
composition according
packaged
transparent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP99963312A
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German (de)
English (en)
French (fr)
Other versions
EP1141206A1 (en
Inventor
Frank Theodor Van De Scheur
Myongsuk Bae-Lee
Eric Charles Ehrnsperger
Esther Unilever Research Vlaardingen GEERLINGS
Pieter Leendert Goedendorp
Willem Robert Van Dijk
Marinela Buscan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • This invention relates to the field of liquid detergents, in particular to a packaged transparent liquid detergent composition.
  • 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 (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.
  • 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.
  • 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.
  • the present invention provides a packaged liquid detergent composition according to claim 1 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).
  • a transparent container e.g., polyethylene
  • UV light e.g., UV-B light
  • Another embodiment of the invention provides a packaged liquid detergent composition
  • 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.
  • the presently claimed invention provides a packaged detergent composition as defined by claim 1 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.
  • the enzymes in said packaged detergent composition have 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 37°C.
  • 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.
  • transparency may be defined as absorbency being less than 0.6 or the transmittance greater than 25%, wherein % transmittance equals:: 1 10 Absorbency x 100%
  • 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.
  • PE polyethylene
  • PP polypropylene
  • PC polycarbonate
  • PETE polyethylene terephthalate
  • Polyethylene containers were used for UV stability tests in the present invention and had transparency of 8% at 310 nm, 17.5% at 400 nm, 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.
  • 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.
  • the container is suitable for easy handling.
  • 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 the container.
  • 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.
  • the container may comprise a re-closable aperture of such a size and position which renders it suitable for convenient refilling.
  • 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 TetrapakTM like containers.
  • the liquid detergent according to the present invention may be aqueous or non-aqueous.
  • Aqueous liquids may be internally or externally structured.
  • 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, carbopolTM and carbopol-like polymers and mixtures thereof.
  • 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.
  • 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.
  • 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.
  • absorbency in the visible light wavelength about 410 to 800 nm
  • it is considered to be transparent/translucent.
  • transparent liquid detergent 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: 1 10 absorbency x 100%
  • Enzyme deactivation as a result of UV-damage may occur at very low transmissions of UV-B radiation.
  • 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.
  • 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 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 C 10 to C 16 benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
  • the primary and secondary alkyl sulphates can be made by reacting long chain alpha-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 C 10 to C 18 primary normal alkyl sodium and potassium sulfonates, with the C 10 to C 15 primary normal alkyl sulfonate salt being more preferred.
  • 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.
  • normal alkyl and branched chain alkyl sulfates e.g., primary alkyl sulfates
  • anionic component e.g., sodium alkyl sulfates
  • 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 normal 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.
  • R 1 -O(CH 2 CH 2 O) p -SO 3 M The preferred higher alkyl polyethoxy sulfates used in accordance with the present invention are represented by the formula: R 1 -O(CH 2 CH 2 O) p -SO 3 M, where R 1 is C 8 to C 20 alkyl, preferably C 10 to C 18 and more preferably C 12 to C 15 ; 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 C 12 to C 15 alcohol sulfate having the formula: C 12-15 -O-(CH 2 CH 2 O) 3 -SO 3 Na
  • alkyl ethoxy sulfates examples include C 12-15 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C 12 primary alkyl diethoxy sulfate, ammonium salt; C 12 primary alkyl triethoxy sulfate, sodium salt; C 15 primary alkyl tetraethoxy sulfate, sodium salt; mixed C 14-15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and mixed C 10-18 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.
  • the surfactant composition may be nonionic surfactant.
  • 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.
  • 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.
  • 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.
  • the nonionic surfactants are polyalkoxylated lipophiles wherein the desired hydrophile-tipophile 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 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.
  • 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.
  • 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 hydroxyl group. Examples include C 13 -C 15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C 13 -C 15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C 13 -C 15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide or mixtures of any of the above.
  • Dobanol 91-5 is an ethoxylated C 9 -C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
  • preferred nonionic surfactants include the C 12 -C 15 primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 6 to 9 moles, and the C 9 to C 11 fatty alcohols ethoxylated with about 5-6 motes ethylene oxide.
  • 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.
  • compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants known in the art.
  • compositions may contain no cationic surfactants at all.
  • cationics may comprise 0-20%, preferably 1-10% by weight of the total composition.
  • 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 octadecyl-imminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
  • Sodium 3-(dodecylamino)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.
  • 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
  • the preferred surfactant systems of the invention comprise linear alkyl sulphate, LES, nonionic and optionally soap (Monoethanolamine-soap, Na-soap).
  • Builders which can be used according to this invention include conventional 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.
  • 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.
  • 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.
  • Suitable organic alkaline detergency builder salts are: (1) water-soluble amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates (see U.S. Patent No.
  • 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.
  • 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).
  • zeolites or aluminosilicates can be used.
  • One such aluminosilicate which is more fully described in British Pat. No. 1,470,250.
  • a second water-insoluble synthetic aluminosilicate 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.
  • One or more enzymes as described in detail below, may be used in the composition of the invention.
  • 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 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.
  • TJ lipase 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 IAM 1057 available from Amano Pharmaceutical Co., Nagoya, Japan, under the trade-name Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade-name Amano-B), the lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P1338, the lipase ex Pseudomonas sp.
  • Chromobacter viscosum e.g. Chromobacter viscosum var. lipolyticum 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.
  • 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.
  • lipase enzymes 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.
  • 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. 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 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.
  • protease which 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.
  • lipases or proteases In addition to lipases or proteases, it is to be understood that other enzyme such as cellulase (CarezymeTM, ClazinaseTM, CelluzymeTM), 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 cofactors required to promote enzyme activity, i.e., they may be used in enzyme systems, if required.
  • enzymes having mutations at various positions e.g., enzymes engineered for performance and/or stability enhancement
  • DurazymTM is an engineered commercially available enzyme from Novo.
  • Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine, borax and the like.
  • bentonite is a material such as clays, particularly of the water-insoluble types.
  • 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.
  • 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 sorbitol or an aluminum salt of a higher fatty acid, e.g., aluminum stearate, to the 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%.
  • 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 725TM and sodium carboxylmethyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050
  • 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.
  • 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
  • Iragon Blue L2D Detergent Blue 472/572 and ultramarine blue
  • soil release polymers and cationic softening agents may be used.
  • 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 sutfonic acid in its partially and fully ionized forms, poly(methacrylic acid) in its partially and fully ionized forms, poly(phosphoric acid) and its salts, poly(vinylsulfuric acid) and poly(vinyl alcohol-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 Acusol series of polyacrylic acids and copolymers of acrylic and maleic acids from BASF and Rohm & Haas respectively.
  • 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.
  • hydrotropes Other optimal ingredients which may be used are hydrotropes.
  • 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.
  • Preferred hydrotropes in the compositions of the present invention are polyols, which may also act as enzyme stabilizers, such as propylene glycol, ethylene glycol, glycerol, sorbitol, mannitol and glucose.
  • 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:
  • natural polymers include:
  • 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:
  • 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.
  • the capsules can contain also other ingredients:
  • the enzyme encapsulate according to the present invention may comprise polymeric material.
  • 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.
  • 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 encapsulate's 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-shell 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 including protease lipase, amylase, peroxidase, cellulase or a mixture thereof.
  • protease examples include AlcalaseTM, DurazymTM, RelaseTM, SavinaseTM ex Novo Nordisk and OptimaseTM, Purafect TM, ProperaseTM ex Genencor International.
  • lipase examples include LipolaseTM ex Novo Nordisk and LipomaxTM ex Genencor International.
  • cellulase examples include CelluzymeTM and CarezymeTM ex Novo Nordisk, and ClazinaseTM ex Genencor International.
  • amylase examples include TermamylTM ex Novo Nordisk and MaxamylTM ex Genencor International.
  • the enzyme according to the present invention is a protease.
  • the protein content is preferably in the range between 0.1 and 20%, more preferably between 0.5% and 10%, most preferably between 1% and 5%.
  • 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.
  • Enzyme capsules were prepared as follows::
  • a polymer solution was prepared by dissolving 3.3 parts of Polyvinyl Alcohol (Airvol 540 ex Air Products Inc) in 60.7 parts of water. Then 6.0 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 suffate (ex Aldrich) and 0.001 part of antifoam Silicon AF-544 (ex Dow Coming).
  • the enzyme capsules were subsequently separated from the hardening solution by screening. The enzyme activity of these capsules was 5-10 4 GU/g.
  • An enzymatic liquid detergent composition was prepared using the enzyme capsules from example 1 (size fraction from 500 - 1000 ⁇ m (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 ⁇ 10 2 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 7.6-10 2 GU/g in the liquid detergent composition was obtained.
  • 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
  • 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.
  • Table 1 Detergent formulation Ingredient as 100% active wt.%
  • Nonionic surfactant 15.6 Alcohol Ethoxy Sulfate 9.0 Sodium Linear Alkyl Benzene Sulfonate 5.9
  • Propylene Glycol 6.0 Mono-Ethanol Amine 0.2 Sodium Citrate Dihydrate 2.5 Sodium Tetraborate Pentahydrate 1.5
  • 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.
  • Residual enzyme activity % Storage time (Days) Optimase added in solution, in absence of light
  • Optimase added in solution exposed to UV-light
  • Optimase in capsules in absence of light 0 100% 100% 100% 100% 100% 7 50% 37% 63% 59%
  • deactivation is faster when there are no capsules thereby indicating that capsules protect from UV light.
  • a Detergent Formulation (Wisk Free & Clear, shown in ranges) Ingredient as 100% active Wt % Neodol 25-9* 6-8 Alcohol ethoxy sulfate 12-15 Linear alkylbenzene sulfonate 6-9 Sodium citrate, dihydrate 3-6 Propylene glycol 4-8 Sorbitol 3-6 Sodium tetraborate pentahydrate 2-4 Minor additives and water to 100% *C12-C15 ethoxylated alkyl chain ethoxylated with 9 ethylene oxide units.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
EP99963312A 1998-12-16 1999-11-09 Detergent composition Revoked EP1141206B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US21304698A 1998-12-16 1998-12-16
US213046 1998-12-16
PCT/EP1999/008893 WO2000036067A1 (en) 1998-12-16 1999-11-09 Detergent composition

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EP1141206A1 EP1141206A1 (en) 2001-10-10
EP1141206B1 true EP1141206B1 (en) 2003-09-10

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AR (1) AR026104A1 (es)
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DE10111536A1 (de) * 2001-03-10 2002-09-12 Beiersdorf Ag Wäßrige kosmetische und dermatologische Zubereitungen, enthaltend suspendierte Festkörperpartikel, Gasbläschen und/oder Flüssigtröpfchen, ferner enthaltend eine Kombination aus Xanthangummi und Gellangummi
US6420333B1 (en) * 2001-08-28 2002-07-16 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Manufacture of capsules for incorporation into detergent and personal care compositions
GB0129983D0 (en) * 2001-12-14 2002-02-06 Unilever Plc Unit dose products
CN102942998B (zh) * 2012-10-30 2013-12-18 湖南日用化学科学研究所有限公司 一种除蛋白污渍的洗涤助剂
WO2014177709A1 (en) * 2013-05-03 2014-11-06 Novozymes A/S Microencapsulation of detergent enzymes
CN112980607A (zh) * 2021-02-26 2021-06-18 中山百科清洁用品制造有限公司 一种长效驱蚊洗衣液及其制备方法

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FR2136913B1 (es) * 1971-05-07 1973-05-11 Colgate Palmolive Co
EG18543A (en) * 1986-02-20 1993-07-30 Albright & Wilson Protected enzyme systems
GB9110408D0 (en) * 1989-08-24 1991-07-03 Allied Colloids Ltd Polymeric compositions
US5281355A (en) * 1992-04-29 1994-01-25 Lever Brothers Company, Division Of Conopco, Inc. Heavy duty liquid detergent compositions containing a capsule which comprises a component subject to degradation and a composite polymer
ES2147217T3 (es) * 1993-11-12 2000-09-01 Unilever Nv Composicion detergente.
DK0876205T3 (da) * 1995-12-29 2002-08-12 Ciba Spec Chem Water Treat Ltd Partikler med polymerkappe samt deres fremstilling
WO1997026315A1 (en) * 1996-01-18 1997-07-24 Colgate-Palmolive Company Filled package of light duty liquid cleaning composition
AU7578198A (en) * 1997-05-19 1998-12-11 Procter & Gamble Company, The Clear or translucent fabric softener compositions using mixture of solvents
EP0913462A1 (en) * 1997-10-31 1999-05-06 The Procter & Gamble Company Liquid aqueous bleaching compositions packaged in a UV-resistant container

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HUP0104643A3 (en) 2002-12-28
BR9916230A (pt) 2001-09-04
ATE249510T1 (de) 2003-09-15
DE69911254D1 (de) 2003-10-16
DE69911254T2 (de) 2004-04-01
AU1966700A (en) 2000-07-03
WO2000036067A1 (en) 2000-06-22
ES2207318T3 (es) 2004-05-16
TW460580B (en) 2001-10-21
HUP0104643A2 (hu) 2002-04-29
CN1330707A (zh) 2002-01-09
TR200101712T2 (tr) 2001-12-21
AR026104A1 (es) 2003-01-29
EP1141206A1 (en) 2001-10-10
ZA200104082B (en) 2002-06-18
AU746412B2 (en) 2002-05-02

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