EP1144580B2 - Compositions d'enzymes liquides transparentes/translucides dans des bouteilles incolores comprenant des antioxydants - Google Patents

Compositions d'enzymes liquides transparentes/translucides dans des bouteilles incolores comprenant des antioxydants Download PDF

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Publication number
EP1144580B2
EP1144580B2 EP99962197.2A EP99962197A EP1144580B2 EP 1144580 B2 EP1144580 B2 EP 1144580B2 EP 99962197 A EP99962197 A EP 99962197A EP 1144580 B2 EP1144580 B2 EP 1144580B2
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Prior art keywords
enzyme
lipase
alkyl
sodium
composition
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EP1144580A2 (fr
EP1144580B1 (fr
EP1144580A3 (fr
Inventor
Myongsuk Unilever Research U.S. Inc. BAE-LEE
Feng-Lung Gordon Hsu
Dennis Stephen Lever Brothers Development MURPHY
Kristina Marie Lever Brothers Development NEUSER
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to DE69920272.8T priority Critical patent/DE69920272T3/de
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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
    • 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
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • the present invention relates to enzyme-containing aqueous, transparent or translucent heavy duty liquid laundry detergents in clear bottles comprising antioxidants.
  • the antioxidants protect enzymes present in the HDL composition from damage by harmful UV radiation thereby preserving the enzyme activity.
  • UV light is meant light having wavelength of about 250 to about 460 nanometers (nm).
  • UVA generally is in range 320-400 nm, UVB about 290 to 320 nm and UVC below 290 nm, down to about 250 nm.
  • UV absorbers can be added to the bottle material during manufacture of clear bottles to protect them from becoming brittle and to protect the ingredients inside the bottle.
  • GB 2228940 the use of a dicarboxylate in polyester bottles to protect contents - mainly food - from 320-360 nm is described.
  • EP 0461537A2 the use of film formers for blocking UV radiation from passing through glass bottles is described. While use of such ingredients can block the transmission of UV light through clear bottles, UV absorbers for inclusion in bottle material are expensive, and must be added when bottle material is hot and molten and there is the risk of burning the operator.
  • WO 97/26315 discloses transparent containers with specific chromaticity defined by x and y values. Specific dyes are used in the liquid to match the container. The reference neither teaches nor suggests transparent liquids with the specific combination of antioxidant and enzyme capsules of the invention.
  • GB 1,303,810 discloses clear liquid medium and visually distinct components suspended in the medium. Detergent compositions containing antioxidants and enzyme capsule are not disclosed.
  • U.S. Patent No. 3,812,042 to Verdier discloses clear packages containing liquids with a viscosity and clarity control system comprising urea, lower aliphatic alcohol and optional hydrotrope.
  • WO-A-95/30730 discloses liquid detergents comprising surfactant; enzyme and antioxidant.
  • the present invention relates to a composition in a clear bottle according to claim 1 and a method according to claim 2.
  • the invention relates to enzyme containing transparent/translucent liquid duty liquids in clear bottles comprising antioxidants to protect against loss of enzyme activity (e.g., caused by the light hitting enzyme through the clear bottle).
  • Antioxidants used in the invention are ascorbic acid, BHA, BHT and mixtures thereof. Although it is not bound by the theory, antioxidants delay oxidation reaction by inhibiting the formation of free radicals in the initiation steps. This would inhibit the chain reaction of radical transfer by acting as hydrogen donors or free radical acceptors.
  • Antioxidants are used in an amount of 0.001 to 3%, preferably 0.005 to 2%, more preferably 0.01 to 1%.
  • compositions used in the invention contains one or more surface active agents (surfactants) selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
  • surfactants 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.
  • the surfactant should comprise at least 10% by wt. of the composition, e.g., 11% to 85%, preferably at least 15% to 70% of the total composition, more preferably 16% to 65%; even more preferably 20% to 65%.
  • Nonionic synthetic organic detergents which can be used with the invention, alone or in combination with other surfactants, are described below.
  • nonionic detergents are characterized by the presence of an organic 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. Pat. Nos. 4,316,812 and 3,630,929 .
  • the nonionic detergents 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 detergent 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 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. NeodolTM 25-7 and NeodolTM 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 about 12 to 15 carbon atoms, with about 7 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.
  • 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
  • Dobanol 23-7 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 7 to 9 moles, and the C 9 to C 11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
  • R is a monovalent organic radical containing from 6 to 30 (preferably from 8 to 18) carbon atoms
  • R' is a divalent hydrocarbon radical containing from about 2 to 4 carbons atoms
  • O is an oxygen atom
  • y is a number which can have an average value of from 0 to about 12 but which is most
  • a particularly preferred group of glycoside surfactants for use in the practice of this invention includes those of the formula above in which R is a monovalent organic radical (linear or branched) containing from 6 to 18(especially from about 8 to about 18) carbon atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number having an average value of from 1 to about 4 (preferably from about 1 to 4).
  • Nonionic surfactants particularly useful for this application include, but are not limited to: alcohol ethoxylates (e.g. Neodol 25-9 from Shell Chemical Co.), alkyl phenol ethoxylates (e.g. Tergitol NP-9 from Union Carbide Corp.), alkylpolyglucosides (e.g. GlucaponTM 600CS from Henkel Corp.), polyoxyethylenated polyoxypropylene glycols (e.g. PluronicTM L-65 from BASF Corp.), sorbitol esters (e.g. EmsorbTM 2515 from Henkel Corp.) , polyoxyethylenated sorbitol esters (e.g.
  • EmsorbTM 6900 from Henkel Corp.
  • alkanolamides e.g. AlkamideTM DC212/SE from Rhone-Poulenc Co.
  • N-alkypyrrolidones e.g. SurfadoneTM LP-100 from ISP Technologies Inc.
  • Nonionic surfactant is used in the formulation from about 0% to about 70%, preferably between 5% and 50%, more preferably 10-40% by weight.
  • Mixtures of two or more of the nonionic surfactants can be used.
  • 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 sulfonate or sulfate group.
  • the anionic surface active agents include the alkali metal (e.g. sodium and potassium) water soluble higher alkyl benzene sulfonates, alkyl sulfonates, alkyl sulfates and the alkyl polyether sulfates. They may also include fatty acid or fatty acid soaps.
  • the preferred anionic surface active agents are the alkali metal, ammonium or alkanolamide salts of higher alkyl benzene sulfonates and alkali metal, ammonium or alkanolamide salts of higher alkyl sulfonates.
  • Preferred higher alkyl sulfonates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to I8 carbon atoms.
  • the alkyl group in the alkyl benzene sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms.
  • a particularly preferred alkyl benzene sulfonate is the sodium or potassium dodecyl benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
  • the primary and secondary alkyl sulfonates can be made by reacting long chain alpha-olefins with sulfites or bisulfites, e.g. sodium bisulfite.
  • the alkyl sulfonates can also be made by reacting long chain normal paraffin hydrocarbons with sulfur dioxide and oxygen as described in U.S. Pat. Nos. 2,503,280 , 2,507,088 , 3,372,188 and 3,260,741 to obtain normal or secondary higher alkyl sulfonates 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 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 alkyl benzene sulfonate can be used in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight.
  • the alkali metal sulfonate can be used in admixture with the alkylbenzene sulfonate in an amount of 0 to 70%, preferably 10 to 50% by weight.
  • normal alkyl and branched chain alkyl sulfates e.g., primary alkyl sulfates
  • anionic component e.g., sodium sulfate
  • the higher alkyl polyether 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'-O(CH 2 CH 2 O) p -SO 3 M The preferred higher alkyl poly ethoxy sulfates used in accordance with the present invention are represented by the formula: R'-O(CH 2 CH 2 O) p -SO 3 M, where R' 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 benzene, alkyl sulfonates, or alkyl sulfates.
  • the alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfonate or sulfonate, in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight of entire composition.
  • Anionic surfactants particularly useful for this application include, but are not limited to: linear alkyl benzene sulfonates (e.g. VistaTM C-500 from Vista Chemical Co.), alkyl sulfates (e.g. PolystepTM B-5 from Stepan Co.), polyoxyethylenated alkyl sulfates (e.g. StandapolTM ES-3 from Stepan Co.), alpha olefin sulfonates (e.g. WitconateTM AOS from Witco Corp.), alpha sulfo methyl esters (e.g. Alpha-StepTM MC-48 from Stepan Co.) and isethionates (e.g. JordaponTM CI from PPG Industries Inc.).
  • linear alkyl benzene sulfonates e.g. VistaTM C-500 from Vista Chemical Co.
  • alkyl sulfates e.g. PolystepTM B-5 from Stepan Co.
  • Anionic surfactant is used in the formulation from about 0% to about 60%, preferably between 5% and 40%, more preferably 8 to 25% by weight.
  • 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 .
  • compositions used in 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.
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be a straight chain or a branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
  • Examples of compounds falling within this definition are sodium 3(dodecylamino)propionate, sodium 3-(dodecylamino)propane-I-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium octadecylimminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
  • Sodium 3-(dodecylamino)propane-I-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.
  • zwitterionic surfactants which may be used are set forth in U.S. Pat. No. 4,062,647 .
  • the amount of amphoteric used may vary from 0 to 50% by weight, preferably 1 to 30% by weight.
  • compositions used in the invention are preferably isotropic (by which is generally understood to be a homogenous phase when viewed macroscopically) and either transparent or translucent.
  • Total surfactant used must be at least 10%, preferably at least 15%, more preferably at least 20% by wt.
  • Builders which can be used according to this invention include conventional alkaline detergency builders, inorganic or organic, which can be used at levels from about 0% to about 50% by weight of the composition, preferably from 3% to about 35% by weight.
  • electrolyte means any water-soluble salt.
  • the composition comprises at least 1.0% by weight, more preferably at least 5.0% by weight, most preferably at least 10.0% by weight of electrolyte.
  • the 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 sulfate or chloride.
  • the inorganic builder comprises all or part of the electrolyte.
  • the composition may comprise at least 1%, preferably at least 3%, preferably 3% to as much as 50% by weight electrolyte.
  • compositions used in the invention are capable of suspending particulate solids, although particularly preferred are those systems where such solids are actually in suspension.
  • the solids may be undissolved electrolyte, the same as or different from the electrolyte in solution, the latter being saturated electrolyte. Additionally, or alternatively, they may be materials which are substantially insoluble in water alone. Examples of such substantially insoluble materials are aluminosilicate builders and particles of calcite abrasive.
  • suitable inorganic alkaline detergency builders which may be used are water-soluble alkali metal phosphates, polyphosphates, borates, silicates and also carbonates.
  • suitable 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. Pat. 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/TPS).
  • zeolites or aluminosilicates can be used.
  • One such aluminosilicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Na x [(AlO 2 ) y .SiO 2 ), wherein x is a number from 1.0 to I.2 and y is 1, said amorphous material being further characterized by a Mg++ exchange capacity of from about 50 mg eq. CaCO 3 /g. and a particle diameter of from 0.01 mm to 5 mm.
  • This ion exchange builder is more fully described in British Patent No. 1,470,250 .
  • a second water-insoluble synthetic aluminosilicate ion exchange material useful herein is crystalline in nature and has the formula Na z [(AlO 2 ) y (SiO 2 )] x H 2 O, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from 15 to 264; said aluminosilicate ion exchange material having a particle size diameter from 0.1 mm to 100 mm; a calcium ion exchange capacity on an anhydrous basis of at test about 200 milligrams equivalent of CaCO 3 hardness per gram; and a calcium exchange rate on an anhydrous basis of at least 2 grains/gallon/minute/gram.
  • These synthetic aluminosilicates are more fully described in British Patent No. 1,429,143 .
  • Enzymes which may be used in the subject invention are described in greater detail below.
  • 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 immune diffusion procedure according to Ouchterlony ( Acta. Med. Scan., 133. pages 76-79 (1930 ).
  • the preparation of the antiserum is carried out as follows:
  • Equal volumes of 0.1 mg/ml antigen and of Freund's adjuvant (complete or incomplete) are mixed until an emulsion is obtained.
  • Two female rabbits are injected 45 with 2 ml samples of the emulsion according to the following scheme:
  • the serum containing the required antibody is prepared by centrifugation of clotted blood, taken on day 67.
  • the titre of the anti-TJ-lipase antiserum is determined by the inspection of precipitation of serial dilutions of antigen and antiserum according to the Ouchteriony procedure. A dilution of antiserum was the dilution that still gave a visible precipitation with an antigen concentration of 0.1 mg/ml.
  • 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.
  • 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 0.1-10, more preferably 0.5-7, 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 AlcalaseTM, SavinaseTM, EsperaseTM, all of NOVO Industri A/S; MaxataseTM and MaxacalTM of Gist-Brocades; KazusaseTM of Showa Denko; BPN and BPN' proteases 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 be specific choice of proteolytic enzyme.
  • lipases or proteases In addition to lipases or proteases, it is to be understood that other enzymes such as cellulases, oxidases, amylases, peroxidases and the like which are well known in the art may also be used with the composition used in 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 are also contemplated by the invention.
  • One example of an engineered commercially available enzyme is Durazym from Novo.
  • Alkalinity buffers which may be added to the compositions of the invention include monoethanolamine, triethanolamine, borax, sodium silicate and the like.
  • Hydrotropes which may be added to the invention include ethanol, sodium xylene sulfonate, sodium cumene sulfonate and the like.
  • bentonite This material is primarily montmorillonite which is a hydrated aluminum silicate in which about 1/6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc. may be loosely combined.
  • the bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 30% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meg 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 .
  • detergent additives of 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 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
  • a preferred anti-redeposition agent is sodium carboxylmethyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050.
  • a deflocculating polymer comprises a hydrophilic backbone and one or more hydrophobic side chains.
  • deflocculating polymer of the invention is described in greater detail in U.S. Pat. No. 5,147,576 .
  • the deflocculating polymer generally will comprise, when used, from 0.1 to 5% of the composition, preferably 0.1 to 2% and most preferably, 0.5 to 1.5%.
  • Optical brighteners for cotton, polyamide and polyester fabrics can be used.
  • Suitable optical brighteners include TinopalTM, 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. silicone 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 472/372 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 472/372 and ultramarine blue
  • soil release polymers and cationic softening agents may be used.
  • compositions used in the invention may contain all or some the following ingredients: zwitterionic surfactants (e.g. MirataineTM BET C-30 from Rhone-Poulenc Co.), cationic surfactants (e.g. SchercamoxTM DML from Scher Chemicals, Inc.), fluorescent dye, antiredeposition polymers, antidye transfer polymers, soil release polymers, protease enzymes, lipase enzymes, amylase enzymes, cellulase enzymes, peroxidase enzymes, enzyme stabilizers, perfume, opacifiers, UV absorbers, builders, and suspended particles of size range 300-5000 microns.
  • zwitterionic surfactants e.g. MirataineTM BET C-30 from Rhone-Poulenc Co.
  • cationic surfactants e.g. SchercamoxTM DML from Scher Chemicals, Inc.
  • fluorescent dye e.g. MirataineTM BET C-30 from Rhone-Poulenc Co
  • compositions used in the invention have at least 50% transmittance of light using a 1 centimeter cuvette, at a wavelength of 410-800 nanometers, preferably 570-690 nm wherein the composition is substantially free of dyes.
  • transparency of the composition may be measured as having an absorbency in the visible light wavelength (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 410 to 800 nm
  • it is considered to be transparent/translucent.
  • Enzyme deactivation as a result of UV-damage may occur at very low transmission of UV-B radiation.
  • Clear bottle materials with which this invention may be used include, but are not limited to: polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamides (PA) and/or polyethylene terephthalate (PETE), polyvinylchloride (PVC); and polystyrene (PS).
  • PP polypropylene
  • PE polyethylene
  • PC polycarbonate
  • PA polyamides
  • PETE polyethylene terephthalate
  • PVC polyvinylchloride
  • PS polystyrene
  • the transparent or clear container used in the invention has a transmittance of more than 25%, more preferably more than 30%, more preferably more than 40%, more preferably more than 50% in the visible part of the spectrum (410-800 nm).
  • absorbency of bottle may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals: 1 10 absorbancy ⁇ 100 %
  • the container is considered to be transparent/translucent or clear.
  • Enzyme deactivation as a result of UV-damage may occur at very low transmission of UV-B radiation through the container wall.
  • the container used in the present invention may be of any form or size suitable for storing and packaging liquids for household use.
  • the container may have any size but usually the container will have a maximal capacity of 0.05 to 15 L, preferably, 0.1 to 5 L, more preferably from 0.2 to 2.5 L.
  • the container is suitable for easy handling.
  • the container may have 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 means for reclosing the container.
  • the pouring means may be of any size of form but, preferably will be wide enough for convenient dosing the liquid detergent composition.
  • the closing means may be 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.
  • Fan is included so as to maintain the internal temperature throughout the duration of an experiment. This ensures that any effects seen are the result of ultraviolet light alone and not heat.
  • Samples are placed in open containers and put in box. Open containers are used so as to limit interference of the container material on the light rays. An open container of water is added to the box as well. This water keeps atmosphere at a constant humidity and slows evaporation from the open samples. After a given period of time, samples are removed from the box, reconsidered for the evaporation of water and tested for UV effects.
  • Sunlight is an important cause of damage to plastics, textiles, paints and other organic materials.
  • UV light makes up only about 5% of sunlight, it is responsible for most of the photochemical damage. This is because the photochemical effectiveness of light increases with decreasing wavelength.
  • Short wavelength ultraviolet light has long been recognized as responsible for most of this damage.
  • Accelerated weathering testers are widely used for research and development, quality control, and material certification. They employ a variety of light sources to simulate sunlight and the damage cause by sunlight.
  • UVA-340 lamp was chosen. Most of this lamp's emission in the UV-A region, with a small amount in the UV-B. This lamp is an excellent simulation of sunlight from about 370 nm, down to the solar cut-off of 295 nm.
  • the samples contained either 25 mM ascorbic acid, 2.5 mM BHA, or 2.5 mM BHT as a protecting agent. This corresponded to 0.044 wt.% ascorbic acid, 0.045 wt.% BHA and 0.055 wt.% BHA.
  • the control sample did not contain any such protecting agents. Results were as follows (Table 2a): Table 1.
  • a Detergent Formulation 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% *C 12 -C 15 alkoxylated (9EO) chain group Table 2a.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Cosmetics (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Wrappers (AREA)

Claims (2)

  1. Composition nettoyante liquide multi-usages transparente ou translucide dans une bouteille claire, comprenant :
    (a) de 10 à 85 % en poids d'un tensioactif sélectionné dans le groupe constitué des tensioactifs anioniques, non ioniques, cationiques, amphotères, zwittérioniques, et des mélanges de ceux-ci ;
    (b) de 0,001 à 5 % en poids d'une enzyme sélectionnée dans le groupe constitué des protéases, des lipases, des cellulases, des oxydases, des amylases et des mélanges de celles-ci ; et
    (c) de 0,001 à 3 % en poids d'un antioxydant sélectionné parmi l'acide ascorbique, le BHA, le BHT, et des mélanges de ceux-ci ;
    dans laquelle la composition a une capacité de transmission de la lumière de 50 % ou plus en utilisant une cuvette de 1 cm à une longueur d'ondes de 410 - 800 nanomètres ; et
    dans laquelle la bouteille a une capacité de transmission de la lumière supérieure à 25 % à une longueur d'onde de 410 - 800 nm.
  2. Méthode pour prévenir la dégradation enzymatique d'une enzyme dans une composition nettoyante liquide multi-usages transparente ou translucide dans une bouteille claire comprenant :
    (a) de 10 à 85 % en poids d'un tensioactif sélectionné dans le groupe constitué des tensioactifs anioniques, non ioniques, cationiques, amphotères, zwittérioniques, et des mélanges de ceux-ci ;
    (b) de 0,001 à 5 % en poids d'une enzyme sélectionnée dans le groupe constitué des protéases, des lipases, des cellulases, des oxydases, des amylases et des mélanges de celles-ci ; et
    dans laquelle la composition a une capacité de transmission de la lumière de 50 % ou plus en utilisant une cuvette de 1 cm à une longueur d'ondes de 410 - 800 nanomètres ; et
    dans laquelle la bouteille a une capacité de transmission de la lumière supérieure à 25 % à une longueur d'onde de 410 - 800 nm, ledit procédé comprenant l'ajout d'un antioxydant sélectionné parmi l'acide ascorbique, le BHA, le BHT, et des mélanges de ceux-ci à ladite composition, dans une quantité allant de 0,001 à 3 % en poids de la composition.
EP99962197.2A 1998-12-16 1999-11-30 Compositions d'enzymes liquides transparentes/translucides dans des bouteilles incolores comprenant des antioxydants Expired - Lifetime EP1144580B2 (fr)

Priority Applications (1)

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DE69920272.8T DE69920272T3 (de) 1998-12-16 1999-11-30 Durchsichtige oder lichtdurchlässige flüssige enzym- und antioxidantenthaltende zusammensetzungen in klaren flaschen

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US21304498A 1998-12-16 1998-12-16
US213044 1998-12-16
PCT/EP1999/009376 WO2000036062A2 (fr) 1998-12-16 1999-11-30 Compositions d'enzymes liquides transparentes/translucides dans des bouteilles incolores comprenant des antioxydants

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EP1144580B2 true EP1144580B2 (fr) 2014-11-26

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US7074581B2 (en) * 2002-08-09 2006-07-11 Sysmex Corporation Reagent for assaying lipid
JP2007524744A (ja) * 2004-02-24 2007-08-30 ノボザイムス アクティーゼルスカブ 液状洗剤中の酵素の安定化
EP1700904A1 (fr) * 2005-03-11 2006-09-13 Unilever N.V. Composition detergente liquide
US20070267444A1 (en) * 2006-05-05 2007-11-22 De Buzzaccarini Francesco Concentrated compositions contained in bottom dispensing containers
DE102009028891A1 (de) 2009-08-26 2011-03-03 Henkel Ag & Co. Kgaa Verbesserte Waschleistung durch Radikalfänger
CN115895795B (zh) * 2022-12-26 2024-06-25 媞颂日化用品(广州)有限公司 一种含生物表面活性剂的清洁组合物及其制备方法和应用

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FR2136913B1 (fr) * 1971-05-07 1973-05-11 Colgate Palmolive Co
JPS5438605B2 (fr) * 1974-06-07 1979-11-22
US4238345A (en) * 1978-05-22 1980-12-09 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4243543A (en) * 1979-05-11 1981-01-06 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US4462922A (en) * 1981-11-19 1984-07-31 Lever Brothers Company Enzymatic liquid detergent composition
GB8311314D0 (en) * 1983-04-26 1983-06-02 Unilever Plc Aqueous enzyme-containing compositions
GB8520550D0 (en) * 1985-08-16 1985-09-25 Unilever Plc Detergent compositions
EP0342177B1 (fr) * 1988-05-12 1995-07-12 The Procter & Gamble Company Compositions détergentes liquides renforcées, contenant des surfactants anioniques et nonioniques, des agents de renforcement et un enzyme protéolitique
GB2232420A (en) * 1989-05-30 1990-12-12 Unilever Plc Liquid detergent compositions
US5789364A (en) * 1993-02-17 1998-08-04 The Clorox Company High water liquid enzyme prewash composition
US5466394A (en) * 1994-04-25 1995-11-14 The Procter & Gamble Co. Stable, aqueous laundry detergent composition having improved softening properties
CZ311096A3 (en) * 1994-04-29 1997-05-14 Procter & Gamble Cellulose preparations for conditioning fabrics
CA2189544C (fr) * 1994-05-06 2000-06-13 Kenneth Michael Kemen Detergent liquide contenant un amide polyhydroxyle d'acide gras et un sel toluene sulfonate
WO1997026315A1 (fr) * 1996-01-18 1997-07-24 Colgate-Palmolive Company Conditionnement contenant une composition de nettoyage liquide pour lavages delicats
CA2269352A1 (fr) * 1996-10-21 1998-04-30 The Procter & Gamble Company Composition concentree d'assouplissant de textile
AU3486399A (en) * 1998-04-09 1999-11-01 Procter & Gamble Company, The Dishwashing detergent product having a ultraviolet light resistant bottle

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WO2000036062A2 (fr) 2000-06-22
EP1144580A2 (fr) 2001-10-17
TR200101716T2 (tr) 2002-05-21
ATE276341T1 (de) 2004-10-15
ZA200104132B (en) 2002-05-21
EP1144580B1 (fr) 2004-09-15
WO2000036062A3 (fr) 2001-11-01
CN1380900A (zh) 2002-11-20
EP1144580A3 (fr) 2002-09-11
AR021681A1 (es) 2002-07-31
CA2355058A1 (fr) 2000-06-22
AU749498B2 (en) 2002-06-27
DE69920272D1 (de) 2004-10-21
DE69920272T2 (de) 2005-09-22
HUP0600532A2 (en) 2006-10-28
BR9916246A (pt) 2001-10-02
ES2228144T3 (es) 2005-04-01
AU1861500A (en) 2000-07-03
DE69920272T3 (de) 2015-01-08
ES2228144T5 (es) 2015-02-04

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