EP0533239A2 - Compositions détergentes aqueuses et liquides - Google Patents

Compositions détergentes aqueuses et liquides Download PDF

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Publication number
EP0533239A2
EP0533239A2 EP92202668A EP92202668A EP0533239A2 EP 0533239 A2 EP0533239 A2 EP 0533239A2 EP 92202668 A EP92202668 A EP 92202668A EP 92202668 A EP92202668 A EP 92202668A EP 0533239 A2 EP0533239 A2 EP 0533239A2
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EP
European Patent Office
Prior art keywords
enzyme
weight
bleach
acid
composition
Prior art date
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Granted
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EP92202668A
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German (de)
English (en)
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EP0533239B1 (fr
EP0533239A3 (en
Inventor
Alan D. Unilever Res. Vlaardingen Lab. Tomlinson
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0533239A3 publication Critical patent/EP0533239A3/en
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    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • This invention relates to aqueous liquid cleaning compositions comprising an enzyme and encapsulated bleach particles.
  • aqueous liquid cleaning compositions comprising an enzyme and encapsulated bleach particles.
  • enzymatic aqueous liquid cleaning compositions especially but not exclusively adapted for use in automatic dishwashing machines, comprising an enzyme, encapsulated bleach particles and a reducing agent.
  • Cleaning compositions having a combination of bleaching action and enzymatic degradation of biochemical soils which comprise a slow release oxidant bleach composition in the form of encapsulated bleach particles which delay the appearance of the full concentration of the oxidant bleach but having the tendency to release a small deactivating amount of the oxidant, prior to the full concentration of the bleach being released, a biological soil-degrading enzyme and an amount of a chemical reducing agent effective to delay the appearance of an enzyme-deactivating concentration of oxidant bleach composition until the full concentration of the oxidant bleach composition is released, are known and described in US Patent Specification 4,421,664.
  • a reducing agent such as sodium sulphite
  • scavenger for the oxidant as proposed in US Patent 4,421,664 does not improve the enzyme stability sufficiently enough to arrive at a commercially viable product with adequate and consistent performance of both the enzyme and the bleach.
  • the reducing agent is not sufficiently effective to scavenge the oxidant for a sufficient amount of time.
  • the enzyme stability in such aqueous liquid cleaning compositions can be substantially improved if the composition fulfils the following two conditions, i.e. a water content of not more than 55% by weight and containing a reducing agent in an amount of from 0.01 to 0.5% by weight.
  • the invention provides an improved aqueous liquid cleaning composition
  • a detergency builder comprising a detergency builder, an enzyme, encapsulated bleach particles and a reducing agent, characterized in that the composition has a water content of not more than 55% by weight, preferably not more than 50% by weight, and the reducing agent is present in an amount of from 0.01 to 0.5% by weight.
  • aqueous liquid used herein encompasses low-viscosity liquids to the more highly viscous liquids as well as gels and pastes, having water contents of from about 10-55% by weight, preferably from 25-55% by weight, and more preferably from 35-50% by weight.
  • the composition of the invention is a mildly alkaline aqueous liquid.
  • the neat composition will have a pH of from about 5.0 to about 10.5, preferably from about 6.5 to 10.5, more preferably from about 8 to 9.5.
  • Soluble detergency builder salts useful herein can be of the poly-valent inorganic and poly-valent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergency builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates and silicates.
  • Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates and hexametaphosphates.
  • suitable organic alkaline detergency builder salts are (1) water-soluble amino polyacetates, e.g. sodium and potassium ethylenediamine tetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g. sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and lithium salts of methylenediphosphonic acid and the like.
  • water-soluble amino polyacetates e.g. sodium and potassium ethylenediamine tetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates
  • water-soluble salts of phytic acid e.g. sodium and potassium phytates
  • water-soluble polyphosphonates including sodium, potassium and lithium salts of
  • Additional organic builder salts useful herein include the polycarboxylate materials described in US Patent Specification N° 2,264,103, including the water-soluble alkali metal salts of mellitic acid and citric acid, dipicolinic acid, oxydisuccinic acid and alkenyl succinates.
  • the water-soluble salts of polycarboxylate polymers and copolymers, such as are described in US Patent Specification N° 3,308,067, are also suitable herein.
  • alkali metal salts of the foregoing inorganic and organic poly-valent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanolammonium, e.g. triethanolammonium, diethanolammonium, and the like, water-soluble salts of any of the foregoing builder anions are useful herein.
  • Suitable builders is that of the so-called water-insoluble calcium ion-exchange builder materials.
  • examples thereof include the various types of water-insoluble crystalline or amorphous alumino silicates, of which zeolites are the best-known representatives.
  • Other useful materials are, for example, the layered silicates, such as a product sold by Hoechst under the trade name SKS-6.
  • compositions of the invention are preferably free of phosphate builders for environmental and ecological reasons.
  • Preferred builders for use in the invention are sodium citrate, sodium carbonate, and sodium bicarbonate and mixtures thereof, or the potassium salts thereof.
  • the potassium salts may be preferred for solubility reasons.
  • the amount of builders in the composition is from about 5 to 60% by weight, more preferably from 25 to about 40% by weight.
  • Enzymes are used for many purposes in various fields where biochemical reactions occur.
  • an enzyme can be described as a catalyst capable of permitting a biochemical reaction to quickly occur and can be classified according to the type of reaction they catalyze.
  • Enzymes are characterized by a high specificity, that is to say, each enzyme can catalyze a single reaction of one substance or a very small number of closely related substances.
  • enzymes suitable for use in the cleaning compositions of this invention include lipases, peptidases, amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removability.
  • lipases are classified as EC class 3, hydrolases, subclass EC 3.1, preferably carboxylic ester hydrolases EC 3.1.1.
  • lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases are lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases.
  • Amylases belong to the same general class as lipases, subclass EC 3.2, especially EC 3.2.1 glycose hydrolases such as 3.2.1.1. alpha-amylase with the systematic name alpha-1,4-glucan-4-glucanohydrolase; and also 3.2.1.2, beta-amylase with the systematic name alpha-1,4-glucan maltohydrolase.
  • Proteases belong to the same class as lipases and amylases, subclass EC 3.4, particularly EC 3.4.4 peptide peptido-hydrolases such as EC 3.4.4.16 with the systematic name subtilopeptidase A.
  • Enzymes serving different functions can also be used in the practice of this invention, the selection depending upon the composition of biochemical soil, intended purpose of a particular composition, and the availability of an enzyme to degrade or alter the soil.
  • Lipases sometimes called esterases, hydrolyze fatty soils.
  • Lipases suitable for use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strain of bacteria and fungi.
  • lipases suitable for use herein can be derived from Pseudomonas , Aspergillus , Pneumococcus , Staphylococcus , Toxins, Mycobacterium Tuberculosis , Mycotorula Lipolytica , and Sclerotinia microorganisms, and can be made using recombinant DNA manufacturing techniques.
  • Suitable animal lipases are found in the body fluids and organs of many species.
  • a preferred class of animal lipase herein is the pancreatic lipase.
  • Lipase can be employed in the present cleaning compositions in an amount from about 0.005% to about 10%, preferably from 0.01 to 5% of the cleaning composition, on a pure enzyme basis.
  • the enzymes most commonly used in machine dishwashing compositions are amylolytic enzymes.
  • amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those prepared and described in British Patent Specification N° 1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945 A.
  • Examples of such amylolytic enzymes are amylolytic enzymes produced and distributed under the trade name of SO-95® or Termamyl® by Novo Industri A/S, Copenhagen, Denmark. These amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram.
  • amylolytic activity can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Vol. I (1955), page 149.
  • composition of the invention preferably also contains a proteolytic enzyme.
  • subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis , such as the commercially available subtilisins Maxatase®' supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase®, supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from Novo Industri A/S under the registered trade names of Esperase® and Savinase®.
  • the preparation of these and analogous enzymes is described in British Patent Specification N° 1,243,784.
  • protease useful herein is a fairly recent commercial product sold by Novo Industri A/S under the trade name Durazym®, as described in WO-A-89/06279.
  • the enzymes can be presented as granules, e.g. marumes, prills, T-granules etc., and may have enzyme activities of from about 500 to 1700 glycine units/miiligram.
  • enzyme preparations are also commercially supplied as liquids or slurries e.g. Termamyl 300 L, Savinase 16.0 L, Savinase 16.0 SL.
  • All these enzymes can each be present in a weight percentage amount of from 0.2 to 5% by weight, such that for amylolytic enzymes the final composition will have amylolytic activity of from 102 to 106 Maltose units/kg, and for proteolytic enzymes the final composition will have proteolytic enzyme activity of from 106 to 109 Glycine Units/kg.
  • Enzyme granules containing only minor proportions, e.g. less than 30%, particularly not more than 10% by weight, of chloride to substantially nil, are preferably used in the compositions of the invention.
  • US Patent N° 4,279,764 to Brubaker shows encapsulation of a mixture of an organic nitrogen-containing halogen bleaching agent, an N-H-containing compound, and a soluble inorganic hydratable salt.
  • US Patent N° 3,036,013 to Jaszka teaches encapsulated calcium hypochlorite bleach.
  • the coatings can be applied in a variety of well-known methods including tumbling the coating and coated compound in a rolling mill, spraying a solution or suspension of the coating into a fluidized bed of the compound to be coated, precipitating the coating from a solvent on to the compound to be coated which is in suspension in the solvent, etc.
  • a preferred encapsulated bleach particle for use in the present invention is that as described in the above-mentioned European patent applications, comprising 35-55% by weight of the particle of a single coat of paraffin wax and 45-65% by weight of a core of a chlorine or peroxygen bleach compound, the paraffin wax having a melting point of between 35°C and about 50°C, preferably from 40°C to 50°C, and having penetration values of from 10 to 60 mm at 25°C.
  • the bleach to be encapsulated in the coating may be a chlorine- or bromine-releasing agent or a peroxygen compound.
  • suitable reactive chlorine- or bromine-oxidizing materials are heterocyclic N-bromo and N-chloro imides such as trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water-solubilizing cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethyl-hydantoin are also quite suitable.
  • Dry, particulate, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
  • Chlorinated trisodium phosphate is another core material.
  • Chloroisocyanurates are, however, the preferred bleaching agents.
  • Potassium dichloroisocyanurate is sold by Monsanto Company as ACL-59®.
  • Sodium dichloroisocyanurates are also available from Monsanto as ACL-60®, and in the dihydrate form, from the Olin Corporation as Clearon CDB-56®, available in powder form (particle diameter of less than 150 microns); medium particle size (about 50 to 400 microns); and coarse particle size (150-850 microns). Very large particles (850-1700 microns) are also found to be suitable for encapsulation.
  • peroxyacids usable in the present invention are solid and, preferably, substantially water-insoluble compounds.
  • substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
  • peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as:
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N',N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US Patent Specification 4,751,015.
  • TAED N,N,N',N'-tetraacetyl ethylene diamine
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • SBOBS sodium benzoyloxybenzene sulphonate
  • SPCC cationic peroxyacid precursor
  • Inorganic peroxygen-generating compounds may also be suitable as cores for the particles of the present invention.
  • examples of these materials are salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US Patents 5,041,232 and 5,047,163, is to be incorporated, this can be presented in the form of a second encapsulate separately from the bleach capsule.
  • the amount of encapsulates used in the compositions of the invention may vary within the range of about 0.5% to about 3% as available chlorine (Avcl).
  • a suitable range will be from 0.5% to 3% avO (available oxygen).
  • Reducing agents useful to prevent the appearance of an enzyme-deactivating concentration of oxidant bleach compound include reducing agent that can substantially reduce Cl2, HClO and other oxidizing chlorine-containing compositions to Cl ⁇ ions or can substantially reduce hydrogen peroxide or peroxy acid bleaches to unoxidized species.
  • the reducing agent should not damage the object or material to be cleaned or substantially chemically change the enzyme, or other cleaning composition components such as the detergent, builder, etc.
  • Useful reducing agents include reducing sulphur-oxy acids and salts thereof.
  • Most preferred for reasons of availability, low cost, and high performance are the alkali metal and ammonium salts of sulphuroxy acids including ammonium sulphite ((NH4)2SO3), sodium sulphite (Na2SO3), sodium bisulphite (NaHSO3), sodium metabisulphite (Na2S2O3), potassium metabisulphite (K2S2O5), lithium hydrosulphite (Li2S2O4), etc., sodium sulphite being particularly preferred.
  • ammonium sulphite (NH4)2SO3)
  • sodium sulphite Na2SO3
  • sodium bisulphite NaHSO3
  • sodium metabisulphite Na2S2O3
  • K2S2O5 potassium metabisulphite
  • Li2S2O4 lithium hydrosulphite
  • Another useful reducing agent is ascorbic acid. These reducing agents must be used at sufficient amounts effective to scavenge the chlorine or oxidizing bleach leakage. It will be appreciated that these amounts may vary from case to case depending on the type and quality of the encapsulated bleach particles, but normally a range of about 0.01% to about 0.5% by weight, preferably from about 0.02% to about 0.2% by weight, will be sufficient. An amount lower than 0.01% may not be effective and an amount higher than 0.5% may not be necessary and, besides, in the case of sodium sulphite, is not wanted because of its smell.
  • Optional ingredients are, for example, the well-known enzyme stabilizers such as the polyalcohols, e.g. glycerol, and borax; anti-scaling agents; crystal-growth inhibitors, threshold agents; thickening agents; perfumes and dyestuffs and the like.
  • the well-known enzyme stabilizers such as the polyalcohols, e.g. glycerol, and borax; anti-scaling agents; crystal-growth inhibitors, threshold agents; thickening agents; perfumes and dyestuffs and the like.
  • a small amount of low- to non-foaming nonionic surfactant which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to some protein soil.
  • an excessive proportion of nonionic surfactant should be avoided.
  • nonionic surfactants for use in the invention are the low- to non-foaming ethoxylated propoxylated straight-chain alcohols of the Plurafac® RA series, supplied by the Eurane Company; of the Lutensol® LF series, supplied by the BasF Company; of the Triton® DF series, supplied by the Rohm & Haas Company; and Synperonics, supplied by the ICI Company.
  • Another optional but highly desirable additive ingredient with multi-functional characteristics, particularly in non-phosphate compositions is from 1% to 15%, preferably about 5% by weight, of a polymeric material having a molecular weight of from 1,000 to 2,000,000, and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone methyl- or ethyl-, vinyl ethers and other polymerizable vinyl monomers.
  • polymeric materials are polyacrylic acid or polyacrylate; polymaleic acid or polyacrylate; polymaleic acid/acrylic acid copolymer; 70:30 acrylic acid/hydroethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/maleic acid copolymers; methyl- and ethylvinylether/maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer. These polymers are believed to function as co-builders, although under certain conditions they may also function as main builders.
  • compositions of the present invention may also comprise, and preferably do, a thickener, for example a polymer such as a suitable acrylate, methacrylate (or copolymer thereof) or a cellulose such as hydroxymethyl cellulose.
  • a thickener for example a polymer such as a suitable acrylate, methacrylate (or copolymer thereof) or a cellulose such as hydroxymethyl cellulose.
  • Typical inclusion levels of thickener are from 0.1% to 10%, e.g. from 0.5% to 5% by weight of the total composition.
  • Buffering agents may also be necessary to adjust and maintain the alkalinity and pH of the composition at the desired level. These are, for example, the alkali metal carbonates, bicarbonates and borates. Also sodium and/or potassium hydroxide may be used.
  • composition I % by weight Carbopol® 941 1.50 NaOH (pellets) 0.80 Borax 3.00 Glycerol 6.00 Polymer (Sokalan® CP7) 5.00 Sodium citrate 30.00 Sodium sulphite 0.04 Chlorine bleach capsules 1) 4.30 Proteolytic enzyme (Savinase ® 16.0L) 0.30 Amylase (Termamyl® 300 L) 0.30 Water to 100.00 (abt. 49%). 1) The chlorine bleach capsules used herein comprise about 50% of Na-DCCA core and 50% of a paraffin wax coating, giving approx. 1.20% avCl. (see EP-A-0,436,971).
  • the order of addition during manufacture should be that the sodium sulphite is added as near as possible to the addition of the bleach encapsulation and definitely before the enzymes.
  • Composition I was tested in a Miele 595SC dishwashing machine at a temperature of 55°C, using water of 14°FH.
  • FIG. 1 shows the dramatic drops of Savinase residual activity in compositions containing more than 55% water.
  • composition III % by weight Carbopol® 941 1.50 NaOH pellets 0.80 Borax 3.00 Glycerol 6.00 Polymer (Sokalan® CP7) 5.00 Sodium citrate 30.50 Sodium sulphite 0.00 - 0.04 - 0.10 MPS bleach capsules 1) 5.00 Proteolytic enzyme (Savinase ® 16.0L) 0.30 Amylase (Termamyl® 300 L) 0.30 Water to 100.00 (approx. 47%). 1) The MPS bleach capsules used herein are encapsulates comprising potassium monopersulphate (50% by weight) as the core bleach material provided with 50% by weight of a paraffin wax coating and prepared according to the method as described in EP-A-0,436,971.
  • compositions were stored for 6 weeks at 37°C, whereafter the residual activities of Savinase and Termamyl were determined.
  • This Example shows enzyme stability as a function of sulphite level in an accelerated storage test.
  • the experiments were carried out with the formulations of Example I with varying levels of sodium sulphite. The compositions were stored at 50°C for 6 hours. The results are tabulated below.
  • Sulphite level (%) Residual Activity (%) Savinase Amylase 0 0 0 0.02 4 5 0.04 5 7.5 0.10 30 37.5 0.20 67 82.5

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  • Engineering & Computer Science (AREA)
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EP92202668A 1991-09-17 1992-09-03 Compositions détergentes aqueuses et liquides Expired - Lifetime EP0533239B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919119936A GB9119936D0 (en) 1991-09-17 1991-09-17 Aqueous liquid cleaning compositions
GB9119936 1991-09-17

Publications (3)

Publication Number Publication Date
EP0533239A2 true EP0533239A2 (fr) 1993-03-24
EP0533239A3 EP0533239A3 (en) 1993-08-04
EP0533239B1 EP0533239B1 (fr) 1998-04-01

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EP (1) EP0533239B1 (fr)
JP (1) JPH0791559B2 (fr)
AU (1) AU2289392A (fr)
BR (1) BR9203530A (fr)
CA (1) CA2078157A1 (fr)
DE (1) DE69224950T2 (fr)
ES (1) ES2114908T3 (fr)
GB (1) GB9119936D0 (fr)
TR (1) TR26328A (fr)
ZA (1) ZA927109B (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0596550A2 (fr) * 1992-11-03 1994-05-11 Unilever N.V. Composition détergente liquide contenant un agent structurant biodégradable
WO1995033817A1 (fr) * 1994-06-07 1995-12-14 Unilever N.V. Particules encapsulees contenant un tensioactif et permettant d'obtenir des taux ameliores de liberation et de dissolution
EP0791647A3 (fr) * 1996-02-21 1998-02-25 Clariant GmbH Agent de blanchement
WO2001005928A1 (fr) * 1999-07-14 2001-01-25 Johnsondiversey, Inc. Composition detergente et procede de lavage du linge
WO2001029167A1 (fr) * 1999-10-15 2001-04-26 The Procter & Gamble Company Composition enzymatique liquide de nettoyage presentant une stabilite d'enzyme amylase amelioree
WO2001096518A1 (fr) * 2000-06-15 2001-12-20 Unilever N.V. Composition detergente liquide concentree
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
WO2004053042A1 (fr) 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide a plusieurs composants
EP0780466B2 (fr) † 1995-12-22 2005-01-19 Kao Corporation Produit granulé contenant une enzyme, méthodes pour sa préparation et compositions contenant le granulat
WO2005042685A1 (fr) * 2003-10-16 2005-05-12 Reckitt Benckiser N.V. Composition detergente contenant des particules d'agent de blanchiment enrobees
EP2199386A1 (fr) 1993-10-08 2010-06-23 Novozymes A/S Variants d'amylase
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
US8709575B2 (en) 2006-04-26 2014-04-29 Dsm Ip Assets B.V. Multilayered material sheet and process for its preparation
US8999911B2 (en) 2011-11-04 2015-04-07 Bissell Homecare, Inc. Enzyme cleaning composition and method of use
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9625237B2 (en) 2006-04-26 2017-04-18 Dsm Ip Assets B.V. Mutilayered material sheet and process for its preparation
US9879206B2 (en) 2013-03-14 2018-01-30 Ecolab Usa Inc. Enzyme-containing detergent and presoak composition and methods of using
EP4032966A1 (fr) * 2021-01-22 2022-07-27 Novozymes A/S Composition enzymatique liquide avec piégeur de sulfite

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HUP0300840A2 (hu) 2000-07-28 2003-07-28 Henkel Kommanditgesellschaft Auf Aktien Új, Bacillus sp. A 7-7 (DSM 12368)-ból extrahált amilolitikus enzim, valamint használata mosó- és tisztítószerekben
WO2002044350A2 (fr) 2000-11-28 2002-06-06 Henkel Kommanditgesellschaft Auf Aktien Nouvelle cyclodextrine-glucanotransferase (cgtase) issue de bacillus agaradherens (dsm 9948) et produits detergents et de nettoyage comprenant cette nouvelle cyclodextrine-glucanotransferase
JP4708597B2 (ja) * 2001-05-16 2011-06-22 四国化成工業株式会社 殺菌剤組成物
WO2022210453A1 (fr) * 2021-03-31 2022-10-06 花王株式会社 Composition de détergent pour lave-vaisselle automatique
JP2023158259A (ja) * 2022-04-18 2023-10-30 花王株式会社 自動食器洗浄機用洗浄剤組成物

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DE2337338A1 (de) * 1972-07-27 1974-02-07 Interox Chemicals Ltd Gegen zersetzung mindestens teilweise stabilisierte persauerstoffverbindungen in form von mindestens teilweise mit einem ueberzug versehenen teilchen und diese verbindungen enthaltende waschmittel
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Cited By (34)

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EP0596550A3 (en) * 1992-11-03 1996-07-03 Unilever Nv Liquid detergent composition containing biodegradable structurant.
EP0596550A2 (fr) * 1992-11-03 1994-05-11 Unilever N.V. Composition détergente liquide contenant un agent structurant biodégradable
EP2199386A1 (fr) 1993-10-08 2010-06-23 Novozymes A/S Variants d'amylase
WO1995033817A1 (fr) * 1994-06-07 1995-12-14 Unilever N.V. Particules encapsulees contenant un tensioactif et permettant d'obtenir des taux ameliores de liberation et de dissolution
EP0780466B2 (fr) † 1995-12-22 2005-01-19 Kao Corporation Produit granulé contenant une enzyme, méthodes pour sa préparation et compositions contenant le granulat
EP0791647A3 (fr) * 1996-02-21 1998-02-25 Clariant GmbH Agent de blanchement
WO2001005928A1 (fr) * 1999-07-14 2001-01-25 Johnsondiversey, Inc. Composition detergente et procede de lavage du linge
AU759577B2 (en) * 1999-07-14 2003-04-17 Diversey, Inc. A detergent composition and laundry washing method
WO2001029167A1 (fr) * 1999-10-15 2001-04-26 The Procter & Gamble Company Composition enzymatique liquide de nettoyage presentant une stabilite d'enzyme amylase amelioree
WO2001096518A1 (fr) * 2000-06-15 2001-12-20 Unilever N.V. Composition detergente liquide concentree
AU2001267456B2 (en) * 2000-06-15 2004-01-15 Unilever Plc Concentrated liquid detergent composition
US6569827B2 (en) 2000-06-15 2003-05-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Concentrated liquid detergent composition
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
WO2004053042A1 (fr) 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide a plusieurs composants
WO2005042685A1 (fr) * 2003-10-16 2005-05-12 Reckitt Benckiser N.V. Composition detergente contenant des particules d'agent de blanchiment enrobees
CN100422301C (zh) * 2003-10-16 2008-10-01 雷克特本克斯尔荷兰有限公司 经被覆的漂白剂颗粒
US9903689B2 (en) 2006-04-26 2018-02-27 Dsm Ip Assets B.V. Multilayered material sheet and process for its preparation
US9863742B2 (en) 2006-04-26 2018-01-09 Dsm Ip Assets B.V. Multilayered material sheet and process for its preparation
US9702664B2 (en) 2006-04-26 2017-07-11 Dsm Ip Assets B.V. Multilayered material sheet and process for its preparation
US8709575B2 (en) 2006-04-26 2014-04-29 Dsm Ip Assets B.V. Multilayered material sheet and process for its preparation
US9625237B2 (en) 2006-04-26 2017-04-18 Dsm Ip Assets B.V. Mutilayered material sheet and process for its preparation
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
US8999911B2 (en) 2011-11-04 2015-04-07 Bissell Homecare, Inc. Enzyme cleaning composition and method of use
US9879206B2 (en) 2013-03-14 2018-01-30 Ecolab Usa Inc. Enzyme-containing detergent and presoak composition and methods of using
US10604726B2 (en) 2013-03-14 2020-03-31 Ecolab Usa Inc. Enzyme-containing detergent and presoak composition and methods of using
EP4032966A1 (fr) * 2021-01-22 2022-07-27 Novozymes A/S Composition enzymatique liquide avec piégeur de sulfite
WO2022157311A1 (fr) * 2021-01-22 2022-07-28 Novozymes A/S Composition d'enzyme liquide avec piégeur de sulfite

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BR9203530A (pt) 1993-04-13
AU2289392A (en) 1993-03-18
ZA927109B (en) 1994-03-17
JPH05202393A (ja) 1993-08-10
TR26328A (tr) 1995-03-15
CA2078157A1 (fr) 1993-03-18
DE69224950T2 (de) 1998-08-13
GB9119936D0 (en) 1991-10-30
JPH0791559B2 (ja) 1995-10-04
EP0533239B1 (fr) 1998-04-01
ES2114908T3 (es) 1998-06-16
DE69224950D1 (de) 1998-05-07
EP0533239A3 (en) 1993-08-04

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