EP0628625B1 - Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln - Google Patents

Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln Download PDF

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Publication number
EP0628625B1
EP0628625B1 EP93870099A EP93870099A EP0628625B1 EP 0628625 B1 EP0628625 B1 EP 0628625B1 EP 93870099 A EP93870099 A EP 93870099A EP 93870099 A EP93870099 A EP 93870099A EP 0628625 B1 EP0628625 B1 EP 0628625B1
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EP
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Prior art keywords
lipase
bleach
acid
protease
weight
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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.)
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EP93870099A
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English (en)
French (fr)
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EP0628625A1 (de
Inventor
Marina Trani
Carlo Ricci
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to EP93870099A priority Critical patent/EP0628625B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69324802T priority patent/DE69324802T2/de
Priority to ES93870099T priority patent/ES2131103T3/es
Priority to CA002164587A priority patent/CA2164587A1/en
Priority to JP7501929A priority patent/JPH09501451A/ja
Priority to CN94192823A priority patent/CN1066193C/zh
Priority to AU70507/94A priority patent/AU678027B2/en
Priority to BR9406791A priority patent/BR9406791A/pt
Priority to PCT/US1994/006189 priority patent/WO1994029423A1/en
Priority to ZA943979A priority patent/ZA943979B/xx
Publication of EP0628625A1 publication Critical patent/EP0628625A1/de
Application granted granted Critical
Publication of EP0628625B1 publication Critical patent/EP0628625B1/de
Priority to GR990401142T priority patent/GR3030162T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • bleaching agent various stains or soils on fabrics, textiles and hard surfaces are oxidized. Because of their oxidizing power peroxygen bleaching compounds like hydrogen peroxide, sodium perborate or sodium percarbonate have been found very useful in bleach formulations.
  • additive of certain organic compounds, including activators such as tetracetyl ethylene diamine (TAED), to for instance perborate bleaches can improve the bleaching performance because of the formation of peracids.
  • activators such as tetracetyl ethylene diamine (TAED)
  • TAED tetracetyl ethylene diamine
  • EP-A-206 390 discloses the inclusion of a certain, immunologically defined class of lipases in a detergent composition which comprises a mixture of an anionic and a nonionic detergent.
  • lipase shows a good activity, also in dry matrixes containing a high bleach level, it appears however that when a protease (for instance Savinase® 4.0 T, ex Novo) is added the lipase activity becomes much more prone to the attack by the protease.
  • a protease for instance Savinase® 4.0 T, ex Novo
  • EP-A-415 652 describes enzyme-containing oxidant bleach compositions providing enzyme stability during prolonged storage in the presence of oxidants, while supporting enzyme solubility.
  • the improved product is prepared by coating or encapsulating the enzyme with a water soluble alkali metal silicate coating including at least one protective agent being selected from transition metals andlor reducing agents.
  • US-A-4,106,991 describes improved formation of enzymes granulates through inclusion within the composition of finely divided cellulose fibres.
  • Waxy substance can optionally be employed for the granulating agent or to coat the granulate.
  • detergent compositions or additives with a high level of bleach, a lipase and a double coated protease deliver an excellent performance profile with respect to lipolytic activity.
  • a lipase and a double coated protease for instance Savinase R 4.0 CT +, ex Novo
  • the lipolytic activity remains more or less the same as in the situation that no protease at all is present in the composition or additive. This is clearly evidenced by the dingy cleaning and bleachable stain removal performances while the significant advantage for enzymatic stain removal by the proteolytic enzyme is maintained.
  • the present invention thus relates to a detergent composition or additive comprising a bleach activator, a high level of bleach delivering an available active oxygen in the composition from 3% to 11% by weight and a lipase, characterized by further comprising a double coated protease.
  • bleach activation mechanism achieved via for instance maleic acrylic copolymer or anhydrides and lipase, continues to work with a very high efficiency.
  • Activation systems will complement the actions of known bleach activators such as TAED, NOBS, BOBS, iso NOBS, PAG, TAGU, sulfonimines, metalloporphyrines, organo complexes of manganese, quarternary ammonium or phosphonium bleach precursors such as (trimethyl ammonium toluoyloxybenzene sulphonate) or acetylated glycerol fatty esters. They will also complement the actions of preformed peracids such as DPDA, NAPAA, PAP (N,N Phtaloylimidopercaproic acid), mono and dicarboxylic acids.
  • Dry compositions including a hydrogen peroxide source perborate, percarbonate, etc.
  • liquid compositions including hydrogen peroxide in itself can have significantly enhanced bleaching activation if they also include anhydrides and lipase.
  • Anhydrides commercially available like succinic and maleic are indicative for the inclusion in a dry bleach composition in conjunction with lipase. However, other anhydrides not having a cyclic or even a symmetric structure can also be included.
  • Polymeric anhydrides are also very suitable as well as co-polymers including anhydride monomers.
  • Acrylic acid and maleic anhydrides co-polymers are preferred in this respect.
  • a typical formulation based on the invention comprises : Anhydrous sodium percarbonate 25-60% Tetra acetyl ethylene diamine (TAED) up to 20% Anhydrous Citric acid 5-20% Sodium Citrate 0-10% Silicate SKS-6 0-20% Sodium Sulphate 0-40% Lipolase® 100T (Novo) 0.1-10% Savinase® 4.0CT + (Novo) 0.05-10% Maleic acrylic copolymer (granular Sokalan CP5) 2-10% Perfume 0.10-0.20% FWA (Tynopal® CBS-X) 0.04-0.10% Encapsulated BH-base 0.02-0.06%
  • the lipase used in the present invention is included in the detergent and bleaching composition e.g. in such an amount that the final composition has a lipolytic enzyme activity of from 10 to 0.005 LU/mg, preferably 5 to 0.05 LU/mg of the composition.
  • An alternative definition of the lipase unit is given in EP-A-0 258 068 (Novo), which mentions (inter alia) lipases suitable for use in the practice of this invention.
  • the lipase(s) can be used in its (their) non-purified form or in a purified form, e.g., purified with the aid of well-known adsorption methods, such as phenyl sepharose adsorption techniques.
  • the detergent composition or additive of the invention may be formulated in any convenient form, preferably as a powder.
  • This composition may have different applications and can be used in dry bleach formulations and detergent formulations including laundry and automatic dishwashing detergent formulations as mentioned above.
  • compositions of the invention are of use in laundry dry bleaches both in machine and by hand.
  • the dosage is usually 5gr - 80gr per wash whereas the wash solution could change depending on the geography and may vary form 20 - 60 liters/wash.
  • compositions of the invention are also of use in machine dishwashing processes of the conventional type performed using a dishwasher machine, which may be selected from any of those commonly available on the market.
  • machine dishwashing processes comprise treating soiled articles, such as crockery, glassware, hollowware and cutlery, with an aqueous liquid having dissolved or dispersed therein an effective amount of the detergent composition as described herein above.
  • an effective amount of the detergent composition it is generally meant from 8g to 60g of detergent composition per wash, dissolved or dispersed in a wash solution volume of from 3 to 10 litres, as are typical product dosages employed in conventional machine dishwashing processes.
  • the wash temperature may be in the range 40 o C to 65 o C as commonly is employed in such processes.
  • a rinse aid composition may also be used, if desired.
  • Detergent compositions or additives of the invention may contain as above-mentioned other detergent ingredients known in the art as e.g. builders, anti soil redeposition agents, perfumes, surfactants, anti-dye transfer ingredients, optical brighteners, other enzymes (e.g. proteases and amylases) etc.
  • other detergent ingredients known in the art as e.g. builders, anti soil redeposition agents, perfumes, surfactants, anti-dye transfer ingredients, optical brighteners, other enzymes (e.g. proteases and amylases) etc.
  • detergent compositions comprise surfactants which may be of the anionic, non-ionic,amphoteric, cationic or zwitteronic type as well as mixtures of these types.
  • anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source preferably from a C 16 -C 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C 14-15 alkyl sulphates.
  • An example of a preferred ethoxy sulphate is the so-called AE3S (C 12-15 alkyl 3 times ethoxylated sulphate).
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • Nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nil-LAS containing detergent composition or additive is used according to the invention.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the detergent composition or additive preferably comprises anionic surfactant to non-ionic surfactant in a ratio between 1 : 1 to 10 : 1.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C 8 -C 20 , preferably C 10 -C 14 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • amphoteric surfactants such as polyamine-based species.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C 8 -C 16 , preferably C 10 -C 14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent compositions can comprise from 1%-70% by weight of surfactant, but usually the surfactant is present in the compositions herein an amount of from 1% to 30%, more preferably from 2-15% by weight. More surfactant would be detrimental to lipase activity.
  • Builder materials will typically be present at from 0% to 90%, preferably up to 30% of the detergent compositions herein.
  • compositions herein should preferably be free or substantially free of phosphate-containing builders (substantially free being herein defined to constitute less than 1% of the total detergent builder system).
  • the builder system herein may consist of water-soluble builders, water-insoluble builders, or mixtures thereof. However, where the detergent compositions are for use in an automatic dishwashing process the builder material is most preferably water-soluble.
  • Water insoluble builders can be an inorganic ion exchange material,commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B, P, MAP or HS.
  • Preferred aluminosilicate ion-exchange materials have the unit cell formula M Z [(A10 2 ) z (SiO 2 ) y ] xH 2 O wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline containing from 10% to 28%, more preferably from 18% to 22% water.
  • the above aluminosilicate ion exchange materials are further charaterized by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the aluminosilicate ion exchange materials are further characterized by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is described in detail in GB-A-1,429,143.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula Na 12 [(A10 2 ) 12 (SiO 2 ) 12 ] xH 2 O wherein x is from 20 to 30, especially 27.
  • Zeolite X of formula Na 86 [(A10 2 ) 86 (SiO 2 ) 106 ] - 10 .276H 2 O is also suitable, as well as Zeolite HS of formula Na 6 [(A10 2 ) 6 (SiO 2 ) 6 ] 7.5 H 2 O).
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 5 ).
  • the high Ca ++ /Mg ++ binding capacity is mainly a cation exchange mechanism. In hot water, the material becomes more soluble.
  • the water-soluble builder can be a monomeric or oligomeric carboxylate chelating agent.
  • Suitable carboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
  • builder materials that can form part of the builder system for the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates and silicates.
  • Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • compositions of the invention may fully contain from 0.05% to 5% by weight of the composition, preferably from 0.05% to 1% by weight, most preferably from 0.1% to 0.5% by weight of a chelant (heavy metal sequestrant).
  • a chelant hereinavy metal sequestrant
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 4 EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg 2 EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • chelants include the organic phosphonates, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal ion to said phosphonate compound being at least 1:1. Such complexes are described in US-A-4,259,200.
  • the organic phosphonate compounds where present are in the form of their magnesium salt.
  • the level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred.
  • Other chelants suitable for inclusion herein include amino polycarboxylate chelants such as EDTA and HEDTA.
  • compositions will typically include optional ingredients that normally form part of detergent compositions like antiredeposition and soil suspension agents, optical brighteners, suds suppressors, anticaking agents, dyes and pigments; such optional ingredients can be added in varying amounts as desired.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2 1 disulphonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2' - disulphonate, disodium 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, monosodium 4',4"-bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate, dis
  • any particulate inorganic perhydrate bleach can be used.
  • the inorganic perhydrate is used in an amount delivering in the composition an active oxygen from 3% to 11% by weight, more preferably from 4% to 8.5% by weight, and most preferably from 4% to 7% by weight.
  • Preferred examples of such bleaches are sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.
  • Another preferred separately mixed ingredient is a peroxy carboxylic acid bleaching agent and salts thereof, which is preferably added in a prilled or agglomerated form.
  • Peroxygen bleaching agents are combined with bleach activators, which lead to the in situ production in aqueous solution (i.e. during the washing process of the peroxy acid corresponding to the bleach activator).
  • bleach activators which lead to the in situ production in aqueous solution (i.e. during the washing process of the peroxy acid corresponding to the bleach activator).
  • suitable compounds of this type are disclosed in British Patent Nos. 1586769 and 2143231 and a method for their formation into a prilled form is described in European Published Patent Application No. 0 062 523.
  • Preferred examples of such compounds are tetracetyl ethylene diamine, sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US-A-4 818 425 and nonylamide of peroxyadipic acid as described for instance in US-A-4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in EP-A-0 624 154.
  • TBS n-nonanoyloxybenzenesulphonate
  • ATC acetyl triethyl citrate
  • Bleach activators are for instance normally employed at levels of from 1% to 24% by weight, more frequently from 1% to 18% and preferably from 2% to 14% by weight of the composition.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 millimicrons to 20 millimicrons and a specific surface area above 50 m 2 /g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3,933,672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially availably from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • the incorporation of the suds modifiers is preferably made as separate particulates, and this permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.
  • Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al U.S. Patent No. 3,933,672.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH 3 (PEG) 43 ) 0.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) 0.4 ]T(PO-H) 0.25 ((PEG) 43 CH 3 ) 0.75 where PEG is -(OC 2 H 4 )O-,PO is (OC 3 H 6 O) and T is (pcOC 6 H 4 CO).
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • Certain polymeric materials such as polyvinyl pyrrolidones typically of MW 5000-20000, preferably 10000-15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.
  • Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1,400,898. Organic fabric softening agents include the water-insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
  • Levels of smectite clay are normally in the range from 5% to 20%, more preferably from 8% to 15% by weight with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or di-long-chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • compositions according to the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation and combinations of any of these techniques.
  • the compositions according to the present invention can be prepared with different bulk densities, from conventional granular products to so-called "concentrated" products (i.e. with a bulk density above 600g/l).
  • Tests were conducted in a European washing machine at 40C° with medium water hardness 239,4 ppm (14g/Us gallon). For each wash cycle 70 g of each formulation was added to the wash on top of 170 g of powder detergents. Each result is an average of 6 replicates done with each product tested. All results represent a comparison of the cleaning results achieved with Al or A2 (described above) vs. a common reference which is a commonly used dry bleach composition based on perborate and sold in Southern Europe (Ace Color).
  • results from 0 to 0.5 units indicate that there is no visible difference between the removal achieved with the reference and the test product.
  • Results from 0.6 to 1.0 units indicate that there is a small, but visible difference between the removal delivered by the reference and the test product.
  • Results from 1.1 to 2.0 units indicate that the two products deliver removals that are clearly different and easily detectable by eyesight. Positive results indicate better removal vs. the reference.
  • lipolase® 100 T and/or different types of savinase® to a matrix not containing any bleach (100% sodium sulphate) and to a matrix containing a high level of bleach e.g. like Al or A2. Results are as follows : 0.5% lipolase 0.5% lipolase 0.5% lipolase 0.5% lipolase 0.5% savinase 4.0T 0.5% savinase 4.0 CT+ Sodium sulphate matrix 0.50 0.50 0.52 High level bleach matrix 0.44 0.26 0.45
  • the coating is generally composed by polyethyleneglycol 4000 (PEG) and/or polyvinyl pyrrolidone (PVP), and a cellulose derivative.
  • the coating material may also contain other ingredients working as fillers, coating or granulating agents, antioxidants (e.g. Na 2 SO 4 ,CaCO 3 ,NaCl, talc, TiO 2 , magnesium silicate, sorbitol or copolymers of acrylic acid or metacrylic acid and other units).
  • the very good compatibility betwee savinase® 4.0 CT +, and lipolase® is may be due to the high level of PEG and/or PVP included in the coating.
  • PEG and PVP are materials that can deliver under specific conditions a reversible inhibition effect on savinase and thus enhances probably the compatibility with lipolase.
  • lipolase® stabilization when the protease inhibiting ingredients (like PEG and/or PVP) are incorporated in the coating of lipolase itself instead of in the coating of the protease is part of our invention.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Reinigungsmittelzusammensetzung oder -additiv, umfassend einen Bleichaktivator, einen hohen Anteil an Bleichmittel, welches in der Zusammensetzung 3 - 11 Gew.-% verfügbaren aktiven Sauerstoff vorsieht, und eine Lipase, dadurch gekennzeichnet, daß sie weiterhin eine doppelt beschichtete Protease umfaßt.
  2. Reinigungsmittelzusammensetzung oder -additiv nach Anspruch 1, wobei das Bleichmittel wasserfreies Natriumpercarbonat ist.
  3. Reinigungsmittelzusammensetzung oder -additiv nach mindestens einem der Ansprüche 1 - 2, wobei die doppelt beschichtete Protease mit Polyethylenglykol und/oder Polyvinylpyrrolidon und einem Cellulasederivat beschichtet ist.
  4. Verwendung einer Reinigungsmittelzusammensetzung oder - additivs nach Anspruch 1, wobei die lipolytische Aktivität in der Waschlösung unverändert bleibt.
  5. Verwendung einer Reinigungsmittelzusammensetzung oder -additivs nach Anspruch 4 zur Entfernung von Fett und/oder bleichbarem und/oder proteinhaltigem Schmutz in der Waschlösung.
EP93870099A 1993-06-07 1993-06-07 Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln Expired - Lifetime EP0628625B1 (de)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DE69324802T DE69324802T2 (de) 1993-06-07 1993-06-07 Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln
ES93870099T ES2131103T3 (es) 1993-06-07 1993-06-07 Proteasa compatible con lipasa en composiciones de blanqueo secas, concentradas.
EP93870099A EP0628625B1 (de) 1993-06-07 1993-06-07 Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln
JP7501929A JPH09501451A (ja) 1993-06-07 1994-06-02 乾燥濃縮漂白剤組成物中のリパーゼと相容性の二重被覆プロテアーゼ
CN94192823A CN1066193C (zh) 1993-06-07 1994-06-02 在干燥的浓缩漂白剂组合物中与脂肪酶相容的双涂层蛋白酶
AU70507/94A AU678027B2 (en) 1993-06-07 1994-06-02 Double coated protease compatible with lipase in dry concentrated bleach compositions
CA002164587A CA2164587A1 (en) 1993-06-07 1994-06-02 Double coated protease compatible with lipase in dry concentrated bleach compositions
BR9406791A BR9406791A (pt) 1993-06-07 1994-06-02 Protease revestida dupla compatível com lipase em composições alvejantes concentradas em pó
PCT/US1994/006189 WO1994029423A1 (en) 1993-06-07 1994-06-02 Double coated protease compatible with lipase in dry concentrated bleach compositions
ZA943979A ZA943979B (en) 1993-06-07 1994-06-07 Protease compatible with lipase in dry concentrated bleach compositions
GR990401142T GR3030162T3 (en) 1993-06-07 1999-05-07 Protease compatible with lipase in dry, concentrated bleach compositions.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93870099A EP0628625B1 (de) 1993-06-07 1993-06-07 Mit Lipase verträgliche Protease in trockenen konzentrierten Bleichmitteln

Publications (2)

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EP0628625A1 EP0628625A1 (de) 1994-12-14
EP0628625B1 true EP0628625B1 (de) 1999-05-06

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EP (1) EP0628625B1 (de)
JP (1) JPH09501451A (de)
CN (1) CN1066193C (de)
AU (1) AU678027B2 (de)
BR (1) BR9406791A (de)
CA (1) CA2164587A1 (de)
DE (1) DE69324802T2 (de)
ES (1) ES2131103T3 (de)
GR (1) GR3030162T3 (de)
WO (1) WO1994029423A1 (de)
ZA (1) ZA943979B (de)

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
GB9407534D0 (en) * 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
DE19501120A1 (de) * 1995-01-17 1996-07-18 Henkel Kgaa Enzymhaltiges bleichendes Waschmittel
ATE189696T1 (de) * 1995-08-25 2000-02-15 Henkel Kgaa Verwendung von lipasen in niederalkalischen mitteln zum maschinellen geschirrspülen
MX2009003467A (es) * 2006-10-06 2009-04-14 Danisco Us Inc Genencor Div Composiciones enzimaticas libres de celulasa y celulas hospederas para producir las mismas.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4106991A (en) * 1976-07-07 1978-08-15 Novo Industri A/S Enzyme granulate composition and process for forming enzyme granulates

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8514707D0 (en) * 1985-06-11 1985-07-10 Unilever Plc Enzymatic detergent composition
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
WO1987007292A1 (en) * 1986-05-21 1987-12-03 Novo Industri A/S Coated detergent enzymes
ES2058119T3 (es) * 1986-08-29 1994-11-01 Novo Nordisk As Aditivo detergente enzimatico.
US4965012A (en) * 1987-04-17 1990-10-23 Olson Keith E Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
DK571587D0 (da) * 1987-11-02 1987-11-02 Novo Industri As Enzymatisk detergentsammensaetning
JPH02208400A (ja) * 1989-02-07 1990-08-17 Lion Corp 漂白剤組成物
US5107854A (en) * 1989-05-19 1992-04-28 Boulder Impact Monitors, Inc. Orthopedic limb load monitor
EP0506791B1 (de) * 1989-12-21 1993-09-08 Novo Nordisk A/S Enzymhaltige zubereitung und eine solche zubereitung enthaltendes detergens
US5281356A (en) * 1993-03-25 1994-01-25 Lever Brothers Company Heavy duty liquid detergent compositions containing non-proteolytic enzymes comprising capsules comprising proteolytic enzyme and composite polymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4106991A (en) * 1976-07-07 1978-08-15 Novo Industri A/S Enzyme granulate composition and process for forming enzyme granulates

Also Published As

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AU678027B2 (en) 1997-05-15
AU7050794A (en) 1995-01-03
EP0628625A1 (de) 1994-12-14
CA2164587A1 (en) 1994-12-22
ZA943979B (en) 1995-02-02
DE69324802D1 (de) 1999-06-10
WO1994029423A1 (en) 1994-12-22
JPH09501451A (ja) 1997-02-10
CN1127522A (zh) 1996-07-24
ES2131103T3 (es) 1999-07-16
GR3030162T3 (en) 1999-08-31
BR9406791A (pt) 1996-01-30
CN1066193C (zh) 2001-05-23
DE69324802T2 (de) 1999-12-09

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